TWI612070B - Adamantane-containing dendrimer shape memory polyurethane and preparation method thereof - Google Patents

Description

Adamantane-containing dendrimer shape memory polyurethane and Preparation method

The invention relates to a shape memory polyurethane and a preparation method thereof, in particular to an adamantane-containing dendrimer shape memory polyurethane and a preparation method thereof.

There are many types of smart materials, including piezoelectric materials, smart gels, ceramic materials, shape memory alloys and shape memory polymers. The ability of polymers to respond to external stimuli such as heat and light has attracted extensive scientific interest in the scientific community. Known as one of the most important new materials in the 21st century. In recent years, it has been found that shape memory polymers have the advantages of high elasticity, high elongation, solvent resistance, acid resistance and wear resistance compared with alloys and ceramic materials, coupled with rapid and simple preparation procedures, shape memory polymers. Materials have unique advantages and potential.

The recovery principle of shape memory polymer materials can be divided into: heat induction type, electric induction type, light induction type, and chemical induction type. Among them, the thermoresponsive shape-memory effect polymer which forms a shape memory effect by temperature can be further divided into two types: (1) glass transition temperature (T _g ) type, and (2) melting temperature ( T _m ) type, this type is the most active in research and development because of its convenience. In addition to the combination of soft and hard segments, shape memory effects and polymer configurations are related to the microstructure of the material.

Adamantane is a rigid cyclic aliphatic structure with stable structure, good heat resistance and high symmetry. Therefore, the introduction of adamantane structure has become a field of many polymer research fields in recent years. one. How to use the excellent properties of adamantane, applied to the design of shape memory polyurethane materials, is also worthy of attention.

Therefore, there is a need in the industry for preparing an adamantane-containing dendrimer-shaped shape memory polyurethane and a preparation method thereof, and the adamantane-containing dendrimer is bonded to a hard segment of a polyurethane to prepare A shape memory polyurethane material having good thermal and mechanical properties, high crystallinity, and good shape recovery.

In view of the above disadvantages of the prior art, the main object of the present invention is an adamantane-containing dendrimer shape memory polyurethane and a preparation method thereof, and the adamantane-containing dendrimer is introduced into a polyamine group. After the acid ester side chain, a shape memory polyurethane (SPU) is obtained.

The invention utilizes a reaction selective monomer 4-isocyanate-4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (IDD), which has a high structural reaction. Isocyanate functional group, which can react rapidly with active hydrogen, and the other end of the azetidine-2,4-dione functional group has high selectivity characteristics only for reaction with primary amine, IDD and diethylenetriamine (abbreviation) DETA) is a building unit, and repeats the staggered addition reaction to obtain a high yield and high algebra content of adamantane. The diol dendrimer is introduced into the side chain of the polyurethane polymer to enhance the physical properties and shape memory of the material.

In order to achieve the above object, according to one aspect of the present invention, there is provided an adamantane-containing dendrimer shape memory polyurethane material having a structure of the formula (I): Wherein, the structure of R1 is formed by reacting diisocyanates, and the R2 system comprises the following structure: Or one of the groupings; and y>0. The adamantane-containing dendrimer shape memory polyurethane material of the above formula (I), wherein the diisocyanate compound comprises Methylene di-p-phenyl diisocyanate, 1 , Hexamethylene diisocyanate, Isophorone diisocyanate, Dicyclohexylmethane-4-4'-diisocyanate or one of the groups, ie R1 From the following groups: , , , Or one of the grouped groups.

The adamantane dendrimer-shaped shape memory polyurethane material of the above formula (I), wherein the structure of R1 is methylene di-p-phenyl diisocyanate ) reacted, that is, R1 is , the material is a structure of the general formula (Ia): Among them, R2 contains the following structure: Or one of the groupings; and y>0.

The above formula (I) contains an adamantane dendrimer shape memory polyurethane material, wherein the n segment is a polycaprolactone (PCL) having a molecular weight of 1000 ~4000; the x segment is the soft segment of the shape memory polyurethane material; the y segment is the hard segment of the shape memory polyurethane material, and the extender is adamantane The diol dendrimer has a weight ratio of x to y segments of y/(x+y)=0.4~0.6; the molecular weight of the polyurethane material ranges from 7500 to 11000.

