CN109912773A - A kind of shape memory polyurethane and preparation method thereof - Google Patents
A kind of shape memory polyurethane and preparation method thereof Download PDFInfo
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- CN109912773A CN109912773A CN201910250967.8A CN201910250967A CN109912773A CN 109912773 A CN109912773 A CN 109912773A CN 201910250967 A CN201910250967 A CN 201910250967A CN 109912773 A CN109912773 A CN 109912773A
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Abstract
The invention discloses a kind of shape memory polyurethanes and preparation method thereof.The preparation method includes making the first hybrid reaction system reaction comprising polycaprolactone diols, diisocyanate, catalyst and organic solvent, and base polyurethane prepolymer for use as is made；And make the second hybrid reaction system reaction comprising the base polyurethane prepolymer for use as, spiral non-planar chain extender or plane chain extender and organic solvent, obtained reaction product is solidified later, obtains shape memory polyurethane.Preparation method of the invention is easy to operate, synthesis process is efficient, and obtained shape memory polyurethane has excellent triple shape-memory properties and mechanical stretch performance, the elongation at break 500~600% of the polyurethane；15~20MPa of tensile strength；It thermally decomposes 280~320 DEG C of initial temperature.Secondary cycle shape fixed rate 91~99% in shape memory curve, 95~99% or more secondary cycle shape recovery rate.
Description
Technical field
The invention belongs to shape memory polyurethane and intelligent macromolecule material technical fields, in particular to a kind of to use spiral
The method that non-planar or plane chain extender prepare shape memory polyurethane.
Background technique
Shape-memory polymer (shape memory polymer, abbreviation SMP) is used as a kind of intelligent macromolecule material, main
To realize shape memory effect by the control of molecular structure and vitrifying characteristic, SMP material have at low cost, light weight,
The features such as deflection is big and plasticity is strong, and there is the advantages such as good biocompatibility and degradability, such polyurethane intelligence
Energy material has extensive potential application prospect in biomedical materials field.
Shape memory polyurethane (shape memory polyurethane, abbreviation SMPU) generally has two phase structure, i.e.,
Stationary phase and can anti-phase, the hard section part of polyurethane forms stationary phase by hydrogen bond or crystallization, and effect is original for product
The memory and reply of shape, soft segment part absorb the stress that force arrives polymer as reversible phase, and effect is to generate product
It deforms and fixes the shape.The advantage of SMPU material is at low cost, light weight, and has wide recovery of shape temperature, high
Shape recovery rate, good processing characteristics and biocompatibility.
So far, some document patent reports are excellent by Soft hard segment structure design and proportion adjustment processability
The method of shape memory polyurethane, as CN106632961A disclose it is a kind of utilize 4,4 '-'-biphenyl diphenol chain extenders prepare shape
The method of memory polyurethane, it is by polycaprolactone diols, 4, and 4 '-'-biphenyl diphenols (BP) and hexa-methylene isocyanates are at 80 DEG C
Under the conditions of polymerize to obtain SMPU, which uses Molecular Design chain extender for the first time, and cross-linking modified mechanism preparation comprehensive performance is good
Good shape memory polyurethane material.CN106496513A discloses a kind of hydroxyl aminimide and prepares shape memory polyurethane
Preparation method, it has synthesized hydroxyl aminimide, as chain extender, in conjunction with polycaprolactone diols and diisocyanate
It polymerize to obtain the preferable SMPU of comprehensive performance, can be realized shape memory function at 70 DEG C.But there is also certain limitations for the invention
Property, it is all stiffening ring by the chain extender that Molecular Design is quoted, greatly improves hard segment content, be unfavorable for the tough of such SMPU
Property, to limit its application range.
CN107163211A discloses a kind of preparation method of adamantane type polycaprolactone type shape memory polyurethane.It is adopted
Crosslinking knot is obtained with the bridging agent of the star-like polycaprolactone of tetrahydroxy adamantane base and 6-caprolactone, diisocyanate and small molecule
Structure is stable, frame-type SMPU, introduces this caged rigid body of adamantane in the material, have it is straight symmetrical, it is highly stable
Rigid structure is conducive to the thermal stability and mechanical performance that improve SMPU.And the SMPU material advantage is that frame structure is held
It easily adjusts, has preferable shape memory effect preferable in 34.5~104.5 DEG C of ranges.But its raw material is not cheap, convenient easy
, it is limited in the extensive use of industrialized production.
