CN110964175A - Glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange, preparation method and application - Google Patents
Glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of elastomers, and particularly relates to a glass-like polyurethane elastomer based on tert-butyl carbamate alcohol exchange, a preparation method and application thereof, wherein the glass-like polyurethane elastomer based on tert-butyl carbamate alcohol exchange is prepared from the following raw materials in parts by mass: 45-60 parts of polymer diol, 15-30 parts of diisocyanate, 2-12 parts of polyisocyanate and 8-20 parts of chain extender; wherein the chain extender is dihydric tertiary alcohol. The glass-like polyurethane elastomer based on the tertiary carbamate alcohol ester exchange prepared by using the chain extender of the dibasic tertiary alcohol, the polyisocyanate, the polymer diol and the diisocyanate as raw materials has good mechanical properties, the tensile strength can reach 20MPa, and the reversible exchange can be realized at the temperature of 100-120 ℃ without a catalyst, so that the purpose of reprocessing or shaping is achieved, and the glass-like polyurethane elastomer can be used for flexible electronic devices and biomedical materials.
Description
Technical Field
The invention belongs to the technical field of elastomers, and particularly relates to a glass-like polyurethane elastomer based on tert-butyl carbamate alcohol transesterification, a preparation method and application.
Background
The high polymer material can be divided into thermoplastic material and thermosetting material according to the processing performance, wherein the thermoplastic material can be repeatedly processed and used, and the heat resistance and the dimensional stability of the thermoplastic material are relatively poor; thermosetting materials have excellent heat resistance, dimensional stability and mechanical properties, but are insoluble and infusible due to a cross-linked structure formed by irreversible covalent bonds, and thus are difficult to reuse. In order to solve the contradiction between the two, the glass-like polymer is obtained by introducing exchangeable dynamic covalent bonds into the polymer material for crosslinking, has normal-temperature thermosetting property and high-temperature plasticity, and can achieve the purpose of combining the processing property of the thermoplastic material with the mechanical property of the thermosetting material, thereby receiving wide attention.
In recent years, dynamic covalent bonds such as transesterification, carbonate exchange, carbamate exchange, amine/imine exchange, N-alkyl exchange, olefin metathesis, silica, boroxy and disulfide bond have been reported in succession. Leibler et al use bisphenol A glycidyl ether and curing agent polybasic acid or anhydride to prepare epoxy resin glass macromolecule, and utilize zinc acetate or zinc acetoacetate to catalyze ester exchange so as to implement reprocessing of epoxy resin, but its reprocessing temperature is higher than 150 deg.C. Chen et al introduced disulfide bonds into epoxy resins in order to lower the reprocessing or shaping temperature, and found that the crosslinked epoxy resins can be reprocessed or shaped at 100 ℃ under the synergistic effect of double dynamic covalent bonds, but the mechanical strength is less than 2 MPa. The glass-like polymer is insoluble in a solvent at normal temperature and has thermosetting property, but the reprocessing or shaping temperature is relatively high when the mechanical property is good, and the mechanical property of the material can be sacrificed when the reprocessing or shaping temperature is reduced, namely a certain contradiction exists between the reprocessing or shaping temperature and the mechanical property. Therefore, there is a great challenge to prepare glass-like polymers excellent in mechanical properties under mild reprocessing or shaping conditions.
The polyurethane is a hard and soft block polymer with urethane repeating units formed by polymer polyol, polyisocyanate, small molecular polyol and the like, has excellent mechanical properties, and the urethane can show the characteristic of dynamic covalent bonds. Zheng et al utilizes transesterification of primary alcohol carbamate to achieve re-shaping of thermoset polyurethane, but the re-shaping temperature is still higher than 130 ℃, and a catalyst is used.
At present, related documents report about glass-like polyurethane elastomers, but glass-like polyurethane elastomers containing a carbamate structure are not seen yet under high conditions such as 180 ℃.
Disclosure of Invention
One of the purposes of the invention is to provide a glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange, which has good mechanical property, and can realize reversible exchange at 100-120 ℃ without a catalyst, so as to achieve the purpose of reprocessing or shaping.
The invention also aims to provide a preparation method of the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol, which has the advantages of few reaction steps, no need of adding a catalyst and easy adjustment.
The invention also aims to provide application of the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol.
