CN101747486B - Light-induced shape-memory polymer and preparation method thereof - Google Patents

Light-induced shape-memory polymer and preparation method thereof Download PDF

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CN101747486B
CN101747486B CN200910156931XA CN200910156931A CN101747486B CN 101747486 B CN101747486 B CN 101747486B CN 200910156931X A CN200910156931X A CN 200910156931XA CN 200910156931 A CN200910156931 A CN 200910156931A CN 101747486 B CN101747486 B CN 101747486B
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transition temperature
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omega end
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CN101747486A (en
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吴林波
靳春丽
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Zhejiang University ZJU
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Abstract

The invention discloses a light-induced shape-memory polymer and a preparation method thereof. The light-induced shape-memory polymer is a thermoplastic polyurethane multi-block copolymer having N-substituted cinnamamide photosensitive structure units, wherein the main transformation temperature of a soft block is no more than 50 DEG C. The light-induced shape-memory polymer is prepared by reactions of an N-dihydroxyalkyl cinnamamide photosensitive monomer, an alpha,omega-hydroxyl-terminated polymer, a low-molecular weight chain extender and diisocyanate. The light-induced shape-memory polymer has easily-adjustable structural behaviors, can be degradable or nondegradable, has high processability, can obtain a temporary shape under the action of an external force and the irradiation of ultraviolet light with a wavelength greater than 260 nanometers, and can restore original shape under the irradiation of ultraviolet light with a wavelength smaller than 260 nanometers. Without temperature dependency, the light-induced shape-memory effectexcitation of the light-induced shape-memory polymer can be performed at room temperature and also can be performed at a long distance by means of optical fibers and the like. The preparation method is simple, feasible, universal and favorable for the realization of commercialization.

Description

A kind of light-induced shape-memory polymer and preparation method thereof
Technical field
The present invention relates to functional high molecule material and preparation method thereof, relate in particular to a kind of light-induced shape-memory polymer and preparation method thereof.
Background technology
Shape-memory polymer is the functional or intelligent polymer of a class, after its original shape that is obtained by once shaped is become interim shape by secondary processing, and its energy " memory " original shape, and under extraneous hormesis, recover original shape.Utilize its shape memory function, shape-memory polymer can be widely used in structural connection, wrapping material, printing material, textiles etc.In the shape-memory polymer, biodegradable shape memory polymeric is owing to have degraded and absorbed and shape memory function simultaneously, can also be as the carrier of medical embedded material and medicine sustained release, as suture, prevent that pipeline restenosis implant frame, blood vessel joint/colligation, tendon from fixing, bone is fixed etc.(SMA) compares with shape memory alloy, and biodegradable shape memory polymeric has following superiority: (1) dependent variable is big, can reach more than 100%, and SMA only 8%; (2) biodegradable, postoperative need not take out, and the patient can exempt the misery of second operation; (3) can accept nuclear magnetic resonance check; (4) lighter to the compressing damage of adjoining tissue; (5) easy to process, can make undersized interim shape, be particularly suitable for Minimally Invasive Surgery.
In the shape-memory polymer, the external stimulus means of triggering shape memory effect have multiple, and as heat, light, electricity, magnetic etc., even absorption moisture also can be used for triggering shape memory effect.Wherein, it is the emphasis of researching and developing at present that heat triggers (or claiming thermal shape memory), as US6160084, US20040015187, US20060140999, US6281262, US6281262, WO9942147, CN1852931, CN03114594.9, CN1693362, CN1563132, CN1569261, CN1544096, CN1887364, CN1820793, CN1911983, CN1563132, CN1693362, CN1693362, Polymersfor Advanced Technologies (16:608-615,2005), Science reports such as (296:1673-6,2002).2005, " Nature " (434 14 phases of volume, P879-882) magazine was reported two kinds of not biodegradable light-induced shape-memory polymers.They are respectively by the radical crosslinking multipolymer that contains photosensitive group of free radical copolymerization method preparation and the interpenetrating net polymer that contains the star light-sensitive compound for preparing by interact network method.Device through machine-shaping at room temperature is out of shape through the external force effect, after the UV-irradiation of wavelength greater than 260 nanometers, deformation is partly fixed, and through the UV-irradiation of another wavelength less than 260 nanometers, shape is recovered.
