CN107163211B - A kind of preparation method of shape memory polyurethane - Google Patents
A kind of preparation method of shape memory polyurethane Download PDFInfo
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- CN107163211B CN107163211B CN201710542066.7A CN201710542066A CN107163211B CN 107163211 B CN107163211 B CN 107163211B CN 201710542066 A CN201710542066 A CN 201710542066A CN 107163211 B CN107163211 B CN 107163211B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G63/02—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
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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
- C08G63/78—Preparation processes
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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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
- C08G2280/00—Compositions for creating shape memory
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Abstract
The present invention provides a kind of preparation method of shape memory polyurethane, is related to polyurethane material preparation technical field.Method includes: by 1, 3, 5, 7- tetrahydroxy adamantane, 6-caprolactone, catalyst and solvent, it is reacted 20~50 hours under conditions of inert gas and 70-130 DEG C, obtain the star-like poly-epsilon-caprolactone of adamantyl, 1, 3, 5, the molar ratio of 7- tetrahydroxy adamantane and the 6-caprolactone is 1:40~240, by the star-like poly-epsilon-caprolactone of adamantyl and long chain diol, isocyanates is uniformly mixed, catalysts and solvents are added, and it is reacted 3~9 hours at 50-100 DEG C, obtain isocyanate-terminated base polyurethane prepolymer for use as, the mass ratio of the star-like poly-epsilon-caprolactone of adamantyl and long chain diol is 9:1~1:9, bridging agent is added in base polyurethane prepolymer for use as, so that bridging agent is reacted with the isocyanates in base polyurethane prepolymer for use as, obtain adamantane The shape memory polyurethane of base cross-linking type.Shape memory polyurethane made from this method has good shape memory effect, expands range.
Description
Technical field
The invention belongs to polyurethane material preparation technical field more particularly to a kind of preparation sides of shape memory polyurethane
Method.
Background technique
Shape-memory polymer is that one kind is capable of fixing temporary shapes, and environmental stimuli (such as: heat, light, magnetism or chemistry)
Under the action of be returned to the intelligent macromolecule material of original shape.Wherein, it improves the structure design of SMPs and improves SMPs's
Functional characteristic is the direction of current SMPs development, and the hot spot of current intelligent macromolecule material research.
Thermotropic induction shape memory polyurethane refers to can deform at a certain temperature, and can be in room temperature or the condition of low temperature
It is lower to keep deformed deformation, when temperature is increased to the shape note that when specifically responding temperature, can be returned to original shape
Recall polymer material.Since the temperature memory range of thermotropic induction shape memory polyurethane is wide, light weight, good weatherability, raw material
Be easy to get, deformation quantity is big and repeats the advantages that deformation effects are good, be one of faster shape memory polymer material of development.Thermotropic sense
Answer shape memory polyurethane weaving, biologic medical and in terms of all have very huge potential value.
But the shape fixed rate and shape recovery rate of thermotropic induction shape memory polyurethane in the prior art are low, note
It is poor to recall effect, cannot be widely used.
Summary of the invention
The present invention provides a kind of preparation method of shape memory polyurethane, it is intended to solve thermotropic induction shape in the prior art
The problem of shape fixed rate and shape recovery rate of shape memory polyurethane are low, and memory effect is poor, cannot be widely used.
A kind of preparation method of shape memory polyurethane provided by the invention, comprising:
By 1,3,5,7- tetrahydroxy adamantane, 6-caprolactone, catalyst and solvent, in inert gas and 70-130 DEG C
Under the conditions of react 20~50 hours, obtain the star-like poly-epsilon-caprolactone of adamantyl, described 1,3,5,7- tetrahydroxy adamantanes and institute
The molar ratio for stating 6-caprolactone is 1:40~240；
The star-like poly-epsilon-caprolactone of the adamantyl is uniformly mixed with long chain diol, diisocyanate, described in addition
Catalyst and the solvent, and reacted 3~9 hours at 50-100 DEG C, obtain isocyanate-terminated base polyurethane prepolymer for use as, institute
The mass ratio for stating the star-like poly-epsilon-caprolactone of adamantyl and long chain diol is 9:1~1:9；
Bridging agent is added in the base polyurethane prepolymer for use as so that the bridging agent with it is different in the base polyurethane prepolymer for use as
Polyisocyanate reactant obtains the shape memory polyurethane of adamantyl cross-linking type.
