CN103059274B - Aliphatic polyester/calcium carbonate composite material and its preparation method - Google Patents
Aliphatic polyester/calcium carbonate composite material and its preparation method Download PDFInfo
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Abstract
The invention discloses an aliphatic polyester/calcium carbonate composite material. The composite material is obtained through in-situ ring-opening polymerization of 0.3-10 parts of calcium carbonate and 100 parts of a lactone monomer, wherein calcium carbonate is/is not subjected to surface modification treatment, and the morphology of the calcium carbonate has a dandelion shape formed through the self-assembling of sheet-shaped, spherical, silkworm cocoon-shaped, rhombohedral, rod-shaped, hollow bamboo shoot-shaped, dead tree trunk-shaped, bunchy, cactus-shaped, petal-shaped, cockscomb-shaped or nanometer rods, or has a hemispheric shape self-assembled through nanometer rods. The invention also discloses a preparation method of the composite material. Calcium carbonate utilized in the invention has abundant morphologies, and has a large contact area with a matrix, so the organic and inorganic endophilicity in the composite material is increased, and simultaneously calcium carbonate can be uniformly dispersed in the matrix, thereby the toughness of the aliphatic polyester matrix is well enhanced, and the composite mateiral can be well applied in the biomedical fields of bone restoration, bone fixation and the like.
Description
Technical field
The invention belongs to polymer/inorganic particle matrix material and preparing technical field thereof, be specifically related to a kind of aliphatic polyester/calcium carbonate composite material and preparation method thereof.
Background technology
Aliphatic polyester all has good biocompatibility, biological degradability and Bioabsorbable as poly(lactic acid) (PLA), Ju ε – caprolactone (PCL), poly-dioxy pimelinketone (PPDO) etc., in biomedical materials field development rapidly, not only be used as the reparation of operating sutures, orthopaedics repair materials, skin and cornea etc., and also have huge applications potentiality in fields such as orthopaedics immobilization material, intravascular stent and pharmaceutical carriers, thereby be closely subject to countries in the world investigator's common concern decades.
Desirable bone renovating material should be to promote by the triple mechanism of bone forming, bone conduction and bone inductive effect the material of knitting, and should possess controlled degradation property, good biocompatibility and the suitable features such as mechanical property.Although having good biodegradability, biocompatibility and formability, aliphatic polyester can, separately as the frame material of bone tissue engineer, but there is shortcomings: (1) physical strength is lower; (2) wetting ability is poor, cell adsorptive power a little less than; (3) can there is aseptic inflammation reaction (Du, J.M. in the tissue of implanting after live body; Liu, J. M.; Li, Z. M.; Han, Z. H.; Huang, B. X.; Zhang, Y. Microp. Mesop. Mater. 2005,145-149.).At present, think that the reason that occurs aseptic inflammation may can cause the relevant (Zheng Lei of local pH value decline with the acid degradation product generating in polymer degradation processes; Before king; Pei Guoxian. Chinese Reconstructive surgery magazine 2000,14,175-180).
For overcoming the above-mentioned defect of aliphatic polyester, improve the validity of its bone defect repair, use the composite organic-inorganic material approximate with nature bone as bone impairment renovation material, be conducive to undoubtedly form in the interface of area of new bone between osseous tissue and material.Calcium carbonate is a kind of Inorganic biomatetials, has good biocompatibility and degradation property, can not produce the toxic reaction of part or whole body after implanting to human body, and NIP and rejection can the direct combinations with the osseous tissue of body, and have osteoinductive.Can cushion the acid degradation product that aliphatic polyester degraded produces, the aseptic inflammation reaction of avoiding it to bring simultaneously.Therefore, the biomaterial of calcium carbonate and the reparation of the compound formation artificial bone of aliphatic polyester is had to good application prospect.
