CN109485846B - Photochromic self-repairing intelligent nylon 6 and preparation method thereof - Google Patents
Photochromic self-repairing intelligent nylon 6 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses photochromic self-repairing intelligent nylon 6 and a preparation method thereof, belonging to the technical field of intelligent materials. According to the invention, the ureido pyrimidone structure and the spiropyran ring structure are introduced into a nylon 6 macromolecular chain, the color of the nylon material can be reversibly changed by utilizing the breakage and reconstruction of the spiropyran ring, and quadruple hydrogen bonds are easily reversibly formed among the ureido pyrimidone molecular structures so as to realize self-repairing of the nylon 6 material during degradation. The preparation method designed by the invention is easy to operate, short in reaction time, simple in post-treatment and high in yield, and the prepared nylon material has a long service life, can show color change under different illumination, and has a wide application prospect in the field of photochromic materials.
Description
Technical Field
The invention relates to a nylon material, belongs to the technical field of intelligent materials, and particularly relates to photochromic self-repairing intelligent nylon 6 and a preparation method thereof.
Background
Polyamide (nylon) as one of five engineering plastics has the characteristics of high tensile strength, large elastic modulus, excellent wear resistance, excellent self-lubricating property and the like, and therefore, the polyamide (nylon) is widely applied to the industries such as automobile manufacturing industry, electronic and electrical industry, mechanical equipment, packaging and the like. However, when the nylon material is applied to the mechanical industry as a structural member, the alternating stress applied to the nylon material during the use process easily causes fatigue cracks in the nylon material and leads to early failure of the material, thereby shortening the service life of the nylon material. In addition, when fatigue cracks are generated in the nylon material, the micro-changes in the nylon material cannot be visually displayed to a user by the conventional nylon material, so that an early warning effect is exerted. Therefore, a novel nylon material is developed, so that the nylon material has the functions of resisting fatigue crack propagation and self-warning, is very important for prolonging the service life of nylon and reducing the accident risk caused by structural part damage, and has a wide application market.
At present, the high molecular self-repairing material is widely concerned, and the importance of the high molecular self-repairing material is that the service life of the material can be prolonged, the material can be repaired in the using process of the material, and particularly, the material is required to have the self-repairing function in places inaccessible to people, such as space stations or severe conditions, corrosive and radiation environments. The early self-repairing high polymer materials mainly focus on microcapsules and microtubules to break and initiate repolymerization to realize external aid type repair of damage, for example, Chinese invention patent application (application publication No. CN103594559A, application publication No. 2014-02-19) discloses a preparation method of a self-repairing solar cell back film, the application discloses that an epoxy resin adhesive is preferably selected, terminal amino in a nylon molecular structure is used as a curing agent in epoxy resin, when a nylon back plate is subjected to external acting force, the self-repairing agent (microcapsule product) pre-embedded in the back plate can quickly release a core, the epoxy resin and the nylon terminal amino in the nylon back plate react, curing and crosslinking are performed, and cracks caused by the external force can be quickly repaired to obtain higher performance.
However, this self-healing property is usually achieved only twice, and the damage cannot be repaired repeatedly. However, the polymer material has an adjustable chemical structure, and the chain segment structure of the polymer material is designed by controlling the polymerization process, so that the regulation and control of the material performance can be easily realized.
In the development process of the intrinsic self-repairing polymer, hydrogen bonds play an important role, have reversibility, cooperativity and dynamic characteristics, can realize mutual conversion of fracture-recombination in the polymer, and further resist the expansion of microcracks, wherein hydrogen bond type self-repairing polymers which are invented by Netherlands scientist Meijer and the like and take 2-urea-4-pyrimidone derivatives (UPy) as end groups are commercialized (produced by SuperaPolix company, and the trade name is SuperB), UPy self-supplementation can form quadruple hydrogen bond dimers, UPy base hydrogen bonds are destroyed during heating and formed during cooling, and the hydrogen bond type self-repairing polymers have reversibility. The self-healing behavior of the UPy-based hydrogen bond type supramolecular polymer depends on that the polymer is in a liquid state at high temperature, can fill cracks, and is in a solid state at room temperature to realize self-healing.