Therefore, in the prior art thermotropic induction shape memory polyurethane there are shape fixed rate and shape recovery rate are low, and
Its shape memory effect is poor, and the problems such as cannot be used widely.
Summary of the invention
Shape memory is prepared the main purpose of the present invention is to provide a kind of spiral non-planar or plane chain extender to gather
The method of urethane, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation methods of shape memory polyurethane comprising:
Keep the first hybrid reaction system comprising polycaprolactone diols, diisocyanate, catalyst and organic solvent anti-
It answers, base polyurethane prepolymer for use as is made；And
Make to include the base polyurethane prepolymer for use as, spiral non-planar chain extender or plane chain extender and organic solvent
The reaction of second hybrid reaction system, later solidifies obtained reaction product, obtains shape memory polyurethane.
The embodiment of the invention also provides the shape memory polyurethanes prepared by preceding method.
Further, the elongation at break of the polyurethane is 500~600%, preferably 500~570%, tensile strength
For 15~20MPa, thermally decomposing initial temperature is 280~320 DEG C；The polyurethane has triple shape-memory properties, described poly-
In the shape memory curve of urethane secondary cycle shape fixed rate be 91~99%, secondary cycle shape recovery rate be 95~
99%.
Compared with prior art, the beneficial effect comprise that
The preparation method of shape memory polyurethane provided by the invention is easy to operate and synthesis process is efficient, non-using spiral
Plane or plane chain extender construct non-planar or plane type polyurethane, and obtained shape memory polyurethane is with excellent
Different triple shape-memory properties and mechanical stretch performance, the elongation at break 500~600% of the polyurethane；Tensile strength 15
~20MPa；It thermally decomposes 280~320 DEG C of initial temperature.Secondary cycle shape fixed rate 91~99% in shape memory curve,
95~99% or more secondary cycle shape recovery rate.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the conjunction for preparing shape memory polyurethane in an exemplary embodiments of the invention using spiral non-planar chain extender
At process schematic.
Fig. 2 is the FT-IR of the shape memory polyurethane in the embodiment of the present invention 1 using the preparation of spiral non-planar chain extender
Figure.
Fig. 3 is the shape of the shape memory polyurethane in the embodiment of the present invention 1 using the preparation of spiral non-planar chain extender
Memory curve (DMA) figure.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution mainly passes through certain types of Molecular Design, has screened a series of non-flat noodles peace noodles of spirals
Chain extender, series SMPU is made in conjunction with polycaprolactone diols and diisocyanate, wherein the shape of spiral non-planar is remembered
Function polyurethane is recalled, with superior shape-memory properties.It as follows will be to the technical solution, its implementation process and principle etc.
It is further explained.
A kind of preparation method for shape memory polyurethane that the one aspect of the embodiment of the present invention provides includes:
Keep the first hybrid reaction system comprising polycaprolactone diols, diisocyanate, catalyst and organic solvent anti-
It answers, base polyurethane prepolymer for use as is made；And
Make to include the base polyurethane prepolymer for use as, spiral non-planar chain extender or plane chain extender and organic solvent
The reaction of second hybrid reaction system, later solidifies obtained reaction product, obtains shape memory polyurethane.
In some embodiments, the preparation method specifically includes: by polycaprolactone diols, diisocyanate, urging
Agent and organic solvent uniformly mix, and form the first hybrid reaction system, later in 55~65 DEG C of 30~90min of microwave reaction,
The base polyurethane prepolymer for use as is made.
In some embodiments, the weight average molecular weight of the polycaprolactone diols is 1000~5000.
Further, the hydroxyl value of the polycaprolactone diols is 110~125mg KOH/g.
In some embodiments, the diisocyanate includes methyl diphenylene diisocyanate (MDI), isophorone
Diisocyanate (IPDI), hexamethylene diisocyanate (HDI), paraphenylene diisocyanate (PPDI), 1,5- naphthalene diisocyanate
Any one in ester (1,5-NDI), toluene di-isocyanate(TDI) (TDI), dicyclohexyl diisocyanate (HMDI) etc. or two kinds
Above combination, but not limited to this.
In some embodiments, the catalyst includes that organotin class polyurethane catalyst for synthesizing, organo-bismuth are birdsed of the same feather flock together
Any one in urethane catalyst for synthesizing and titanate ester polyurethane catalyst for synthesizing etc. or two or more combinations, but
It is without being limited thereto.