At present, the preparation method of aliphatic polyester/inorganic particle composite material mainly contains solution blending, melt blending and three kinds of methods of in-situ polymerization.(the W. Bai such as Bai Wei, D.L. Chen, Z.P. Zhang, Q. Li, D.J. Zhang, and C.D.Xiong, J. Biomed. Mater. Res. Part B, 2009,90,945.) by simple solution blending, prepare PPDO/ inorganic particle composite material, and studied inorganic particulate as the impact on composite materials property such as calcium carbonate.Due to the consistency of calcium carbonate and polymer P PDO poor (can obviously observe micron order calcium carbonate granule the scanning electron microscope providing from document), cause the calcium carbonate that only adds 1wt% just to make the elongation at break of PPDO reduce by 22.2%.In addition, in preparation process, the method is to take poisonous phenol tetrachloroethane as solvent, and this not only causes high cost, also can bring the problems such as environmental pollution, is not suitable for industry and applies.Melt-blending process is to prepare the most economical method of matrix material, and its advantage is that preparation and the synthetic of polymkeric substance of nanoparticle can carry out respectively, and easily controls size and the form of nanoparticle.(Liu, the H. such as Liu; Han, C. Y.; Dong, L. S. Polymer composites, 2010,31,1653-1661) just utilize melt-blending process to prepare PCL/CaCO
3matrix material, and studied crosslinked and the uncrosslinked impact on composite property.No matter result from research, whether be cross-linked, calcium carbonate add the tensile strength that all can improve material, still for uncrosslinked system, adding of calcium carbonate but makes its elongation at break that decline has occurred.The reason that causes this situation is that nanoparticle self is easily reunited, and melt blending is difficult to realize the dispersed of nanoparticle.In addition aliphatic polyester/the inorganic particle composite material obtaining by melt blending, the link between polyester and inorganic particle completes by physical action substantially, and under external force, inorganic particle is easy to come off and then reunite.And adopt in-situ polymerization mode can solve compatibility problem between various auxiliary agents, filler and the polymkeric substance that polymer blending modification occurs and the scattering problem in polymkeric substance, can also be used for connecting polymkeric substance and inorganic materials by chemical bonding simultaneously, can effectively improve the performance of polymkeric substance, further expand its Application Areas.(Li, the Y. H. such as Li; Sun. S. X. Z. Biomacromolecules 2010,11,1847 – 1855) by original position melt polymerization by the compound nano composite material that obtains of the MgO of Pfansteihl and surface hydroxylation.By the MgO(PLA-g-MgO of the PLA grafting to separating) carry out infrared and thermogravimetric analysis, confirmed that the lip-deep hydroxyl of PLA and MgO chemical action has occurred and formed grafts; Stereoscan photograph shows that MgO not only can be dispersed in PLA matrix by homogeneous, and combines closely with PLA matrix.Although the polymerization that this hydroxylated MgO causes can obtain having the matrix material of better performance, the degradation rate that membership makes aliphatic polyester that adds of MgO is obviously accelerated (Murariu, M.; Doumbia, A.; Bonnaud, L., et al. Biomacromolecules 2011,12,1762 – 1771), and the acid degradation product producing in degradation process, easily cause implant site to occur aseptic inflammation.In biocompatibility, toxicity and the osteoinductive of MgO document at home and abroad, do not report whether can need further to confirm as osseous tissue renovating material simultaneously.
Summary of the invention
The object of the invention is the problem existing for prior art, first a kind of new aliphatic polyester/calcium carbonate composite material is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned aliphatic polyester/calcium carbonate composite material.
Aliphatic polyester/calcium carbonate composite material provided by the invention, is characterized in that this matrix material is to be composited through original position by following component by weight:
100 parts of internal ester monomers,
0.3～10 part, calcium carbonate,
And described calcium carbonate is through surface modification treatment or surface modification treatment not, its pattern is sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, the pencil that nanometer rod self-assembly forms, celestial being's palmate that nanometer rod is self-assembled into, the petal-shaped that nanometer rod is self-assembled into, the taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical, preferably spherical (SCC), silk cocoon shape (PCC), the calcium carbonate of hemispherical (HSCC) pattern that the taraxacum shape (DCC) that nanometer rod is self-assembled into or nanometer rod are self-assembled into.And the intrinsic viscosity of this matrix material is 1.12 ~ 2.25dl/g, tensile strength is 16.6～70.8MPa, and elongation at break is 8.3～1103.6%.The content of calcium carbonate described in above matrix material is preferably 0.3～5 part.
Internal ester monomer described in above matrix material is rac-Lactide (LA), 6-caprolactone (ε-CL) or to any in dioxy pimelinketone (PDO), preferably 6-caprolactone or to dioxy pimelinketone.