For example, Chinese patent application (application publication No. CN106221100A, application publication date: 2016-12-14) discloses a preparation method of a light-driven self-repairing film based on ethylene-butylene copolymer, which comprises the steps of synthesizing UPy-NCO by 2-amino-4-hydroxy-6-methylpyrimidine and hexamethylene diisocyanate, then reacting the product with poly (ethylene-butylene) and 4' -bis (hydroxymethyl) azobenzene, and compounding the two materials to obtain a block copolymer capable of self-repairing under ultraviolet illumination; for another example, the Chinese invention patent application (application publication No. CN107325256A, application publication date: 2017-11-07) discloses a self-repairing polymer material and a preparation method thereof, wherein the preparation method of the application discloses that firstly, an ureido pyrimidone type end-capping agent or chain extender is prepared, and then the random copolymerization reaction of oligomer dihydric alcohol, the chain extender and first diisocyanate is utilized to prepare the polymer material which can be rapidly self-repaired at low temperature and has quadruple hydrogen bond groups at side chains and end groups. Compared with the traditional self-repairing material, the self-repairing material can realize repeated self-repairing at the same position at a lower temperature without adding a repairing agent at a damaged part, and has the advantages of high repairing capability, good mechanical property, good film forming property and transparency of the material, simple process and low cost.
The photochromic polymer material is an 'intelligent' material which can generate performance change along with the change of a light source, and plays an important role in the fields of military camouflage, protective materials, daily necessities, special photosensitive materials, information storage materials, packaging materials and the like. Spiropyrans are a good photo-responsive group and have a photochromic effect. By the design of a molecular structure, the spiropyran is grafted in a polymer chain skeleton to prepare the photoresponsive polymer material.
However, at present, no report is made on introducing a spiropyran structure and a ureido pyrimidinone structure (UPy) into a nylon polymer chain to produce and prepare a polymer material which can show color change under different illuminations and can generate self-repair on the performance degradation of the material so as to delay the aging of the material.
Disclosure of Invention
In order to solve the technical problems, the invention discloses photochromic self-repairing intelligent nylon 6 with photochromic function and self-repairing capability and a preparation method thereof.
In order to achieve the purpose, the invention discloses a photochromic self-repairing intelligent nylon 6, wherein the intelligent nylon 6 can change color when the material is irradiated by different light sources, and can delay the performance degradation of the material through self-repairing, the molecular chain of the intelligent nylon 6 comprises a ureido pyrimidone derivative and a spiropyran derivative, the molecular structural formula of the ureido pyrimidone derivative is shown as the following formula A, and the molecular structural formula of the spiropyran derivative is shown as the following formula B:
the specific preparation process of the ureido pyrimidone derivative shown in the formula A is as follows:
the reagents numbered 1 and 2 in the synthetic route are all the alatin reagents, and the CAS numbers of the reagents are 517-23-7 and 593-85-1 respectively.
And the spiropyran derivative represented by formula B is also an Aladdin reagent (CAS 16111-07-2).
Further, the molecular structural formula of the smart nylon 6 is shown as the following formula I:
further, R is one of hexamethylene, diphenylmethane and methane phenyl, and the molecular structural formula is shown as formula a, formula b and formula c:
formula a:
formula b:
formula c:
therefore, the photochromic self-repairing intelligent nylon 6 disclosed by the invention comprises the following molecular structural formulas:
in order to better realize the technical purpose of the invention, the invention also discloses a preparation method of the photochromic self-repairing intelligent nylon 6, which comprises the following preparation steps:
1) reacting the ureido pyrimidone derivative with diisocyanate to prepare diisocyanate containing a ureido pyrimidone structure, wherein the molecular structural formula is shown as the following formula I-a;
2) under the action of a catalyst, reacting a spiropyran derivative with the formula I-a in the step 1) to prepare a substance containing ureidopyrimidone and a spiropyran structure, wherein the molecular structural formula is shown as the following formula I-b;
3) hydrolyzing caprolactam to obtain terminal amino polycaprolactam, wherein the molecular structural formula is shown as the following formula I-c;
4) reacting the formula I-c and the formula I-b in the step 3) to prepare the photochromic self-repairing intelligent nylon 6, wherein the molecular structural formula of the photochromic self-repairing intelligent nylon 6 is shown as the formula I;
further, the specific reaction process of the step 1) is as follows:
mixing the pyrimidone derivative with diisocyanate according to the mass ratio of 1 (2.05-2.1), and reacting at 70 ℃ for 12h under the protection of a catalyst and inert gas to obtain the diisocyanate containing the ureido pyrimidone structure.
