CN113004513B - Stress response type high-temperature resistant polyamide and synthesis method thereof - Google Patents
Stress response type high-temperature resistant polyamide and synthesis method thereof Download PDFInfo
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- CN113004513B CN113004513B CN202110224359.7A CN202110224359A CN113004513B CN 113004513 B CN113004513 B CN 113004513B CN 202110224359 A CN202110224359 A CN 202110224359A CN 113004513 B CN113004513 B CN 113004513B
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
Abstract
The invention provides a stress-responsive high-temperature-resistant polyamide and a synthesis method thereof, which are characterized in that deionized water, dibasic acid, diamine and diamine containing a spiro structure are subjected to salt formation, prepolymerization and solid phase viscosity increasing under the action of a catalyst to obtain the stress-responsive high-temperature-resistant polyamide containing the spiro structure, the diamine containing the spiro structure does not show color development under the condition of not receiving stress, and when external force is applied, the spiro structure is damaged and changed in configuration, so that delocalized pi bonds connected with the spiro structure form a larger conjugated system to show color, and the polyamide material has the stress response characteristic. On the other hand, because of the rigidity of the spiral ring structure, the polyamide material also has better high temperature resistance, enlarges the use scene of the polyamide material, and is a new material with good application prospect.
Description
Technical Field
The invention belongs to the field of high-temperature resistant materials, and particularly relates to a stress response type high-temperature resistant polyamide material and a synthesis method thereof.
Background
The main chain of the polyamide material is composed of dibasic acid and diamine, the polyamide material has stable chemical structure and excellent mechanical property, and is widely applied to the fields of automobile industry, electronic industry, aerospace industry, daily consumer goods and the like. The development of the above-mentioned fields, especially the electronic industry, requires more and more intellectualization of the materials used, and it is expected that the materials used will react to external stimuli to make the materials "intelligent". The stress response is a widely applied material, and the material has corresponding feedback to external stress stimulation, such as color change, and can greatly improve the application of the material in the fields of bionics, light storage, display and the like.
The stress-responsive resins can be generally classified into two types, copolymer type and blend type. The blending type is to disperse the dye with stress response into the resin, and when the material deforms due to external force, the interaction force among the dyes is destroyed, so that the color of the material is changed. The copolymerization type is to introduce dye molecules with stress response into a resin molecular chain in a monomer form, and when the material deforms due to external force, the configuration of the dye molecules is changed, so that the color is changed.
The spiropyran-based stress-responsive polymeric materials reported by the Sottos group in 2009 (Nature, 2009, 459, 68-72) were stress-responsive resins that appeared earlier. The spiropyran is a non-conjugated molecule, and because the bond energy of a spiro C-O bond is weaker and can be broken under the action of external force to isomerize to form a structure of the merocyanin, the conjugated chain of the molecule is reformed to emit red fluorescence. In addition to spiropyrans, other mechanochromic groups have been reported to be spirothiopyrans (Angewandte Chemie International Edition, 2016, 55, 3040-. The method can conveniently endow the material with reversible change characteristics. CN109651587A discloses a polyurethane material containing a spiro structure, which can react to external stress to change color.
The molecular chain of the polyamide material does not contain a stress response group, so that the polyamide material does not have a stress response characteristic, and the application scene of the polyamide material is restricted; and the polyamide material has poor high temperature resistance and is difficult to use in extreme environments. Therefore, functionalization of polyamide materials is currently the main direction of research.
Disclosure of Invention
The invention aims to provide stress response type high temperature resistant polyamide and a synthesis method thereof, wherein a dibasic acid containing a spiro group is used as a reaction monomer, and a stress response structure is introduced into a polyamide main chain, so that the material has response to an external force and changes the color of the material. Meanwhile, the spiro group has a rigid structure, and can replace an aliphatic chain structure in polyamide, so that the high temperature resistance of the polyamide material is improved.
To achieve the above object, the stress-responsive high temperature resistant polyamide of the present invention comprises the following structure:
a structure (a) represented by the following general formula (A-I)
In the formula (A-I), R1Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (3).
A structure (b) represented by the following general formula (A-II)
In the formula (A-II), R2Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (3).
A structure (c) represented by the following general formula (A-III)
In the formula (A-III), R3And R4Same or different, each independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20One of the aromatic subunits of (a).
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20The aliphatic subunit of (a). Preferably substituted or unsubstituted, linear or branched, saturated or unsaturated C2-C15The aliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C2-C10The aliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C6-C10The aliphatic subunit of (a).