The preparation method of a kind of shape memory polyurethane provided by the invention, by gathering adamantane and 6-caprolactone
Reaction is closed, the star-like poly-epsilon-caprolactone of adamantyl is obtained.The material molecule chain length, stable structure introduce two in the course of the polymerization process
Isocyanates and bridging agent obtain the shape memory polyurethane of cross-linked structure stabilization, frame-type.Due to stable structure, frame structure
It is easy to adjust, has shape fixed rate >=93%, shape recovery rate >=88% has good shape memory effect, to expand
Application range.
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
Some embodiments of invention.
Fig. 1 is the star-like polycaprolactone (Ad-PCL of adamantyl provided in an embodiment of the present invention4) molecular structure；
Fig. 2 is the star-like polycaprolactone (Ad-PCL of adamantyl provided in an embodiment of the present invention4) nucleus magnetic hydrogen spectrum figure；
Fig. 3 is the differential scanning calorimetry figure of shape memory polyurethane provided in an embodiment of the present invention；
Fig. 4 is the shape fixed rate of test shape memory polyurethane provided in an embodiment of the present invention and the survey of shape recovery rate
Attempt；
Fig. 5 is the recovery of shape variation diagram of shape memory polyurethane corresponding with test chart provided in an embodiment of the present invention.
Specific embodiment
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, and not all embodiments.Based on the embodiments of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of shape memory polyurethane, and this method mainly comprises the steps that
By 1,3,5,7- tetrahydroxy adamantane, 6-caprolactone, catalyst and solvent, in inert gas and 70-130 DEG C
Under the conditions of react 20~50 hours, obtain the star-like poly-epsilon-caprolactone of adamantyl, 1,3,5, the 7- tetrahydroxy adamantane and the ε-
The molar ratio of caprolactone is 1:40~240；
The star-like poly-epsilon-caprolactone of the adamantyl is uniformly mixed with long chain diol, diisocyanate, the catalysis is added
Agent and the solvent, and reacted 3~9 hours at 50-100 DEG C, isocyanate-terminated base polyurethane prepolymer for use as is obtained, the adamantane
The mass ratio of the star-like poly-epsilon-caprolactone of base and long chain diol is 9:1~1:9；
Bridging agent is added in the base polyurethane prepolymer for use as, so that the isocyanates in the bridging agent and the base polyurethane prepolymer for use as
Reaction, obtains the shape memory polyurethane of adamantyl cross-linking type.
In the preparation method of shape memory polyurethane provided by the invention, the C-C of the bond distance of adamantane close to diamond
Bond distance, and adamantane is caged rigid body, has straight symmetrical, highly stable rigid structure, by adamantane and 6-caprolactone
Polymerization reaction is carried out, the star-like poly-epsilon-caprolactone of adamantyl is obtained.The material molecule chain length, stable structure, in the course of the polymerization process
Diisocyanate is introduced, forms isocyanate-terminated base polyurethane prepolymer for use as, and using in the bridging agent and performed polymer of small molecule
Isocyanates reaction, obtain that cross-linked structure is stable, shape memory polyurethane of frame-type.Wherein, shape memory polyurethane
Molecular weight is 500~10000, and due to stable structure, frame structure is easy to adjust, and has shape fixed rate >=93%, recovery of shape
Rate >=88% has good shape memory effect, to expand application range.
Specifically, by 1,3,5,7- tetrahydroxy adamantanes, 6-caprolactone, catalyst and solvent, in inert gas and 70-
It is reacted 20~50 hours under conditions of 130 DEG C, obtains the star-like poly-epsilon-caprolactone of adamantyl.Wherein the star-like poly- ε-of adamantyl oneself
Lactone (Ad-PCL4) molecular structure it is as shown in Figure 1.Nucleus magnetic hydrogen spectrum test is carried out to the star-like poly-epsilon-caprolactone of adamantyl, is obtained
To nucleus magnetic hydrogen spectrum figure as shown in Figure 2, by the characteristic peak demarcated in figure it can be concluded that, the substance be the star-like poly- ε-of adamantyl oneself
Lactone.Preferably, 1,3,5,7- tetrahydroxy adamantanes, 6-caprolactone, catalyst and solvent reaction temperature be 80-120 DEG C,
Reaction time is 30~40 hours, and the molar ratio of 1,3,5,7- tetrahydroxy adamantane and 6-caprolactone is 1:180~240.It is more excellent
Choosing, the molar ratio of 1,3,5,7- tetrahydroxy adamantane and 6-caprolactone is 1:240.The content of 6-caprolactone is higher, obtains
The strand of the star-like poly-epsilon-caprolactone of adamantyl is longer, and molecular weight is higher.The concentration of 1,3,5,7- tetrahydroxy adamantane are as follows:
10wt%, the concentration of 6-caprolactone are as follows: 10wt%, the dosage of catalyst are as follows: 0.1~0.2wt%, the dosage of solvent are as follows: 60~
70wt%, the dosage of bridging agent are 5~15wt%.
