CN111154107B - Multifunctional polysiloxane thermoplastic elastomer and preparation method and application thereof - Google Patents
Multifunctional polysiloxane thermoplastic elastomer and preparation method and application thereof Download PDFInfo
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 62
- -1 polysiloxane Polymers 0.000 title claims abstract description 58
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 238000000034 method Methods 0.000 claims abstract description 21
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 16
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- UGODCLHJOJPPHP-AZGWGOJFSA-J tetralithium;[(2r,3s,4r,5r)-5-(6-aminopurin-9-yl)-4-hydroxy-2-[[oxido(sulfonatooxy)phosphoryl]oxymethyl]oxolan-3-yl] phosphate;hydrate Chemical compound [Li+].[Li+].[Li+].[Li+].O.C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OS([O-])(=O)=O)[C@@H](OP([O-])([O-])=O)[C@H]1O UGODCLHJOJPPHP-AZGWGOJFSA-J 0.000 description 4
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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Abstract
本发明公开了多功能性的聚硅氧烷热塑性弹性体及其制备方法与应用。该弹性体由以下方法制备得到：以1,3‑双(3‑氨基丙基)‑1,1,3,3‑四甲基二硅氧烷和八甲基环四硅氧烷为原料，在催化剂四甲基氢氧化铵·五水合物的作用下反应得到双端氨基聚硅氧烷；然后以双端氨基聚硅氧烷、3,3’,4,4’‑联苯四羧酸二酐和1,3‑双(3‑氨基丙基)‑1,1,3,3‑四甲基二硅氧烷为原料进行反应，得到聚硅氧烷‑聚酰胺酸嵌段共聚物；最后在高温作用下，得到兼具高机械性能和形状记忆功能、自愈合功能的聚硅氧烷‑聚酰亚胺嵌段聚合物。
The invention discloses a multifunctional polysiloxane thermoplastic elastomer and its preparation method and application. The elastomer is prepared by the following method: using 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and octamethylcyclotetrasiloxane as raw materials, Under the action of the catalyst tetramethylammonium hydroxide pentahydrate, the double-terminated aminopolysiloxane was obtained; then the double-terminated aminopolysiloxane, 3,3',4,4'-biphenyltetracarboxylic acid Dianhydride and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are reacted as raw materials to obtain polysiloxane-polyamic acid block copolymer; Finally, under the action of high temperature, a polysiloxane-polyimide block polymer with high mechanical properties, shape memory function and self-healing function is obtained.
Description
Technical Field
The invention relates to a thermoplastic elastomer, in particular to a polysiloxane thermoplastic elastomer with high mechanical property and multiple functions and a preparation method thereof.
Background
As a smart material with stimulus-response function, the shape memory material can respond to external stimuli (such as temperature, light, electric field, magnetic field, etc.) to adjust its shape, so as to return to the material with the preset shape. The shape memory polymer has the advantages of low response temperature, high response speed and the like, and has wide application prospects in the fields of aerospace industry, intelligent biomedical equipment, sensors and the like. The realization of the shape memory function of polymers needs to meet the following structural requirements: the crosslinking points are used for preventing the slippage of molecular chains during the deformation and shape recovery at the transition temperature; the switching phase is used to fix the temporary shape during the pre-deformation phase of the sample and to respond to external stimuli during the recovery phase.
Although many researchers have successively developed various systems of memory polymer materials in the last two decades, research on thermoplastic elastomer materials having a shape memory function has been mainly focused on polyurethane systems. Chinese patents CN 109880054A and CN 109912773A disclose the preparation method of shape memory polyurethane with polycaprolactone diol as soft segment and rigid segment as hard segment. The mechanism of the shape memory is a 'switch' taking a soft segment as the shape memory, and is used for fixing the shape of the sample in the pre-deformation stage and providing good recovery driving force for the shape recovery; while the hard segment serves as a crosslinking point to prevent the molecular chain from slipping during deformation and shape recovery. However, this structure is difficult to achieve shape memory for silicone-soft segment elastomers because the highly compliant, amorphous silicone returns quickly to its original shape after stress removal and does not allow energy storage.
