CN105936667A - Method for improving mechanical properties of polycaprolactone-based biological elastomer - Google Patents

Method for improving mechanical properties of polycaprolactone-based biological elastomer Download PDF

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Publication number
CN105936667A
CN105936667A CN201610153906.6A CN201610153906A CN105936667A CN 105936667 A CN105936667 A CN 105936667A CN 201610153906 A CN201610153906 A CN 201610153906A CN 105936667 A CN105936667 A CN 105936667A
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prepolymer
bioelastomer
preparation
initiator
mechanical performance
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肖艳
郎思睆
郎美东
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

Abstract

The invention provides a method for improving mechanical properties of a polycaprolactone-based biological elastomer. The elastomer prepared by the method has high elasticity, the elastic modulus can be adjusted from 0.1 MPa to 3.0 MPa, the tensile strength can be adjusted from 0.2 MPa to 4.0 MPa, and the elongation at break can be adjusted from 100% to 1000%. The elastomer is biodegradable, the designed structure size is adjusted by a fast printing molding technology, and the elastomer with a three-dimensional structure and arbitrary shape can be obtained. The biological elastomer molded by the 3DP technology can achieve construction of a millimeter level structure, and has good enough strength to maintain the shape.

Description

A kind of method improving polycaprolactone-based bioelastomer mechanical property
Technical field
The present invention relates to a kind of method improving polycaprolactone-based bioelastomer mechanical property, specifically by changing Become polymer molecular weight and its topological structure reaches to change prepolymer viscosity and cross linked polymer mechanical property.And applied to Three-dimensional fast shaping prepares elastomer.
Background technology
The novel biomaterial of degradable biological elastomer is mainly used in soft tissue engineering and delivery system.Manually Synthesized degradable bioelastomer has significant feature at present: three-dimensional crosslinked network is similar to that native elastin；There is height The motility of degree and elasticity；Can stimulate for organizational project structures providing mechanical；The machinery matched with supple body tissue Performance；And the biodegradability widely that can be directly regulated by crosslink density.
But traditional based on PGS, the molding of several big kind polyester shaped material such as PPS, PLA needs at high temperature or organic solvent Curing molding (Synthesis, preparation, in vitro degradation, and application under existence condition Of novel degradable bioelastomers A review, Progress in Polymer Science 37 (2012), 715-765), and in early-stage Study, cross-linking type liquid-state polycaprolactone based elastomeric can be at room temperature without solvent Molding, but mechanical property is the best, limits its application (cross-linking type polycaprolactone and preparation method thereof and use in organizational project On the way, publication number CN103626979A, publication date 2014-3-12).
Summary of the invention
For defect of the prior art, the present invention provides a kind of polycaprolactone-based bioelastomer mechanical property of improving Method.The present inventor is at early-stage Study (cross-linking type polycaprolactone and its production and use, publication number CN103626979A, publication date 20140312) on the basis of through further investigation, design and propose one and can significantly improve life The method of thing mechanics of elastic bodies performance, can significantly improve this bioelastomer mechanical property.This bioelastomer can pass through Increase molecular weight and change topological structure makes mechanical property significantly improve.
It is an object of the invention to be achieved through the following technical solutions:
First aspect, the present invention provides the prepolymer of a kind of strong mechanical performance bioelastomer, including shown in Formulas I, Formula II Structure:
Wherein, m+n value is the integer of 50～400, and mark is photo-crosslinking position；
Wherein, p+q+h+i value is the integer of 50～400, and mark is photo-crosslinking position.
Prepolymer of the present invention is at ambient temperature in water white transparency viscosity flow liquid condition.
Second aspect, the present invention provides the preparation method of a kind of described prepolymer, including initiator and monomer 4-methyl-ε- The step of caprolactone reaction.
Preferably, described initiator is 1:(50～400 with the mol ratio of monomer 4-methyl-epsilon-caprolactone (MeCL)).
It is highly preferred that the mol ratio of described initiator and monomer 4-methyl-epsilon-caprolactone (MeCL) be 1:50,1:100,1: 200,1:250,1:300 or 1:400.