Specifically, the star-like poly-epsilon-caprolactone of adamantyl is uniformly mixed with long chain diol, isocyanates, catalysis is added
Agent and solvent, and reacted 3~9 hours at 50-100 DEG C, obtain isocyanate-terminated base polyurethane prepolymer for use as.Preferably, golden
The mass ratio of the rigid star-like poly-epsilon-caprolactone of alkyl and long chain diol is 9:1~1:9.Wherein, the addition of dihydric alcohol can increase
The length of strand.In reaction system, hydroxyl group in the star-like poly-epsilon-caprolactone of adamantyl and long chain diol with it is different
The molar ratio of ester group in cyanate is 1:1.2~2, preferably 1:1.5, in this way, can make the ester group in isocyanates
Group is sufficiently reacted with the hydroxyl group in the star-like poly-epsilon-caprolactone of adamantyl and long chain diol, obtains isocyanates envelope
The polyurethane at end.
Specifically, isocyanates is 2,4- toluene di-isocyanate(TDI), 3,3 '-dimethyl -4,4 '-diisocyanate ester groups connection
Benzene, 4,4 '-'-diphenylmethane diisocyanates, 1,5- naphthalene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, 1,6- hexa-methylene two are different
Cyanate, trans- Isosorbide-5-Nitrae-cyclohexane diisocyanate, 4,4'-Dicyclohexylmethane diisocyanate and 3- isocyanate group methylene
Base -3,5, any one of 5- trimethylcyclohexylisocyanate.Solvent is toluene, n,N-Dimethylformamide, N, N- diformazan
Any one of yl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and butyl acetate.Long chain diol is poly-epsilon-caprolactone
Glycol, polyadipate diglycol esterdiol, polyethylene glycol adipate glycol, polyadipate -1,4-butanediol ester two
Any one of pure and mild polyglycol ether glycol.
Specifically, bridging agent is added in base polyurethane prepolymer for use as, so that the isocyanic acid in bridging agent and base polyurethane prepolymer for use as
Ester reaction, obtains the shape memory polyurethane of adamantyl cross-linking type.Wherein, the shape memory polyurethane (Ad- obtained
SMPU molecular weight) is 500~10000.Differential scanning calorimetry test is carried out to it, obtains differential scanning amount as shown in Figure 3
Thermal map, as can be seen from Figure, shape memory polyurethane tool is there are two phase transition temperature, and soft segment phase transition temperature is 34.5 DEG C, hard section
Phase transition temperature is 104.5 DEG C, i.e., in the range of 34.5~104.5 DEG C, the shape memory effect of shape memory polyurethane is preferable,
The temperature range is suitable for the application range of general industry.
The shape fixed rate and shape recovery rate of shape memory polyurethane are tested, as shown in Figure 4 and Figure 5, Fig. 4 and
Fig. 5 respectively illustrates the double shape-memory properties of shape memory polyurethane.Wherein, as shown in figure 4, by the poly- ammonia of shape memory
Ester Ad-SMPU is heated, and is kept the temperature under conditions of 55 DEG C, and apply stress, will if Fig. 5 (b), Ad-SMPU are in bending state
Temperature is down to -20 DEG C, goes de-stress, and start to warm up, and the shape of period Ad-SMPU keeps good.When temperature is increased to 55 DEG C
When above, Ad-SMPU is gradually replied by bending state, continues to heat up, and the response rate of Ad-SMPU increases.It can be seen that
Ad-SMPU has good shape fixed rate and shape recovery rate.Further, since the stable structure of adamantane, adamantane is drawn
Enter to can be improved its thermal stability and mechanical performance in shape memory polyurethane.