Described in above matrix material, through surface modification treatment calcium carbonate, be to adopt surface-modifying agent to carry out surface modification to the calcium carbonate of different-shape, surface-modifying agent used is stearic acid, sodium lauryl sulphate, sodium laurylsulfonate or silane coupling agent, the preferred KH550 of silane coupling agent, KH560 or KH570.
The preparation method of above-mentioned aliphatic polyester/calcium carbonate composite material provided by the invention, is characterized in that the processing step of the method and condition are as follows:
Under protection of inert gas; at 0.3～10 weight part through surface modification treatment or do not add the internal ester monomer of 100 weight parts in the calcium carbonate of surface modification treatment; ultrasonic dispersion 0.5～3h at 40～140 ℃; then under 40～160 ℃ of agitation conditions; the catalyzer that to add with internal ester monomer mol ratio be 0.0002～0.005:1; cooling after reaction 3～48 h, pulverize, dry.
The pencil that wherein pattern of calcium carbonate used is sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, nanometer rod is self-assembled into, celestial being's palmate that nanometer rod is self-assembled into, petal-shaped that nanometer rod is self-assembled into, taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical, the calcium carbonate of hemispherical (HSCC) pattern that the taraxacum shape (DCC) that preferably spherical (SCC), silk cocoon shape (PCC), nanometer rod are self-assembled into or nanometer rod are self-assembled into.
The preparation method of above-mentioned aliphatic polyester/calcium carbonate composite material provided by the invention, is characterized in that the processing step of the method and condition optimization are as follows:
Under protection of inert gas; at 0.3～5 weight part through surface modification treatment or do not add the internal ester monomer of 100 weight parts in the calcium carbonate of surface modification treatment; ultrasonic dispersion 1～2h at 50～100 ℃; 1h more preferably; then under 60～160 ℃ of agitation conditions, the catalyzer that to add with internal ester monomer mol ratio be 0.0002:1～0.005:1, cooling after reaction 3～48 h; pulverize, dry.
Wherein the pattern of calcium carbonate used is also for sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, pencil that nanometer rod is self-assembled into, celestial being's palmate that nanometer rod is self-assembled into, petal-shaped that nanometer rod is self-assembled into, taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical, and the calcium carbonate of hemispherical (HSCC) pattern of being self-assembled into of the taraxacum shape (DCC) that preferably spherical (SCC), silk cocoon shape (PCC), nanometer rod are self-assembled into or nanometer rod.
Internal ester monomer described in above method is rac-Lactide, 6-caprolactone or to any in dioxy pimelinketone, preferably 6-caprolactone or to dioxy pimelinketone.
Catalyzer described in above method is any in triethyl aluminum, aluminum isopropylate or stannous octoate.
Used in above method is the surface modification that adopts surface-modifying agent to carry out the calcium carbonate of different-shape through surface modification treatment calcium carbonate, surface-modifying agent used is stearic acid, sodium lauryl sulphate, sodium laurylsulfonate or silane coupling agent, the preferred KH550 of silane coupling agent, KH560 or KH570.
The above or the concrete method of modifying through surface modification treatment calcium carbonate used are as follows:
Surface-modifying agent is dissolved in to the solution that is made into 0.01mol/L in toluene, then adds calcium carbonate powders, after 60 ℃ of supersound process 3 h, centrifugal collection solid, by washing with alcohol twice for gained solid, drying for standby under room temperature.
It is that in 201110054960.4 patent application prepared by disclosed method that the calcium carbonate of the above or different-shape used all adopts application number.
The present invention compared with prior art, has following beneficial effect:
1, various owing to having introduced pattern in aliphatic polyester/calcium carbonate composite material provided by the invention, complex structure, (pattern and structure are more complicated for the calcium carbonate that specific surface area is large, its specific surface area is larger), make the contact area of itself and aliphatic polyester matrix large, and then affinity and the dispersiveness of the organic-inorganic phase of matrix material have been increased, thereby can bring into play and strengthen toughness reinforcing effect aliphatic polyester, can improve tensile strength and the elongation at break of matrix material simultaneously, taraxacum shape calcium carbonate and silk cocoon shape calcium carbonate that particularly nanometer rod is wherein self-assembled into have hollow structure, make internal ester monomer molecule can in-situ polymerization occur in hollow structure and be coated, make the affinity of organic-inorganic phase of matrix material larger, it is more obvious that it strengthens toughness reinforcing effect.