Compare with the thermal shape memory effect, the light-induced shape-memory effect can be utilized ultraviolet excitation in wide temperature range, do not have strong temperature dependency, and can utilize the non-body surface of means position such as optical fiber to realize remote excitation.These characteristics are highly beneficial to some application, the discomfort that when clinical medicine is used, can avoid heat to bring for example, and remote excitation is beneficial to Wicresoft's interventional therapy especially.Therefore, not only to research and develop nondegradable light-induced shape-memory polymer, also be necessary the light-induced shape-memory polymer that synthesizing biological degradable absorbs.Compare with not biodegradable light-induced shape-memory polymer with biodegradable thermal shape memory polymkeric substance, it is much more difficult to prepare biodegradable light-induced shape-memory polymer, also rests in the conceptual design substantially.
Therefore, research and development New Photoinduced shape-memory polymer and preparation method thereof, especially biodegradable light-induced shape-memory polymer and preparation method thereof, especially can be used to prepare the method for non-degradable and biodegradable light-induced shape-memory polymer simultaneously, the problem of technology to be solved is still arranged.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of light-induced shape-memory polymer and preparation method thereof is provided.
Light-induced shape-memory polymer is to contain the N-shown in following 1a, 1b or the 1c to replace the unitary thermoplastic polyurethanes segmented copolymer of cinnamide photosensitive structure, and its main transition temperature of soft section is not higher than 50 ℃; It is not higher than 50 ℃ α by the N-dihydroxyalkyl cinnamamide of (1) 0.5wt%~25wt%, the main transition temperature of (2) 90wt%~20wt%, the small molecule chain extender of omega end hydroxy polymer A, (3) 0~5wt%, the second-order transition temperature of (4) 0~75wt% or fusing point are not less than 50 ℃ and than described α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B makes with (5) di-isocyanate reaction;
A kind of preparation method of light-induced shape-memory polymer is characterized in that following steps:
1) the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, omega end hydroxy polymer A and vulcabond react down at 50-180 ℃ in the presence of the catalyzer of 0~1wt%, isocyanate group and step 1) and 2) in the hydroxyl of all reactants and the mol ratio of amino sum be 1~1.2: 1, make prepolymer;
2) second-order transition temperature of the small molecule chain extender of prepolymer and 0.5~5wt% or 5~75wt% or fusing point are not less than 50 ℃ and than described α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B makes light-induced shape-memory polymer 50-180 ℃ of reaction down.
The preparation method of another kind of light-induced shape-memory polymer comprises the steps:
1) the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, the second-order transition temperature of omega end hydroxy polymer A, 5~75wt% or fusing point are not less than 50 ℃ and than described α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B and vulcabond react down at 50~180 ℃ in the presence of the catalyzer of 0~1wt%, isocyanate group and step 1) and 2) in the hydroxyl of all reactants and the mol ratio of amino sum be 1~1.2: 1, make prepolymer;
2) small molecule chain extender with prepolymer and 0.5~5wt% reacts down at 50-180 ℃, makes described light-induced shape-memory polymer.
The preparation method of another kind of light-induced shape-memory polymer is: the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, omega end hydroxy polymer A and vulcabond directly react down at 50-180 ℃ in the presence of the catalyzer of 0~1wt%, the mol ratio of isocyanate group and total hydroxyl is 1~1.2: 1, makes described light-induced shape-memory polymer.
Described N-dihydroxyalkyl cinnamamide is N, N-dihydroxy ethyl cinnamide, N, N-dihydroxy sec.-propyl cinnamide or N-[2-hydroxyl-1-(methylol) ethyl]-cinnamide; Described small molecule chain extender is an ethylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, phenylenediamine, benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane or 3,3 '-two chloro-4,4 '-diaminodiphenylmethane; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl cyclohexane vulcabond, 2,4,4-trimethyl cyclohexane vulcabond, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate or tetramethylxylylene diisocyanate; Described catalyzer is stannous octoate, dibutyl tin laurate.
Described α, omega end hydroxy polymer A be main transition temperature be not higher than 50 ℃ and contain α, the polyester of omega end hydroxyl, polyethers, polysiloxane, polycarbonate, polyesteramide, polyether ester, polyestercarbonate or polyolefine; Described α, omega end hydroxy polymer B are that second-order transition temperature or fusing point are not less than 50 ℃ and than described α, the main transition temperature of omega end hydroxy polymer A high at least 20 ℃ and contain α, the polyester of omega end hydroxyl, polycarbonate, polyesteramide or polyolefine.
