CN104292481A - Method for preparing synergetic enhanced polylactic acid biological composite material - Google Patents
Method for preparing synergetic enhanced polylactic acid biological composite material Download PDFInfo
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- CN104292481A CN104292481A CN201410519186.1A CN201410519186A CN104292481A CN 104292481 A CN104292481 A CN 104292481A CN 201410519186 A CN201410519186 A CN 201410519186A CN 104292481 A CN104292481 A CN 104292481A
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- polylactic acid
- cellulose nano
- nano whisker
- sisal cellulose
- ampoule
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 104
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 230000002195 synergetic effect Effects 0.000 title abstract 3
- 244000198134 Agave sisalana Species 0.000 claims abstract description 100
- 229920002678 cellulose Polymers 0.000 claims abstract description 100
- 239000001913 cellulose Substances 0.000 claims abstract description 100
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003708 ampul Substances 0.000 claims description 70
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 60
- 239000000178 monomer Substances 0.000 claims description 60
- -1 poly(lactic acid) Polymers 0.000 claims description 58
- 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 43
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 238000000746 purification Methods 0.000 claims description 40
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 30
- 239000011173 biocomposite Substances 0.000 claims description 27
- 235000014655 lactic acid Nutrition 0.000 claims description 21
- 239000004310 lactic acid Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 241000237502 Ostreidae Species 0.000 claims description 20
- 239000000084 colloidal system Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- 235000020636 oyster Nutrition 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007781 pre-processing Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000005728 strengthening Methods 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 2
- 239000012620 biological material Substances 0.000 abstract description 7
- 230000005501 phase interface Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000007685 Pleurotus columbinus Nutrition 0.000 description 1
- 240000001462 Pleurotus ostreatus Species 0.000 description 1
- 235000001603 Pleurotus ostreatus Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical class NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for preparing a synergetic enhanced polylactic acid biological composite material. According to the method, an excellent interface bonding is formed by utilizing the interaction between an active group on nano-hydroxyapatite and a polylactic acid molecular chain, and a nano-hydroxyapatite layer is deposited on the surface of a polylactic acid oligomer grafted sisal cellulose nano-whisker/polylactic acid biological material by adopting an in situ precipitation so as to prepare the sisal cellulose nano-whisker/nano-hydroxyapatite/polylactic acid biological composite material which has the advantages of excellent phase interface bonding force and stability, good chemical performance and biocompatibility. The preparation process is simple and environmental friendly, and the prepared sisal cellulose nano-whisker/nano-hydroxyapatite synergetic enhanced polylactic acid biological composite material has excellent phase interface bonding force and stability and excellent mechanical performance and biological compatibility.
Description
Technical field
The invention belongs to technical field of composite preparation, particularly a kind of sisal cellulose nano whisker/nanometer hydroxyapatite works in coordination with the preparation method strengthening poly(lactic acid) Biocomposite material.
Background technology
After Poly-L-lactic acid (PLLA) implants as bone transplantation substitute material, along with the healing gradually of bone wound, can be degraded gradually by ester linkage hydrolyzing, and be finally decomposed into water and carbonic acid gas, be absorbed by the body or excrete, take out without the need to second operation, simplify operative procedure and improve result for the treatment of, thus become biomaterial study hotspot (Q.W. Zhang of new generation, V.N. Mochalin, I. Neitzel, et al. Mechanical properties and biomineralization of multifunctional nanodiamond-PLLA composites for bone tissue engineering [J]. Biomaterials, 2012, 33 (20): 5067-5075.).Mechanical property and degradation property (the A. Hidayat of matrix material effectively can be improved by natural plant fibre enhancing modified poly(lactic acid), S. Tachibana. Characterization of polylactic acid (PLA)/kenaf composite degradation by immobilized mycelia of Pleurotus ostreatus [J]. International Biodeterioration & Biodegradation, 2012,71:50-54.).But poly(lactic acid) biomaterial causes inflammatory reaction effectively to be solved not yet due to the acid product produced in degradation process.Nanometer hydroxyapatite particle (10 ~ 100 nm), all similar to the phosphatic rock crystallite in people's bone on its size, the Nomenclature Composition and Structure of Complexes, there is outstanding physico-chemical property and biology performance (Wang X, Li Y, Wei J, et al. Development of biomimetic nano-hydroxyapatite/poly (hexamethylene adipamide) composites [J]. Biomaterials, 2002,23 (24): 4787-4791.); The surface effects of nano material makes its surface atom have many dangling bondss simultaneously, has nonsaturation, thus has very high chemically reactive.(the Cheng Junqiu such as Cheng Junqiu, Duan Ke, Weng Jie, Deng. the preparation of porous nano hydroxyapatite lactic acid composite material and Interface Study [J] thereof. chemical research and application, 2001,13 (5): 517-520.) nanometer hydroxyapatite is directly scattered in PLA solution through sonic oscillation, prepare polylactic acid/nano-hydroxyapatite matrix material by thermally induced phase separation technique, there is good interface gluing effect, biocompatibility, absorbability, biological activity and synosteosis ability.
