CN104744656A - Method for preparing star-shaped biodegradable shape-memory-polymer nano composite material - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
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- C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
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Abstract
The invention relates to a method for preparing a star-shaped biodegradable shape-memory-polymer nano composite material. According to the shape-memory composite material, POSS and isocyanate chain segments are taken as a hard phase, and poly-D,L-lactide and polytetramethylene ether glycol are taken as a soft phase. The method for preparing the shape-memory composite material comprises the steps of firstly preparing polyhedral silsesquioxane, of which eight vertexes are provided with hydroxyl groups, initiating the ring-opening polymerization of D,L-lactide with polyhedral silsesquioxane so as to prepare star-shaped POSS-PLA of a certain molecular weight, and then, coupling to polytetramethylene ether glycol through diisocyanate, thereby forming a three-dimensional reticulated copolymer. The shape-memory composite material prepared by the method has the characteristics of strong deformation holding ability, high shape recovery rate, good shape memory performance and repeatability, biodegradation and the like; furthermore, due to the adding of inorganic nanoparticle POSS, the recovery stress of a shape memory polymer is increased.
Description
Technical field
The invention belongs to biomaterial for medical purpose field, relate to a kind of preparation method of star-like biodegradable shape memory polymeric nano composite material.
Background technology
The develop rapidly of society science and technology, the progress of development to human society of material serves positive effect.Meanwhile, development and each interdisciplinary intersection of different field are had higher requirement to the performance of material and function, and the requirement of people to material is more and more higher.Under such background, various type material arises at the historic moment.Have in microtexture intrinsic sensing, execution, control and the information processing function intelligent material be exactly wherein a kind of, its structure not only has the bearing function that common material has, and also has specific perception and response function.As a kind of type material, intelligent material is more and more subject to the attention of numerous scholars.
Shape-memory polymer (SMPs) namely refers to have certain original shape, after distortion is fixed under certain ambient conditions effect, by the outside stimulus such as heat, electricity, magnetic, light, can return back to the polymkeric substance of its original shape.Shape-memory polymer can be divided into according to different stimulation means: thermotropic shape-memory polymer, electroluminescent type shape-memory polymer, mangneto type shape-memory polymer, photic type shape-memory polymer and the driving shape-memory polymer of its solution etc.20th century the mid-80, shape-memory polymer enters the high speed development stage, up to now, the shape-memory polymer developed mainly contains shape memory polyurethane, shape memory epoxy resin, styryl shape-memory polymer, shape memory vinylbenzene, shape memory cyanate, shape memory using trans-polyisoprene etc.
Shape-memory polymer has replys deformation quantity greatly, and memory effect is remarkable, and machine-shaping is easy, good insulating, not corrosion, easy coloring, can print, the features such as low price, obtain application at aerospace, electronics, machinery and increasing civil area.And some shape-memory polymers also have good biocompatibility and degradability, in bio-medical field, be widely used as pharmaceutical carrier, timbering material etc.The problems such as but compare with other shape-memory materials, it is not high enough that shape-memory polymer exists physical strength, and shape recovery force is little, recovery rate is slow, and repetitive memory effect is undesirable, and lax and creep is serious, greatly limit its range of application.To this, some researchists are devoted to study the shape-memory polymer with novel texture, to improve mechanical property and the shape memory recoverability of shape-memory polymer.Wherein method is exactly adopt the filler adding high-modulus in shape-memory polymer to carry out a modification, and the performance improving shape-memory polymer achieves unusual effect.
Poly(lactic acid) has excellent biocompatibility and absorbability, nontoxic, nonirritant, and it can decompose completely under the effect such as microorganism, water, acid, alkali of occurring in nature, and final product is CO
2and H
2o, environmentally safe (Fan Xin, Chen Jian, Ruan Jianming, Zou Jianpeng, Zhou Zhongcheng, Liu Ying, Zhang Haipo. polylactic acid-based Biodegradable material progress [J]. Materials Science and Engineering of Powder Metallurgy, 2008,04:187-194).The application of polytetramethylene ether diol in medical macromolecular material is increasingly extensive, as medically can be used for manufacturing catheter, bags of blood, gas bushing, condom, baby diaper and all kinds of artificial limb, have good biocompatibility (Yu Jiankun. the economic profile of polytetrahydrofuran and process progress [J]. chemical propellant and macromolecular material, 2006,4 (4): 7 ~ 11).