2, due to the calcium carbonate of introducing in aliphatic polyester/calcium carbonate composite material provided by the invention, not only specific surface area is large, also because it has been carried out to surface modification, and then increased the consistency with matrix, avoided reunion, thereby can be when matrix material obtains enhancing toughening effect, promote wetting ability and the biocompatibility of matrix material, meet the requirement as osseous tissue material.
3, due to the calcium carbonate of introducing in aliphatic polyester/calcium carbonate composite material provided by the invention, can cushion the acid degradation product of aliphatic polyester, and because thering is the difference of different-shape and add-on, the degradation rate of aliphatic polyester is affected to different characteristics again, thereby the aseptic inflammation reaction that not only can avoid prior art to bring, the degradation rate that can also add calcium carbonate kind and content to control aliphatic polyester by selection adapts to different demands.
4, due to biodegradable aliphatic polyester/different-shape calcium carbonate composite material intensity provided by the invention and toughness all higher, thereby not only can be used for bio-medical field, as reparation of operating sutures, orthopaedics repair materials, skin and cornea etc., and also there are huge applications potentiality in fields such as orthopaedics immobilization material, intravascular stent and pharmaceutical carriers.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of PPDO homopolymer (PPDO) and the hemispherical calcium carbonate of PPDO/nanometer rod self-assembly (HSCC) matrix material, and in figure, (a) is pure PPDO; (b) be PPDO/0.3% HSCC; (c) be PPDO/0.6% HSCC; (d) be PPDO/1% HSCC; (e) be PPDO/3% HSCC; (f) be PPDO/5% HSCC.As seen from the figure, calcium carbonate is dispersed at PPDO matrix surface, and there is no obvious phase separation with the matrix of PPDO.Calcium carbonate and matrix PPDO that this explanation is dispersed in matrix material have good affinity and consistency.
Fig. 2 is PPDO/CaCO prepared by PPDO homopolymer and aliphatic polyester/different-shape calcium carbonate [being rhombohedron shape calcium carbonate (RCC), the hemispherical calcium carbonate of nanometer rod self-assembly (HSCC)]
3matrix material is quality residual rate curve over time in degradation process.As seen from the figure, the degradation rate of PPDO/1% RCC and PPDO/3% HSCC is than the obvious increase of PPDO homopolymer and PPDO/1% HSCC, the degradation rate increase of PPDO/3% HSCC may be because the content increase of calcium carbonate has promoted the degraded of PPDO, the degradation rate increase of PPDO/1% RCC may be because RCC is rhombohedral calcium carbonate, with substrate contact be not very tight, calcium carbonate has wetting ability simultaneously, and moisture is easily entered, and accelerates its degraded.
PPDO/CaCO prepared by Fig. 3 PPDO homopolymer and aliphatic polyester/different-shape calcium carbonate [being rhombohedron shape calcium carbonate (RCC), the hemispherical calcium carbonate of nanometer rod self-assembly (HSCC)]
3matrix material is △ pH curve over time in degradation process.As seen from the figure, the △ pH of matrix material increase in time changes not obvious, but pure PPDO increases in time, and △ pH is that straight line rises.The introducing of this explanation calcium carbonate can make △ pH change to reduce, and that is to say that calcium carbonate can alleviate the acid product that PPDO degraded produces, and avoids its aseptic inflammation reaction bringing, and realizes the controllability of PPDO degraded.
Embodiment
Provide embodiment below so that the present invention is further described; be necessary to point out that following examples can not be interpreted as limitation of the scope of the invention, the person skilled in the art in this field has made some nonessential improvement and has adjusted the present invention according to the invention described above content and still belonged to protection scope of the present invention.
What deserves to be explained is, 1) calcium carbonate of following examples surface modification treatment used all adopts aforesaid method to carry out modification, wherein embodiment 1～5 surface-modifying agent used is stearic acid, embodiment 6～14 surface-modifying agent used is sodium laurylsulfonate, and embodiment 16～18 surface-modifying agent used is KH550.2) umber of following examples and comparative example material used is weight part.3) intrinsic viscosity of following examples and comparative example is tested at 30.0 ± 0.1 ℃, and solvent is phenol tetrachloroethane; Tensile property is according to GB/T 1040.3-2006 standard testing, and test result sees attached list.