The scheme adopted by the invention for realizing one of the purposes is as follows: a glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange is prepared from the following raw materials in parts by mass:
wherein the chain extender is dihydric tertiary alcohol.
The mechanism of the reshaping experiment of the glass-like polyurethane elastomer prepared by adopting the raw materials, particularly the dibasic tertiary alcohol chain extender, is not to be heated and melted into fluid, but is not to be melted, and is based on the exchange reaction of the carbamic acid tertiary alcohol ester.
The mechanism of the exchange reaction of the tertiary carbamate in the glass-like polyurethane elastomer based on the tertiary carbamate exchange is as follows:
preferably, the polymer diol is polytetrahydrofuran ether glycol, polyethylene glycol or polypropylene glycol; the number average molecular weight of the polymer dihydric alcohol is 1000-3000.
Preferably, the diisocyanate is any one of diphenylmethane diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the polyisocyanate is any one of hexamethylene diisocyanate trimer, diphenylmethane diisocyanate trimer, and isophorone diisocyanate trimer.
Preferably, the chain extender is any one of 2, 4-dimethyl-2, 4-pentanediol, 2, 5-dimethyl-2, 5-hexanediol and 2, 6-dimethyl-2, 6-heptanediol.
Preferably, the molecular chain of the glass-like polyurethane elastomer based on the tertiary carbamate alcohol exchange has a tertiary carbamate alcohol ester bond capable of being exchanged at 100-120 ℃.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the glass-like polyurethane elastomer based on the transesterification of the tertiary carbamate alcohol comprises the following steps:
(1) drying and dehydrating polymer dihydric alcohol, and then reacting with diisocyanate at 50-75 ℃ to obtain isocyanate end-capped prepolymer;
(2) and (2) defoaming the prepolymer obtained in the step (1) at 50-75 ℃, uniformly mixing the prepolymer with polyisocyanate and a chain extender in a solvent, defoaming at 20-40 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
In the step (1), the polymer glycol is dried and dehydrated at the temperature of 100 ℃ and 130 ℃.
Preferably, in the step (2), the solvent is any one of acetone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in the step (2), the vulcanization is carried out for 5-24 hours at 80-120 ℃.
The scheme adopted by the invention for realizing the third purpose is as follows: the application of the glass-like polyurethane elastomer based on the tertiary alcohol carbamate ester exchange in flexible electronic devices and biomedical materials.
The invention has the following advantages and beneficial effects: the glass-like polyurethane elastomer based on the tertiary carbamate alcohol ester exchange prepared by using the chain extender of the dibasic tertiary alcohol, the polyisocyanate, the polymer diol and the diisocyanate as raw materials has good mechanical properties, the tensile strength can reach 20MPa, and the reversible exchange can be realized at the temperature of 100-120 ℃ without a catalyst, so that the purpose of reprocessing or shaping is achieved, and the glass-like polyurethane elastomer can be used for flexible electronic devices and biomedical materials.
According to the preparation method, firstly, polymer dihydric alcohol and diisocyanate are adopted to react to prepare the polyurethane prepolymer, and then the polyurethane prepolymer is subjected to chain extension and crosslinking with dibasic tertiary alcohol chain extender and polyisocyanate to obtain the glass-like polyurethane elastomer based on the tertiary alcohol carbamate ester exchange, so that the reaction steps are few, no catalyst is required to be added, and the industrial production is favorably realized.
Drawings
FIG. 1 is an infrared spectrum of a tertiary-alcohol-carbamate glass polymer elastomer prepared by the present invention;
FIG. 2 is a graph showing the mechanical properties of a tertiary-alcohol-carbamate-based glass polymer elastomer prepared in example 2 of the present invention;
FIG. 3 shows the reshaping behavior of the tertiary-alcohol-carbamate-based glass polymer elastomer prepared by the present invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
In the embodiment of the invention: the infrared spectrum analysis adopts a Nicolet 5700 type Fourier transform infrared spectrometer and adopts a reflection mode at 4000-400 cm-1Recording the infrared absorption peak of the sample in the range; the gel fraction test adopts a Soxhlet extraction method to test the mass percentage of the cross-linked part of the sample, and the extraction solvent is acetone. The mechanical property test adopts a UTM 6503 type electronic universal tester (Shenzhen Sansi longitudinal and transverse science and technology Co., Ltd.) to carry out tensile property characterization at room temperature, the sample refers to the sample No. 2 in the national standard GB 529--1。
Example 1
A glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange and a preparation method thereof. The preparation method in this example is:
removing water from 54-60 parts by mass of polymer diol at 100 ℃, and then reacting with 15-20 parts by mass of diisocyanate at 50 ℃ to obtain isocyanate end-capped prepolymer;
and (2) defoaming the prepolymer obtained in the step at 50 ℃, uniformly mixing the prepolymer with 6-12 parts by mass of polyisocyanate and 8-16 parts by mass of dihydric tertiary alcohol chain extender in a solvent, defoaming at 20 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
The polymer dihydric alcohol is polytetrahydrofuran ether glycol, and the number average molecular weight of the polymer dihydric alcohol is 1000.