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the degradable star-type nano composite material of shape memory function.
The preparation method of the star-like biodegradable shape memory polymeric nano composite material that the present invention proposes, it is characterized in that this composite material of shape memory is star-like segmented copolymer, is hard phase with POSS, isocyanic ester segment.PDLLA, polytetramethylene ether diol are soft phase; Prepare the polyhedral silsesquioxane (POSS-(OH) that eight summits are hydroxyl
8), cause D with it, the ring-opening polymerization of L-rac-Lactide, obtains star-like POSS-PLA, and then pass through vulcabond coupling with polytetramethylene ether diol, form three-dimensional netted polymer nanocomposites, concrete steps are as follows:
(1) ring-opening polymerization: POSS-(OH)
8cause D; the ring-opening polymerization of L-rac-Lactide, polymerization temperature 125-135 DEG C, time 18-24 hour; nitrogen protection; add dissolution with solvents after polymerization terminates, then it is slowly instilled precipitation agent and polymkeric substance is precipitated, purified product; vacuum-drying; obtain white flock degradable high polymer material, this material is terminal hydroxy group star-type polymer POSS-PLA, control POSS-(OH)
8be 1:484-1:3272 with the mol ratio of DL-rac-Lactide;
(2) chain extension: terminal hydroxy group star-type polymer POSS-PLA step (1) obtained is dissolved in anhydrous methylene chloride, adds polytetramethylene ether diol, adds vulcabond and catalyzer after dissolving after it dissolves, and stirs 4 ~ 6 hours under normal temperature and pressure;
(3) crosslinked film forming: the solution that step (2) obtains is poured in Teflon mould; the lower nature solvent flashing of nitrogen at room protection 24 hours; then put into 75-80 DEG C of baking oven to be cross-linked, 48 as a child the shape-memory polymer nano composite material of sheet.
In the present invention, in step (1), the preparation method of the polyhedral silsesquioxane that eight summits are hydroxyl is:
(1) POSS-(Cl)
8preparation: methyl alcohol, (3-chloropropyl) trimethyl silane, hydrochloric acid stirred at ambient temperature 5 weeks, after filtration white powder, use deionized water wash.Wherein, the massfraction of methyl alcohol, (3-chloropropyl) trimethyl silane, hydrochloric acid is respectively: 88.37%, 4.93%, 6.7%;
(2) by POSS-(Cl)
8, ethanol, tetrahydrofuran (THF), Ag
2o and deionized water mixing, vigorous stirring under dark surrounds, 74 DEG C are refluxed 48 hours, filter, and obtain white solid after revolving steaming.Wherein POSS-(Cl)
8, ethanol, tetrahydrofuran (THF), Ag
2the massfraction of O and deionized water is 2.22%, 43.88%, 49.45%, 2.225% and 2.225%.
In the present invention, catalyzer used in step (2) is the one in stannous octoate or tin protochloride, and catalyst charge is the 0.05-1.0 wt% of D, L-rac-Lactide total amount.
In the present invention, in step (1), solvent used is any one in tetrahydrofuran (THF), chloroform, DMF or methylene dichloride, and precipitation agent used is any one in methyl alcohol, ether or normal hexane.
In the present invention, in step (1), the molecular weight of the POSS-PLA of synthesis is 60000-300000; The molecular weight of polytetramethylene ether diol is 2000.
In the present invention, the vulcabond described in step (2) is 1,6-hexamethylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, 4, the one in 4 '-methylene-diphenyl isocyanic ester or 2,4 toluene diisocyanate.
beneficial effect of the present invention is:
Organism degradable star-type shape memory nano composite material described in the present invention, has certain transition temperature T
0.When temperature is higher than T
0time, polymkeric substance can random variation.Temperature drops to T
0lower shape is fixed.When temperature is elevated to T again
0time above, rise and return to original shape.Its this shape memory nano composite material has that deformation hold facility is strong, shape recovery rate is high, shape-memory properties is reproducible and the various features such as biodegradable.And inorganic nano-particle POSS add the recovery stress that improve shape-memory polymer.