The invention further provides a method for preparing an adamantane-containing dendrimer shape memory polyurethane having the general formula (I), the steps comprising: (1) 2-adamantylamine and 4 -isocyanate-4-(3,3-dimethyl 2-isocyanate-4-(3,3-dimethyl-2,4-dioxo-azetidine)diphenyl methane is reacted in a solvent and purified. a first intermediate [G0.5]-Ada; (2) reacting the first intermediate [G0.5]-Ada with diethylenetriamine in a solvent to obtain a first branch a molecule [G1.0]-Ada; (3) the first dendrimer [G1.0]-Ada and 4-isocyanate-4-(3,3-dimethyl-2,4-oxo- 4-isocyanate-4-(3,3-dimethyl-2,4-dioxo-azetidine)diphenyl methane is reacted in a solvent to obtain a second intermediate [G1. 5]-Ada; (4) repeating the above steps to prepare a third intermediate [G2.5]-Ada; (5) the first intermediate [G0.5]-Ada, the second intermediate [G1 .5]-Ada or a third intermediate [G2.5]-Ada and N-(3-aminopropyl)diethanolamine are reacted in a solvent to obtain at least one chain. a structure comprising an adamantane glycol dendrimer; (6) reacting a polycaprolactone diol oligomer and a diisocyanates in another solvent; (7) adding the at least one The adamantane-containing dendrimer polymer of the chain structure continues to react to obtain an adamantane-containing dendrimer shape memory polyurethane material.

The solvent of the above steps (1) to (5) is tetrahydrofuran, and the other solvent of the step (6) to the step (7) is toluene; the reaction temperature of the step (1) is 40 Below °C; the reaction time of step (7) is between 2 hours and 6 hours.

The adamantanediol dendrimer having at least one chain structure of the above step (5) is [G0.5]-Ada diol, [G1.5]-Ada diol or [G2.5]-Ada diol , is the structure of the following formula:

The adamantane-containing dendrimer shape memory polyurethane material synthesized by the invention enhances the polyurethane material by introducing the adamantane glycol dendrimer into the side chain of the material. Mechanical properties; as the dendrimer algebra increases, the crystallinity of the soft segment increases, thereby increasing the overall crystallinity of the polyurethane material; in the shape recovery test, due to the bulky rule tree The introduction of the polymer causes the soft segment of the polyurethane to have a large arrangement space, and provides a basis for the recovery of the material, so that the recovery rate of the polyurethane material is more than 90%.

The above summary and the following detailed description and drawings are intended to further illustrate the manner, means and effects of the present invention in achieving its intended purpose. Other purposes and advantages of this creation will be explained in the following description and drawings.

S101-S107‧‧‧Steps

The first figure is a flow chart of the preparation method of the adamantane-containing dendrimer shape memory polyurethane of the present invention; the second figure is the adamantane-containing dendrimer polymerization of at least one chain structure of the embodiment of the present invention. Schematic diagram of the synthesis of the material; the third diagram is a schematic diagram of the synthesis of the adamantane-containing dendrimer shape memory polyurethane for the embodiment of the present invention; and the fourth diagram is the FTIR of the adamantanediol-containing dendrimer of the embodiment of the present invention. The first graph is the ¹ H-NMR spectrum of the adamantanediol-containing dendrimer of the embodiment of the present invention; the sixth diagram is the MALDI TOF mass spectrometry of the adamantanediol-containing dendrimer according to the embodiment of the present invention. Figure 7 is a FTIR spectrum of the adamantane-containing dendrimer shape memory polyurethane of the present invention; the eighth figure is an adamantane-containing dendrimer shape memory cluster according to an embodiment of the present invention. The TGA analysis chart of the urethane; the ninth figure is the DSC analysis chart of the adamantane-containing dendrimer shape memory polyurethane for the embodiment of the present invention; the tenth figure is the embodiment of the invention containing the diamond Alkali dendrimer shape memory polyamine The tensile diagram of the carbamate; the eleventh figure is a shape memory test chart of the adamantane dendrimer shape memory polyurethane of the embodiment of the present invention.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily understand the advantages and effects of the present invention from the disclosure of the present disclosure.

The present invention proposes to prepare a novel state shape memory polyurethane. The regular dendrites containing adamantane are introduced into the side chain of the polyurethane as a hard segment to enhance the shape memory effect of the material. The preparation method must first react with the reaction selectivity 4-isocyanate-4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (IDD) with amantadine. A single-stranded ruled dendrimer, and then repeated use of diethylenetriamine (DETA) to react with IDD to complete a multi-stranded adamantane regular dendrimer; a regular dendrimer as a glycol chain extender Thereafter, a regular dendrimer shape memory polyurethane having an adamantane side chain was prepared.