In a preferred embodiment, said R1、R2、R3、R4The same or different, are independently selected from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octyleneAnd one of the group consisting of a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group. One of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene is preferable. Further, one of hexylene, heptylene, octylene, nonylene and decylene is preferable.
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20The cycloaliphatic subunit of (a). Preferably substituted or unsubstituted, linear or branched, saturated or unsaturated C6-C10The cycloaliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C6The cycloaliphatic subunit of (a).
In a preferred embodiment, said R1、R2、R3、R4The same or different, are independently selected from cyclopropane subunit, cyclobutane subunit, cyclopentane subunit, cyclohexane subunit, cycloheptane subunit, cyclooctane subunit, cyclononane subunit, cyclodecane subunit. Cyclohexane subunits are preferred.
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted C6-C20The aromatic subunit of (3).
In a preferred embodiment, said R1、R2、R3、R4The same or different, independently selected from phenylene, methylphenyl, dimethylphenylene, trimethylphenylene, tetramethylphenylene, ethylphenylene, methylethylphenylene, diethylphenylene.
The invention also provides a synthesis method of the stress response type high temperature resistant polyamide, which is prepared by polycondensation of the following raw materials:
a compound (A) represented by the following general formula (B-I)
In the formula (B-I), R1Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (3).
A compound (B) represented by the following general formula (B-II)
H2N-R2、-NH2 (B-II)
In the formula (B-II), R2Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (3).
A compound (C) represented by the following general formula (B-III)
In the formula (B-III), R3And R4Same or different, each independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20One of the aromatic subunits of (a).
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20The aliphatic subunit of (a). Superior foodOptionally substituted or unsubstituted, linear or branched, saturated or unsaturated C2-C15The aliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C2-C10The aliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C6-C10The aliphatic subunit of (a).
In a preferred embodiment, said R1、R2、R3、R4The same or different, independently selected from one of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene. One of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene is preferable. Further, one of hexylene, heptylene, octylene, nonylene and decylene is preferable.
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20The cycloaliphatic subunit of (a). Preferably substituted or unsubstituted, linear or branched, saturated or unsaturated C6-C10The cycloaliphatic subunit of (a). Substituted or unsubstituted, linear or branched, saturated or unsaturated C6The cycloaliphatic subunit of (a).
In a preferred embodiment, said R1、R2、R3、R4The same or different, are independently selected from cyclopropane subunit, cyclobutane subunit, cyclopentane subunit, cyclohexane subunit, cycloheptane subunit, cyclooctane subunit, cyclononane subunit, cyclodecane subunit. Cyclohexane subunits are preferred.
In a preferred embodiment, said R1、R2、R3、R4Same or different, independently selected from substituted or unsubstituted C6-C20The aromatic subunit of (3).
In a preferred embodiment, said R1、R2、R3、R4The same or different, independently selected from phenylene, methylphenyl, dimethylphenylene, trimethylphenylene, tetramethylphenylene, ethylphenylene, methylethylphenylene, diethylphenylene.
The synthesis method of the stress response type high temperature resistant polyamide comprises the following steps.
S1, putting deionized water, a compound (A), a compound (B) and a compound (C) into a high-temperature high-pressure kettle, wherein the molar ratio of the compound (A) to the sum of the molar numbers of the compound (B) and the compound (C) is 1 (1.01-1.02). Adding a catalyst, sealing, replacing with a non-reactive gas, heating to 100-180 ℃, and reacting at constant temperature for a period of time. The molar ratio of the compound (B) to the compound (C) is 95: 5-5: 95, preferably 90: 10-50: 50, and more preferably 80: 20.
S2, heating the product obtained in the step S1 to 150-300 ℃, condensing for a period of time, dehydrating to obtain a prepolymer, draining water, relieving pressure, and cooling to obtain the prepolymer.
S3, transferring the prepolymer obtained in the step S2 to a vacuum drum reactor, sealing, replacing with non-reactive gas grease, keeping the pressure in the reactor at 10-1000 Pa, heating to 180-350 ℃, judging the reaction end point according to the viscosity, cooling and discharging to obtain the stress-responsive high-temperature-resistant polyamide.
In a preferred embodiment, the step S1 specifically includes:
s11, adding deionized water into a high-temperature high-pressure kettle, and adding a compound (A), a compound (B) and a compound (C), wherein the molar ratio of the compound (A) to the compound (B) to the compound (C) is 1 (1.01-1.02).