Preferably, described initiator includes terephthalyl alcohol, tetramethylolmethane；Different points are obtained for initiator with benzene dimethanol The linear pre-polymer of son amount, the change of chain length can change the mechanical property of prepolymer viscosity and cross linked polymer；With season penta Tetrol is the mechanical property that initiator change cross linked polymer topological structure can change prepolymer viscosity and cross linked polymer.
Above-mentioned preparation method is by using different initiator to change the topological structure of crosslinkable prepolymer, viscous to regulate and control prepolymer Degree and bioelastomer mechanical property；Regulation and control prepolymer molecular weight controllable prepolymer viscosity and mechanics of elastic bodies performance.
The third aspect, the present invention provides a kind of strong mechanical performance bioelastomer based on described prepolymer, described biology The mechanical property of elastomer is by increasing molecular weight, changing topological structure realization adjustment；Its elastic modelling quantity at 0.1MPa～ Between 3.0MPa adjustable, hot strength is adjustable at 0.2MPa～4.0MPa, elongation at break is adjustable at 100%～1000%.
Bioelastomer of the present invention is Biodegradable cross-linked polymer.
Fourth aspect, the present invention provides the preparation method of a kind of described strong mechanical performance bioelastomer, including by inciting somebody to action Described prepolymer mixes with light trigger, the step of curing molding.
Preferably, described light trigger includes dimethoxybenzoin.
Preferably, described light trigger and prepolymer mol ratio are 1:(10～20).
Owing to prepolymer of the present invention is that liquid is flowable, it is not necessary to heat or to add solvent the most plastic.
Preferably, also include after described curing molding using 3DP technology that bioelastomer is printed as the three of arbitrary character Dimension structure.Bioelastomer by above 3DP technology molding, it is possible to achieve the structure of grade structure, has the best intensity Maintain its shape.
5th aspect, the present invention provides a kind of described strong mechanical performance bioelastomer use in preparing organization bracket On the way.
The experiment proved that this bioelastomer can make mechanical property show by increasing molecular weight or change topological structure Write and improve.Elastomer prepared by logical this method has high resiliency, and elastic modelling quantity is adjustable between 0.1MPa～3.0MPa, hot strength Adjustable at 0.2MPa～4.0MPa, elongation at break is adjustable at 100%～1000%.And this elastomer has biodegradable Property, by printing speed forming technique adjusted design physical dimension, the elastomer of the three dimensional structure of available arbitrary shape.3DP The bioelastomer of technology molding, it is possible to achieve the structure of grade structure, has the best intensity to maintain its shape.
Compared with prior art, the present invention possesses following beneficial effect:
(1) with earlier patent application CN103626979A and the " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone And application " disclosed in technical scheme compare, the present invention obtain prepolymer molecular weight higher, the scope of prepolymer molecular weight is more Greatly, changing its topological structure, and the most still keep liquid unformed, curing molding mode is more preferable, and resulting materials is suitable for Wider.
(2) with earlier patent application CN103626979A and the " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone And application " disclosed in technical scheme compare, the present invention, by changing initiator (terephthalyl alcohol) and the ratio of monomer, changes Initiator type i.e. uses tetramethylolmethane and changes the ratio of tetramethylolmethane and monomer so that exist at the higher prepolymer of the degree of polymerization After photo-crosslinking, its mechanical property has obtained significantly promoting, and wherein with terephthalyl alcohol as initiator, its hot strength is bigger, mould Amount is bigger, and elongation at break is bigger, and increases along with the increase of the front prepolymer repetitive of crosslinking；With tetramethylolmethane for causing Agent, adds intensity, modulus and elongation at break, increases afterwards along with the increase of the front prepolymer repetitive of crosslinking first reduces；Separately On the one hand so that the surface of cross linked polymer is more hydrophobic；And so that the viscosity of prepolymer is significantly increased, advantageously in Using 3D printing shaping, 3D printing shaping can build more accurately complicated three dimensional structure.