Please refer to the first figure, which is a flow chart of a method for preparing an adamantane dendrimer shape memory polyurethane according to the present invention. As shown in the figure, the present invention provides a method for preparing an adamantane dendrimer shape memory polyurethane, the steps comprising: (1) 2-adamantylamine and 4-isocyanate- 4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (4- Isocyanate-4-(3,3-dimethyl-2,4-dioxo-azetidine)diphenyl methane) is reacted in a solvent to obtain a first intermediate [G0.5]-Ada, S101; (2) An intermediate [G0.5]-Ada is reacted with diethylenetriamine in a solvent to obtain a first dendrimer [G1.0]-Ada, S102; (3) the first Dendrimer [G1.0]-Ada and 4-isocyanate-4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (4-isocyanate-4- (3,3-dimethyl-2,4-dioxo-azetidine)diphenyl methane) is reacted in a solvent to obtain a second intermediate [G1.5]-Ada, S103; (4) repeating the above steps to prepare a a third intermediate [G2.5]-Ada, S104; (5) the first intermediate [G0.5]-Ada, the second intermediate [G1.5]-Ada or the third intermediate [G2. 5]-Ada and N-(3-aminopropyl)diethanolamine are reacted in a solvent to obtain an adamantanediol-containing dendrimer having at least one chain structure, S105 (6) reacting the polycaprolactone diol oligomer and the diisocyanates in another solvent, S106; (7) adding the at least one chain The configuration having the adamantane diol dendrimer reaction was continued to give a polyurethane material having the adamantane dendrimer shape memory, S107.

Example:

4-isocyanate-4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (4-isocyanate-4-(3,3-dimethyl-2,4- Synthesis of dioxo-azetidine)diphenyl methane (IDD): methylenedi-p-phenyl diisocyanate (MDI) and isobutylene chloride (isobutyryl chloride) is dissolved in xylene, the molar ratio of MDI to isobutylene chloride is 1:0.7, heated to 130 ° C, catalyzed by triethylamine, stirred for 3 to 4 hours, then lowered to 0 ° C An orange liquid will be produced, and the filtrate obtained by filtration will be purified by recrystallization from cyclohexane to give the compound of IDD.

Synthesis of the first intermediate [G0.5]-Ada: an excess of 1.5 times of IDD was dissolved in dry tetrahydrofuran (THF) at room temperature 20 ° C, and 2-adamantanamine was slowly added dropwise ( 2-adamantylamine). After 4 hours at room temperature, the primary amine on 2-adamantanamine completely reacted with the isocyanate on IDD to form [G0.5]-Ada. After the reaction is completed, the excess IDD and other impurities are washed by heating and stirring, and the product is crystallized and precipitated, and the precipitated white solid [G0.5]-Ada (G represents different algebra) is obtained as a single chain. A dendrimer of structure. The reaction scheme is as shown in the second diagram (A).

In the reaction of the first intermediate [G0.5]-Ada, since the reaction utilizes an excess of IDD, it is observed that a characteristic absorption peak of 2260 cm ^-1 isocyanate (isocyanate) functionality will appear in the FTIR chart after completion of the reaction. And purified by suspension, it can be found 2260cm ^-1 isocyanate disappeared, Urea (urea) of the absorption peak at 3356cm ^-1 double bond NH functional group characteristic absorption peaks of 1653cm ^-1 and carboxyhemoglobin. The characteristic absorption peaks of the azetidine-2,4-dione functional groups at 1740 cm ^-1 and 1856 cm-1 were also observed in the FTIR chart. In addition to the FTIR pattern, in the ¹ H-NMR (DMSO-d ₆ ) spectral analysis, NH peaks at 5.79 and 8.14 ppm of urea were produced, and the chemical shifts and integral values of the respective hydrogens were consistent with the structure.

Synthesis of the first dendrimer [G1.0]-Ada: [G0.5]-Ada and diethylenetriamine were heated at 60 ° C under THF for 3-4 hours, and purified to obtain [ G1.0]-Ada is a dendrimer of a complex chain structure. The reaction scheme is as shown in the second diagram (B).

Synthesis of the second intermediate [G1.5]-Ada: [G1.0]-Ada was dissolved in THF and purified by IDD to obtain [G1.5]-Ada, and then the THF was removed, followed by methanol. After purification, [G1.5]-Ada was obtained. The reaction scheme is as shown in the second diagram (C).