Further, the catalyst preferably includes in stannous octoate, dibutyl tin dilaurate and butyl titanate etc.
Any one or two or more combinations, but not limited to this.
Further, the equivalent proportion of the catalyst and polycaprolactone diols is 1.0~1.5:100.
Further, the organic solvent is the good molten of synthesis of polyurethane for adjusting viscosity, the organic solvent
Agent, such as be preferably methylene chloride, dichloroethanes, chloroform, carbon tetrachloride, acetone, tetrahydrofuran (THF), N, N- bis-
Any one in methylformamide (DMF), n,N-dimethylacetamide (DMAc) etc. or two or more combinations, but be not limited to
This.
In some embodiments, the preparation method specifically includes: the base polyurethane prepolymer for use as, spiral is non-planar
Type chain extender or plane chain extender and organic solvent uniformly mix, and the second hybrid reaction system are formed, later in 60~90 DEG C
(preferably 70~80 DEG C) 30~90min of microwave reaction, then it is placed in mold preheated at 50~80 DEG C, later in 50~90 DEG C
Lower vacuum solidification 12~for 24 hours, obtain the shape memory polyurethane.
Further, the polycaprolactone diols, diisocyanate and spiral non-planar chain extender or plane expand
The molar ratio of chain agent is 1:3~5:2~4.
In some embodiments, the spiral non-planar chain extender or plane chain extender that the present invention uses are non-for spiral
Plane or plane polyalcohol are two phenolic hydroxyl groups of neighbour or boric acid two with polynary phenyl ring synthesized by Molecular Design
The combination of one or both of hydroxyl, but not limited to this.
In some preferred embodiments, the plane chain extender includes any one of I a of formula, II a, III a, III a2, IV a
Or two or more structures, but not limited to this.
In some preferred embodiments, the spiral non-planar chain extender includes I b of formula, I b2、Ⅱb、Ⅱb2、Ⅱb3、Ⅲb、
Ⅲb2、Ⅲb3、Ⅳb、Ⅳb2Any one of or two or more structures, but not limited to this.
Among some more specifically embodiments, a kind of preparation method of shape memory polyurethane of the invention includes
Following steps:
It will be put into round-bottomed flask in the polycaprolactone diols of 5.00~8.00g, 2.40~2.80g diisocyanate be added
Ester adds dibutyl tin dilaurate and 20ml tetrahydrofuran (THF) dissolution of 1.0~1.5%eqv, in 55~65 later
Base polyurethane prepolymer for use as is made in DEG C 30~90min of microwave reaction, and acetone-di-n-butylamine titration, which determines, is added spiral non-planar
30~50mLN, dinethylformamide (DMF), in 70 is added in the amount (0.18~0.40g) of chain extender or plane chain extender
30~90min of microwave reaction at~80 DEG C, finally pours into mold preheated at 50~80 DEG C, the vacuum drying oven at 50~90 DEG C
Solidification 12~for 24 hours, obtain polyurethane film.
The other side of the embodiment of the present invention additionally provides the shape memory polyurethane prepared by preceding method.
Further, the elongation at break of the shape memory polyurethane is 500~600%, preferably 500~570%,
Tensile strength is 15~20MPa, and thermal decomposition initial temperature is 280~320 DEG C；The polyurethane has triple shape memories
Can, secondary cycle shape fixed rate is 91~99% in the shape memory curve of the polyurethane, secondary cycle shape recovery rate
It is 95~99%.
In conclusion the preparation method of shape memory polyurethane of the invention is easy to operate and synthesis process is efficient, use
Spiral non-planar or plane chain extender construct non-planar or plane type polyurethane, and obtained shape memory polyurethane
With excellent triple shape-memory properties and mechanical stretch performance, b3The elongation at break 500~600% of the polyurethane；It draws
Stretch 15~20MPa of intensity；It thermally decomposes 280~320 DEG C of initial temperature.Secondary cycle shape fixed rate 91 in shape memory curve
~99%, 95~99% or more secondary cycle shape recovery rate.