The diisocyanate is diphenylmethane diisocyanate.
The polyisocyanate crosslinking agent is hexamethylene diisocyanate trimer.
The dibasic tertiary alcohol chain extender is 2, 4-dimethyl-2, 4-pentanediol.
The solvent is N, N-dimethylformamide.
The vulcanization temperature is 80 ℃, and the vulcanization time is 24 h.
To further validate the tertiary alcohol carbamate exchange based glass-like polyurethane elastomer prepared in this example, the product prepared in this example was characterized by infrared spectroscopy. As shown in FIG. 1, is represented by the band appearing at 3317cm-1Expansion vibration peak at N-H bond, 1723cm-1Peak of C ═ O stretching vibration and 1101cm of carbamate-1The stretching vibration peak at the ether linkage C-O can indicate that the desired product is formed.
The glass-like polyurethane elastomer prepared in this example based on the transesterification of carbamic acid tert-alcohol was tested: the gel fraction is 92-96%, which indicates that the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester is of a cross-linked network structure.
In order to further verify the mechanical properties of the glass-like polyurethane elastomer prepared by the embodiment based on the tertiary alcohol carbamate exchange, a tensile testing machine is used for testing the product prepared by the embodiment, the tensile strength can reach 20.0-23.0 MPa, the elongation at break is 721-850%, and the prepared glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has good mechanical properties.
To further verify the reshaping performance of the glass-like polyurethane elastomer based on the trans-esterification of carbamic acid, prepared in this example, as shown in fig. 3, the prepared sample strip was fixed in a mold having a certain shape to change the shape, maintained at 120 ℃ for 2h, and taken out after cooling to obtain the reshaped shape. This is because the tertiary carbamate ester bond in the sample undergoes an exchange reaction at high temperature with the external force provided by the mold, and a structural rearrangement is achieved to eliminate internal stress so that the shape does not return to the original shape. Thus, the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol ester can be shaped again and has good flexibility.
Example 2
A glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange and a preparation method thereof. The preparation method in this example is:
removing water from 49-55 parts by mass of polymer diol at 110 ℃, and then reacting with 20-25 parts by mass of diisocyanate at 60 ℃ to obtain isocyanate end-capped prepolymer;
and (2) defoaming the prepolymer obtained in the step at 60 ℃, uniformly mixing the prepolymer with 4-8 parts by mass of polyisocyanate and 12-18 parts by mass of dihydric tertiary alcohol chain extender in a solvent, defoaming at 30 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
The polymer dihydric alcohol is polytetrahydrofuran ether glycol, and the number average molecular weight of the polymer dihydric alcohol is 3000.
The diisocyanate is diphenylmethane diisocyanate.
The polyisocyanate crosslinking agent is hexamethylene diisocyanate trimer.
The dibasic tertiary alcohol chain extender is 2, 5-dimethyl-2, 5-hexanediol.
The solvent is N, N-dimethylacetamide.
The vulcanization temperature is 100 ℃, and the vulcanization time is 12 h.
To further validate the tertiary alcohol carbamate exchange based glass-like polyurethane elastomer prepared in this example, the product prepared in this example was characterized by infrared spectroscopy. As shown in FIG. 1, is represented by the band appearing at 3317cm-1Expansion vibration peak at N-H bond, 1723cm-1Peak of C ═ O stretching vibration and 1101cm of carbamate-1The stretching vibration peak at the ether linkage C-O can indicate that the desired product is formed.