Chinese patent CN 102604298A discloses a method for preparing a shape memory composite based on polydimethylsiloxane, which is a blended or semi-interpenetrating network composite formed by in-situ compounding linear or cross-linked vinyl polymer and polydimethylsiloxane with or the end capped by hydroxyl. The method is mainly used for compounding polydimethylsiloxane and shape memory polymer to develop a novel shape memory composite material. However, the method can not substantially prepare the composite material with too high content of polysiloxane; secondly, the composite material does not have repeatable processability, which causes waste of resources.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a method for preparing a polysiloxane thermoplastic elastomer having excellent biocompatibility and both high tensile strength and versatility.
The invention also provides the application of the polysiloxane thermoplastic elastomer in biomedical devices.
The purpose of the invention is realized by the following technical scheme:
a method for preparing multifunctional polysiloxane thermoplastic elastomer comprises the following steps:
(1) synthesis of a Diaminopolysiloxane: mixing 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane serving as raw materials with a catalyst, and heating to react to obtain colorless and transparent double-end aminopolysiloxane; the catalyst is tetramethyl ammonium hydroxide pentahydrate; the molar ratio of the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to the octamethylcyclotetrasiloxane is 1: 3-35;
(2) synthesis of polysiloxane-Polyamic acid Block copolymer: under the protection atmosphere, dissolving and mixing double-end amino polysiloxane, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and a chain extender through a polar solvent, and reacting at normal temperature to obtain a colorless and transparent polysiloxane-polyamic acid block copolymer with the solid content of 15-50%; the chain extender is one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and low molecular weight amino-terminated polysiloxane;
(3) imidization reaction: reacting the product obtained in the step (2) at 150-200 ℃ for 6-12 h; after the reaction is finished, removing the solvent to obtain dark brown polysiloxane-polyimide segmented copolymer particles;
(4) preparation of elastomer sample bars: hot-pressing and molding the polysiloxane-polyimide segmented copolymer particles obtained in the step (3); and then cold pressing and shaping are carried out, thus obtaining the multifunctional polysiloxane thermoplastic elastomer with the gradient glass transition structure.
To further achieve the object of the present invention, preferably, in the step (1), the amount of the catalyst is 0.01 to 0.05% by mass of the octamethylcyclotetrasiloxane.
Preferably, in the step (1), the heating reaction is carried out at 85-90 ℃ for 4-12 h, and then at 135-150 ℃ for 1-1.5 h.
Preferably, in the step (1), the number average molecular weight of the double-terminal aminopolysiloxane is 1X 103～1×104。
Preferably, in the step (2), the polar solvent is one or more of N-methylpyrrolidone and o-dichlorobenzene; in the step (2), the protective gas is inert gas such as nitrogen or argon; the reaction time at normal temperature is 6-24 h.
Preferably, in the step (2), the number average molecular weight of the low molecular weight double-terminal aminopolysiloxane is 5X 102～9×102(ii) a The low molecular weight double-end amino polysiloxane is prepared by the following method: mixing 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane serving as raw materials with a catalyst, and heating for reaction; process for controlling 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxaneThe molar ratio is 1: 1-2; the catalyst is tetramethyl ammonium hydroxide pentahydrate.
Preferably, in the step (3), the solvent removal after the reaction is finished is to remove most of the solvent by using a rotary evaporator at 150 ℃, and then to remove the residual solvent by placing the solvent in a vacuum oven with the temperature of 100 ℃ and the vacuum degree of-0.1 MPa for 6-20 h.
In the step (4), the hot-press molding temperature is 50-120 ℃, and the time is 10 min; the cold pressing and shaping refers to die pressing for 10min under the conditions of pressure of 15MPa and normal temperature.
The polysiloxane thermoplastic elastomer has a gradient glass transition structure and has high tensile strength, a shape memory function and a self-healing function. The gradient glass transition structure means that the transition region from the polysiloxane-rich soft phase (with the lowest glass transition temperature) to the polyimide-rich hard phase (with the highest glass transition temperature) has the characteristic of wide glass transition temperature.
The multifunctional polysiloxane thermoplastic elastomer is applied to biomedical devices.
Compared with the prior art, the invention has the following advantages and effects:
(1) the polysiloxane thermoplastic elastomer prepared by the invention has a gradient glass transition structure. The thermodynamic incompatibility between the soft polysiloxane segments and the hard polyimide-chain extender segments, as well as the rigid and linear nature of the polyimides, promotes the formation of a continuous phase structure with the hard polyimide-chain extender segments surrounding the soft polysiloxane segments. Meanwhile, the chain extender improves the thermodynamic difference between polyimide and polysiloxane, and promotes the formation of the wide glass transition temperature with gradient characteristics. This structure provides a premise for the realization of the shape memory function of the present invention.