Synthesis of second dendrimer [G2.0]-Ada and third intermediate [G2.5]-Ada: [G1.5]-Ada and diethylenetriamine heated under THF 3 ~4 hours, after purification, [G2.0]-Ada was obtained. Repeat the same steps to get [G2.5]-Ada. The reaction scheme is as shown in the second diagram (D).

Synthesis of adamantane-containing dendrimers of at least one chain structure: [G0.5]-Ada, [G1.5]-Ada and [G2.5]-Ada, respectively, with N-(3-amino Propyl)N-(3-aminopropyl)diethanolamine (APDEA) was reacted in THF at 80 ° C for 4 hours, and purified to obtain an adamantane-containing dendrimer having at least one chain structure, respectively [G0.5]-Ada diol, [G1.5]-Ada diol and [G2.5]-Ada diol. The reaction scheme is as shown in the second diagram (E).

Synthesis of adamantane-containing dendrimer shape memory polyurethane: as shown in Table 1, a formulation table for synthesizing adamantane side chain dendrimers of the present embodiment, wherein the x segment represents The soft segment of the polyurethane, the y segment represents the hard segment of the polyurethane, the weight percentage of the hard segment is 45, 50 and 55 wt%, respectively, the code is SPU45, SPU50 and SPU55; G represents a different algebra of the adamantane-containing dendrimer. Capa ^TM 2303 polycaprolactone diol oligomer (molecular weight 3000) was dissolved in toluene according to the molar number of different samples in the formula, and methylenedi-isobutyl phthalate was added. P-phenyl diisocyanate (MDI for short) and catalyst T-12 (dibutyltin dilaurate), the temperature is controlled at 65 ° C, reaction for 0.5 hours, to obtain NCO terminal functional group polyurethane prepolymerization (prepolymer); followed by the addition of different aldamane-containing dendrimer dendrimers ([G0.5]-Ada diol, [G1.5]-Ada diol and [G2.5]-Ada diol) as The chain extender is further reacted for 3.5 hours to complete the chain extension, and the product is placed in an oven at 60 ° C for 24 hours to form a film of adamantane-containing dendritic polyurethane (ie, the adamantane-containing dendrimer of the present invention). Shape memory polyurethane) SPU45-G0.5, SPU50-G0.5, SPU55-G0.5, SPU45-G1.5, SPU50-G1.5, SPU50-G1.5, SPU45-G2.5 , SPU50-G2.5 and SPU55-G2.5. The reaction process is shown in the third figure.

Please refer to the fourth figure, which is an FTIR spectrum diagram of the adamantanediol dendrimer according to an embodiment of the present invention. As shown in the figure, the addition of the OH functional group of [G2.5]-Ada diol can be observed to make the characteristic absorption peak of the NH functional group of 3356 cm ^-1 broad, and the azetidine-2,4-dione functional group is 1740 cm ^{-1 .} And the characteristic absorption peak of 1856 cm ^-1 completely disappeared.

Please refer to the fifth figure, which is a ¹ H-NMR spectrum of an adamantane glycol dendrimer according to an embodiment of the present invention. By chemical analysis of ¹ H-NMR (DMSO-d ₆ ), the chemical shifts and integral values of each hydrogen of [G2.5]-Ada diol were consistent with the structure.

Please refer to the sixth figure, which is a MALDI TOF mass spectrum of the adamantanediol dendrimer according to an embodiment of the present invention. As shown, the peaks of [M+H] ⁺ =3317.22 and [M+Na] ⁺ =3342.43 of [G2.5]-Ada diol were measured, and all molecular weights were in agreement with the calculated values. Further, a polymer having a PDI of 1.02 single distribution was obtained by measurement by a colloidal permeation chromatography (GPC). It was confirmed by FTIR, ¹ H-NMR and GPC that the [G2.5]-Ada diol compound having two primary alcohol functional groups at the end was synthesized in 80% yield. Table 2 lists the adamantane dendrimers [G0.5]-Ada to [G2.5]-Ada and adamantanediol dendrimer [G0.5]-Ada diol with different algebras analyzed by GPC. The molecular weight determination results of [G1.5]-Ada diol and [G2.5]-Ada diol, and the experimental data measured are close to the theoretically calculated molecular weight.