S12, adding a catalyst into the high-temperature high-pressure kettle. The catalyst is phosphorous acid, hypophosphite or hypophosphite; the hypophosphite is sodium hypophosphite or potassium hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite or calcium hypophosphite.
S13, sealing the high-temperature high-pressure autoclave, and then replacing the high-temperature high-pressure autoclave with non-reactive gas. The non-reactive gas is nitrogen, carbon dioxide, helium, argon, preferably nitrogen.
S14, heating the high-temperature autoclave to 100-180 ℃, preferably 120-160 ℃, and further preferably 140-150 ℃. The heating rate is 5-10 deg.C/min, such as 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min, preferably 5 deg.C/min.
S15, reacting at constant temperature for 5-60 min, preferably 10-60 min, further preferably 20-40 min, and further preferably 30 min.
Optionally, in step S12, an antioxidant, a surfactant, or other additives may be added to the mixture.
In a preferred embodiment, the step S2 specifically includes:
s21, gradually heating the product obtained in the step S1 to 150-300 ℃ under the action of a catalyst, and maintaining the dehydration reaction for 2-5 hours. Wherein the heating rate is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, preferably 2 deg.C/min. The reaction time is preferably 3 to 4 hours, and more preferably 4 hours.
And S22, after the dehydration reaction is finished, draining water to normal pressure, closing a drain valve, cooling to room temperature, and discharging to obtain the prepolymer.
In a preferred embodiment, the step S3 specifically includes:
s31, transferring the prepolymer obtained in the step S2 to a vacuum drum reactor, sealing, replacing with a non-reactive gas, and keeping the pressure in the reactor at 10-1000 Pa, preferably 10-100 Pa, and more preferably 10-50 Pa.
S32, heating the vacuum drum reactor to 180-350 ℃, preferably 200-300 ℃, and further preferably 240-260 ℃. The heating rate is 10-30 ℃/min, preferably 15-25 ℃/min, and further preferably 20 ℃/min. The rotating speed of the rotary drum is 5-15 rpm, preferably 5-10 rpm, and more preferably 10 rpm.
And S33, judging a reaction end point according to the viscosity of the product. Specifically, sampling is carried out at a sampling valve after the temperature reaches a set temperature, viscosity is measured, when the viscosity meets the requirement, the reaction end point is judged to be reached, and cooling and discharging are carried out to obtain the stress response type high temperature resistant polyamide. The viscosity is more than 2.0dl/g, preferably more than 2.1dl/g, more preferably more than 2.2dl/g, still more preferably more than 2.3 dl/g.
The stress-responsive high-temperature-resistant polyamide is synthesized by copolymerization of a compound C containing a spiro structure as a comonomer with dibasic acid and diamine, wherein the compound C has a stress response characteristic, can feed back external stress change and change the conformation of the compound C so as to change the color of the compound C, and the stress condition of the polyamide can be judged by changing the color of the polyamide; on the other hand, the compound C also has a rigid structure, and even if the compound C is copolymerized with aliphatic dibasic acid and aliphatic diamine, the heat resistance of the polyamide can be obviously improved, so that the use scene of the polyamide is expanded. The stress response type high temperature resistant polyamide provided by the invention can improve the high temperature resistance of polyamide and simultaneously has the stress response characteristic, and the use scene of the polyamide material is greatly expanded. The stress response type high temperature resistant polyamide material is a novel intelligent material, can be applied to the traditional fields of polyamide materials, such as automobile industry, electronic industry, aerospace industry, daily consumer goods and the like, can also be applied to the fields of bionics, optical storage, display and the like, and is a novel material with good application prospect.
Detailed Description
The following embodiments of the present invention are further described in conjunction with the detailed description, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein.
Before the present embodiments are further described, it is to be understood that the scope of the present invention includes, but is not limited to, the following specific embodiments. In general, the terminology used in the examples herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. The test methods in the following examples, in which specific conditions are not specified, are generally carried out under conventional conditions or conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Preparation example 1
Compound (C-1) was prepared according to the procedure described in example 1 of CN109651587A, said compound (C-1) having the structure described in formula (C-I):
the method comprises the following specific steps.
Phenolphthalein (10mmol) was dissolved in 40mL of ethanol, ethylenediamine (30mmol) was added to the above system, the system was refluxed and stirred for 24 hours, then the solvent was distilled off under reduced pressure, and the crude product was purified by silica gel chromatography (as a developing solvent, dichloromethane/methanol ═ 5/1) to obtain an intermediate product in 87% yield.
