CN113789052B - Shape memory nylon material and preparation method thereof - Google Patents
Shape memory nylon material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention relates to the technical field of shape memory polymer materials, in particular to a shape memory nylon material and a preparation method thereof. The shape memory nylon material is prepared by taking nylon containing double bonds as a matrix and performing irradiation crosslinking; wherein the nylon matrix is prepared by salt formation preparation, prepolymerization and final polycondensation of a dibasic acid mixture with the molar content of fumaric acid of 2-10% and diamine, and the irradiation crosslinking adopts cobalt ray irradiation. The shape memory nylon material prepared by the invention has excellent comprehensive performance and good shape memory effect, and compared with the traditional shape memory polymer material, the shape memory nylon material also has high and low temperature resistance and excellent chemical stability.
Description
Technical Field
The invention relates to the technical field of shape memory polymer materials, in particular to a shape memory nylon material and a preparation method thereof.
Background
Shape memory materials are materials that can return to their original state in response to external stimuli such as temperature, magnetic fields, light, etc. The shape memory polymer has the characteristics of simple preparation process, low production cost, strong shape memory capability and strong designability, and is widely applied to the fields of medical treatment, self-repairing materials, aerospace, thermal shrinkage materials and the like. The matrix of the shape memory polymer is mainly polyethylene, polyurethane, polyester and the like.
Strictly ice et al prepared a shape memory polyurethane in "research on structure and performance of shape memory polyurethane", which has insufficient mechanical properties and a tensile strength of only 6-20 MPa.
Patent CN107383320 introduces a method for modifying shape memory polyurethane with epoxy resin, which can improve the defects of small restoring force, low strength, easy aging, etc. of shape memory polyurethane; there are many documents and patents that adopt doped fibers, nanoparticles and silicone resin to improve the problems, but the processing complexity is increased, and the problems of compatibility also occur.
Patent CN107320771 provides a PFOE water phase shape memory tissue engineering scaffold and its preparation method, which comprises, synthesizing polyhydroxy polyester (poly octyl fumarate diepoxy) by one step through acid-induced epoxy ring-opening reaction, then carrying out reaction of hydroxyl and hydroxyl by salting out method to obtain shape memory material. The matrix used in this patent is a polyester material and has a low molecular weight, which results in insufficient mechanical strength.
In summary, the conventional shape memory polymers have the disadvantages of insufficient mechanical strength, poor chemical stability and the like due to the limitation of the matrix, so that the application of the shape memory materials is limited.
Nylon is a good engineering plastic, molecular chains contain a large number of polar amido bonds, and strong hydrogen bond acting force exists among the molecular chains; the nylon molecular chains are arranged orderly and have high crystallinity; in addition, the molecular chain of the nylon also contains methylene, so that the nylon has better flexibility. The nylon has the advantages of excellent mechanical properties, excellent low-temperature performance, excellent electrical insulation, excellent chemical stability and the like. If the nylon material is used as a matrix to prepare the shape memory material, the shape memory material has more unique performance and market prospect.
At present, shape memory materials taking nylon as a matrix have fewer reports and have obvious defects in performance. Patent CN202110235275 provides a preparation method of amorphous thermoplastic nylon elastomer containing pyrrolidone structure, but the introduction of pyrrolidone structure destroys crystallinity and hydrogen bond of molecular chain, resulting in the decrease of mechanical property. Patent CN200780047322 discloses a preparation method of shape memory nylon fabric, wherein a small amount of diamine or diacid containing aromatic structure is introduced into nylon 6 or nylon 66, which endows nylon material with shape memory performance, but the mechanical strength and the deformation can be relatively insufficient.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the shape memory nylon material has excellent comprehensive performance and good shape memory effect, and compared with the traditional shape memory polymer material, the shape memory nylon material also has high and low temperature resistance and excellent chemical stability; the invention also provides a preparation method of the composition.
The shape memory nylon material is prepared by taking nylon containing double bonds as a matrix and performing irradiation crosslinking; the structural formula of the nylon containing double bonds is as follows:
the structural formula of the shape memory nylon material is as follows:
wherein m is an even number, n, x and y are integers, m is more than or equal to 2 and less than or equal to 10, n is more than or equal to 4 and less than or equal to 10, x is more than or equal to 1 and less than or equal to 2000, y is more than or equal to 1 and less than or equal to 2000, and x (x + y) = (2-10): 100.