The present invention utilizes the active group on nanometer hydroxyapatite and the interaction between polylactic acid molecule chain to form good interface cohesion, and adopt in situ deposition method at the sisal cellulose nano whisker/poly(lactic acid) biomaterial surface depositing nano hydroxyapatite layer of grafted polylactic acid oligopolymer, simultaneously, by the relation between research nanometer hydroxyapatite layer thickness and composite property, preparation has good phase interface bonding strength and stability, sisal cellulose nano whisker/nano hydroxyapatite/polylactic acid Biocomposite material the material of outstanding mechanical property and biocompatibility.This thinking has no bibliographical information.
Summary of the invention
The object of this invention is to provide a kind of sisal cellulose nano whisker/nanometer hydroxyapatite and work in coordination with the preparation method strengthening poly(lactic acid) Biocomposite material.
Thinking of the present invention: utilize the active group on nanometer hydroxyapatite and the interaction between polylactic acid molecule chain to form good interface cohesion, and adopt in situ deposition method at the sisal cellulose nano whisker/poly(lactic acid) biomaterial surface depositing nano hydroxyapatite layer of grafted polylactic acid oligopolymer, prepare the sisal cellulose nano whisker/nano hydroxyapatite/polylactic acid Biocomposite material material with good phase interface bonding strength and stability, outstanding mechanical property and biocompatibility.
Concrete steps are:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to below 1Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 120 ~ 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3 ~ 4 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value more than 11 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value more than 11 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution more than 11, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is the one in 0.5:0.8:99,1:1.6:98,2.5:4:95,5:8:90,10:16:80,15:24:70,20:32:60 and 25:40:50.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 70 ~ 80 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
The inventive method preparation technology is simple, environmental protection, and prepared sisal cellulose nano whisker/nanometer hydroxyapatite is worked in coordination with and strengthened poly(lactic acid) Biocomposite material and have good phase interface bonding strength and stability, excellent mechanical property and biocompatibility.
Embodiment
embodiment 1:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 0.5:0.8:99.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 2:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 1:1.6:98.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 3:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 2.5:4:95.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 4:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 5:8:90.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 5:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 10:16:80.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 6:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 15:24:70.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 7:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 20:32:60.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
embodiment 8:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature.
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to 0.8Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000.
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3.5 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer.
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering.
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution.
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value 11.5 with ammoniacal liquor.
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution 11.5, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is 25:40:50.