Please refer to the seventh figure, which is an FTIR spectrum diagram of an adamantane dendrimer shape memory polyurethane, which is an embodiment of the present invention. FIG. (A),, Urea (urea), Amide (Amides) and Urethane (urethane) functional group at 3350cm ^-NH-1, 2950,2920 and 2850 cm ^-1 characteristic absorption peaks appear CH ₂ There is also a large amount of 2271 cm ^-1 isocyanate present; after the chain extension (b), it can be found that the material has no characteristic absorption peak of isocyanate, and in addition to the characteristic absorption peak of urethane (ethylene urethane) at 1731 cm ^-1 There are also characteristic absorption peaks of malonamide (carbon-oxygen double bond) and urea of 1660 cm ^-1 . In addition, with the increase of the adamantane dendrimer algebra, the characteristic absorption peak of 1660 cm ^-1 is more obvious, because the malonamide and urea density of the adamantane-containing dendrimers are greatly increased with the increase of algebra.

In order to understand the thermal properties and crystallization characteristics of the adamantane-containing dendrimer shape memory polyurethane of the present invention, different samples were subjected to thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) to determine the sample. Thermal cracking temperature (T _d ), soft segment glass transition temperature (T _gs ), crystallization temperature (T _c ), crystalline enthalpy (H _c ), soft segment melting point (T _ms ), soft segment melting heat (H _ms ), crystallinity (X _c ), the results are shown in Table 3. Please refer to the eighth figure, which is a TGA analysis diagram of an adamantane dendrimer shape memory polyurethane using an embodiment of the present invention. As shown in the figure, the introduction of different adamina-containing side chain regular dendrimers did not significantly change the thermal cracking temperature, and the polyurethanes had a T _{d of} about 5 wt% at 220 °C. Please refer to the ninth drawing, which is a DSC analysis diagram of an adamantane dendrimer shape memory polyurethane according to an embodiment of the present invention. As shown in the ninth and third tables, it is found that the heat of fusion of the soft segment of the polyurethane increases as the proportion of the soft segment increases; in addition, the crystallinity of the soft segment and the introduced adamantane side There are significant differences in the chain. As the side chain regular dendrimer algebra increases, the crystallinity increases under the same soft segment, which means that the adamantane-containing dendrimer promotes hard segment crystallization, from the soft segment T _gs along with algebra The increase and decrease can also prove that the regular dendrimer containing adamantane promotes the phase separation of the soft and hard segments.

Please refer to the tenth drawing, which is a tensile diagram of an adamantane dendrimer shape memory polyurethane according to an embodiment of the present invention. The mechanical properties of the adamantane-containing dendrimers were analyzed by a universal tensile machine. As shown in the figure, the stress changes under different strains were observed, and the hard segments were 45% of the adamantane-like polymer side chains. Amino acid esters, the algebraic increase can increase the mechanical properties; that is, the introduction of a rigid adamantane segment, in addition to enhancing the mechanical properties, the adamantane dendrimer side chain also enhances the polyamine group Crystallinity of the acid ester.

Please refer to FIG. 11 for a shape memory test diagram of an adamantane dendrimer shape memory polyurethane according to an embodiment of the present invention. Test party In order to cut the material into the shape of the ASTM standard test piece D638, the deformation temperature of the material of the invention falls about 40 ° C, so the material is stretched twice at a high temperature of 70 ° C and cooled to 10 ° C. The size of the material memory is called shape retention; after heating the material to 70 ° C, the material will return to its original shape, and the size of the material recovery is called shape recovery. Repeat the above steps of raising and lowering the temperature to observe the number of times the material can be used. The test results show that SPU45-G2.5, SPU50-G2.5 and SPU55-G2.5 have close to 100% shape retention; while the shape recovery rate is close to 100%, the hard segment content is different and there are differences. From the experimental data in Figure 11, it is shown that the ratio of the soft segment can be increased in the case of introducing the same high algebraic adamantane glycol-containing polymer side chain, which can increase the shape memory effect because the side chain has just Under the hard adamantane segment, it also enhances the crystallinity of the soft segment and enhances the recovery basis of the material.

The adamantane-containing dendrimer shape memory polyurethane of the present invention and a preparation method thereof, wherein the adamantane-containing regular dendrimer is introduced into a polyurethane. The effect of hard segment content on the polyurethane was investigated by controlling the ratio of hard segments. Due to the bulky rule, the adamantane dendrimer is introduced, so that the soft segment of the polyurethane has a large arrangement space, which enhances the crystallinity of the material and increases the shape recovery rate. In the shape recovery test, with the introduction of the adamantane-containing dendrimer and the increase in algebra, the recovery rate is over 90%, and even 100% recovery rate can be achieved. The adamantane dendrimer shape memory polyurethane of this study has good Its thermal properties and mechanical properties, high crystallinity and good shape recovery rate make it more widely used in the future.