The preparation method of the shape memory nylon material comprises the following steps:
(1) preparing nylon salt: reacting a diacid mixture with the fumaric acid molar content of 2-10% with diamine in water, and drying to obtain a nylon salt;
(2) pre-polymerization: reacting nylon salt, water and a polymerization inhibitor under the conditions of high temperature and high pressure, discharging water vapor, vacuumizing and reacting to obtain a prepolymer, cooling the prepolymer while the prepolymer is hot, and granulating to obtain prepolymer particles;
(3) final polycondensation: carrying out polycondensation reaction on the prepolymer particles in a nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking: and (3) performing cobalt ray irradiation crosslinking on the nylon resin to obtain the nylon material with the shape memory performance.
In the step (1), except fumaric acid, the structural general formulas of the rest dibasic acid components in the dibasic acid mixtureIs COOH (CH)2)mCOOH, wherein m is an even number between 2 and 10; the remaining diacid component is preferably at least one of succinic acid, adipic acid, sebacic acid, and dodecanedioic acid, commonly known as nylon 46, nylon 66, nylon 610, nylon 612, nylon 1010, and nylon 1212.
The double bond-containing dibasic acid is introduced into the nylon matrix, so that double bonds exist in the molecular chain of the nylon matrix, the content of the double bonds is regulated and controlled by controlling the content of the double bond-containing dibasic acid, the content of the double bond-containing dibasic acid is too low, and the cross-linking points are insufficient; too much double bond-containing dibasic acid content affects the performance of the nylon matrix, and excessive crosslinking makes it difficult for the shape memory material to change appearance.
Common and easily-obtained dicarboxylic acid containing double bonds comprises fumaric acid, heptadecenoic acid, octadecene dicarboxylic acid and the like, and when the fumaric acid is introduced into common nylon 46, nylon 1212 and other matrixes, the mechanical property of the obtained nylon containing double bonds is basically consistent with that of the corresponding nylon material. If other dibasic acid (octadecene dibasic acid and the like) is introduced, the mechanical property of the nylon containing double bonds is obviously reduced due to the fact that the molecular chain is too long, the compatibility with the dibasic acid in the nylon is poor, and the regularity of the molecular chain of the nylon is poor. The molecular chain of the fumaric acid is short, the nylon system has strong inclusion capacity to the fumaric acid, and the mechanical property of the nylon containing double bonds is basically unchanged, so the fumaric acid is the first-choice diacid of the nylon shape memory material.
The structural general formula of diamine is NH2(CH2)nNH2Wherein n is an integer between 4 and 10; commonly used diamines are butanediamine, pentanediamine, hexanediamine, and the like.
The molar ratio of the diacid mixture to the diamine is 1 (1.01-1.05). In order to better regulate the proportion of acid amine, the pH value of the system is stabilized between 7.0 and 8.0 after the reaction is finished by auxiliary regulation in a pH measuring mode, so that the production error is reduced.
The amount of water is 1 to 15 times, preferably 2 to 8 times, the total mass of the diacid mixture and diamine.
When preparing the nylon salt, firstly, mixing the dibasic acid mixture with water, heating to 40-70 ℃, adding the diamine, heating to 50-80 ℃, and carrying out heat preservation reaction for 1-2 hours.
In the step (2), the mass ratio of the nylon salt to the water is (1-5) to 1.
The polymerization inhibitor is hydroquinone or p-hydroxyanisole, and the dosage of the polymerization inhibitor is 0.25-0.5% of the total mass of the nylon salt. The self-polymerization of the unsaturated dibasic acid chain segment can be effectively avoided by adding the polymerization inhibitor.
In one embodiment, when preparing the prepolymer, mixing the nylon salt, the polymerization inhibitor and water, placing the mixture in a high-temperature high-pressure reaction kettle, heating the mixture to 220 ℃ at the heating rate of 50-70 ℃/h, and keeping the temperature for 0.5-2 h; then the temperature is raised to 240 ℃ within 0.5-1h, and the temperature is kept for 1-2 h; then discharging the water vapor in the reaction kettle, wherein the air release time is 0.5-3h, vacuumizing the reaction kettle, and continuously reacting for 0.5-2h at the temperature of 200-250 ℃ to obtain the prepolymer.
In the case of pelletizing the prepolymer, a pelletizer may be used, and the particle diameter of the prepolymer particles is 0.1 to 5mm, preferably 0.25 to 2 mm.
In the step (3), the polycondensation reaction temperature is 200-240 ℃, and the reaction time is 1-8 h.