Specifically, catalyst is any one of stannous iso caprylate, dibutyl tin dilaurate.Bridging agent is 1,2- second two
Alcohol, 1,3-PD, 1,4-butanediol, N- methyl-1,4- glycol, 1,5-PD, 1,6- hexylene glycol, 1,8- ethohexadiol, 1,
9- nonanediol, 1,10- certain herbaceous plants with big flowers glycol, Isosorbide-5-Nitrae-cyclohexane dimethanol, diglycol, Isosorbide-5-Nitrae-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexyl two
Methanol, 1,6- hexylene glycol, 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1,6- hexamethylene diamine or 1, bis- tetramethyl of 3-, two silicon
Any one of oxygen alkane.
Embodiment 1
Under inert gas protection, be added 1,3,5,7- tetrahydroxy adamantanes into reaction flask, 6-caprolactone, catalyst with
And solvent, catalyst are stannous iso caprylate, solvent is toluene, and by freezing, pumping, ventilation, circulation removes oxygen and moisture three times
Afterwards, which is placed in oil bath pan after being heated to 90 DEG C, reaction 24 hours, revolving removes solvent, obtains adamantyl star
Type polycaprolactone.Wherein, 1, the molar ratio of 3,5,7- tetrahydroxy adamantanes and 6-caprolactone is 1:60, and stannous iso caprylate is
0.1wt%, solvent 70wt%.
The star-like poly-epsilon-caprolactone of obtained adamantyl is added to 1,6- hexamethylene diisocyanate, poly-epsilon-caprolactone
Glycol (molecular weight 5000), catalyst stannous iso caprylate, in the mixed system of reaction dissolvent n,N-Dimethylformamide, stirring is equal
It is even, it is reacted at 80 DEG C, obtains performed polymer.Then small 1,4-butanediol connection performed polymer is added, is dried to obtain cross-linking type
Adamantyl shape memory polyurethane；Obtained cross-linked polyurethane is placed under the conditions of temperature is 90 DEG C drying 12 hours, is obtained
Cross-linking type adamantyl shape memory polyurethane.
Embodiment 2
Under inert gas protection, be added 1,3,5,7- tetrahydroxy adamantanes into reaction flask, 6-caprolactone, catalyst with
And solvent, catalyst are stannous iso caprylate, solvent is toluene, and by freezing, pumping, ventilation, circulation removes oxygen and moisture three times
Afterwards, which is placed in oil bath pan after being heated to 90 DEG C, reaction 24 hours, revolving removes solvent, obtains adamantyl star
Type polycaprolactone.Wherein, 1,3,5,7- tetrahydroxy adamantanes: the molar ratio of 6-caprolactone is 1:100, and stannous iso caprylate is
0.1wt%, solvent 70wt%；
The star-like poly-epsilon-caprolactone of obtained adamantyl is added to 1,6- hexamethylene diisocyanate, poly-epsilon-caprolactone
Glycol (molecular weight 5000), catalyst stannous iso caprylate, in the mixed system of reaction dissolvent n,N-Dimethylformamide, stirring is equal
It is even, it is reacted at 80 DEG C, obtains performed polymer.Then small 1,4-butanediol connection performed polymer is added, is dried to obtain cross-linking type
Adamantyl shape memory polyurethane；Obtained cross-linked polyurethane is placed under the conditions of temperature is 90 DEG C drying 12 hours, is obtained
Cross-linking type adamantyl shape memory polyurethane.
Embodiment 3
Under inert gas protection, be added 1,3,5,7- tetrahydroxy adamantanes into reaction flask, 6-caprolactone, catalyst with
And solvent, catalyst are stannous iso caprylate, solvent is toluene, and by freezing, pumping, ventilation, circulation removes oxygen and moisture three times
Afterwards, which is placed in oil bath pan after being heated to 90 DEG C, reaction 24 hours, revolving removes solvent, obtains adamantyl star
Type polycaprolactone.Wherein, 1,3,5,7- tetrahydroxy adamantanes: the molar ratio of 6-caprolactone is 1:140, and stannous iso caprylate is
0.1wt%, solvent 70wt%；
The star-like poly-epsilon-caprolactone of obtained adamantyl is added to 1,6- hexamethylene diisocyanate, poly-epsilon-caprolactone
Glycol (molecular weight 5000), catalyst stannous iso caprylate, in the mixed system of reaction dissolvent n,N-Dimethylformamide, stirring is equal
It is even, it is reacted at 80 DEG C, obtains performed polymer.Then small 1,4-butanediol connection performed polymer is added, is dried to obtain cross-linking type
Adamantyl shape memory polyurethane；Obtained cross-linked polyurethane is placed under the conditions of temperature is 90 DEG C drying 12 hours, is obtained
Cross-linking type adamantyl shape memory polyurethane.