Embodiment 1
Under protection of inert gas; at 0.3 part, in the flaky calcium carbonate of surface modification treatment, add 100 parts of ε – CL monomers; ultrasonic dispersion 0.5h at 90 ℃; then under 100 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.0005; cooling after reaction 24h, pulverize, dry.
Embodiment 2
Under protection of inert gas; at 0.6 part, in the bar-shaped calcium carbonate of surface modification treatment, add 100 parts of ε – CL monomers; ultrasonic dispersion 1h at 40 ℃; then under 80 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.0002; cooling after reaction 48h, pulverize, dry.
Embodiment 3
Under protection of inert gas; at 2 parts, in the silk cocoon shape calcium carbonate (PCC) of surface modification treatment, add 100 parts of ε – CL monomers; ultrasonic dispersion 3h at 80 ℃; then under 100 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.0005; cooling after reaction 24h, pulverize, dry.
Embodiment 4
Under protection of inert gas; in 5 parts of taraxacum shape calcium carbonate (DCC) that are self-assembled into through the nanometer rod of surface modification treatment, add 100 parts of ε – CL monomers; ultrasonic dispersion 1h at 50 ℃; then under 60 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.0008; cooling after reaction 48h, pulverize, dry.
Embodiment 5
Under protection of inert gas; at 0.8 part, in the rhombohedron shape calcium carbonate (RCC) of surface modification treatment, add 100 parts of ε – CL monomers; ultrasonic dispersion 3h at 60 ℃; then under 100 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.001; cooling after reaction 24h, pulverize, dry.
Embodiment 6
Under protection of inert gas; at 0.3 part, in the silk cocoon shape calcium carbonate (PCC) of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 1h at 40 ℃; then under 40 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 12h, pulverize, dry.
Embodiment 7
Under protection of inert gas; at 0.6 part, in the taraxacum shape calcium carbonate (DCC) of the nanometer rod self-assembly of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 3h at 50 ℃; then under 60 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 3h, pulverize, dry.
Embodiment 8
Under protection of inert gas; in being self-assembled into hemispherical calcium carbonate (HSCC), 1 part of nanometer rod through surface modification treatment adds the PDO monomer of 100 parts; ultrasonic dispersion 1h at 60 ℃; then under 40 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 12h, pulverize, dry.
Embodiment 9
Under protection of inert gas; in being self-assembled into hemispherical calcium carbonate (HSCC), 3 parts of nanometer rod through surface modification treatment add the PDO monomer of 100 parts; ultrasonic dispersion 2h at 60 ℃; then under 60 ℃ of agitation conditions; the triethyl aluminum agent that to add with monomer mole ratio be 0.002; cooling after reaction 6h, pulverize, dry.
Embodiment 10
Under protection of inert gas; at 5 parts, in the silk cocoon shape calcium carbonate (PCC) of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 1h at 70 ℃; then under 80 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 12h, pulverize, dry.
Embodiment 11
Under protection of inert gas; at 7 parts, in the taraxacum shape calcium carbonate (DCC) of the nanometer rod self-assembly of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 2h at 60 ℃; then under 60 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 24h, pulverize, dry.
Embodiment 12
Under protection of inert gas; in 10 parts of spherical calcium carbonates through surface modification treatment (SCC), add the PDO monomer of 100 parts; ultrasonic dispersion 1h at 60 ℃; then under 60 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 12h, pulverize, dry.
Embodiment 13
Under protection of inert gas; in 4 parts of spherical calcium carbonates through surface modification treatment (SCC), add the PDO monomer of 100 parts; ultrasonic dispersion 1h at 60 ℃; then under 100 ℃ of agitation conditions; the triethylaluminium catalyst that to add with monomer mole ratio be 0.003; cooling after reaction 6h, pulverize, dry.
Embodiment 14
Under protection of inert gas; at 2 parts of petal-shaped calcium carbonate that are self-assembled into through the nanometer rod of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 3h at 80 ℃; then under 80 ℃ of agitation conditions; the aluminum isopropylate catalyzer that to add with monomer mole ratio be 0.00125; cooling after reaction 3h, pulverize, dry.