The glass-like polyurethane elastomer prepared in this example based on the transesterification of carbamic acid tert-alcohol was tested: the gel fraction is 90-94%, which indicates that the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester is of a cross-linked network structure.
In order to further verify the mechanical properties of the glass-like polyurethane elastomer prepared in the embodiment based on the tertiary alcohol carbamate exchange, a tensile testing machine is used for testing the product prepared in the embodiment, as shown in fig. 2, the tensile strength can reach 26.3-29.3 MPa, the elongation at break is 860-996%, and the prepared glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has good mechanical properties.
To further verify the reshaping performance of the glass-like polyurethane elastomer based on tertiary alcohol carbamate exchange prepared in this example, as shown in fig. 3, the prepared sample strip was fixed in a mold having a certain shape to change the shape, maintained at 110 ℃ for 2h, and taken out after cooling to obtain the reshaped shape. This is because the tertiary carbamate ester bond in the sample undergoes an exchange reaction at high temperature with the external force provided by the mold, and a structural rearrangement is achieved to eliminate internal stress so that the shape does not return to the original shape. Thus, the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol ester can be shaped again and has good flexibility.
Example 3
A glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange and a preparation method thereof. The preparation method in this example is:
removing water from 45-51 parts by mass of polymer dihydric alcohol at 120 ℃, and then reacting with 20-25 parts by mass of diisocyanate at 75 ℃ to obtain isocyanate end-capped prepolymer;
and (2) defoaming the prepolymer obtained in the step at 75 ℃, uniformly mixing the prepolymer with 6-12 parts by mass of polyisocyanate and 14-20 parts by mass of dihydric tertiary alcohol chain extender in a solvent, defoaming at 40 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
The polymer dihydric alcohol is polyethylene glycol, and the number average molecular weight of the polymer dihydric alcohol is 2000.
The diisocyanate is hexamethylene diisocyanate.
The polyisocyanate crosslinking agent is diphenylmethane diisocyanate trimer.
The dibasic tertiary alcohol chain extender is 2, 5-dimethyl-2, 5-hexanediol.
The solvent is acetone.
The vulcanization temperature is 120 ℃, and the vulcanization time is 5 h.
To further validate the tertiary alcohol carbamate exchange based glass-like polyurethane elastomer prepared in this example, the product prepared in this example was characterized by infrared spectroscopy. As shown in FIG. 1, is represented by the band appearing at 3317cm-1Expansion vibration peak at N-H bond, 1723cm-1Peak of C ═ O stretching vibration and 1101cm of carbamate-1The stretching vibration peak at the ether linkage C-O can indicate that the desired product is formed.
In order to further verify the mechanical properties of the glass-like polyurethane elastomer prepared by the embodiment based on the tertiary alcohol carbamate exchange, a tensile testing machine is used for testing the product prepared by the embodiment, the tensile strength can reach 27.6-30.6 MPa, the elongation at break is 796-926%, and the prepared glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has better mechanical properties.
The glass-like polyurethane elastomer prepared in this example based on the transesterification of carbamic acid tert-alcohol was tested: the gel fraction is 91-95%, which indicates that the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester is of a cross-linked network structure.
To further verify the reshaping performance of the glass-like polyurethane elastomer based on the trans-esterification of carbamic acid, prepared in this example, as shown in fig. 3, the prepared sample strip was fixed in a mold having a certain shape to change the shape, maintained at 120 ℃ for 2h, and taken out after cooling to obtain the reshaped shape. This is because the tertiary carbamate ester bond in the sample undergoes an exchange reaction at high temperature with the external force provided by the mold, and a structural rearrangement is achieved to eliminate internal stress so that the shape does not return to the original shape. Thus, the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol ester can be shaped again and has good flexibility.
Example 4
A glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange and a preparation method thereof. The preparation method in this example is:
removing water from 45-51 parts by mass of polymer diol at 130 ℃, and then reacting with 25-30 parts by mass of diisocyanate at 60 ℃ to obtain isocyanate end-capped prepolymer;
and (2) defoaming the prepolymer obtained in the step at 60 ℃, uniformly mixing the prepolymer with 4-8 parts by mass of polyisocyanate and 14-20 parts by mass of dihydric tertiary alcohol chain extender in a solvent, defoaming at 30 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
The polymer diol is polypropylene glycol, and the number average molecular weight of the polymer diol is 2000.