Below with reference to several preferred embodiments and attached drawing, further details of the technical solution of the present invention, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, those of ordinary skill in the art's every other embodiment obtained without making creative work, all belongs to
In the scope of protection of the invention.The implementation condition used in following embodiment can do further adjustment according to actual needs,
The implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
As shown in fig.1, the polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, it is added
2.62g dicyclohexyl diisocyanate (HMDI) adds 20ml tetrahydrofuran (THF) and the tin dilaurate two of 1%eqv later
The performed polymer of polyurethane is made in 60 DEG C of microwave reaction 45min in butyl tin, and acetone-di-n-butylamine titration, which determines, is added chain extension
The amount of agent Formula II b is 1.36g, is added 15ml n,N-Dimethylformamide (DMF), the microwave reaction 60min at 70 DEG C, finally
Mold preheated at 80 DEG C is poured into, vacuum drying oven solidifies 16h at 80 DEG C, obtains shape memory polyurethane (labeled as poly-
Urethane PU-1), the performance test results are shown in Table 1.
The FT-IR of the obtained shape memory polyurethane of the present embodiment schemes referring to Fig. 2, shape memory curve (DMA) figure please join
Read Fig. 3.
Embodiment 2
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.50g diphenyl methane is added
Diisocyanate (MDI), adds 20ml dichloroethanes and the dibutyl tin dilaurate of 1%eqv later, anti-in 60 DEG C of microwaves
45min is answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender Formula II b is added is
1.38g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 70 DEG C is finally poured at 60 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 14h at 80 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -2), property
Energy test result is shown in Table 1.
Embodiment 3
The polycaprolactone diols that 10.00g molecular weight is 2000 is put into round-bottomed flask, 2.62g diphenylmethyl is added
Alkane diisocyanate (MDI) adds 20ml n,N-Dimethylformamide (DMF) and two fourth of tin dilaurate of 1%eqv later
The performed polymer of polyurethane is made in 65 DEG C of microwave reaction 45min in Ji Xi, and acetone-di-n-butylamine titration, which determines, is added chain extender
The amount of Formula II b is 1.36g, is added 15ml n,N-dimethylacetamide (DMAc), the microwave reaction 60min at 75 DEG C, finally
Mold preheated at 70 DEG C is poured into, vacuum drying oven solidifies 21h at 70 DEG C, obtains shape memory polyurethane (labeled as poly-
Urethane PU-3), the performance test results are shown in Table 1.
Embodiment 4
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.50g isophorone two is added
Isocyanates (IPDI), adds the dibutyl tin dilaurate of 20ml tetrahydrofuran (THF) and 1%eqv later, micro- in 60 DEG C
Wave reacts 45min, and the performed polymer of polyurethane is made, and acetone-di-n-butylamine titration determines that the amount that chain extender Formula II b is added is
1.35g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 78 DEG C is finally poured at 65 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 18h at 80 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -4), property
Energy test result is shown in Table 1.
Embodiment 5
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 3.0g toluene diisocyanate is added
Acid esters (TDI), adds the dibutyl tin dilaurate of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 60 DEG C of microwaves
45min to be answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines the amount 1.37g that chain extender Formula II b is added,
It is added 15ml n,N-Dimethylformamide (DMF), the microwave reaction 60min at 70 DEG C finally pours into mould preheated at 75 DEG C
Tool, vacuum drying oven solidifies 15h at 80 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -5), performance test
It the results are shown in Table 1.
Embodiment 6
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1.2%eqv later, in 65 DEG C of microwaves
45min is reacted, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender Formula II b is added is
1.34g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 65 DEG C is finally poured at 50 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 21h at 70 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -6), property
Energy test result is shown in Table 1.
Embodiment 7
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the dibutyl tin dilaurate of 20ml tetrahydrofuran (THF) and 1.1%eqv later, in 60 DEG C
Microwave reaction 45min, is made the performed polymer of polyurethane, and acetone-di-n-butylamine titration determines the amount that chain extender III b2 is added
It for 1.39g, is added 15ml n,N-dimethylacetamide (DMAc), the microwave reaction 60min at 72 DEG C is finally poured at 55 DEG C
Preheated mold, vacuum drying oven solidifies 19h at 80 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -7),
Its performance test results is shown in Table 1.
Embodiment 8
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1.2%eqv later, in 65 DEG C of microwaves
45min is reacted, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender formula IV b is added is
1.81g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 78 DEG C is finally poured at 55 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 17h at 70 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -8), property
Energy test result is shown in Table 1.