In the step (4), the dosage of the cobalt rays is 20-80 kGy. After irradiation, double bonds in a nylon molecular chain are opened, cross-linking is generated among molecules, and a cross-linked part becomes a fixed phase. The shape memory material can not be completely melted at high temperature, can change the shape under external force, and continuously keeps the external force to crystallize and fix the shape at low temperature; when heated again, the uncrosslinked part is melted, the stationary phase is not changed, and the original shape is recovered due to no external force. The material cannot generate effective deformation and shape memory effect due to too low irradiation dose, and the material is aged and the service life of the material is shortened due to too high irradiation dose, which not only causes energy waste.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nylon is used as the matrix of the shape memory material, and has better mechanical property than a polyester material, and the prepared shape memory material has excellent comprehensive performance;
(2) according to the invention, fumaric acid is introduced into a nylon material matrix, the fumaric acid has a similar structure with other dibasic acids such as succinic acid and adipic acid, and contains double bonds, so that the nylon material is endowed with shape memory performance, and the shape memory effect is controllable by adjusting the content of the fumaric acid;
(3) the invention adopts cobalt ray irradiation to crosslink the nylon matrix, has simple and convenient operation and avoids pollution caused by adopting a crosslinking assistant;
(4) the shape memory nylon material prepared by the invention has excellent comprehensive performance and good shape memory effect, has high and low temperature resistance and excellent chemical stability compared with the traditional shape memory polymer material, and can be applied to severe environments such as high temperature, low cold and the like in aerospace and the like.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
(1) Preparing nylon salt:
mixing 1mol of a dibasic acid mixture (the molar ratio of fumaric acid to adipic acid is 6: 94) with 800g of water, heating to 40 ℃, slowly adding 1.02mol of hexamethylenediamine, heating to 50 ℃ after the addition is finished, keeping the temperature for reaction for 2 hours, stabilizing the pH value of a system at 7.2-7.4 after the reaction is finished to obtain a nylon salt solution, and drying to obtain the nylon salt;
(2) pre-polymerization:
mixing 250g of nylon salt, 0.625g of p-hydroxyanisole and 50g of water, placing the mixture in a high-temperature high-pressure reaction kettle, heating to 220 ℃ at a heating rate of 70 ℃/h, keeping the temperature for 0.5h, heating to 240 ℃ within 1h, and keeping the temperature for 2 h; then slowly discharging water vapor in the reaction kettle for 1h, vacuumizing the reaction kettle, continuously reacting for 2h at 200 ℃ to obtain prepolymer, discharging the prepolymer into a cooling tank while the prepolymer is hot, and feeding the prepolymer into a granulator to prepare prepolymer particles with the particle size of 1 mm;
(3) final polycondensation:
reacting the prepolymer particles for 6 hours at 240 ℃ in the nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking:
and (3) performing cobalt ray irradiation crosslinking on the nylon resin, wherein the dosage is 60kGy, so as to obtain the nylon material with the shape memory effect.
Example 2
(1) Preparing nylon salt:
mixing 1mol of a dibasic acid mixture (the molar ratio of fumaric acid to adipic acid is 2: 98) with 500g of water, heating to 50 ℃, slowly adding 1.05mol of pentamethylene diamine, heating to 60 ℃ after the addition is finished, keeping the temperature for reaction for 2 hours, stabilizing the pH value of a system at 7.5-7.9 after the reaction is finished to obtain a nylon salt solution, and drying to obtain the nylon salt;
(2) pre-polymerization:
mixing 250g of nylon salt, 1.25g of p-hydroxyanisole and 100g of water, placing the mixture in a high-temperature high-pressure reaction kettle, heating to 180 ℃ at a heating rate of 50 ℃/h, keeping the temperature for 2h, heating to 200 ℃ within 0.5h, and keeping the temperature for 2 h; then slowly discharging water vapor in the reaction kettle, wherein the gas discharging time is 0.5h, vacuumizing the reaction kettle, continuously reacting for 1h at 250 ℃ to obtain a prepolymer, discharging the prepolymer to a cooling tank while the prepolymer is hot, and feeding the prepolymer into a granulator to prepare prepolymer particles with the particle size of 0.1 mm;
(3) final polycondensation:
reacting the prepolymer particles for 6 hours at 210 ℃ in the nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking:
and (3) performing cobalt ray irradiation crosslinking on the nylon resin, wherein the dosage is 20kGy, so as to obtain the nylon material with the shape memory effect.