(2) The polysiloxane thermoplastic elastomer prepared by the invention has a shape memory function. The hard phase with gradient glass transition temperature surrounding the polysiloxane soft phase layer by layer serves as a shape memory 'switch' for the shape fixation of the material in the pre-deformation stage and the function of releasing stored energy to provide shape recovery driving force, and the nano-domain with the highest glass transition temperature in the innermost layer of the hard phase serves as a cross-linking point to prevent molecular chain slippage in the deformation and shape recovery processes. Thus, the polymer has excellent thermotropic shape memory function, i.e., a rapid shape recovery rate, a high shape fixation rate, and a shape recovery rate.
(3) The polysiloxane thermoplastic elastomer prepared by the invention has high tensile strength. In the prepared polysiloxane-based elastomer, a phase separation structure is formed in which a soft polysiloxane is surrounded by a polyimide-chain extender hard segment, and the continuous polyimide-chain extender hard segment has excellent external force resistance, so that the final product has high tensile strength.
(4) The polysiloxane thermoplastic elastomer prepared by the invention has self-repairing performance. At high temperatures (. about.T)gIn the environment of 10 ℃, the reversibility of pi-pi conjugation effect between polyimides in the hard segment and the high flexibility of the soft phase polysiloxane chain segment endow the soft phase polysiloxane chain segment with good self-repairing performance. The self-repairing efficiency of the tensile strength of the material prepared by the invention (example 1) reaches 74% after the material is placed at-80 ℃ for 8h, so that the service life of the material is effectively prolonged.
(5) The polyimide adopted in the hard segment has good biocompatibility, so that the polysiloxane-polyimide block polymer is expected to expand the application of the shape memory material in the field of biomedical devices.
(6) The polymer material prepared by the invention is easy to form and shape, can be processed into a complex shape and is easy to operate. Meanwhile, the invention utilizes reversible pi-pi conjugation to form a continuous hard phase structure, and the continuous hard phase structure has repeatable processing performance at high temperature (60-110 ℃), which has important significance for environmental protection and resource saving.
Drawings
FIG. 1 is a schematic diagram of the reaction principle of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of comparative example 1;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of example 1;
FIG. 4 is a graph showing the change in glass transition temperature of the samples of comparative examples 1 and 2 and examples 4 and 5;
FIG. 5 shows examples 1, 4 and 5 at TgFigure illumination of shape recovery process at +5 ℃;
FIG. 6 is a shape memory curve of the polymer obtained in example 1 characterized by DMA stretching;
FIG. 7 shows the self-healing tensile curve of the polymer obtained in example 1.
Detailed Description
For a better understanding of the present invention, the following examples and drawings are included to illustrate the present invention, but the examples should not be construed as limiting the scope of the present invention.
FIG. 1 is a schematic diagram of the synthetic principles of examples 1 to 5. In the figure, BPDA, APPS and APTMDS refer to 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, amino-terminated polysiloxane and 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane respectively, wherein BPDA and BPDA-APTMDS are taken as hard segments and APPS is taken as soft segments in the product. Due to the linearity and rigidity of BPDA and BPDA-aptms, the flexibility of the APPS molecular chain, and the large thermodynamic incompatibility between the two, etc., the APPS is more prone to curl into a "soft phase" (polysiloxane phase) that is distributed into the BPDA and BPDA-aptms "hard phases" (polyimide phase). As shown in fig. 3, the light portions represent the polyimide phase and the dark portions represent the polysiloxane phase, forming a continuous phase with the polysiloxane soft phase distributed into the polyimide hard phase.
Example 1
(1) To a round bottom flask with mechanical stirring, reflux condenser and inert guard was added 127.55g octamethylcyclotetrasiloxane (0.43mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.12g tetramethylammonium hydroxide (25% in methanol) as a catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; finally, carrying out reduced pressure distillation on the mixture for 2 hours at the temperature of 150 ℃ in a rotary evaporator to remove small molecular substances, thus obtaining the colorless and transparent double-end amino polysiloxane, which is named as APPS-1500.