Embodiment 9
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 65 DEG C of microwaves
45min to be answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender Formulas I a is added is 0.44g,
It is added 15ml n,N-Dimethylformamide (DMF), the microwave reaction 60min at 80 DEG C finally pours into mould preheated at 80 DEG C
Tool, vacuum drying oven solidification for 24 hours, obtains shape memory polyurethane (labeled as polyurethane PU -9), performance test at 70 DEG C
It the results are shown in Table 1.
Embodiment 10
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 65 DEG C of microwaves
45min is answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender formula III a is added is
1.32g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 75 DEG C is finally poured at 75 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 22h at 70 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -10), property
Energy test result is shown in Table 1.
Embodiment 11
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 65 DEG C of microwaves
45min is answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender formula III a2 is added is
1.33g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 70 DEG C is finally poured at 65 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 17h at 80 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -11), property
Energy test result is shown in Table 1.
Embodiment 12
The polycaprolactone diols that 5.00g molecular weight is 5000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the triethylenediamine of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 65 DEG C of microwaves
45min is answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender formula IV a is added is
1.58g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 60min at 75 DEG C is finally poured at 75 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 20h at 70 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -12), property
Energy test result is shown in Table 1.
Embodiment 13
The polycaprolactone diols that 10.00g molecular weight is 2000 is put into round-bottomed flask, two isocyanide of dicyclohexyl is added
Acid esters (HMDI), adds the dibutyl tin dilaurate of 20ml tetrahydrofuran (THF) and 1%eqv later, anti-in 55 DEG C of microwaves
90min is answered, the performed polymer of polyurethane is made, acetone-di-n-butylamine titration determines that the amount that chain extender Formula II b is added is
2.71g, is added 15ml n,N-Dimethylformamide (DMF), and the microwave reaction 30min at 90 DEG C is finally poured at 80 DEG C and preheated
The mold crossed, vacuum drying oven solidifies 12h at 90 DEG C, obtains shape memory polyurethane (labeled as polyurethane PU -13), property
Energy test result is shown in Table 1.
Embodiment 14
The polycaprolactone diols that 15.00g molecular weight is 3000 is put into round-bottomed flask, 2.62g dicyclohexyl is added
Diisocyanate (HMDI) adds 20ml n,N-Dimethylformamide (DMF) and two fourth of tin dilaurate of 1.3%eqv later
The performed polymer of polyurethane is made in 65 DEG C of microwave reaction 30min in Ji Xi, and acetone-di-n-butylamine titration, which determines, is added chain extender
The amount of Formula II b is 4.07g, is added 15ml n,N-dimethylacetamide (DMAc), the microwave reaction 60min at 75 DEG C, finally
Mold preheated at 70 DEG C is poured into, vacuum drying oven solidifies 13h at 70 DEG C, obtains shape memory polyurethane (labeled as poly-
Urethane PU-14), the performance test results are shown in Table 1.
Embodiment 15
The polycaprolactone diols that 5.00g molecular weight is 1000 is put into round-bottomed flask, 2.62g dicyclohexyl two is added
Isocyanates (HMDI), adds the dibutyl tin dilaurate of 20ml tetrahydrofuran (THF) and 1.5%eqv later, in 60 DEG C
Microwave reaction 45min, is made the performed polymer of polyurethane, and acetone-di-n-butylamine titration determines that the amount that chain extender II b is added is
1.36g is added 15ml n,N-dimethylacetamide (DMAc), the microwave reaction 90min at 60 DEG C, finally pours into pre- at 55 DEG C
The mold that heat is crossed, vacuum drying oven solidification for 24 hours, obtains shape memory polyurethane (labeled as polyurethane PU -15) at 50 DEG C,
The performance test results are shown in Table 1.
The obtained product of 1-15 of the embodiment of the present invention shows triple shape memories, it may be assumed that when polymer sample rods are drawn at 70 DEG C
Reaching shape becomes 200%.After 20 DEG C of fixed a period of times, obtaining fixed shape becomes 132% to get to the interim shape of first time
Shape is deformed, first time shape fixed rate is about 98.2%, same process, realize that second of shape fixed rate is about 99.3%, the
Secondary shape recovery rate is about 99.4%.Realize that third time shape fixed rate is about 73.8%, third time shape recovery rate is about
98.3%, show that the polyurethane has preferable triple shape-memory properties.