Described α, omega end hydroxy polymer A be main transition temperature be not higher than 50 ℃ and contain α, the polycaprolactone of omega end hydroxyl, poly-(trimethylene carbonate), poly-succinic hexylene glycol ester, poly butylene succinate, poly-succinic propylene glycol ester, polyethylene glycol succinate, poly-succinic glycol ether ester, poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polypropylene adipate (PPA), polyethylene glycol adipate, poly-hexanodioic acid glycol ether ester or their multipolymer; Perhaps be main transition temperature be not higher than 50 ℃ and contain α, the polyoxyethylene glycol of omega end hydroxyl, polypropylene glycol, polytetrahydrofuran and their multipolymer; Perhaps be main transition temperature be not higher than 50 ℃ and contain α, the polyhutadiene of omega end hydroxyl, polyisoprene or perbutan.
Described α, omega end hydroxy polymer B is that second-order transition temperature or fusing point are not less than 50 ℃ and than described α, the main transition temperature of omega end hydroxy polymer A high at least 20 ℃ and contain α, the poly(lactic acid) of omega end hydroxyl, polyglycolic acid, PPDO, poly butylene succinate, polyethylene glycol succinate, poly adipate succinic acid ester, polybutylene terephthalate, polyethylene terephthalate, Poly(Trimethylene Terephthalate), poly terephthalic acid cyclohexanedimethanoester ester or their multipolymer.
Light-induced shape-memory polymer provided by the invention replaces the unitary thermoplasticity ammonia of cinnamide photosensitive structure ester class segmented copolymer for containing N-, has good forming process, and can in wide temperature range, utilize ultraviolet excitation, there is not strong temperature dependency; Can utilize the non-body surface of means position realization remote excitations such as optical fiber.
The both nondegradable light-induced shape-memory polymer of light-induced shape-memory polymer provided by the invention, also biodegradable light-induced shape-memory polymer, can regulate its biological degradability and other performance by the segmented structure that changes in the segmented copolymer, to satisfy in use requirement to mechanical property and degradation rate.
Biodegradable light-induced shape-memory polymer provided by the invention, in the time of when clinical application, can avoiding thermal shape memory to the susceptibility of body temperature and the discomfort that inconvenience that brings and heat are brought; Also can utilize the characteristics that can realize remote excitation to realize the shape recovery in vivo, conveniently be used for Wicresoft's interventional therapy.
Preparation method's simple possible of light-induced shape-memory polymer provided by the invention, has versatility, both can be used for the preparation of biodegradable light-induced shape-memory polymer, also can be used for the preparation of nondegradable light-induced shape-memory polymer, helped realizing commercialization.
Description of drawings
Fig. 1 is the infrared spectra of light-induced shape-memory polymer 1.1727cm -1, 1757cm -1The place is the ester group absorption peak in polycaprolactone and the poly(lactic acid), 1603cm -1And 1649cm -1Absorption for the two keys of phenyl ring and CH=CH in the photosensitive structure unit;
Fig. 2 is a light-induced shape-memory polymer 1 1H NMR nuclear-magnetism spectrum.6.8-7.6ppm be the chemical shift of the two keys of phenyl ring in the cinnamoyl and CH=CH; 1-1.5ppm and 5.0ppm is the chemical shift of CH3 and CH in the polymer segment; Other is the chemical shift of hydrogen atom in polycaprolactone and the connector element.
Embodiment
Light-induced shape-memory polymer provided by the invention is to contain the thermoplastic polyurethanes multi-block polymer that N-replaces cinnamide photosensitive structure unit, soft section and hard section.Its soft section is polymer A segment (hereinafter to be referred as the A segment), and soft section main transition temperature (main transition temperature is the second-order transition temperature of amorphous polymer or the melt temperature of crystalline polymer) is not higher than 50 ℃; Hard section is diamino ester or two urea structure uints, perhaps constitute hard section jointly by diamino ester or two urea structure uints and small molecule chain extender residue, perhaps by diamino ester or two urea structure uints and the hard section of the common formation of polymer B segment (hereinafter to be referred as the B segment), it is high at least 20 ℃ that the second-order transition temperature of hard section or fusing point are not less than 50 ℃ and the main transition temperature than soft section, and hard section can form the physical crosslinking structure.