Accompanying drawing explanation
By the detailed description non-limiting example made with reference to the following drawings of reading, the further feature of the present invention, Purpose and advantage will become more apparent upon:
Fig. 1 is embodiment 5 polycaprolactone-based cross linked polymer contact angle: (A) BDM-PMCL and (B) 4s-PE-PMCL；
Fig. 2 is the degradation curve of embodiment 6 polycaprolactone-based cross linked polymer: (A) cross linked polymer is at 0.1mol/L Degraded in NaOH solution；(B) cross linked polymer degraded in PBS buffer solution；
Fig. 3 is that embodiment 7 polycaprolactone based elastomeric prints structure three dimensional structure (have printed 7 layers in figure) by 3D.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in the technology of this area Personnel are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into the present invention Protection domain.
(1) with benzene dimethanol (or tetramethylolmethane) as initiator, with compound shown in formula IV as monomer, stannous iso caprylate is Catalyst, aggregated reaction obtains polymer shown in Formulas I a, then Formulas I a end group double bondization cross-linking obtains the I of formula, the most instead Answer formula as follows:
Or, with tetramethylolmethane as initiator, with compound shown in formula IV as monomer, stannous iso caprylate is catalyst, through poly- Closing reaction and obtain polymer shown in formula Formula II a, then Formula II a end group double bondization crosslinking are obtained Formula II, concrete reaction equation is as follows:
(2) change the ratio of monomer shown in initiator and formula IV, obtain prepolymer and Formula II a of different m+n values in Formulas I a The prepolymer of middle different p+q+h+i value.
Embodiment 1
The present embodiment provides BDM-PMCL different molecular weight prepolymer to be prepared, and preparation method is with reference to earlier patent application CN103626979A [0038], compared with earlier patent application, is in place of change, terephthalyl alcohol (BDM, initiator) and 4- The ratio initiator of methyl-epsilon-caprolactone (MeCL) and the mol ratio of monomer be respectively 1:50,1:100,1:200,1:250,1: 300、1:400；I.e. being respectively adopted polymerization degree n in the present embodiment is 50,100,200,250,300,400 six gradients, it is thus achieved that BDM-PMCL prepolymer Ia.
Terminal groups modification method obtains BDM-PMCL prepolymer Ib afterwards with reference to earlier patent application CN103626979A [0038], Composition see table 1.
The synthesis of table 1 polycaprolactone-based linear pre-polymer and component characterize
BDM-PMCL prepolymer Ib prepared by the present embodiment and earlier patent application CN103626979A, " based on 4-methyl- The synthesis of the amorphous polyester of 6-caprolactone and application thereof " gained correspondence product compares, and advantage is:
(1) present invention is through changing the ratio of initiator and monomer, obtains the degree of polymerization relatively earlier application CN103626979A " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone and application thereof " higher prepolymer (pre-in first patent The ratio that polymers is taked is 1:20), in terms of prepolymer molecular weight, this method gained prepolymer between 6000 to 52000, pole The earth increases the molecular weight of prepolymer, say, that it is (right that the polymer chain segment length of prepolymer is greatly improved Leaping of matter is belonged to from the point of view of this area), it is longer that this allows for polymer segment, and the compliance of segment is more preferable, and polymer chain conformation is more Many, define a lot of chain entanglements between segment, this is advantage not available for material in priority patent.
(2) viscosity relatively earlier patent application CN103626979A of prepolymer using the present embodiment to prepare is higher, this 3D printing shaping has critically important effect.
(3) prepolymer prepared by the present embodiment is at room temperature, still presents liquid viscous state, and this is follow-up prepolymer Molding application aspect provides great advantage and facility.
In sum, the present embodiment is the improvement project of earlier patent application, obtains more preferable, more after improvement Beneficial effect, and these effects are not that this area is readily available, and are not foreseeable, therefore possess creativeness.
Embodiment 2
The present embodiment provides the preparation of 4s-PE-PMCL prepolymer, and preparation method is with reference to earlier patent application CN103626979A [0038], changes by initiator as tetramethylolmethane into, and changes tetramethylolmethane (PE) and 4-methyl-epsilon-caprolactone (MeCL) mol ratio is respectively 1:50,1:100,1:200,1:250,1:300,1:400, is respectively adopted polymerization in the present embodiment Degree n is that 50,100,200,250,300,400 six gradients obtain 4s-PE-PMCL prepolymer IIa.