Embodiment 15
Under protection of inert gas; in being self-assembled into hemispherical calcium carbonate (HSCC), the nanometer rod of 1 part of long time without surface modification treatment adds the PDO monomer of 100 parts; ultrasonic dispersion 1h at 60 ℃; then under 100 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.004; cooling after reaction 48h, pulverize, dry.
Embodiment 16
Under protection of inert gas; in 3 parts of celestial being's palmate calcium carbonate that are self-assembled into through the nanometer rod of surface modification treatment, add the PDO monomer of 100 parts; ultrasonic dispersion 1h at 60 ℃; then under 100 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.0025; cooling after reaction 48h, pulverize, dry.
Embodiment 17
Under protection of inert gas; in being self-assembled into pencil calcium carbonate, 3 parts of nanometer rod through surface modification treatment add the LA monomer of 100 parts; ultrasonic dispersion 3h at 100 ℃; then under 160 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.005; cooling after reaction 5h, pulverize, dry.
Embodiment 18
Under protection of inert gas; at 5 parts, in the hollow bamboo shoots shape calcium carbonate of surface modification treatment, add the LA monomer of 100 parts; ultrasonic dispersion 2h at 140 ℃; then under 160 ℃ of agitation conditions; the stannous octoate catalyst that to add with monomer mole ratio be 0.005; cooling after reaction 5h, pulverize, dry.
Comparative example 1
Under protection of inert gas, the triethylaluminium catalyst that to add with monomer mole ratio in 100 parts of PDO monomers be 0.0025, cooling react 12h at 60 ℃ after, pulverize, dry.
Comparative example 2
Under protection of inert gas, the stannous octoate catalyst that to add with monomer mole ratio in 100 Fen ε – CL monomers be 0.0005, cooling react 24h at 100 ℃ after, pulverize, dry.
Comparative example 3
Under protection of inert gas, the stannous octoate catalyst that to add with monomer mole ratio in 100 parts of LA monomers be 0.0002, cooling react 5h at 160 ℃ after, pulverize, dry.
From following table, can find out, the introducing of calcium carbonate is not very large (this makes the test result of its mechanical property have certain comparability) on the intrinsic viscosity impact of matrix material, and the introducing of a small amount of calcium carbonate (≤5%) just can obviously improve its elongation at break, play toughening effect, tensile strength also improves simultaneously, especially for PCL/ calcium carbonate composite material system.In embodiment 4, by after the introducing of the taraxacum shape calcium carbonate (DCC) of 5% nanometer rod self-assembly, the tensile strength of matrix material can be increased to 52.9 MPa, elongation at break can be increased to 1103.6 %, compare with the pure PCL of comparative example 2, its tensile strength has increased by 234.8%, and elongation at break has increased by 120.3%.The silk cocoon shape calcium carbonate (PCC) that embodiment 3 adds also has same enhancing toughening effect.And the RCC adding and sheet, bar-shaped calcium carbonate, to PCL/CaCO
3the raising effect of composite materials property is but relatively little.This shows, the pattern of calcium carbonate is to PCL/CaCO
3the performance of matrix material is to have a great impact.On the one hand because PCC and DCC have complicated pattern and structure, its specific surface area is much bigger than RCC and sheet, bar-shaped calcium carbonate, make the contact area of they and PCL matrix larger, on the other hand because PCC and DCC have hollow structure, can in hollow structure, there is in-situ polymerization and be coated in ε-CL monomer molecule, so just increase the affinity of the organic-inorganic phase of matrix material, thereby made composite property obtain significantly improving.For PPDO/ calcium carbonate composite material system, the pattern of calcium carbonate also has similar impact to matrix material.As the tensile strength of adding the embodiment 7 of DCC is 69.7 MPa, elongation at break is 636.6%, just than the tensile strength of the pure PPDO of comparative example 1, has increased by 97.5%, and elongation at break has increased by 128.3%.For the calcium carbonate of other patterns on the impact of composite property also because the complicacy of its pattern is determined.