The intermediate (8mmol), anhydrous potassium carbonate, bromoethylamine (1.5mmol) were added to acetone as a solvent. The reaction system was stirred overnight at 90 ℃ after freezing, vacuum-pumping and nitrogen-feeding three times. The crude product was purified by silica gel column chromatography and the conjugate was discarded (eluent n-hexane/ethyl acetate of 1: 0 to 990: 10) to give compound (C) represented by formula C-I. The yield was 42%.1H NMR(400MHz，CDCl3) Information: 7.91(d,1H),7.58(m,1H),7.04-7.18(m,6H),6.86(d,2H),6.63(d,2H),5.34(s,1H),5.11(s,4H),4.28(t,2H),3.31-3.46(m,4H),2.99(t, 2H).
Example 1
The monomers of the stress-responsive high-temperature resistant polyamide described in this example are compound (a), compound (B) and compound (C). The compound (A) is adipic acid, the compound (B) is hexamethylenediamine, and the compound (C) is a compound (C-1) which has a structure shown in a formula (C-I) and is prepared by adopting the method shown in preparation example 1.
S1, putting deionized water, adipic acid, hexamethylene diamine and a compound (C-1) into a high-temperature autoclave, wherein the molar ratio of the adipic acid to the sum of the molar amounts of the hexamethylene diamine and the compound (C-1) is 1:1.01, and the molar ratio of the hexamethylene diamine to the compound (C-1) is 80: 20. Adding sodium hypophosphite, sealing, replacing with nitrogen gas for three times, heating to 150 deg.C, heating at 5 deg.C/min, and reacting at constant temperature under pressure for 30 min.
S2, heating the high-temperature high-pressure kettle to 250 ℃ at the speed of 2 ℃/min, carrying out dehydration reaction for 4h, draining water, releasing pressure to normal pressure, cooling, discharging and granulating to obtain the prepolymer.
S3, transferring the prepolymer into a vacuum drum reactor, sealing, replacing with nitrogen for three times, and keeping the pressure in the reactor at 50 Pa. The temperature is raised to 300 ℃ at the speed of 20 ℃/min, and the rotating speed of the rotary drum is 10 rpm. And sampling at a sampling valve after the temperature reaches a set temperature, measuring the viscosity, stopping the reaction when the viscosity reaches 2.0dl/g, cooling, and discharging to obtain the stress response type high-temperature resistant polyamide.
Example 2
Example 1 was repeated, except that the molar ratio of the hexamethylenediamine and the compound (C-1) was set to 90:10 on the basis of example 1, and the other conditions were not changed.
Example 3
Example 1 was repeated, except that the molar ratio of the hexamethylenediamine and the compound (C-1) was set to 95:5 on the basis of example 1, and the other conditions were not changed.
Example 4
Example 1 was repeated, except that on the basis of example 1 the adipic acid was replaced by a mixed acid of adipic acid and terephthalic acid in a molar ratio of 1:1, the other conditions being unchanged.
Example 5
Example 1 was repeated, except that the hexamethylenediamine was replaced by an equimolar amount of decamethylenediamine on the basis of example 1, and the other conditions were not changed.
Example 6
Example 1 was repeated, except that the hexamethylenediamine was replaced by an equimolar amount of dodecyldiamine on the basis of example 1, and the other conditions were not changed.
Comparative example 1
Example 1 was repeated, except that an equimolar amount of the compound (C-1) was replaced with hexamethylenediamine based on example 1, and the other conditions were not changed.
Comparative example 2
Example 1 was repeated, except that the compound (C-1) was replaced with p-phenylenediamine in an equimolar amount based on example 1, and other conditions were not changed.
In the viscosity testing method, concentrated sulfuric acid is used as a solvent, and the intrinsic viscosity is measured by adopting an extrapolation method.
The melting point is measured by a DCS method, the temperature range is 30-360 ℃, the heating rate is 10 ℃/min, and the protective gas is nitrogen.
The tensile strength and elongation at break tests described in the present invention were performed using conventional spline testing methods. The sample strip is a standard sample strip and is formed by injection molding of the stress response type high-temperature resistant polyamide.