Terminal groups modification method obtains BDM-PMCL prepolymer afterwards with reference to earlier patent application CN103626979A [0038] IIb, composition see table.
The synthesis of table 2 polycaprolactone-based star type prepolymer and component characterize
BDM-PMCL prepolymer IIb prepared by the present embodiment and earlier patent application CN103626979A, " based on 4-first The synthesis of the amorphous polyester of base-6-caprolactone and application thereof " gained correspondence product compares, and advantage is；
(1) the present embodiment is through changing initiator, causes with tetramethylolmethane, and it is star-like for making prepolymer, changes prepolymer Topological structure so that it is possessing more can covalent cross-linking point.Change the ratio of initiator and monomer, obtain the degree of polymerization the most special Profit application CN103626979A and " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone and application thereof " higher pre-polymerization Thing (ratio that the prepolymer in first patent is taked is 1:20), in terms of prepolymer molecular weight, this method gained prepolymer from Between 6000 to 52000, greatly increase the molecular weight of prepolymer, say, that the polymer chain segment length of prepolymer obtains Significantly promoting, it is longer that this allows for polymer segment, and the compliance of segment is more preferable, and polymer chain conformation is more, segment Between define a lot of chain entanglements, this is advantage not available for material in prior art.It is initiator with terephthalyl alcohol Prepolymer contrasts, in the prepolymer of same molecular amount, tetramethylolmethane can the point of covalent cross-linking more, but between crosslinking points Chain length be initiator prepolymer with terephthalyl alcohol compared with shorter, this allows for segment compliance and compares less.
(2) the present embodiment use this method the prepolymer arrived viscosity relatively earlier patent application CN103626979A before more Height, this has critically important effect in 3D printing shaping.
(3) at room temperature, prepolymer prepared by the present embodiment still presents liquid viscous state, and this is follow-up prepolymer Molding application aspect provides great advantage and facility.
In sum, the present embodiment is the improvement project of earlier patent application, obtains more preferable, more after improvement Beneficial effect, and these effects are not that this area is readily available, and are not foreseeable, therefore possess creativeness.
Embodiment 3
The present embodiment relates to the preparation method of a kind of strong mechanical performance bioelastomer, comprises the steps:
Method as described in embodiment 1, it is thus achieved that the prepolymer that molecular weight is different, is abbreviated as: a:BDM-PMCL respectively50, b: BDM-PMCL100, c:BDM-PMCL200, d:BDM-PMCL250, e:BDM-PMCL300, f:BDM-PMCL400。
Light trigger (dimethoxybenzoin), light trigger and prepolymer mole it is separately added in above-mentioned six kinds of prepolymers Ratio is 1:20, adds tetrafluoroethene template after mixing, irradiates 10min with the ultraviolet light light respectively of 500W, 365nm, is fixed Six kinds of cross linked polymer samples of size.Use GB sample preparation, prepare dumbbell shape batten, test mechanical property with universal testing machine Can, extension test is at room temperature carried out.Result is as shown in table 3.
The extension test of cross linked polymer I under table 3 room temperature condition
Analyzed from table 3, after the degree of polymerization is more than 50, between 50～300 degree of polymerization, cross linked polymer springform Amount, hot strength increase along with the increase of crosslinking prepolymer repetitive, after the degree of polymerization arrives 300, single along with repeating again The increase of unit and reduce on a small quantity, when by fixing External Force Acting, the elongation at break of cross linked polymer is along with crosslinking pre-polymerization The increase of thing repetitive and increase.
Embodiment 4
The present embodiment relates to the preparation method of a kind of strong mechanical performance bioelastomer, comprises the steps:
Method as described in embodiment 2, it is thus achieved that the prepolymer that molecular weight is different, is abbreviated as: a:4s-PE-PMCL respectively50, b: 4s-PE-PMCL100, c:4s-PE-PMCL200, d:4s-PE-PMCL250, e:4s-PE-PMCL300, f:4s-PE-PMCL400。
Light trigger (dimethoxybenzoin) light trigger and prepolymer mole it is separately added in above-mentioned six kinds of prepolymers Than adding tetrafluoroethene template after mixing for 1:10, irradiate 10min with the ultraviolet light light respectively of 500W, 365nm, obtain fixing big Six kinds of little cross linked polymer samples.Use GB sample preparation, prepare dumbbell shape batten, test mechanical property with universal testing machine, Extension test is at room temperature carried out.Result is as shown in table 4.