Example 3
(1) Preparing nylon salt:
1mol of a dibasic acid mixture (the molar ratio of fumaric acid to adipic acid is 10: 90) is mixed with 1800g of water, the temperature is raised to 70 ℃, 1.01mol of butanediamine is slowly added, the temperature is raised to 80 ℃ after the addition is finished, the temperature is kept for reaction for 1h, the pH value of a system is stabilized at 7.2-7.6 after the reaction is finished, a nylon salt solution is obtained, and the nylon salt is obtained by drying treatment;
(2) pre-polymerization:
200g of nylon salt, 0.5g of hydroquinone and 50g of water are mixed and placed in a high-temperature high-pressure reaction kettle, the temperature is raised to 210 ℃ at the heating rate of 60 ℃/h, the temperature is kept for 1h, the temperature is raised to 240 ℃ within 1h, and the temperature is kept for 2 h; then slowly discharging water vapor in the reaction kettle for 3h, vacuumizing the reaction kettle, continuously reacting for 1h at 230 ℃ to obtain prepolymer, discharging the prepolymer into a cooling tank while the prepolymer is hot, and feeding the prepolymer into a granulator to prepare prepolymer particles with the particle size of 5 mm;
(3) final polycondensation:
reacting the prepolymer particles for 1h at 230 ℃ in the nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking:
and (3) performing cobalt ray irradiation crosslinking on the nylon resin, wherein the dosage is 80kGy, so as to obtain the nylon material with the shape memory effect.
Example 4
(1) Preparing nylon salt:
mixing 1mol of a dibasic acid mixture (the molar ratio of fumaric acid to sebacic acid is 6: 94) with 800g of water, heating to 50 ℃, slowly adding 1.02mol of hexamethylene diamine, heating to 60 ℃ after the addition is finished, carrying out heat preservation reaction for 1.5h, stabilizing the pH value of a system at 7.4-7.7 after the reaction is finished to obtain a nylon salt solution, and drying to obtain a nylon salt;
(2) pre-polymerization:
mixing 150g of nylon salt, 0.75g of hydroquinone and 50g of water, putting the mixture into a high-temperature high-pressure reaction kettle, heating the mixture to 220 ℃ at the heating rate of 70 ℃/h, keeping the temperature for 0.5h, heating the mixture to 240 ℃ within 1h, and keeping the temperature for 2 h; then slowly discharging water vapor in the reaction kettle for 1h, vacuumizing the reaction kettle, continuously reacting for 0.5h at 220 ℃ to obtain prepolymer, discharging the prepolymer into a cooling tank while the prepolymer is hot, and feeding the prepolymer into a granulator to prepare prepolymer particles with the particle size of 0.75 mm;
(3) final polycondensation:
reacting the prepolymer particles for 8 hours at 200 ℃ in the nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking:
and (3) performing cobalt ray irradiation crosslinking on the nylon resin, wherein the dosage is 50kGy, so as to obtain the nylon material with the shape memory effect.
Comparative example 1
This comparative example is different from example 1 only in that the dibasic acid mixture was replaced with an equimolar amount of adipic acid in step (1) and the nylon resin obtained in step (3) did not contain a double bond.
Comparative example 2
This comparative example differs from example 1 only in that in step (1), fumaric acid was replaced with an equimolar amount of octadecenedioic acid.
Comparative example 3
This comparative example differs from example 1 only in that in step (1), the molar ratio of fumaric acid to adipic acid was adjusted from 6:94 to 15: 85.
Comparative example 4
The difference between the comparative example and the example 1 is that in the step (2), no polymerization inhibitor, namely p-hydroxyanisole, is added, and the elongation at break of the nylon material obtained in the step (4) is lower than 200%, so that the shape memory effect performance can not be detected.
Comparative example 5
This comparative example is different from example 1 only in that the irradiation crosslinking treatment of step (4) was not performed.
Comparative example 6
The comparative example is different from example 1 only in that in the step (4), the dosage for the cobalt ray irradiation crosslinking is adjusted to 5kGy, the elongation at break of the obtained nylon material is less than 200%, and the shape memory effect performance test cannot be carried out.
Comparative example 7
This comparative example is different from example 1 only in that in step (4), the dose for cobalt ray irradiation crosslinking was adjusted to 100 kGy.