TABLE 1 respective Properties of stress-responsive high-temperature resistant polyamides synthesized in examples and comparative examples
The stress-responsive high-temperature resistant polyamide injection-molded sample bars in the examples 1 to 6 are white under the condition of no external force, and are changed from white to light purple in the stretching process, so that the stress-responsive high-temperature resistant polyamide material has the stress response characteristic and can perform color feedback on the external force.
The stress-responsive high-temperature resistant polyamide described in example 1 was melt-spun into a fiber at a spinning temperature of 330 ℃, a spinneret size of 2mm x 20, a spinning speed of 200m/min, and a draw ratio of 2.5. The resulting fibers appeared white and elastic, and a sample of the fibers was stretched, and it was seen that the fibers changed from white to light purple in the stretching process. When the external force is removed, the deformation is recovered, the color of the fiber is slowly lightened from light purple, and finally the fiber is changed into white. The foregoing phenomenon was still observed upon further stretching of the fiber sample.
The stress response type high temperature resistant polyamide provided by the invention adopts the compound C as a comonomer, and is copolymerized with common dibasic acid and diamine monomers in a polyamide synthesis process, so that the main chain of the product has a spiral structure. The compound C has a spiro structure, so that the whole material has no color, when an external force is applied to the stress-responsive high-temperature-resistant polyamide material, the material deforms, the spiro structure of the compound C is destroyed, the configuration is changed, and a larger conjugated system is formed by the delocalized pi bond connected with the compound C, so that the color is displayed. The examples 1-6 of the invention prove that the stress response type high temperature resistant polyamide containing the compound C structure has the stress response characteristic and can generate color change to external force. When the compound is replaced by common diamine or aromatic amine which can also increase the high-temperature resistance of polyamide, the obtained polyamide material has no stress response characteristic.
Meanwhile, the structural unit of the compound C in the stress response type high temperature resistant polyamide also has higher rigidity, so that the heat resistance of the polyamide can be effectively improved, the compound C added into the aliphatic polyamide can have the same heat resistance as the aliphatic high temperature resistant polyamide, and the use scene of the polyamide is expanded.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (16)
1. A stress response type high temperature resistant polyamide is characterized by comprising the following structure:
a structure (a) represented by the following general formula (A-I)
In the formula (A-I), R1Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (a);
a structure (b) represented by the following general formula (A-II)
In the formula (A-II), R2Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (a);
a structure (c) represented by the following general formula (A-III)
In the formula (A-III), R3And R4Same or different, each independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A cycloaliphatic subunit ofSubstituted or unsubstituted C6-C20One of the aromatic subunits of (a).
2. The stress-responsive, high temperature resistant polyamide of claim 1, wherein R is1、R2、R3、R4The same or different, independently selected from one of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene.
3. The stress-responsive, high temperature resistant polyamide of claim 2, wherein R is1、R2、R3、R4The same or different, and is independently selected from one of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene.
4. The stress-responsive, high temperature resistant polyamide of claim 2, wherein R is1、R2、R3、R4The same or different, is independently selected from one of hexylene, heptylene, octylene, nonylene and decylene.
5. The stress-responsive, high temperature resistant polyamide of claim 1, wherein R is1、R2、R3、R4The same or different, are independently selected from cyclopropane subunit, cyclobutane subunit, cyclopentane subunit, cyclohexane subunit, cycloheptane subunit, cyclooctane subunit, cyclononane subunit, cyclodecane subunit.
6. The stress-responsive, high temperature resistant polyamide of claim 1, wherein R is1、R2、R3、R4The same or different, are independently selected from phenylene, methylphenyl, dimethylphenylene, trimethylphenylene, tetramethylphenyleneAnd one of a phenylene group, an ethylphenylene group, a methylethylphenylene group, and a diethylphenylene group.
7. The synthesis method of the stress-response high-temperature-resistant polyamide as claimed in claim 1, wherein the stress-response high-temperature-resistant polyamide is prepared by polycondensation of the following raw materials:
a compound (A) represented by the following general formula (B-I)
In the formula (B-I), R1Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (a);
a compound (B) represented by the following general formula (B-II)
H2N-R2-NH2 (B-II)
In the formula (B-II), R2Selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted, linear or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20The aromatic subunit of (a);
a compound (C) represented by the following general formula (B-III)
In the formula (B-III), R3And R4Same or different, each independently selected from substituted or unsubstituted, linear or branched, saturated or unsaturated C1-C20Substituted or unsubstituted aliphatic subunit ofStraight or branched, saturated or unsaturated C3-C20A substituted or unsubstituted C6-C20One of the aromatic subunits of (a).