The diisocyanate is dicyclohexylmethane diisocyanate.
The polyisocyanate crosslinking agent is isophorone diisocyanate trimer.
The dibasic tertiary alcohol chain extender is 2, 6-dimethyl-2, 6-heptanediol.
The solvent is N, N-dimethylacetamide.
The vulcanization temperature is 100 ℃, and the vulcanization time is 12 h.
To further validate the tertiary alcohol carbamate exchange based glass-like polyurethane elastomer prepared in this example, the product prepared in this example was characterized by infrared spectroscopy. As shown in FIG. 1, is represented by the band appearing at 3317cm-1Expansion vibration peak at N-H bond, 1723cm-1Peak of C ═ O stretching vibration and 1101cm of carbamate-1The stretching vibration peak at the ether linkage C-O can indicate that the desired product is formed.
The glass-like polyurethane elastomer prepared in this example based on the transesterification of carbamic acid tert-alcohol was tested: the gel fraction is 89-93%, which indicates that the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester is of a cross-linked network structure.
In order to further verify the mechanical properties of the glass-like polyurethane elastomer prepared by the embodiment based on the tertiary alcohol carbamate exchange, a tensile testing machine is used for testing the product prepared by the embodiment, the tensile strength can reach 29.2-32.2 MPa, the elongation at break is 780-910%, and the prepared glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has good mechanical properties.
To further verify the reshaping performance of the glass-like polyurethane elastomer based on tertiary alcohol carbamate exchange prepared in this example, as shown in fig. 3, the prepared sample strip was fixed in a mold having a certain shape to change the shape, maintained at 110 ℃ for 2h, and taken out after cooling to obtain the reshaped shape. This is because the tertiary carbamate ester bond in the sample undergoes an exchange reaction at high temperature with the external force provided by the mold, and a structural rearrangement is achieved to eliminate internal stress so that the shape does not return to the original shape. Thus, the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol ester can be shaped again and has good flexibility.
Example 5
A glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange and a preparation method thereof. The preparation method in this example is:
removing water from 49-55 parts by mass of polymer dihydric alcohol at 120 ℃, and then reacting with 25-30 parts by mass of diisocyanate at 50 ℃ to obtain isocyanate end-capped prepolymer;
and (2) defoaming the prepolymer obtained in the step at 50 ℃, uniformly mixing the prepolymer with 2-6 parts by mass of polyisocyanate and 12-18 parts by mass of dihydric tertiary alcohol chain extender in a solvent, defoaming at 30 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
The polymer diol is polypropylene glycol, and the number average molecular weight of the polymer diol is 3000.
The diisocyanate is diphenylmethane diisocyanate.
The polyisocyanate crosslinking agent is diphenylmethane diisocyanate trimer.
The dibasic tertiary alcohol chain extender is 2, 6-dimethyl-2, 6-heptanediol.
The solvent is N, N-dimethylacetamide.
The vulcanization temperature is 120 ℃, and the vulcanization time is 5 h.
To further validate the tertiary alcohol carbamate exchange based glass-like polyurethane elastomer prepared in this example, the product prepared in this example was characterized by infrared spectroscopy. As shown in FIG. 1, is represented by the band appearing at 3317cm-1Expansion vibration peak at N-H bond, 1723cm-1Peak of C ═ O stretching vibration and 1101cm of carbamate-1The stretching vibration peak at the ether linkage C-O can indicate that the desired product is formed.
The glass-like polyurethane elastomer prepared in this example based on the transesterification of carbamic acid tert-alcohol was tested: the gel fraction is 88-92%, which indicates that the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester is of a cross-linked network structure.
In order to further verify the mechanical properties of the glass-like polyurethane elastomer prepared by the embodiment based on the tertiary alcohol carbamate exchange, a tensile testing machine is used for testing the product prepared by the embodiment, the tensile strength can reach 25.4-28.4 MPa, the elongation at break is 829-960%, and the prepared glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has good mechanical properties.