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 75 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
Claims (1)
1. the collaborative preparation method strengthening poly(lactic acid) Biocomposite material, is characterized in that concrete steps are:
(1) by sisal cellulose nano whisker with purify after L-lactide monomer mix in molar ratio and be placed in pretreated ampoule, for subsequent use; L-lactide monomer after described purification is prepared by lactic acid underpressure distillation; Described sisal cellulose nano whisker is 1:1 with the mol ratio that mixes of the L-lactide monomer after purification; The preprocessing process of described ampoule is process 2 hours at 400 DEG C, and then vacuum cooling is to room temperature;
(2) initiator stannous octoate is joined in step (1) ampoule for subsequent use, then vacuumize, by pressure drop in ampoule bottle to below 1Pa, with alcohol blast burner, ampoule is sealed; The ratio of the amount of substance of the L-lactide monomer after the purification that the stannous octoate added and step (1) use is 1:12000;
(3) ampoule packaged for step (2) is placed in the thermostatic drying chamber of 120 ~ 125 DEG C, after L-lactide monomer after to be purified is all melted, L-lactide monomer after the ampoule that fluctuates makes purification mixes with initiator stannous octoate, then put into thermostatic drying chamber and carry out prepolymerization 3 ~ 4 hours, obtain the sisal cellulose nano whisker of grafted polylactic acid oligopolymer;
(4) the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (3) is warming up to 140 DEG C, proceed polyreaction, room temperature is naturally cooled to after reaction terminates, namely obtained sisal cellulose nano whisker/poly(lactic acid) Biocomposite material, namely obtains the sisal cellulose nano whisker/polylactic acid powder of grafted polylactic acid oligopolymer after shattering;
(5) by the sisal cellulose nano whisker of grafted polylactic acid oligopolymer obtained for step (4)/polylactic acid powder dispersion in deionized water, obtained solution;
(6) take nitrocalcite to be dissolved in deionized water and to prepare the ca nitrate soln that concentration is 0.5mol/L, and regulate its pH value more than 11 with ammoniacal liquor;
(7) take primary ammonium phosphate to be dissolved in deionized water and to prepare the ammonium dihydrogen phosphate that concentration is 0.3mol/L, and regulate its pH value more than 11 with ammoniacal liquor;
(8) solution that solution obtained for step (6) and step (7) obtain slowly is added drop-wise in the obtained solution of step (5), and quick vigorous stirring, by the pH value of ammoniacal liquor regulator solution more than 11, continue stirring 4 hours, obtained nanometer hydroxyapatite suspension colloid; Wherein, the mass ratio of nitrocalcite, primary ammonium phosphate and sisal cellulose nano whisker/lactic acid composite material is the one in 0.5:0.8:99,1:1.6:98,2.5:4:95,5:8:90,10:16:80,15:24:70,20:32:60 and 25:40:50;
(9) nanometer hydroxyapatite suspension colloid obtained for step (8) is left standstill, ageing is after 24 hours, continue to be heated to 70 ~ 80 DEG C, with deionized water wash, filtration, until supernatant liquor is in neutral, obtain oyster white mud, after oyster white mud is freezing in liquid nitrogen, be placed in the dry rear grind into powder of freeze drier, namely obtained sisal cellulose nano whisker/nanometer hydroxyapatite is collaborative strengthens poly(lactic acid) Biocomposite material.
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| CN107227006A (en) * | 2017-06-20 | 2017-10-03 | 苏州奥宇包装科技有限公司 | A kind of graphene oxide modified polylactic acid composite material and preparation method thereof |
| CN109135212A (en) * | 2017-06-16 | 2019-01-04 | 赵云飞 | The preparation method of sisal fiber composite material |
| CN109381746A (en) * | 2018-10-15 | 2019-02-26 | 湖南师范大学 | A kind of preparation method and applications of lignin modification nanometer hydroxyapatite |
| CN109420201A (en) * | 2017-09-05 | 2019-03-05 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of cellulose-polylactic acid-glycolic base apatite compound rest |
| CN110157170A (en) * | 2019-06-05 | 2019-08-23 | 东华大学 | A kind of polylactic acid/nano cellulose/hydroxyapatite composite material and its preparation |
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| CN101230189B (en) * | 2008-01-29 | 2010-06-02 | 武汉理工大学 | Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material |
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| CN109135212A (en) * | 2017-06-16 | 2019-01-04 | 赵云飞 | The preparation method of sisal fiber composite material |
| CN107227006A (en) * | 2017-06-20 | 2017-10-03 | 苏州奥宇包装科技有限公司 | A kind of graphene oxide modified polylactic acid composite material and preparation method thereof |
| CN109420201A (en) * | 2017-09-05 | 2019-03-05 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of cellulose-polylactic acid-glycolic base apatite compound rest |
| CN109381746A (en) * | 2018-10-15 | 2019-02-26 | 湖南师范大学 | A kind of preparation method and applications of lignin modification nanometer hydroxyapatite |
| CN110157170A (en) * | 2019-06-05 | 2019-08-23 | 东华大学 | A kind of polylactic acid/nano cellulose/hydroxyapatite composite material and its preparation |
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Application publication date: 20150121 Assignee: Guilin Qi Hong Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044172 Denomination of invention: A Preparation Method for Synergistic Reinforcement of Polylactic Acid Biocomposites Granted publication date: 20170215 License type: Common License Record date: 20231024 |