Embodiment 4
Under inert gas protection, be added 1,3,5,7- tetrahydroxy adamantanes into reaction flask, 6-caprolactone, catalyst with
And solvent, catalyst are stannous iso caprylate, solvent is toluene, and by freezing, pumping, ventilation, circulation removes oxygen and moisture three times
Afterwards, which is placed in oil bath pan after being heated to 90 DEG C, reaction 24 hours, revolving removes solvent, obtains adamantyl star
Type polycaprolactone.Wherein, 1,3,5,7- tetrahydroxy adamantanes: the molar ratio of 6-caprolactone is 1:190, stannous iso caprylate are as follows:
0.1wt%, solvent are as follows: 70wt%；
The star-like poly-epsilon-caprolactone of obtained adamantyl is added to 1,6- hexamethylene diisocyanate, poly-epsilon-caprolactone
Glycol (molecular weight 5000), catalyst stannous iso caprylate, in the mixed system of reaction dissolvent n,N-Dimethylformamide, stirring is equal
It is even, it is reacted at 80 DEG C, obtains performed polymer.Then small 1,4-butanediol connection performed polymer is added, is dried to obtain cross-linking type
Adamantyl shape memory polyurethane；Obtained cross-linked polyurethane is placed under the conditions of temperature is 90 DEG C drying 12 hours, is obtained
Cross-linking type adamantyl shape memory polyurethane.
Embodiment 5
Under inert gas protection, be added 1,3,5,7- tetrahydroxy adamantanes into reaction flask, 6-caprolactone, catalyst with
And solvent, catalyst are stannous iso caprylate, solvent is toluene, and by freezing, pumping, ventilation, circulation removes oxygen and moisture three times
Afterwards, which is placed in oil bath pan after being heated to 90 DEG C, reaction 24 hours, revolving removes solvent, obtains adamantyl star
Type polycaprolactone.Wherein, 1,3,5,7- tetrahydroxy adamantanes: the molar ratio of 6-caprolactone is 1:240, stannous iso caprylate are as follows:
0.1wt%, solvent are as follows: 70wt%；
The star-like poly-epsilon-caprolactone of obtained adamantyl is added to 1,6- hexamethylene diisocyanate, poly-epsilon-caprolactone
Glycol (molecular weight 5000), catalyst stannous iso caprylate, in the mixed system of reaction dissolvent n,N-Dimethylformamide, stirring is equal
It is even, it is reacted at 80 DEG C, obtains performed polymer.Then small 1,4-butanediol connection performed polymer is added, is dried to obtain cross-linking type
Adamantyl shape memory polyurethane；Obtained cross-linked polyurethane is placed under the conditions of temperature is 90 DEG C drying 12 hours, is obtained
Cross-linking type adamantyl shape memory polyurethane.