Accompanying drawing explanation
Fig. 1: star-like biodegradable shape memory polymeric nano composite material structural representation prepared by embodiment 1.
Fig. 2: the relation in star-like biodegradable shape memory polymeric nano composite material shape-memory properties test prepared by embodiment 1 between temperature, stress, strain.
Embodiment
The present invention is further illustrated below by embodiment.
embodiment 1
In the beaker of 2.5L, put into 1.8L methyl alcohol, 79.5g (3-chloropropyl) Trimethoxy silane, 90ml hydrochloric acid, at room temperature stir 5 weeks, filter to obtain white powder, with deionized water wash and dry must POSS-(Cl)
8.4.71g AgNO is added in 100ml round-bottomed flask
3, add 30ml deionized water and dissolved.With vigorous stirring the aqueous solution containing 1.11g NaOH is added above-mentioned solution.Generate brown Ag
2o precipitates, suction filtration, deionized water wash three times.3g POSS-(Cl) is added in 250ml round-bottomed flask
8, 75ml ethanol, 75ml tetrahydrofuran (THF), above-mentioned Ag
2o and 3ml deionized water together joins in solution, system vigorous stirring 48 hours in dark conditions, 74 DEG C of backflows.Filter twice, revolve steaming after getting clear liquid and obtain white solid, be i.e. POSS-(OH)
8
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 7.258g(0.0504 mol) add in the round-bottomed flask of 50ml drying, add 0.0874g(1.04 × 10
-4mol) POSS-(OH)
8, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then add precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flocculent polymer.Molecular weight is 6.3 ten thousand.The white flocculent polymer 1.17g obtained is dissolved in 14ml anhydrous methylene chloride, adds 0.298g polytetramethylene ether diol, after it dissolves completely, add 0.031g 1,6-hexamethylene diisocyanate and the sub-tin of 0.01 wt% chain extension octoate catalyst.Stirred at ambient temperature 4h, pours Teflon mould into, room temperature, N
2the lower solvent flashing 24h of protection, puts into 78 DEG C of curing oven 48h and obtains shape-memory polymer nano composite material.
As shown in Figure 2, this figure is the relation in the test of star-like biodegradable shape memory polymeric nano composite material shape-memory properties between temperature, stress, strain.From figure, data can calculate, and the shape memory response rate of twice circulation is respectively 90.99% and 91.5%.Shape fixed rate is all higher than 99%.
embodiment 2
POSS-(OH)
8preparation method as embodiment 1.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056mol) add in the round-bottomed flask of 50ml drying, add 0.0414g(4.93 × 10
-5mol) POSS-(OH)
8, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then add precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flocculent polymer.Molecular weight is 12.8 ten thousand.The white flocculent polymer 1.396g obtained is dissolved in 14ml anhydrous methylene chloride, add 0.0875g polytetramethylene ether diol, 0.0166g 1,6-hexamethylene diisocyanate and the sub-tin of 0.01 wt% chain extension octoate catalyst is added after it dissolves completely.Stirred at ambient temperature 4h, pours Teflon mould into, room temperature, N
2the lower solvent flashing 24h of protection, puts into 78 DEG C of curing oven 48h and obtains shape-memory polymer nano composite material.
embodiment 3
POSS-(OH)
8preparation method as embodiment 1.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 7.98g(0.055mol) add in the round-bottomed flask of 50ml drying, add 0.0258g(3.08 × 10
-5mol) POSS-(OH)
8, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then add precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flocculent polymer.Molecular weight is 24.4 ten thousand.The white flocculent polymer 1.44g obtained is dissolved in 14ml anhydrous methylene chloride, add 0.0472g polytetramethylene ether diol, 0.0089g 1,6-hexamethylene diisocyanate and the sub-tin of 0.01 wt% chain extension octoate catalyst is added after it dissolves completely.Stirred at ambient temperature 4h, pours Teflon mould into, room temperature, N
2the lower solvent flashing 24h of protection, puts into 78 DEG C of curing oven 48h and obtains shape-memory polymer nano composite material.