Comparative example 8
Compared with the cross-linked polyethylene/nano calcium carbonate nano composite material disclosed in the literature "research on shape memory performance of cross-linked polyethylene/nano calcium carbonate nano composite material, Lecheng et al, plastics industry, Vol.41, No. 11" (nano calcium carbonate mass fraction is 0.4%, DCP mass fraction is 0.6%), the performance test method and preparation method are described in the literature.
Comparative example 9
Compared with the shape memory polyurethane (code C3) disclosed in the literature "research on structure and performance of shape memory polyurethane, Seiko et al, polyurethane industry, volume 18, No. 3", the performance test method and preparation method are described in the literature.
The shape memory materials prepared in examples 1-4 and comparative examples 1-7 are subjected to performance tests, and splines are prepared according to GB/T1040-:
(1) the tensile strength and the elongation at break are tested according to GB/T1040-2006, the test temperature is 25 ℃, and the tensile speed is 50 mm/min.
(2) The shape memory effect is tested by an electronic universal tester with a temperature control chamber, and the testing method is as follows:
firstly, the length is L0Keeping the sample strip at 230 ℃ for 10min, stretching the sample strip at a stretching speed of 10mm/min to 200% deformation, and keeping for 10 min;
② the temperature is reduced to 30 ℃, the sample is crystallized and shaped for 10min, and the length of the sample strip is recorded as L1；
Removing stress, and testing the length L of the sample strip after 10min2；
Fourthly, the temperature is raised to 230 ℃ again and kept for 10min, the temperature is cooled to 30 ℃ again and kept for 30min, and the length L of the sample strip is recorded3；
Calculating: shape fixation rate: rf= (L2- L0)/ (L1- L0)×100%；
Shape recovery rate: rr= (L2- L3)/ (L2- L0)×100%。
Note: the shape memory property test cannot be performed when the elongation at break of the test specimen is less than 200%.
TABLE 1 test results of shape memory materials of examples and comparative examples
| Examples of the invention | Tensile strength/MPa | Elongation at break/% | Shape fixation rate/%) | Shape recovery rate/%) |
| Example 1 | 95.1 | 570.9 | 99.8 | 99.1 |
| Example 2 | 86.1 | 201.8 | 99.5 | 98.5 |
| Example 3 | 101.4 | 741.0 | 99.2 | 99.3 |
| Example 4 | 94.3 | 480.6 | 99.5 | 99.0 |
| Comparative example 1 | 75.0 | 30.4 | - | - |
| Comparative example 2 | 45.5 | 450.1 | 99.7 | 95.0 |
| Comparative example 3 | 152.8 | 39.2 | - | - |
| Comparative example 4 | 81.8 | 55.6 | - | - |
| Comparative example 5 | 82.1 | 58.8 | - | - |
| Comparative example 6 | 89.0 | 160.9 | - | - |
| Comparative example7 | 90.1 | 490.7 | 99.7 | 98.7 |
| Comparative example 8 | 11.5 | 380 | 99.7 | 97.5 |
| Comparative example 9 | 18.5 | 450 | 99.8 | 96.8 |
As can be seen from Table 1, in examples 1 to 4 of the present invention, a certain amount of fumaric acid is introduced into a nylon material matrix, and cobalt ray irradiation with a proper dosage is adopted to crosslink the nylon matrix, so that the nylon material has excellent shape memory properties; compared with the embodiment 1, the nylon matrix has no double bonds, and the shape memory effect cannot be endowed to the material even after irradiation; compared with the embodiment 1, the comparative example 2 adopts other unsaturated dibasic acid (octadecene dibasic acid) to replace fumaric acid, introduces double bonds into a nylon matrix, has lower tensile strength, and can not have good mechanical property while endowing the material with shape memory property; compared with the example 1, the unsaturated nylon material has the advantages that the unsaturated nylon material is excessively crosslinked and the elongation at break is reduced sharply due to excessive fumaric acid introduced in the synthesis process; compared with the embodiment 1, the comparative example 4 has the advantages that no polymerization inhibitor is added in the nylon material synthesis process, so that the unsaturated dibasic acid can be polymerized, the aim of effective crosslinking can not be achieved, and effective deformation and shape memory effects can not be generated; compared with the example 1, although fumaric acid and unsaturated bonds are introduced into the nylon material, if the nylon material is not irradiated or the irradiation dose is lower, the material cannot generate effective deformation and shape memory effect, and the excessive irradiation dose can not only waste energy, but also promote the aging of the material and shorten the service life of the material.