Among the present invention, not having B segment and A segment when having only the A segment is biodegradable segment, when perhaps containing A segment and B segment and they simultaneously and being biodegradable segment, light-induced shape-memory polymer provided by the invention is a biodegradable shape memory polymeric; There are not B segment and A segment to be not biodegradable segment when having only the A segment, when perhaps containing A segment and B segment and they simultaneously and being not biodegradable segment, light-induced shape-memory polymer provided by the invention is not biodegradable shape-memory polymer; Have and have only a kind of during for biodegradable segment among containing A segment and B segment and they simultaneously, light-induced shape-memory polymer provided by the invention is the shape-memory polymer of part biological degraded.
Under external force, this polymkeric substance deforms, and simultaneously with the UV-irradiation of wavelength greater than 260 nanometers, the initial ring addition reaction of photosensitive structure unit generates extra photocrosslinking structure, this polymkeric substance can be kept or the interim shape after partly maintenance is out of shape; Under the UV-irradiation of another wavelength less than 260 nanometers, the photocrosslinking structure is untied during use, recovers its original shape.
Among the present invention, light-induced shape-memory polymer adopts N-dihydroxyalkyl cinnamamide photosensitive monomer, α, and omega end hydroxy polymer, small molecule chain extender etc. make with di-isocyanate reaction, and preparation method and traditional polyurethane preparation method are similar, simple possible.Photosensitive monomer, α, omega end hydroxy polymer A and B, small molecule chain extender are the reactant that contains reactive hydrogen (hydroxyl or amino), its consumption is the percentage ratio based on the total mass (being photosensitive monomer, α, omega end hydroxy polymer A and B, small molecule chain extender sum) of all active hydrogen reaction things.Can not add catalyzer during preparation, also can add urethane synthetic custom catalysts.When the biodegradable light-induced shape-memory polymer of preparation, can adopt the stannous octoate that authenticates by FDA as catalyzer, to guarantee the product excellent biological compatibility.Catalyst levels contains 0~1wt% of active hydrogen reaction thing total mass for all.The following control of the consumption of vulcabond: the hydroxyl of isocyanate group and all reactants and the mol ratio of amino sum are 1~1.2: 1.
Among the present invention, adopt the electronic material trier that has installed ultraviolet lamp additional, by photic mechanical cycles measuring light-induced shape-memory effect.Sample is stretched to strain stress with the speed of 10mm/min mKeeping under the constant situation of strain, sample at the UV-irradiation certain hour that the wavelength of certain light intensity is, is being removed external force, with the strain stress under the vernier caliper measurement stress-free conditions u, press R fu/ ε mCalculate strain fixed rate R fThen, this sample at the UV-irradiation certain hour that the wavelength of certain light intensity is, is measured residual strain ε p, press R r=(ε mp)/ε mCalculate strain recovery rate R r
The embodiment that the invention is further illustrated by the following examples, but scope of the present invention is not limited to these embodiment.
Embodiment 1
1) in flask, add α, omega end liquid hydroxyl polycaprolactone (molecular weight is 530,3.1 grams), N, N-dihydroxy ethyl cinnamide (2.5 gram) and 1,4-dioxane 24 grams are put into oil bath, be heated to 80 ℃ under stirring, and logical nitrogen are handled 0.5 hour; The stannous octoate and the hexamethylene diisocyanate that add 0.2wt% again, isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1.1: 1, in nitrogen protection and 80~85 ℃ reaction 3 hours down, make pre-polymer solution.
2) in pre-polymer solution, add α, omega end hydroxyl poly (l-lactic acid) (170 ℃ of fusing points, 4.4 grams), 1,4-dioxane 55.6 grams are nitrogen protection and 80~85 ℃ of following reactions 6 hours; Pour reaction product solution in glass dish film forming, treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 1.
Embodiment 2
1) in flask, add α, omega end liquid hydroxyl polycaprolactone (molecular weight is 530,1.5 grams) and N, N-dihydroxy ethyl cinnamide (1.0 gram) is put into oil bath, be heated to 50 ℃ under stirring, and logical nitrogen is handled 0.5 hour; Add hexamethylene diisocyanate and 1 again, 4-dioxane 24 gram, isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1.1: 1, reacted 8 hours down nitrogen protection and 50 ℃, make pre-polymer solution;
2) add α in pre-polymer solution, omega end hydroxyl poly (l-lactic acid) (170 ℃ of fusing points, 7.5 grams) is nitrogen protection and 80~85 ℃ of following reactions 6 hours; Pour reaction product solution in glass dish film forming, treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 2.