Table
For the performance of aliphatic polyester/calcium carbonate composite material that further prepared by investigation the present invention, the matrix material that the present invention is prepared part embodiment and pure PPDO have carried out following test:
1) observation of fracture morphology
To test sample brittle failure in liquid nitrogen, after then section metal spraying being processed, be the fracture morphology that Philips XL-3 scanning electronic microscope (FEI, USA) is observed matrix material by model, the results are shown in Figure 1.
2) test of degradation property
Sample thin slice is cut to the fritter into 1cm * 1cm.After weighing, (weight before sample degradation is designated as W
0) be placed in the buffered soln (pH=7.4) being mixed with Sodium phosphate dibasic and potassium primary phosphate, in the baking oven of 37 ℃ of constant temperature, carry out Degrading experiment.Because aliphatic polyester can produce carboxylated compound in degradation process, can cause the acidity of degraded environment to rise, therefore every a buffered soln of replacing in 1 week, constant with the pH value of the environment that guarantees to degrade.Test result is shown in Fig. 2,3.
Claims (6)
1. aliphatic polyester/calcium carbonate composite material, is characterized in that this matrix material is to be formed through in-situ polymerization by following component by weight:
100 parts of internal ester monomers,
0.3～10 part, calcium carbonate,
And described internal ester monomer is to dioxy pimelinketone; Described calcium carbonate is through surface modification treatment, the pencil that its pattern is sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, nanometer rod is self-assembled into, celestial being's palmate that nanometer rod is self-assembled into, petal-shaped that nanometer rod is self-assembled into, taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical, the intrinsic viscosity of this matrix material is 1.12～2.25dl/g, tensile strength is 16.6～70.8MPa, and elongation at break is 8.3～1103.6%.
2. aliphatic polyester/calcium carbonate composite material according to claim 1, is characterized in that calcium carbonate described in this matrix material is 0.3～5 part.
3. according to aliphatic polyester/calcium carbonate composite material described in claim 1 or 2, the pattern that it is characterized in that calcium carbonate described in this matrix material be the taraxacum shape that is self-assembled into of spherical, silk cocoon shape, nanometer rod or nanometer rod be self-assembled into hemispherical in any.
4. a preparation method for aliphatic polyester/calcium carbonate composite material described in claim 1, is characterized in that the processing step of the method and condition are as follows:
Under protection of inert gas; at 0.3～10 weight part, in the calcium carbonate of surface modification treatment, add the internal ester monomer of 100 weight parts; ultrasonic dispersion 0.5～3h at 40～140 ℃; then under 40～160 ℃ of agitation conditions; the catalyzer that to add with internal ester monomer mol ratio be 0.0002～0.005:1, cooling after reaction 3～48h, pulverize; dry
Wherein internal ester monomer used is to dioxy pimelinketone; The pencil that the pattern of calcium carbonate used is sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, nanometer rod is self-assembled into, celestial being's palmate that nanometer rod is self-assembled into, petal-shaped that nanometer rod is self-assembled into, taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical.
5. the preparation method of aliphatic polyester/calcium carbonate composite material according to claim 4, is characterized in that the processing step of the method and condition are as follows:
Under protection of inert gas; at 0.3～5 weight part, in the calcium carbonate of surface modification treatment, add the internal ester monomer of 100 weight parts; ultrasonic dispersion 1～2h at 50～100 ℃; then under 60～160 ℃ of agitation conditions; the catalyzer that to add with internal ester monomer mol ratio be 0.0002～0.005:1, cooling after reaction 3～48h, pulverize; dry
Wherein internal ester monomer used is to dioxy pimelinketone; The pencil that the pattern of calcium carbonate used is sheet, spherical, silk cocoon shape, rhombohedron shape, bar-shaped, hollow bamboo shoots shape, withered trunk shape, cockscomb shape, nanometer rod is self-assembled into, celestial being's palmate that nanometer rod is self-assembled into, petal-shaped that nanometer rod is self-assembled into, taraxacum shape that nanometer rod is self-assembled into or nanometer rod are self-assembled into any in hemispherical.
6. according to the preparation method of aliphatic polyester/calcium carbonate composite material described in claim 4 or 5, the pattern that it is characterized in that calcium carbonate described in the method be the taraxacum shape that is self-assembled into of spherical, silk cocoon shape, nanometer rod or nanometer rod be self-assembled into hemispherical in any.
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