The extension test of cross linked polymer II under table 4 room temperature condition
Being analyzed from table 4, along with the increase of molecular weight, the hot strength of cross linked polymer is in first increases and then decreases, disconnected Split percentage elongation first increases and then decreases, wherein 4s-PE-PMCL250Sample compared with other samples, hot strength and elongation at break All reach maximum.
Embodiment 5
Method as described in embodiment 4, obtains six kinds of cross linked polymer samples of fixed size.By six kinds of samples by static state Contact angle measurement characterizes the hydrophilic and hydrophobic of cross linked polymer.It is quiet that method as described in embodiment 3 prepares cross linked polymer sample State contact angle result is similar with it.Result is as shown in Figure 1.
As shown in Figure 1, cross linked polymer is hydrophobic, along with the increase cross linked polymer surface contact angle of the degree of polymerization increases, dredges Aqueous strengthens.Change over time, cross linked polymer surface contact angle has the trend of reduction.Never the while of between, contact angle is permissible Finding out, cross linked polymer surface is relatively hydrophobic, and after 60s, contact angle is basicly stable.Test result indicate that, can be adjusted by the regulation degree of polymerization The hydrophilic and hydrophobic on joint cross linked polymer surface.
Embodiment 6
The present embodiment relates to the test of photocrosslinkable polymer external degradation, and concrete operations and result are as follows:
Method as described in embodiment 3, prepares cross linked polymer sample, sample is cut into 10 × 5 × 2mm size sample respectively Bar, is added separately in physiological conditions PBS buffer solution (pH=7.4) and in accelerated degradation NaOH solution (0.1M), will It is placed in isothermal vibration incubator, and under the conditions of 37 DEG C, concussion speed is that 80r/min cultivates, and is cultivating different time interval After, the taking-up drying of residue cross linked polymer is weighed.All samples parallel laboratory test 3 times, result is expressed as mean+SD. Concrete outcome is shown in Fig. 2.
As shown in Figure 2, the degraded of PMCL cross linked polymer is compared with PCL cross linked polymer, and faster, crosslinking is poly-for degradation rate The hydrolysis being degraded to ester bond of compound, and the degradation rate in NaOH solution is faster.
Embodiment 7
Method as described in embodiment 1, prepares the prepolymer that molecular weight is different respectively, is abbreviated as respectively:
A:BDM-PMCL50, b:BDM-PMCL100, c:BDM-PMCL200, d:BDM-PMCL250, e:BDM-PMCL300, f: BDM-PMCL400。
Take above-mentioned six kinds of samples, as a example by b, b is added light trigger mixing and is placed in 3D printing head, at room temperature bar Under part, computer controls printer, prints layer by layer, successively accumulates, and is solidified under the ultraviolet light of 500W, wavelength 365nm irradiates Type.As shown in Figure 3.
This elastomer can realize printing speed molding arbitrary shape, the bioelastomer of 3DP technology molding, it is possible to achieve The structure of grade structure, has the best intensity to maintain its shape.
With end group double bond 4s-PE-PMCL prepolymer, repeat above-mentioned experiment, similar conclusion can be obtained, at this most one by one Repeat.
Comparative example 1
The concrete scheme of this comparative example is identical with earlier patent application CN103626979A, and the performance of resulting polymers is:
In first patent, the degree of polymerization be 20,40,60 prepolymer crosslinking after its mechanical property along with repetitive before crosslinking Increase and decline, and in the present invention, the initiator used is the same with monomer, after changing its ratio, the degree of polymerization is big After width promotes, segment lengthens so that form chain entanglement between segment, and the degree of polymerization is the prepolymer friendship of 50,100,200,250,300 After connection, its mechanical property increases along with the increase of the front repetitive of crosslinking, and in mechanical property, its intensity is higher, and modulus is more Greatly, elongation at break is bigger.