(2) Adding 3.71g of N-methylpyrrolidone/o-dichlorobenzene solution of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (12.6mmol) into a double-neck round-bottom flask provided with a constant-pressure dropping funnel and an inert protection device, then sequentially dropwise adding 15.00g of APPS-1500(10.0mmol) o-dichlorobenzene solution and 0.50g of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (2.0mmol) o-dichlorobenzene solution, and reacting for 12 hours at normal temperature to obtain the polysiloxane-polyimide acid block copolymer; then, the double-port round bottom flask filled with the reaction product solution is provided with a magneton stirring device, a reflux condenser pipe, a nitrogen ventilating device and a water separator, and is transferred to an oil bath kettle at 180 ℃, and the polysiloxane-polyimide block copolymer is obtained after reaction for 8 hours.
(3) And (3) carrying out hot press molding on the dried sample at 80 ℃ for 10min, then carrying out cold press molding at normal temperature for 10min, and finally cutting the obtained sample into sample strips with different sizes as required.
Example 2
The same as example 1 except that the molar ratio of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride to APPS-1500 to 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane added in step 2 was 17.8:10:7, and the hot press molding temperature in step 3 was 90 ℃.
Example 3
The same as example 1 except that the molar ratio of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride to APPS-1500 to 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane added in step 2 was 23.1:10:12, and the hot press molding temperature in step 3 was 100 ℃.
Example 4
The same as example 1 except that the molar ratio of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride to APPS-1500 to 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane added in step 2 was 28.4:10:17, and the hot press molding temperature in step 3 was 110 ℃.
Example 5
(1) To a round bottom flask with mechanical stirring, reflux condenser and inert guard was added 236.08g octamethylcyclotetrasiloxane (0.95mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.21g tetramethylammonium hydroxide (25% in methanol) as catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; finally, distilling at 150 ℃ under reduced pressure in a rotary evaporator for 2h to remove small molecular substances, thus obtaining the colorless and transparent double-end amino polysiloxane which is named as APPS-3000.
(2) Adding 8.36g of N-methylpyrrolidone/o-dichlorobenzene solution of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (28.4mmol) into a double-neck round-bottom flask provided with a constant-pressure dropping funnel and an inert protection device, then sequentially dropwise adding 30.00g of APPS-3000(10.0mmol) o-dichlorobenzene solution and 8.50g of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (17.0mmol) o-dichlorobenzene solution, and reacting for 12 hours at normal temperature to obtain the polysiloxane-polyimide acid block copolymer; then, the double-port round bottom flask filled with the reaction product solution is provided with a magneton stirring device, a reflux condenser pipe, a nitrogen ventilating device and a water separator, and is transferred to an oil bath kettle at 180 ℃, and the polysiloxane-polyimide block copolymer is obtained after reaction for 8 hours.
(3) And (3) carrying out hot press molding on the dried sample at 80 ℃ for 10min, then carrying out cold press molding at normal temperature for 10min, and finally cutting the obtained sample into sample strips with different sizes as required.
Example 6
(1) To a round bottom flask with mechanical stirring, reflux condenser and inert guard was added 231.36g octamethylcyclotetrasiloxane (0.78mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.2g tetramethylammonium hydroxide (25% in methanol) as a catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; finally, distilling at 150 ℃ under reduced pressure in a rotary evaporator for 2h to remove small molecular substances to obtain colorless and transparent double-end amino polysiloxane, which is named as APPS-2500.
(2) To a round bottom flask connected to a mechanical stirrer, reflux condenser and inert guard were added 29.66g octamethylcyclotetrasiloxane (0.1mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.044g tetramethylammonium hydroxide (25% in methanol) as a catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; and finally, carrying out reduced pressure distillation on the mixture for 2 hours at 130 ℃ in a rotary evaporator to remove small molecular substances, thus obtaining the low-molecular-weight double-end amino polysiloxane as a chain extender, which is named as APPS-500.
(3) Adding 8.36g of N-methylpyrrolidone/o-dichlorobenzene solution of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (28.4mmol) into a double-neck round-bottom flask provided with a constant-pressure dropping funnel and an inert protection device, then sequentially dropwise adding 25.00g of APPS-2500(10.0mmol) o-dichlorobenzene solution and 8.50g of APPS-500(17.0mmol) o-dichlorobenzene solution, and reacting for 12 hours at normal temperature to obtain a polysiloxane-polyimide acid block copolymer; then, the double-port round bottom flask filled with the reaction product solution is provided with a magneton stirring device, a reflux condenser pipe, a nitrogen ventilating device and a water separator, and is transferred to an oil bath kettle at 180 ℃, and the polysiloxane-polyimide block copolymer is obtained after reaction for 8 hours.