Embodiment 3
1) in flask, adds α, omega end hydroxyl polycaprolactone-glycolide copolymer (molecular weight is 2000, about 25 ℃ of fusing point) 8 gram and N-[2-hydroxyl-1-(methylol) ethyls]-cinnamide 1.5 grams, put into oil bath, be heated to 80 ℃ under stirring, and logical nitrogen was handled 0.5 hour; The toluene solution (containing stannous octoate 0.04 gram, toluene 4 grams), toluene 24 gram and the tolylene diisocyanates that add stannous octoate again; isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1: 1; nitrogen protection and 80~85 ℃ of following reactions 3 hours, make pre-polymer solution.
2) add 1 in pre-polymer solution, 4-butyleneglycol 0.5 gram is nitrogen protection and 80~85 ℃ of following reactions 6 hours; Pour reaction product solution in glass dish film forming, treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 3.
Embodiment 4
Add α in flask, the omega end hydroxyl gathers adipate glycol propylene glycol copolyesters (be waxy solid under the room temperature, fusing point is no more than 50 ℃) 9 gram and N, N-dihydroxy ethyl cinnamide 1 gram, put into oil bath, be heated to 80 ℃ under stirring, and logical nitrogen was handled 0.5 hour; Add toluene 24 gram and diphenylmethanediisocyanates again, isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1.1: 1, reacted 8 hours down nitrogen protection and 80~85 ℃; Pour reaction product solution in glass dish film forming, treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 4.
Embodiment 5
1) in flask, add α, liquid polydimethylsiloxane 2 gram and the N of omega end hydroxyl, N-dihydroxy ethyl cinnamide 0.05 gram is put into oil bath, be heated to 180 ℃ under stirring, and logical nitrogen is handled 0.5 hour; Be cooled to 100 ℃, add tolylene diisocyanate again, the mol ratio of total hydroxyl of isocyanate group and all reactants is 1.1: 1, nitrogen protection and 50 ℃ of following reactions 3 hours, makes prepolymer.
2) add α in prepolymer, omega end hydroxyl polybutylene terephthalate (molecular weight about 2000, about 160 ℃ of fusing point) 7.95 grams in nitrogen protection and 180 ℃ reaction 3 hours down, obtain light-induced shape-memory polymer 5.
Polymkeric substance 5 obtains sheet material through hot pressing.
Embodiment 6
1) in flask, add α, omega end liquid hydroxyl polyhutadiene (molecular weight is 2000, and normal temperature is liquid down) 3 gram and N, N-dihydroxy ethyl cinnamide 1.2 grams are put into oil bath, be heated to 80 ℃ under stirring, and logical nitrogen are handled 0.5 hour; The toluene solution (containing dibutyl tin laurate 0.1 gram, toluene 3 grams), toluene 24 gram and the hexamethylene diisocyanates that add dibutyl tin laurate again; isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1.05: 1; nitrogen protection and 120 ℃ of following reactions 3 hours, make pre-polymer solution.
2) in prepolymer, add α; omega end hydroxyl PPDO (100 ℃ of fusing points) 5.8 grams nitrogen protection and 165 ℃ of following reactions 8 hours, are poured reaction product solution in glass dish film forming; treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 6.
Embodiment 7
1) in flask, adds α, the omega end hydroxyl gathers adipate glycol glycol ether ester (normal temperature is thick liquid down) 7.5 grams, α, the chloroformic solution of omega end hydroxyl poly terephthalic acid Succinic Acid butyleneglycol copolyesters (110 ℃ of fusing points) (containing poly terephthalic acid Succinic Acid butyleneglycol copolyesters 0.5 gram, chloroform 60 grams), and N, N-dihydroxy ethyl cinnamide 1.95 grams, put into oil bath, be heated to 50 ℃ under stirring, and logical nitrogen was handled 0.5 hour; The chloroformic solution that adds stannous octoate again (contains stannous octoate 0.04 gram, 1; 4-dioxane 3 grams), hexamethylene diisocyanate and chloroform 24 grams; isocyanate group and step 1) and 2) in the mol ratio of total hydroxyl of all reactants be 1.2: 1; nitrogen protection and 60 ℃ of following reactions 3 hours, make pre-polymer solution.