The above-described embodiments are merely illustrative of the features and functions of the present invention and are not intended to limit the scope of the technical content of the present invention. Any person skilled in the art can modify and change the above embodiments without departing from the spirit and scope of the creation. Therefore, the scope of protection of this creation should be as listed in the scope of the patent application described later.

S101-S107‧‧‧Steps

Claims (9)

An adamantane-containing dendrimer shape memory polyurethane material having a structure of the formula (I): Wherein the structure of R1 is formed by the reaction of diisocyanates, and the R2 system comprises the following structure: Or one of the groups; and wherein n=9~35, the weight ratio of the x segment to the y segment is y/(x+y)=0.4~0.6, and the molecular weight of the polyurethane material is From 7500 to 11000. The adamantane dendrimer-shaped shape memory polyurethane material according to the formula (I) of claim 1, wherein the diisocyanate compound comprises methylene di-p-phenyl isocyanate (Methylene di -p-phenyl diisocyanate), Hexamethylene diisocyanate, Isophorone diisocyanate, Dicyclohexylmethane-4-4'-diisocyanate or a group One of the groups. The adamantane dendrimer-shaped shape memory polyurethane material according to the formula (I) of claim 1, wherein the molecular weight of the n-chain segment is from 1,000 to 4,000. A method for preparing an adamantane dendrimer shape memory polyurethane material of the formula (I) according to the first aspect of the patent application, the steps comprising: (1) 2-adamantanamine (2- Adamantylamine) with 4-isocyanate-4-(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (4-isocyanate-4-(3,3-dimethyl-2) , 4-dioxo-azetidine)diphenyl methane) is reacted in a solvent to obtain a first intermediate [G0.5]-Ada; (2) the first intermediate [G0.5]-Ada and diethylene glycol The diethylenetriamine is reacted in a solvent to obtain a first dendrimer [G1.0]-Ada; (3) the first dendrimer [G1.0]-Ada and 4-isocyanate-4 are obtained. -(3,3-dimethyl-2,4-oxo-azetidine)diphenylmethane (4-isocyanate-4-(3,3-dimethyl-2,4-dioxo-azetidine)diphenyl Methane) is reacted in a solvent to obtain a second intermediate [G1.5]-Ada; (4) repeating the above steps to prepare a third intermediate [G2.5]-Ada; (5) An intermediate [G0.5]-Ada, a second intermediate [G1.5]-Ada or a third intermediate [G2.5]-Ada with N-(3-aminopropyl)diethanolamine (N-( 3-aminopropyl)diethanolamine) is reacted in a solvent to obtain an adamantanediol-containing dendrimer having at least one chain structure; (6) a polycaprolactone diol oligomer and a diisocyanates are The reaction is carried out in another solvent; (7) the adamantane-containing dendrimer-containing polymer having at least one chain structure is added to continue the reaction to obtain an adamantane-containing dendrimer-shaped shape memory polyurethane material. The method for preparing an adamantane dendrimer shape memory polyurethane material according to the formula (I) of claim 4, wherein the solvent of the step (1) to the step (5) is tetrahydrofuran. (tetrahydrofuran). A method for preparing an adamantane dendrimer-shaped shape memory polyurethane material according to the formula (I) of claim 4, wherein the other solvent system of the step (6) to the step (7) It is toluene. A method for producing an adamantane dendrimer-shaped shape memory polyurethane material according to the formula (I) of claim 4, wherein the reaction temperature in the step (1) is 40 ° C or lower. The method for preparing an adamantane dendrimer shape memory polyurethane material according to the formula (I) of claim 4, wherein the reaction time of the step (7) is between 2 hours and 6 hours. between. The adamantane dendrimer shape memory polyurethane material according to the formula (I) of claim 1, wherein the structure of R1 is methylene di-p-phenyl isocyanate ( Methylene di-p-phenyl diisocyanate) is reacted, and the material is a structure of the formula (Ia): Among them, R2 contains the following structure: Or one of the groups; and wherein n=9~35, the weight ratio of the x segment to the y segment is y/(x+y)=0.4~0.6, and the molecular weight of the polyurethane material is From 7500 to 11000.