(4) And (3) carrying out hot press molding on the dried sample at 80 ℃ for 10min, then carrying out cold press molding at normal temperature for 10min, and finally cutting the obtained sample into sample strips with different sizes as required.
Comparative example 1
Except that the feeding molar ratio of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, the APPS-3000 and the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane in the step 2 is 12.6:10.0: 2; the hot press molding temperature in step 3 was 50 ℃ and the rest was the same as in example 5.
Comparative example 2
Except that the feeding molar ratio of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, the APPS-3000 and the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyl disiloxane in the step 2 is 17.8:10: 7; the hot press molding temperature in step 3 was 60 ℃ and the rest was the same as in example 5.
Comparative example 3
The same as example 5 except that the molar ratio of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride to APPS-3000 to 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane added in step 2 was 23.1:10:12, and the hot press molding temperature in step 3 was 70 ℃.
Comparative example 4
Replacing the chain extender 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane in the step 2 with hexamethylene diamine; the hot press molding temperature in step 3 was 85 ℃ and the rest was the same as in example 1.
Comparative example 5
(1) To a round bottom flask with mechanical stirring, reflux condenser and inert guard was added 177.97g octamethylcyclotetrasiloxane (0.6mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.16g tetramethylammonium hydroxide (25% in methanol) as a catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; finally, distilling at 150 ℃ under reduced pressure in a rotary evaporator for 2h to remove small molecular substances to obtain colorless and transparent double-end aminopolysiloxane, which is named APPS-2000.
(2) To a round bottom flask with mechanical stirring, reflux condenser and inert guard was added 8.31g octamethylcyclotetrasiloxane (0.28mol), 24.85g 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (0.1mol) and 0.086g tetramethylammonium hydroxide (25% in methanol) as catalyst. The reaction temperature is increased to 80 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen; then, the temperature is increased to 150 ℃, and the catalyst is decomposed for 1.2 hours to obtain a crude product; and finally, carrying out reduced pressure distillation on the mixture for 2 hours at 130 ℃ in a rotary evaporator to remove small molecular substances, and obtaining low-molecular-weight double-end amino polysiloxane as a chain extender, which is named as APPS-1000.
(3) Adding 8.36g of N-methylpyrrolidone/o-dichlorobenzene solution of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (28.4mmol) into a double-neck round-bottom flask provided with a constant-pressure dropping funnel and an inert protection device, then sequentially dropwise adding 20.00g of APPS-2000(10.0mmol) o-dichlorobenzene solution and 17g of APPS-1000(17.0mmol) o-dichlorobenzene solution, and reacting for 12 hours at normal temperature to obtain a polysiloxane-polyimide acid block copolymer; then, the double-port round bottom flask filled with the reaction product solution is provided with a magneton stirring device, a reflux condenser pipe, a nitrogen ventilating device and a water separator, and is transferred to an oil bath kettle at 180 ℃, and the polysiloxane-polyimide block copolymer is obtained after reaction for 8 hours.
(4) And (3) carrying out hot press molding on the dried sample at 80 ℃ for 10min, then carrying out cold press molding at normal temperature for 10min, and finally cutting the obtained sample into sample strips with different sizes as required.
FIGS. 2 and 3 are transmission electron micrographs of the materials prepared in comparative example 1 and example 1, respectively, after cryo-microtomy and transmission electron microscopy. In the transmission electron micrograph (fig. 3) of example 1, in which the lighter part is the polyimide phase and the black areas are referred to as the polysiloxane phase, it can be seen that there is a wide transition zone between the two phases, which is characterized by a gradient transition. While such morphology is not observed in the transmission electron micrograph (fig. 2) of comparative example 1, but a uniform phase distribution; comparative example 5 also found the same morphology.
Table 1 shows the mechanical properties and the repeated processing efficiency of comparative examples 1 to 5 and examples 1 to 6 at a drawing rate of 50 mm/min. As can be summarized from the tensile properties of the samples (table 1), the block copolymer having the hard phase structure as the continuous phase has more excellent resistance to external force. As can be seen from the data in Table 1, the polysiloxane-based copolymers having a phase-separated structure provided in inventive example 1(2.07MPa) and example 5(3.02MPa) have higher tensile strength than the polysiloxane-based copolymer having a uniform phase distribution (0.75MPa, comparative example 1). Comparing the tensile strengths of example 5, example 6 and comparative example 5, it can be seen that the block copolymers having a hard phase structure as a continuous phase (examples 5 and 6) significantly improve the tensile strength of the copolymers having similar hard segment contents. Meanwhile, the reversibility of pi-pi conjugation between polyimides enables each sample to have excellent repeated processing performance.