To further verify the reshaping performance of the glass-like polyurethane elastomer based on tertiary alcohol carbamate exchange prepared in this example, as shown in fig. 3, the prepared sample strip was fixed in a mold having a certain shape to change the shape, maintained at 100 ℃ for 2 hours, and taken out after cooling to obtain the reshaped shape. This is because the tertiary carbamate ester bond in the sample undergoes an exchange reaction at high temperature with the external force provided by the mold, and a structural rearrangement is achieved to eliminate internal stress so that the shape does not return to the original shape. Thus, the glass-like polyurethane elastomer based on the transesterification of the carbamic acid tert-alcohol ester can be shaped again and has good flexibility.
Compared with the prior art, the specific implementation mode has the following positive effects:
(1) the glass-like polyurethane elastomer prepared by the invention based on the exchange of the carbamic acid tert-alcohol ester realizes reversible exchange at the temperature of 100-120 ℃ without a catalyst, so that reprocessing or shaping is carried out.
(2) The glass-like polyurethane elastomer prepared by the invention based on the exchange of the carbamic acid tert-alcohol ester has good mechanical property, and the tensile strength can reach more than 20 MPa.
(3) The preparation method adopted by the invention adopts the reaction of polymer polyol and diisocyanate to obtain prepolymer, and then the prepolymer is reacted with dibasic tertiary alcohol and polyisocyanate to obtain the glass-like polyurethane elastomer based on the tertiary alcohol carbamate ester exchange. The method has few synthesis steps, does not need to add a catalyst, and is beneficial to realizing industrial production.
Therefore, the specific embodiment does not need to add a catalyst, and the production process is simple; the prepared glass-like polyurethane elastomer based on the exchange of the carbamic acid tert-alcohol ester has good mechanical property, can realize reversible exchange at the temperature of 100-120 ℃ without a catalyst, can be reprocessed or molded, and can be used for flexible electronic devices and biomedical materials.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. The glass-like polyurethane elastomer based on carbamic acid tert-alcohol ester exchange is characterized by being prepared from the following raw materials in parts by mass:
wherein the chain extender is dihydric tertiary alcohol.
2. The glass-like polyurethane elastomer based on t-carbamate transesterification according to claim 1, wherein: the polymer dihydric alcohol is polytetrahydrofuran ether glycol, polyethylene glycol or polypropylene glycol; the number average molecular weight of the polymer dihydric alcohol is 1000-3000.
3. The glass-like polyurethane elastomer based on t-carbamate transesterification according to claim 1, wherein: the diisocyanate is any one of diphenylmethane diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
4. The glass-like polyurethane elastomer based on t-carbamate transesterification according to claim 1, wherein: the polyisocyanate is any one of hexamethylene diisocyanate trimer, diphenylmethane diisocyanate trimer and isophorone diisocyanate trimer.
5. The glass-like polyurethane elastomer based on t-carbamate transesterification according to claim 1, wherein: the chain extender is any one of 2, 4-dimethyl-2, 4-pentanediol, 2, 5-dimethyl-2, 5-hexanediol and 2, 6-dimethyl-2, 6-heptanediol.
6. The glass-like polyurethane elastomer based on t-carbamate transesterification according to claim 1, wherein: the molecular chain of the glass-like polyurethane elastomer based on the tertiary alcohol carbamate exchange has a tertiary alcohol carbamate ester bond capable of being exchanged at 100-120 ℃.
7. A process for the preparation of the glass-like polyurethane elastomer based on the transesterification of tertiary carbamate according to any one of claims 1 to 6, comprising the following steps:
(1) drying and dehydrating polymer dihydric alcohol, and then reacting with diisocyanate at 50-75 ℃ to obtain isocyanate end-capped prepolymer;
(2) and (2) defoaming the prepolymer obtained in the step (1) at 50-75 ℃, uniformly mixing the prepolymer with polyisocyanate and a chain extender in a solvent, defoaming at 20-40 ℃, pouring, and vulcanizing at a certain temperature for a certain time to obtain the glass-like polyurethane elastomer based on the carbamic acid tert-alcohol ester.
8. The method of claim 7, wherein the method comprises the steps of: in the step (2), the solvent is any one of acetone, N-dimethylformamide and N, N-dimethylacetamide.
9. The method of claim 7, wherein the method comprises the steps of: and (3) in the step (2), vulcanizing for 5-24 hours at 80-120 ℃.
10. Use of the tertiary carbamate-based glass-like polyurethane elastomer of any one of claims 1 to 6 in flexible electronic devices and biomedical materials.
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