Comparative example 2
The concrete scheme of this comparative example is public with " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone and application thereof " The technical scheme opened is identical, and the performance of resulting polymers is:
In " synthesis of amorphous polyester based on 4-methyl-epsilon-caprolactone and application thereof ", cross linked polymer contact angle grinds Studying carefully, after the prepolymer crosslinking that the degree of polymerization is 20, its surface contact angle is 76.9 ° after contact 5s, is 73.2 ° after 60s, and this In invention the degree of polymerization be 50,100,200,250,300 prepolymer crosslinking after its surface contact angle along with the degree of polymerization increase and Increasing, its surface contact angle of cross linked polymer after the degree of polymerization is more than 50 has exceeded 80 °, and the prepolymer that i.e. degree of polymerization is the highest is at light After crosslinking, its surface hydrophobic is higher, and both compare, and prepares its surface of resulting polymers according to this method more hydrophobic, later Application in can give play to advantage.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, this not shadow Ring the flesh and blood of the present invention.

Claims (10)

1. the prepolymer of a strong mechanical performance bioelastomer, it is characterised in that include structure shown in Formulas I, Formula II:
Wherein, m+n value is the integer of 50～400；
Wherein, p+q+h+i value is the integer of 50～400.
2. the preparation method of a prepolymer according to claim 1, it is characterised in that include initiator and monomer 4-first The step of base-6-caprolactone reaction.
The preparation method of prepolymer the most according to claim 2, it is characterised in that described initiator and monomer 4-methyl- The mol ratio of 6-caprolactone is 1:(50～400).
The preparation method of prepolymer the most according to claim 3, it is characterised in that described initiator and monomer 4-methyl- The mol ratio of 6-caprolactone is 1:50,1:100,1:200,1:250,1:300 or 1:400.
5. according to the preparation method of the prepolymer described in claim 2,3 or 4, it is characterised in that described initiator is to benzene two Methanol or tetramethylolmethane.
6. a strong mechanical performance bioelastomer based on the prepolymer described in claim 1, it is characterised in that described biology The mechanical property of elastomer is by increasing molecular weight, changing topological structure realization adjustment；Its elastic modelling quantity at 0.1MPa～ Between 3.0MPa adjustable, hot strength is adjustable at 0.2MPa～4.0MPa, elongation at break is adjustable at 100%～1000%.
7. the preparation method of a strong mechanical performance bioelastomer according to claim 6, it is characterised in that include leading to Cross described prepolymer is mixed with light trigger, the step of curing molding.
The preparation method of strong mechanical performance bioelastomer the most according to claim 7, it is characterised in that described light-initiated Agent is dimethoxybenzoin；Described light trigger is 1:(10～20 with the mol ratio of prepolymer).
The preparation method of strong mechanical performance bioelastomer the most according to claim 7, it is characterised in that described in be solidified into Also include after type that bioelastomer is printed as the step of the three dimensional structure of arbitrary character by employing 3DP technology.
10. a strong mechanical performance bioelastomer according to claim 6 purposes in preparing organization bracket.
CN201610153906.6A 2016-03-17 2016-03-17 Method for improving mechanical properties of polycaprolactone-based biological elastomer Pending CN105936667A (en)

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CN106977885A (en) * 2017-04-14 2017-07-25 东华大学 A kind of preparation method of PPS/PGS composite shapes memory elasticity body
CN108623752A (en) * 2018-04-10 2018-10-09 深圳光华伟业股份有限公司 A kind of UV-cured resin and preparation method, stereoforming method of biology base
CN108559086A (en) * 2018-05-21 2018-09-21 武汉工程大学 A kind of vinyl modified star polyphosphate and its synthetic method
CN112457479A (en) * 2020-11-24 2021-03-09 华东理工大学 Biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent, and preparation method and application thereof
CN112457479B (en) * 2020-11-24 2022-08-09 华东理工大学 Biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto cross-linking agent, and preparation method and application thereof
CN113307938A (en) * 2021-05-17 2021-08-27 广东安拓普聚合物科技有限公司 Polyurethane elastomer composition, polyurethane elastomer and preparation method thereof
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