TABLE 1
| Tensile Strength (MPa) | Elongation at Break (%) | Repetitive work ratio (%) | |
| Comparative example 1 | 0.75 | 102 | 100 |
| Comparative example 2 | 1.18 | 75 | 100 |
| Comparative example 3 | 2.26 | 57 | 100 |
| Comparative example 5 | 0.93 | 98 | 100 |
| Example 1 | 2.07 | 75 | 100 |
| Example 2 | 2.98 | 50 | 100 |
| Example 3 | 4.22 | 41 | 100 |
| Example 4 | 5.27 | 22 | 100 |
| Example 5 | 3.02 | 49 | 100 |
| Example 6 | 2.65 | 53 | 100 |
FIG. 4 is a first derivative plot of DSC testing for comparative examples 1, 2 and examples 4, 5. The test conditions of the DSC test of the sample are that under the nitrogen atmosphere, the sample is firstly heated from minus 50 ℃ to 120 ℃ at the heating rate of 20 ℃/min, and is kept at 120 ℃ for 5min to eliminate the thermal history; then reducing the temperature to-50 ℃ at the speed of 20 ℃/min; then the temperature was again raised to 120 ℃ at a rate of 20 ℃/min. To facilitate the observation and comparison of T of each samplegWe derive the heat flow value obtained from the second temperature rise process in DSC to temperature by using "derivation method" to obtain the curve as shown in fig. 4. The glass transition temperature of the polysiloxane segment is-123 ℃, while the glass transition shown in the DSC curves of examples 4, 5 and comparative example 2 belongs to the polyimide-chain extender "hard phase", each phase maintaining an independent glass transition effect, so that a phase-separated structure is macroscopically represented; whereas comparative example 1 did not show vitrification of the "hard phase" belonging to the polyimide-chain extender in the DSC testAs a result, the polymer does not form a phase separation structure.
Meanwhile, T of examples 4 and 5gAll exhibit a continuous variation from about 40 ℃ up to 100 ℃ exhibiting typical broad glass transition characteristics, consistent with the designed gradient glass transition requirements; whereas comparative example 2 exhibits a very narrow glass transition temperature plateau. Likewise, a narrow glass transition temperature plateau is also present in comparative example 4.
Comparing examples 5, 6 and comparative example 5, it can be seen that the interaction between the hard segments is not affected to form a gradient structure when the molecular weight of the chain extender is slightly increased; but when its molecular weight reaches a certain level, the broad glass transition gradually narrows to finally disappear (comparative example 5). As can be seen from comparative example 5 and comparative example 4, the chain extender having a certain content of silicon-oxygen bonds helps to reduce the huge interfacial tension between the hard phase and the soft phase, and promotes the formation of the gradient glass transition structure.
In conclusion, the invention designs and prepares the gradient TgA phase separated structure of the structure; at gradient TgIn the structure, the innermost segment in the hard phase will constitute the segment with the highest TgThe nano-domains of (a), which serve as cross-linking points to prevent molecular chain slippage during pre-deformation and shape recovery; to have a gradient TgThe transformed nanolayers will serve to fix the temporary shape and store energy. FIG. 5 shows examples 1, 4 and 5 at a temperature TgThe digital photo of the shape recovery process in the water bath at +5 ℃ is obtained by recovering a U-shaped test sample strip in hot water. The specific test method comprises the following steps: (1) each sample was heated to TgKeeping the temperature at +5 ℃ for a proper time, and then applying force to bend the material into a U shape; (2) immediately putting the deformed sample into ice water under a force load for 10min to fix the shape; (3) unload the force and hold at room temperature for 5 hours, then record the shape fixation angle (θ)f) (ii) a (4) The deformed sample was put into hot water having a corresponding temperature for recovery, and the recovery process and the final steady-state shape recovery angle (θ) were recorded by photographingr). Shape fixation ratio (R)f%) and shape recovery ratio (R)rThe calculation formula of (c)%) is shown below.