Compared with the examples 1 to 4, the shape memory effect of the nylon memory material is similar to that of the traditional cross-linked polyethylene shape memory material and polyester shape memory material, but the tensile strength of the nylon memory material is far higher than that of the cross-linked polyethylene shape memory material (about 10 MPa) and that of the polyester shape memory material (about 20 MPa), and compared with the conventional shape memory materials such as cross-linked polyethylene, polyurethane and the like, the nylon memory material has better mechanical property.
Claims (9)
1. A shape memory nylon material is characterized in that: nylon containing double bonds is taken as a matrix, and the shape memory nylon material is obtained through irradiation crosslinking; the structural formula of the nylon containing double bonds is as follows:
the structural formula of the shape memory nylon material is as follows:
wherein m is an even number, n, x and y are integers, m is more than or equal to 2 and less than or equal to 10, n is more than or equal to 4 and less than or equal to 10, x is more than or equal to 1 and less than or equal to 2000, y is more than or equal to 1 and less than or equal to 2000, and x (x + y) = (2-10): 100;
the preparation method of the shape memory nylon material comprises the following steps:
(1) preparing nylon salt: reacting a diacid mixture with the fumaric acid molar content of 2-10% with diamine in water, and drying to obtain a nylon salt;
(2) pre-polymerization: reacting nylon salt, water and a polymerization inhibitor under the conditions of high temperature and high pressure, discharging water vapor, vacuumizing and reacting to obtain a prepolymer, cooling the prepolymer while the prepolymer is hot, and granulating to obtain prepolymer particles;
(3) final polycondensation: carrying out polycondensation reaction on the prepolymer particles in a nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking: and (3) performing cobalt ray irradiation crosslinking on the nylon resin, wherein the dosage of the cobalt ray is 20-80kGy, and thus obtaining the nylon material with the shape memory performance.
2. A method for preparing a shape memory nylon material according to claim 1, which is characterized in that: the method comprises the following steps:
(1) preparing nylon salt: reacting a diacid mixture with the fumaric acid molar content of 2-10% with diamine in water, and drying to obtain a nylon salt;
(2) pre-polymerization: reacting nylon salt, water and a polymerization inhibitor under the conditions of high temperature and high pressure, discharging water vapor, vacuumizing and reacting to obtain a prepolymer, cooling the prepolymer while the prepolymer is hot, and granulating to obtain prepolymer particles;
(3) final polycondensation: carrying out polycondensation reaction on the prepolymer particles in a nitrogen atmosphere to obtain nylon resin with double bonds inside;
(4) irradiation crosslinking: and (3) performing cobalt ray irradiation crosslinking on the nylon resin to obtain the nylon material with the shape memory performance.
3. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (1), except fumaric acid in the dibasic acid mixture, the structural general formula of the rest dibasic acid components is COOH (CH)2)mCOOH, wherein m is an even number between 2 and 10; the structural general formula of diamine is NH2(CH2)nNH2Wherein n is an integer between 4 and 10; the molar ratio of the diacid mixture to the diamine is 1 (1.01-1.05).
4. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (1), when the nylon salt is prepared, firstly, the dibasic acid mixture is mixed with water, the temperature is raised to 40-70 ℃, then, the diamine is added, the temperature is raised to 50-80 ℃, and the heat preservation reaction is carried out for 1-2 hours.
5. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (2), the mass ratio of the nylon salt to the water is 1-5: 1.
6. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (2), the polymerization inhibitor is hydroquinone or p-hydroxyanisole, and the dosage of the polymerization inhibitor is 0.25-0.5% of the total mass of the nylon salt.
7. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (2), when the prepolymer is prepared, the nylon salt, the polymerization inhibitor and water are mixed and placed in a high-temperature high-pressure reaction kettle, the temperature is raised to 220 ℃ at the heating rate of 50-70 ℃/h, and the constant temperature is kept for 0.5-2 h; then the temperature is raised to 240 ℃ within 0.5-1h, and the temperature is kept for 1-2 h; then discharging the water vapor in the reaction kettle, wherein the air release time is 0.5-3h, vacuumizing the reaction kettle, and continuously reacting for 0.5-2h at the temperature of 200-250 ℃ to obtain the prepolymer.
8. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (2), the particle size of the prepolymer particles is 0.1-5 mm.
9. The method for preparing a shape memory nylon material according to claim 2, wherein the method comprises the following steps: in the step (3), the polycondensation reaction temperature is 200-240 ℃, and the reaction time is 1-8 h.
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