embodiment 4
POSS-(OH)
8preparation method as embodiment 1.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 7.26g(0.05mol) add in the round-bottomed flask of 50ml drying, add 0.0129g(1.54 × 10
-5mol) POSS-(OH)
8, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then add precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flocculent polymer.Molecular weight is 30.6 ten thousand.The white flocculent polymer 1.45g obtained is dissolved in 14ml anhydrous methylene chloride, adds 0.038g polytetramethylene ether diol, after it dissolves completely, add 0.0072g 1,6-hexamethylene diisocyanate and the sub-tin of 0.01 wt% chain extension octoate catalyst.Stirred at ambient temperature 4h, pours Teflon mould into, room temperature, N
2the lower solvent flashing 24h of protection, puts into 78 DEG C of curing oven 48h and obtains shape-memory polymer nano composite material.
embodiment 5
POSS-(OH)
8preparation method as embodiment 1.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 7.258g(0.0504 mol) add in the round-bottomed flask of 50ml drying, add 0.0874g(1.04 × 10
-4mol) POSS-(OH)
8, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then add precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flocculent polymer.Molecular weight is 6.3 ten thousand.The white flocculent polymer 0.75g obtained is dissolved in 14ml anhydrous methylene chloride, adds 0.75g polytetramethylene ether diol, after it dissolves completely, add 0.067g 1,6-hexamethylene diisocyanate and the sub-tin of 0.01 wt% chain extension octoate catalyst.Stirred at ambient temperature 4h, pours Teflon mould into, room temperature, N
2the lower solvent flashing 24h of protection, puts into 78 DEG C of curing oven 48h and obtains shape-memory polymer nano composite material.
Claims (6)
1. the preparation method of a star-like biodegradable shape memory polymeric nano composite material, it is characterized in that this composite material of shape memory is star-like segmented copolymer, be hard phase with POSS, isocyanic ester segment, PDLLA, polytetramethylene ether diol are soft phase; Prepare the polyhedral silsesquioxane (POSS-(OH) that eight summits are hydroxyl
8), cause D with it, the ring-opening polymerization of L-rac-Lactide, obtains star-like POSS-PLA, and then pass through vulcabond coupling with polytetramethylene ether diol, form three-dimensional netted polymer nanocomposites, concrete steps are as follows:
(1) ring-opening polymerization: POSS-(OH)
8cause D; the ring-opening polymerization of L-rac-Lactide, polymerization temperature 125-135 DEG C, time 18-24 hour; nitrogen protection; add dissolution with solvents after polymerization terminates, then it is slowly instilled precipitation agent and polymkeric substance is precipitated, purified product; vacuum-drying; obtain white flock degradable high polymer material, this material is terminal hydroxy group star-type polymer POSS-PLA, control POSS-(OH)
8be 1:484-1:3272 with the mol ratio of D, L-rac-Lactide;
(2) chain extension: terminal hydroxy group star-type polymer POSS-PLA step (1) obtained is dissolved in anhydrous methylene chloride, adds polytetramethylene ether diol, adds vulcabond and catalyzer after dissolving after it dissolves, and stirs 4 ~ 6 hours under normal temperature and pressure;
(3) crosslinked film forming: the solution that step (2) obtains is poured in Teflon mould; the lower nature solvent flashing of nitrogen at room protection 24 hours; then put into 75-80 DEG C of baking oven to be cross-linked, 48 as a child the shape-memory polymer nano composite material of sheet.