The mechanics and shape-memory properties test result of 1 the obtained product of embodiment 1-15 of table
In addition, inventor also utilizes the alternate embodiments such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-15 have carried out corresponding test, the content of required verifying and produce with embodiment 1-15
Product are close.So do not explained one by one to the verifying content of each embodiment, only using embodiment 1-15 as representative herein
Illustrate the excellent place of the present patent application.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of shape memory polyurethane, characterized by comprising:
Make the first hybrid reaction system reaction comprising polycaprolactone diols, diisocyanate, catalyst and organic solvent, system
Obtain base polyurethane prepolymer for use as；And
Make second comprising the base polyurethane prepolymer for use as, spiral non-planar chain extender or plane chain extender and organic solvent
The reaction of hybrid reaction system, later solidifies obtained reaction product, obtains shape memory polyurethane.
2. preparation method according to claim 1, it is characterised in that specifically include: by polycaprolactone diols, two isocyanides
Acid esters, catalyst and organic solvent uniformly mix, formed the first hybrid reaction system, later in 55~65 DEG C of microwave reactions 30~
The base polyurethane prepolymer for use as is made in 90min.
3. preparation method according to claim 1 or 2, it is characterised in that: the Weight-average molecular of the polycaprolactone diols
Amount is 1000~5000；And/or the hydroxyl value of the polycaprolactone diols is 110~125mg KOH/g.
4. preparation method according to claim 1 or 2, it is characterised in that: the diisocyanate includes diphenyl methane
Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, paraphenylene diisocyanate, two isocyanide of 1,5- naphthalene
Any one in acid esters, toluene di-isocyanate(TDI) and dicyclohexyl diisocyanate or two or more combinations.
5. preparation method according to claim 1 or 2, it is characterised in that: the catalyst includes organotin class polyurethane
It is any one in catalyst for synthesizing, organo-bismuth class polyurethane catalyst for synthesizing and titanate ester polyurethane catalyst for synthesizing
Kind or two or more combinations；Preferably, the catalyst includes stannous octoate, dibutyl tin dilaurate and butyl titanate
In any one or two or more combinations；
And/or the equivalent proportion of the catalyst and polycaprolactone diols is 1.0~1.5:100.
6. preparation method according to claim 1 or 2, it is characterised in that: the organic solvent is synthesis of polyurethane
Good solvent；Preferably, the organic solvent includes methylene chloride, dichloroethanes, chloroform, carbon tetrachloride, acetone, tetrahydro furan
It mutters, any one or two or more combinations in N,N-dimethylformamide and DMAC N,N' dimethyl acetamide.
7. preparation method according to claim 1, it is characterised in that specifically include: by the base polyurethane prepolymer for use as, spiral
Non-planar chain extender or plane chain extender and organic solvent uniformly mix, and the second hybrid reaction system are formed, later in 60
~90 DEG C of 30~90min of microwave reaction, then it is placed in mold preheated at 50~80 DEG C, the vacuum solidification at 50~90 DEG C later
12~for 24 hours, obtain the shape memory polyurethane；Preferably, the temperature of the microwave reaction is 70~80 DEG C.
8. preparation method according to claim 1 or claim 7, it is characterised in that: the polycaprolactone diols, diisocyanate
It is 1:3~5:2~4 with the molar ratio of spiral non-planar chain extender or plane chain extender；
And/or the spiral non-planar chain extender or plane chain extender include that spiral is non-planar or plane polyalcohol, it is excellent
It is selected as two phenolic hydroxyl group of neighbour with polynary phenyl ring and/or boric acid dihydroxy；Preferably, the spiral non-planar chain extender includes
I b of formula, I b2、Ⅱb、Ⅱb2、Ⅱb3、Ⅲb、Ⅲb2、Ⅲb3、Ⅳb、Ⅳb2Any one of or two or more structures:
Preferably, the plane chain extender includes I a of formula, II a, III a, III a2, any one of IV a or two or more knots
Structure:
9. the shape memory polyurethane prepared by any one of claim 1-8 the method.
10. shape memory polyurethane according to claim 9, it is characterised in that: the elongation at break of the polyurethane is
500~600%, preferably 500~570%, tensile strength is 15~20 MPa, and thermal decomposition initial temperature is 280~320 DEG C；
The polyurethane has triple shape-memory properties, and secondary cycle shape fixed rate is in the shape memory curve of the polyurethane
91~99%, secondary cycle shape recovery rate is 95~99%.
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