Table 2 shows the shape fixation rate and the shape recovery rate of the samples of comparative examples 1 to 5 and examples 1 to 6. From Table 2, it is found that comparative examples 1 and 5 having no phase separation structure and having no wide TgComparative examples 2, 4, which are gradient in character, are extremely poor in shape retention. As can be seen by comparing examples 5 and 6 with comparative example 5 and comparative example 1 with comparative example 4, 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane promotes a broad T at the same hard segment contentgThe formation of gradient features, which in turn help in shape fixation; meanwhile, with the formation and perfection of the gradient structure, energy dissipation due to viscous deformation such as slippage between molecular chains during shape imparting and shape recovery is reduced, thereby causing the sample to exhibit excellent shape recovery behavior. As can be seen from fig. 5, with the perfection of the gradient structure (example 1 > example 4 > example 6), it not only shows excellent shape recovery rate, but also has excellent shape recovery rate, i.e. high recovery rate at the same time.
Meanwhile, according to the shape recovery experimental results of the embodiments 1 to 4, the number and strength of the cross-linking points are gradually increased along with the increase of the content of the hard segment, thereby being beneficial to the storage of energy of the sample in the deformation process. The same conclusion can be drawn in the comparison between example 6 and comparative examples 1-3, that under the same hard segment content, the polysiloxane molecular chain with relatively low molecular weight will increase the interfacial area between two phases, and further increase the number of cross-linking points, and the entropy energy of the sample in the deformation process can be effectively stored by the multiple and strong cross-linking points.
TABLE 2
FIG. 6 is a shape memory curve of the product of example 1 characterized by DMA stretching (solid line in the figure indicates strain, dotted line indicates temperature, and short dashed line indicates stress), and the characterization of the shape memory properties of the polymer is performed on a TA Q800 apparatus, the main steps of which are as follows: (1) at TgKeeping the temperature at +5 ℃ for 5min, and recording the initial strain epsilon0(ii) a (2) Stretching to 5% strain and recording the maximum strain epsilon generated under load during deformationload(ii) a (3) Cooling to 0 deg.C at a rate of 10 deg.C/min, maintaining the load at constant temperature for 10min at that temperature to substantially set the shape, unloading the load, continuing to hold at 0 deg.C for 5min, and recording the strain ε at that timef(ii) a (4) Is heated again to TgThe temperature is kept constant at +5 ℃ for 20min, and the strain epsilon at this time is recordedr. Its shape fixation ratio (R)f%) and shape recovery ratio (R)rThe calculation formula of%) is as follows:
as is apparent from FIG. 6, the copolymer exhibited excellent shape memory properties, with a shape fixation rate and a shape recovery rate of 96.4% and 84.3%, respectively.
FIG. 7 is a graph of the elongation before and after self-repair for 8h for example 1. The specific experimental process is as follows: the specimen was cut off from the middle with a sharp blade, then the cuts were immediately spliced together, and then the sample was set at 80 ℃ to repair, and after 8h, its stress-strain curve at a tensile rate of 50mm/min was tested, with the results shown by the dotted line in fig. 7. Self-healing performance was evaluated by tensile strength and elongation at break respectively using self-healing efficiency (η), η being defined as follows:
tensile strength self-repair efficiency:
elongation at break self-repair rate:
wherein delta0And deltahTensile strength before and after the sample was uncut and repaired, respectively, and ε0And εhThe elongation at break before and after the sample was uncut and repaired are shown, respectively. From the figure, the repairing efficiency of the tensile strength of the sample after 8 hours of repairing is 74%, and the sample has certain self-repairing capability.
The polysiloxane thermoplastic elastomer prepared by the invention has a gradient glass transition structure with polyimide-chain extender hard segments surrounding soft segment polysiloxane, and the continuous polyimide-chain extender as a hard phase has excellent capability of resisting external force, so that the final product has high tensile strength (more than 2 MPa). The continuous hard phase structure formed by utilizing the pi-pi conjugation between the polyimides has reversibility and repeatable processing performance at high temperature (60-110 ℃); at the same time, under appropriate temperature conditions (T)g+10 ℃), and the reversibility of pi-pi conjugation between polyimides in the hard segment and the high flexibility of the soft-phase polysiloxane chain segment endow the polyimide with good self-repairing performance (the self-repairing efficiency of the tensile strength of example 1 reaches 74% after the polyimide is placed at 80 ℃ below zero for 8 hours). The preparation method provided by the invention is simple, convenient and effective, the product has repeatable processing performance and the processing method is simple, and the preparation method meets the requirements and market trends of the current green, environment-friendly and renewable industrial production.