2., according to the preparation method of the star-like biodegradable shape memory polymeric nano composite material described in claim 1, to it is characterized in that in step (1) that the preparation method of the polyhedral silsesquioxane that eight summits are hydroxyl is:
(1) POSS-(Cl)
8preparation: methyl alcohol, (3-chloropropyl) trimethyl silane, hydrochloric acid stirred at ambient temperature 5 weeks, white powder is obtained after filtration, with deionized water wash, wherein, the massfraction of methyl alcohol, (3-chloropropyl) trimethyl silane, hydrochloric acid is respectively: 88.37%, 4.93%, 6.7%;
(2) by POSS-(Cl)
8, ethanol, tetrahydrofuran (THF), Ag
2o and deionized water mixing, vigorous stirring under dark surrounds, 74 DEG C are refluxed 48 hours, filter, and obtain white solid, wherein POSS-(Cl) after revolving steaming
8, ethanol, tetrahydrofuran (THF), Ag
2the massfraction of O and deionized water is 2.22%, 43.88%, 49.45%, 2.225% and 2.225%.
3. the preparation method of star-like biodegradable shape memory polymeric nano composite material according to claim 1, it is characterized in that catalyzer used in step (2) is the one in stannous octoate or tin protochloride, catalyst charge is the 0.05-1.0 wt% of D, L-rac-Lactide total amount.
4. the preparation method of star-like biodegradable shape memory polymeric nano composite material according to claim 1, it is characterized in that in step (1), solvent used is tetrahydrofuran (THF), chloroform, N, in dinethylformamide or methylene dichloride any one, precipitation agent used is any one in methyl alcohol, ether or normal hexane.
5. the preparation method of star-like biodegradable shape memory polymeric nano composite material according to claim 1, is characterized in that the molecular weight of the POSS-PLA of synthesis in step (1) is 60000-300000; The molecular weight of polytetramethylene ether diol is 2000.
6. the preparation method of star-like biodegradable shape memory polymeric nano composite material according to claim 1, it is characterized in that the vulcabond described in step (2) is 1,6-hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4, one in 4 '-methylene-diphenyl isocyanic ester or 2,4 toluene diisocyanate.
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| CN105622888A (en) * | 2016-03-28 | 2016-06-01 | 桂林理工大学 | Method for preparing shape memory polymer material with high strength and low response temperature |
| CN108192073A (en) * | 2017-12-23 | 2018-06-22 | 广东互典缓冲材料技术有限公司 | Padded coaming that a kind of wide temperature range domain uses and its preparation method and application |
| CN109575221A (en) * | 2018-12-04 | 2019-04-05 | 镇江利德尔复合材料有限公司 | A kind of polyurethane shape memory material and preparation method thereof strengthened based on organosilicon polymer |
| CN109912774A (en) * | 2019-04-02 | 2019-06-21 | 镇江利德尔复合材料有限公司 | A kind of method of organosilicon reinforcing polyurethane shape-memory material mechanical strength |
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| CN109575221A (en) * | 2018-12-04 | 2019-04-05 | 镇江利德尔复合材料有限公司 | A kind of polyurethane shape memory material and preparation method thereof strengthened based on organosilicon polymer |
| CN109912774A (en) * | 2019-04-02 | 2019-06-21 | 镇江利德尔复合材料有限公司 | A kind of method of organosilicon reinforcing polyurethane shape-memory material mechanical strength |
| CN110123467A (en) * | 2019-05-21 | 2019-08-16 | 尤美医疗科技(大连)有限公司 | Gear division correction stealth facing and its application method with shape memory function |
| CN111848908A (en) * | 2020-07-17 | 2020-10-30 | 苏州玻导材料有限公司 | Polyhedral oligomeric silsesquioxane based nano polyurethane material and preparation method thereof |
| CN115887761A (en) * | 2023-02-23 | 2023-04-04 | 四川兴泰普乐医疗科技有限公司 | Sinus stent and preparation method thereof |
| CN117209887A (en) * | 2023-09-06 | 2023-12-12 | 广东科净塑料制品有限公司 | High-toughness durable polypropylene material and preparation process thereof |
| CN117209887B (en) * | 2023-09-06 | 2024-04-16 | 珠海市金塑塑料有限公司 | High-toughness durable polypropylene material and preparation process thereof |
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