8. The method for synthesizing the stress-responsive high-temperature resistant polyamide according to claim 7, comprising the steps of:
s1, putting deionized water, a compound (A), a compound (B) and a compound (C) into a high-temperature high-pressure kettle, wherein the molar ratio of the compound (A) to the sum of the molar numbers of the compound (B) and the compound (C) is 1 (1.01-1.02); adding a catalyst, sealing, replacing with a non-reactive gas, heating to 100-180 ℃, and reacting at constant temperature for a period of time; the molar ratio of the compound (B) to the compound (C) is 95: 5-5: 95;
s2, heating the product obtained in the step S1 to 150-300 ℃, condensing for a period of time, dehydrating to obtain a prepolymer, draining water, relieving pressure, and cooling to obtain the prepolymer;
s3, transferring the prepolymer obtained in the step S2 to a vacuum drum reactor, sealing, replacing with non-reactive gas grease, keeping the pressure in the reactor at 10-1000 Pa, heating to 180-350 ℃, judging the reaction end point according to the viscosity, cooling and discharging to obtain the stress-responsive high-temperature-resistant polyamide.
9. The method for synthesizing the stress-responsive high-temperature-resistant polyamide according to claim 8, wherein the molar ratio of the compound (B) to the compound (C) in the step S1 is 90:10 to 50: 50.
10. The method for synthesizing a stress-responsive high-temperature-resistant polyamide according to claim 8, wherein the molar ratio of the compound (B) to the compound (C) in the step S1 is 80: 20.
11. The method for synthesizing the stress-responsive high-temperature resistant polyamide according to claim 8, wherein the step S1 includes:
s11, adding deionized water into a high-temperature high-pressure kettle, and adding a compound (A), a compound (B) and a compound (C), wherein the molar ratio of the compound (A) to the compound (B) to the compound (C) is 1 (1.01-1.02);
s12, adding a catalyst into the high-temperature high-pressure kettle; the catalyst is phosphorous acid, hypophosphite or hypophosphite; the hypophosphite is sodium hypophosphite or potassium hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite or calcium hypophosphite;
s13, sealing the high-temperature high-pressure kettle, and replacing with non-reactive gas; the non-reactive gas is nitrogen, carbon dioxide, helium or argon, preferably nitrogen;
s14, heating the high-temperature autoclave to 100-180 ℃; the heating rate is 5-10 ℃/min;
s15, reacting at constant temperature for 5-60 min;
optionally, an antioxidant, a surfactant adjuvant, is added to the mixture in step S12.
12. The method for synthesizing the stress-responsive high-temperature-resistant polyamide according to claim 11, wherein the temperature rise in the step S14 is 140-150 ℃.
13. The method for synthesizing the stress-responsive high-temperature-resistant polyamide according to claim 11, wherein the temperature rise rate in step S14 is 5 ℃/min.
14. The method for synthesizing the stress-responsive high-temperature resistant polyamide according to claim 8, wherein the step S2 includes:
s21, gradually heating the product obtained in the step S1 to 150-300 ℃ under the action of a catalyst, and maintaining the dehydration reaction for 2-5 hours; wherein the heating rate is 1-5 ℃/min; the reaction time is preferably 3-4 h;
and S22, after the dehydration reaction is finished, draining water to normal pressure, closing a drain valve, cooling to room temperature, and discharging to obtain the prepolymer.
15. The method for synthesizing the stress-responsive high-temperature resistant polyamide according to claim 8, wherein the step S3 includes:
s31, transferring the prepolymer obtained in the step S2 to a vacuum drum reactor, sealing, replacing with non-reactive gas, and keeping the pressure in the reactor at 10-1000 Pa;
s32, heating the vacuum drum reactor to 180-350 ℃; the heating rate is 10-30 ℃/min; the rotating speed of the rotary drum is 5-15 rpm;
s33, judging a reaction end point according to the viscosity of the product; specifically, sampling is carried out at a sampling valve after the temperature reaches a set temperature, viscosity is measured, when the viscosity meets the requirement, the reaction end point is judged to be reached, and cooling and discharging are carried out to obtain the stress response type high temperature resistant polyamide; the viscosity is greater than 2.0 dl/g.
16. The application of the stress-responsive high-temperature-resistant polyamide as the intelligent material as claimed in any one of claims 1 to 6, wherein the stress-responsive high-temperature-resistant polyamide can change color in response to external stress change.
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