Gradient glass transition structure (T) prepared by the inventiongGreater than 60 deg.c) provides a precondition for the realization of the shape memory function of the present invention. The perfect gradient glass transition structure can improve the shape fixing rate of the polysiloxane thermoplastic elastomer to 95 percent, and the thermotropic shape recovery rate of the polysiloxane thermoplastic elastomer can reach more than 84 percent (DMA test). Meanwhile, because the polysiloxane section and the polyimide section adopted by the polysiloxane thermoplastic elastomer have excellent biocompatibility, the biocompatibility is greatly reducedThe small human rejection and the risk of complications will have great potential application prospects, especially in the field of biomedical devices, such as vasodilator devices and the like.
The above-mentioned embodiments are intended to illustrate rather than limit the invention, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A process for the preparation of a multifunctional silicone thermoplastic elastomer, characterized in that it consists of the following steps:
(1) synthesis of a Diaminopolysiloxane: mixing 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane serving as raw materials with a catalyst, and heating to react to obtain colorless and transparent double-end aminopolysiloxane; the catalyst is tetramethyl ammonium hydroxide pentahydrate; the molar ratio of the 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to the octamethylcyclotetrasiloxane is 1: 3-35; the number average molecular weight of the aminobipunctinal polysiloxane is 1X 103～1×104；
(2) Synthesis of polysiloxane-Polyamic acid Block copolymer: under a protective atmosphere, dissolving and mixing the amino-terminated polysiloxane obtained in the step (1), 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and a chain extender by a polar solvent, and reacting at normal temperature to obtain a colorless and transparent polysiloxane-polyamic acid block copolymer with the solid content of 15-50%; the chain extender is one or more of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and low molecular weight amino-terminated polysiloxane; the molar ratio of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride to the amino terminated polysiloxane to the chain extender is 28.4:10: 17. 17.8:10:7 or 23.1:10: 12; the number average molecular weight of the low molecular weight double-end amino polysiloxane is 5 multiplied by 102～9×102；
(3) Imidization reaction: reacting the product obtained in the step (2) at 150-200 ℃ for 6-12 h; after the reaction is finished, removing the solvent to obtain dark brown polysiloxane-polyimide segmented copolymer particles;
(4) preparation of elastomer sample bars: hot-pressing and molding the polysiloxane-polyimide segmented copolymer particles obtained in the step (3); then cold pressing and shaping are carried out to obtain the multifunctional polysiloxane thermoplastic elastomer with the gradient glass transition structure; the hot-press molding temperature is 80-110 ℃.
2. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (1), the dosage of the catalyst is 0.01-0.05% of the mass of the octamethylcyclotetrasiloxane.
3. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (1), the heating reaction is carried out at 85-90 ℃ for 4-12 h, and then at 135-150 ℃ for 1-1.5 h.
4. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (2), the polar solvent is one or more of N-methylpyrrolidone and o-dichlorobenzene; in the step (2), the protective atmosphere is nitrogen or argon inert gas atmosphere; the reaction time at normal temperature is 6-24 h.
5. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (2), the low molecular weight double-terminal amino polysiloxane is prepared by the following method: mixing 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane serving as raw materials with a catalyst, and heating for reaction; controlling the molar ratio of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane to octamethylcyclotetrasiloxane to be 1: 1-2; the catalyst is tetramethyl ammonium hydroxide pentahydrate.
6. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (3), after the reaction is finished, most of the solvent is removed by using a rotary evaporator at 150 ℃, and then the reaction product is placed in a vacuum oven with the temperature of 100 ℃ and the vacuum degree of-0.1 MPa for 6-20 hours to remove the residual solvent.
7. The method of preparing a multifunctional silicone thermoplastic elastomer according to claim 1, characterized in that: in the step (4), the hot-press molding time is 10 min; the cold pressing and shaping refers to die pressing for 10min under the conditions of 15MPa of pressure and normal temperature.
8. A multifunctional silicone thermoplastic elastomer, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. Use of the multifunctional silicone thermoplastic elastomer of claim 8 in biomedical devices.
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| CN101392063B (en) * | 2008-10-31 | 2011-05-18 | 华南理工大学 | Dimethyl silicone polymer-polyamide multi-block elastomer and production method thereof |
| CN109384930A (en) * | 2018-09-30 | 2019-02-26 | 郑州大学 | Acyclic straight polyamide and polysiloxane block copolymers and preparation method thereof |
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