The shape memory polyurethane obtained to above-mentioned 5 embodiments is analyzed under dynamic mechanical analysis stretch mode,
The shape fixed rate for the shape memory polyurethane that first embodiment obtains is 93%, shape recovery rate 88%, second embodiment
The shape fixed rate of obtained shape memory polyurethane is 93.8%, shape recovery rate 90%, the shape that 3rd embodiment obtains
The shape fixed rate of shape memory polyurethane is 95%, shape recovery rate 91%, the poly- ammonia of the shape memory that fourth embodiment obtains
The shape fixed rate of ester is 97%, shape recovery rate 92%, and the shape for the shape memory polyurethane that the 5th embodiment obtains is solid
Determining rate is 98%, shape recovery rate 95%.By above-described embodiment, it is known that, 1,3,5,7- tetrahydroxy adamantane: 6-caprolactone
Molar ratio is that smaller shape fixed rate is and shape recovery rate is higher.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of preparation method of shape memory polyurethane, which is characterized in that the described method includes:
By 1,3,5,7- tetrahydroxy adamantane, 6-caprolactone, catalyst and solvent, in inert gas and 70-130 DEG C of condition
Lower reaction 20~50 hours, obtains the star-like poly-epsilon-caprolactone of adamantyl, wherein and described 1,3,5,7- tetrahydroxy adamantanes and institute
The molar ratio for stating 6-caprolactone is 1:40~240；
The star-like poly-epsilon-caprolactone of the adamantyl is mixed with long chain diol, isocyanates, the catalyst and institute is added
Solvent is stated, and is reacted 3~9 hours at 50-100 DEG C, obtains isocyanate-terminated base polyurethane prepolymer for use as, wherein the gold
The mass ratio of the rigid star-like poly-epsilon-caprolactone of alkyl and long chain diol is 9:1~1:9；
Bridging agent is added in the base polyurethane prepolymer for use as, makes the isocyanates in the bridging agent and the base polyurethane prepolymer for use as
Reaction, obtains the shape memory polyurethane of adamantyl cross-linking type；
The bridging agent is 1,2- ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 1,8- ethohexadiol, 1,9- nonyl
Glycol, 1,10- decanediol, diglycol, Isosorbide-5-Nitrae-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexane dimethanol, 1,6- hexylene glycol, 1,2- second
The mixture of at least one of diamines, 1,3- propane diamine, Putriscine, 1,6- hexamethylene diamine or these substances；
The long chain diol is poly-epsilon-caprolactone glycol, polyadipate diglycol esterdiol, polyadipate ethylene glycol
The mixing of esterdiol, polyadipate-at least one of 1,4-butanediol esterdiol and polyglycol ether glycol or these substances
Object.
2. the method according to claim 1, wherein described 1,3,5,7- tetrahydroxy adamantanes and the ε-are in oneself
The molar ratio of ester is 1:180~240.
3. the method according to claim 1, wherein the star-like poly-epsilon-caprolactone of the adamantyl and long-chain binary
The mass ratio of alcohol is 9:1.
4. described in any item methods according to claim 1~3, which is characterized in that the star-like poly-epsilon-caprolactone of adamantyl
Molar ratio with the ester group in the hydroxyl group and isocyanates in long chain diol is 1:1.2~2.
5. described in any item methods according to claim 1~3, which is characterized in that the isocyanates is that 2,4- toluene two is different
Cyanate, 3,3 '-dimethyl -4,4 '-diisocyanate ester group biphenyl, 4,4 '-'-diphenylmethane diisocyanates, 1,5- naphthalene, two isocyanide
Acid esters, Isosorbide-5-Nitrae-phenylene diisocyanate, 1,6- hexamethylene diisocyanate, trans- Isosorbide-5-Nitrae-cyclohexane diisocyanate, 4,4 '-two
Diphenylmethane diisocyanate and 3- isocyanates methylene -3,5, at least one in 5- trimethylcyclohexylisocyanate
The mixture of kind or these substances.
6. described in any item methods according to claim 1~3, which is characterized in that the solvent is toluene, N, N- dimethyl methyl
At least one of amide, n,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and butyl acetate or these objects
The mixture of matter.
7. described in any item methods according to claim 1~3, which is characterized in that the catalyst be stannous iso caprylate and/or
Dibutyl tin dilaurate.
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| CN108070071B (en) * | 2017-12-06 | 2020-12-04 | 东莞市雄林新材料科技股份有限公司 | Polyurethane memory foam material for mattress and preparation method thereof |
| CN109054353A (en) * | 2018-07-17 | 2018-12-21 | 蔡志浩 | A kind of high-toughness thermoplastic polyurethane elastomer and preparation method thereof |
| CN111234159B (en) * | 2018-11-29 | 2022-01-04 | 中国石油化工股份有限公司 | Triple shape memory polymer and preparation method and application thereof |
| KR102247089B1 (en) * | 2019-08-02 | 2021-04-30 | 한국생산기술연구원 | Composition for forming crosslinked polyurethane-based film, crosslinked polyurethane-based film formed from the composition, articles comprising the crosslinked polyurethane-based film |
| CN110563906B (en) * | 2019-08-15 | 2021-11-16 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
| CN112778481B (en) * | 2019-11-04 | 2022-07-12 | 中国石油化工股份有限公司 | Multiple shape memory polymer and preparation method thereof |
| CN114989379B (en) * | 2022-07-14 | 2023-07-14 | 绍兴迪飞新材料有限公司 | Polyurethane with low polymerization degree, preparation method thereof and application thereof in electrically polarized color-changing optical film |
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