2) in pre-polymer solution, add 4,4 '-diaminodiphenylmethane 0.05 gram, in nitrogen protection and 60 ℃ reaction 8 hours down; Pour reaction product solution in glass dish film forming, treat the solvent final vacuum drying of volatilizing naturally, obtain light-induced shape-memory polymer film 7.
Embodiment 8 light-induced shape-memory effects
Be that to be stretched to strain with the speed of 10mm/min be 20% for the polymeric film 1 usefulness electronic tensile machine of 30mm * 11.6mm * 0.11mm with effective dimensions, under stretched state, keep this strain, with the UV-irradiation of wavelength 365nm 60 minutes, remove external force, strain is 10.8%, and the deformation fixed rate is 54%; Be the UV-irradiation 60 minutes of 254nm with wavelength again, strain is 3.4%, and the deformation recovery rate is 83%.
When initial strain was 30%, its deformation fixed rate and deformation recovery rate were respectively 55% and 77%.When initial strain was 50%, its deformation fixed rate and deformation recovery rate were respectively 52% and 74%.
Other polymkeric substance carries out similar mensuration.Result such as following table.
Table 1 light-induced shape-memory measurement result
Sample number into spectrum Maximum strain ε m(%) Deformation fixed rate R f (%) Deformation recovery rate R r(%)
1 20 30 50 54 55 52 83 77 74
2 50 57 95
3 50 56 92
4 50 51 89
5 30 54 75
6 50 53 92
7 50 50 96

Claims (10)

1. a light-induced shape-memory polymer is characterized in that, it is to contain the N-shown in following 1a, 1b or the 1c to replace the unitary thermoplastic polyurethanes segmented copolymer of cinnamide photosensitive structure, and its main transition temperature of soft section is not higher than 50 ℃; It is not higher than 50 ℃ α by the N-dihydroxyalkyl cinnamamide of (1) 0.5wt%~25wt%, the main transition temperature of (2) 90wt%~20wt%, the small molecule chain extender of omega end hydroxy polymer A, (3) 0~5wt%, the second-order transition temperature of (4) 0~75wt% or fusing point are not less than 50 ℃ and compare α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B makes with (5) di-isocyanate reaction;
Figure FSB00000555009500011
Described main transition temperature is the second-order transition temperature of amorphous polymer or the melt temperature of crystalline polymer.
2. a kind of light-induced shape-memory polymer as claimed in claim 1, it is characterized in that, described N-dihydroxyalkyl cinnamamide is N, N-dihydroxy ethyl cinnamide, N, N-dihydroxy sec.-propyl cinnamide or N-[2-hydroxyl-1-(methylol) ethyl]-cinnamide; Described small molecule chain extender is an ethylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, phenylenediamine, benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane or 3,3 '-two chloro-4,4 '-diaminodiphenylmethane; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl cyclohexane vulcabond, 2,4,4-trimethyl cyclohexane vulcabond, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate or tetramethylxylylene diisocyanate.
3. a kind of light-induced shape-memory polymer as claimed in claim 1, it is characterized in that, described α, omega end hydroxy polymer A be main transition temperature be not higher than 50 ℃ and contain α, the polyester of omega end hydroxyl, polyethers, polysiloxane, polycarbonate, polyesteramide, polyether ester, polyestercarbonate or polyolefine; Described α, omega end hydroxy polymer B are that second-order transition temperature or fusing point are not less than 50 ℃ and than described α, the main transition temperature of omega end hydroxy polymer A high at least 20 ℃ and contain α, the polyester of omega end hydroxyl, polycarbonate, polyesteramide or polyolefine.
4. the preparation method of a light-induced shape-memory polymer as claimed in claim 1 is characterized in that, comprises the steps:
1) the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, omega end hydroxy polymer A and vulcabond react down at 50-180 ℃ in the presence of the catalyzer of 0~1wt%, isocyanate group and step 1) and 2) in the hydroxyl of all reactants and the mol ratio of amino sum be 1~1.2: 1, make prepolymer;
2) second-order transition temperature of the small molecule chain extender of prepolymer and 0.5~5wt% or 5~75wt% or fusing point are not less than 50 ℃ and than described α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B makes light-induced shape-memory polymer 50-180 ℃ of reaction down.
5. the preparation method of a light-induced shape-memory polymer as claimed in claim 1 is characterized in that, comprises the steps:
1) the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, the second-order transition temperature of omega end hydroxy polymer A, 5~75wt% or fusing point are not less than 50 ℃ and than described α, the high at least 20 ℃ α of main transition temperature of omega end hydroxy polymer A, omega end hydroxy polymer B and vulcabond react down at 50~180 ℃ in the presence of the catalyzer of 0~1wt%, isocyanate group and step 1) and 2) in the hydroxyl of all reactants and the mol ratio of amino sum be 1~1.2: 1, make prepolymer;
2) small molecule chain extender with prepolymer and 0.5~5wt% reacts down at 50-180 ℃, makes described light-induced shape-memory polymer.
6. the preparation method of a light-induced shape-memory polymer as claimed in claim 1, it is characterized in that the N-dihydroxyalkyl cinnamamide of 0.5wt%~25wt%, the main transition temperature of 90wt%~20wt% are not higher than 50 ℃ α, omega end hydroxy polymer A and vulcabond directly react down at 50-180 ℃ in the presence of the catalyzer of 0~1wt%, the mol ratio of the hydroxyl that isocyanate group and reactant are total is 1~1.2: 1, makes described light-induced shape-memory polymer.
7. as the preparation method of claim 4,5 or 6 described a kind of light-induced shape-memory polymers, it is characterized in that, described N-dihydroxyalkyl cinnamamide is N, N-dihydroxy ethyl cinnamide, N, N-dihydroxy sec.-propyl cinnamide or N-[2-hydroxyl-1-(methylol) ethyl]-cinnamide; Described small molecule chain extender is an ethylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, phenylenediamine, benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-two chloro-4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane or 3,3 '-two chloro-4,4 '-diaminodiphenylmethane; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl cyclohexane vulcabond or 2,4,4-trimethyl cyclohexane vulcabond, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate or tetramethylxylylene diisocyanate; Described catalyzer is stannous octoate, dibutyl tin laurate.
8. as the preparation method of claim 4,5 or 6 described a kind of light-induced shape-memory polymers, it is characterized in that, described α, omega end hydroxy polymer A be main transition temperature be not higher than 50 ℃ and contain α, the polyester of omega end hydroxyl, polyethers, polysiloxane, polycarbonate, polyesteramide, polyether ester, polyestercarbonate or polyolefine; Described α, omega end hydroxy polymer B are that second-order transition temperature or fusing point are not less than 50 ℃ and than described α, the main transition temperature of omega end hydroxy polymer A high at least 20 ℃ and contain α, the polyester of omega end hydroxyl, polycarbonate, polyesteramide or polyolefine.
9. as claim 4, the preparation method of 5 or 6 described a kind of light-induced shape-memory polymers, it is characterized in that, described α, omega end hydroxy polymer A be main transition temperature be not higher than 50 ℃ and contain α, the polycaprolactone of omega end hydroxyl, poly-(trimethylene carbonate), poly-succinic hexylene glycol ester, poly butylene succinate, the poly-succinic propylene glycol ester, polyethylene glycol succinate, poly-succinic glycol ether ester, poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polypropylene adipate (PPA), polyethylene glycol adipate, poly-hexanodioic acid glycol ether ester or their multipolymer; Perhaps be main transition temperature be not higher than 50 ℃ and contain α, the polyoxyethylene glycol of omega end hydroxyl, polypropylene glycol, polytetrahydrofuran and their multipolymer; Perhaps be main transition temperature be not higher than 50 ℃ and contain α, the polyhutadiene of omega end hydroxyl, polyisoprene or perbutan.
10. as claim 4, the preparation method of 5 or 6 described a kind of light-induced shape-memory polymers, it is characterized in that, described α, omega end hydroxy polymer B is that second-order transition temperature or fusing point are not less than 50 ℃ and than described α, the main transition temperature of omega end hydroxy polymer A high at least 20 ℃ and contain α, the poly(lactic acid) of omega end hydroxyl, polyglycolic acid, PPDO, poly butylene succinate, polyethylene glycol succinate, poly adipate succinic acid ester, polybutylene terephthalate, polyethylene terephthalate, Poly(Trimethylene Terephthalate), poly terephthalic acid cyclohexanedimethanoester ester or their multipolymer.
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