Preferably, the mass ratio between the pyrimidone derivative and the diisocyanate is 1: 2.05.
preferably, the mass ratio between the pyrimidone derivative and the diisocyanate is 1: 2.07.
preferably, the mass ratio between the pyrimidone derivative and the diisocyanate is 1: 2.1.
further, the amount of the catalyst (amount of substance) used in the step 1) is 0.1-0.5 mol% of the diisocyanate.
Preferably, the catalyst dibutyltin dilaurate used in step 1) is 0.3 mol% of the diisocyanate.
Preferably, step 1) and step 2) are both reacted under a nitrogen protective atmosphere.
Further, in the step 2), the mass ratio of the spiropyran derivative to the substance shown in the formula I-a is 1 (5.05-5.1), the reaction temperature is 25 ℃, and the reaction time is 1 h.
Preferably, the ratio of the amount of spiropyran derivative to substance of formula I-a is 1: 5.05.
Preferably, the ratio of the amount of spiropyran derivative to substance of formula I-a is 1: 5.06.
Preferably, the ratio of the amount of spiropyran derivative to substance of formula I-a is 1: 5.07.
Preferably, the ratio of the amount of spiropyran derivative to substance of formula I-a is 1: 5.08.
Preferably, the amount ratio of the spiropyran derivative to the substance of formula I-a is 1: 5.09.
Preferably, the ratio of the amount of spiropyran derivative to substance of formula I-a is 1: 5.1.
Further, the amount of the catalyst (the amount of the substance) used in the step 2) is 0.1-0.5 mol% of the formula I-a.
Preferably, the amount of dibutyltin dilaurate used as the catalyst in step 2) is 0.3 mol% based on formula I-a.
Further, the specific reaction process of the step 4) is as follows: when the formula I-c is in a molten state, adding the product I-b obtained in the step 2) into the molten product, reacting until all solid substances disappear, obtaining the target product photochromic self-repairing intelligent nylon 6, and testing the photochromic and self-repairing performance of the target product.
Preferably, the reaction temperature of the step 4) is 190-250 ℃.
Further, in the step 3), the molecular weight of the formula I-c is 15000-50000 g/mol, the molecular weight is too large, the content of the end group is relatively low, and the reaction efficiency of the end group and the color change and self-repair capability of the later-stage material are influenced.
Preferably, the molecular weight of formula I-c is 15000, 17000, 20000, 35000, 40000, 45000 or 50000 g/mol.
Preferably, the hydrolysis process of step 3) is specifically:
caprolactam is used as a raw material, deionized water is used as a hydrolytic agent, concentrated phosphoric acid is used as a catalyst, wherein the amount of the deionized water is controlled to be 1-2 wt% of the caprolactam, the amount of the concentrated phosphoric acid is controlled to be 1-2 wt% of the caprolactam, and the temperature of the whole reaction system is controlled to be 220-300 ℃ after the whole reaction system is vacuumized.
The intelligent nylon 6 prepared by the invention has the self-repairing principle as follows:
the invention utilizes the process of forming quadruple hydrogen bonds between 2 ureido pyrimidone molecular structures to realize the self-repair of the nylon 6 material, on one hand, when the nylon 6 is greatly acted by the outside or the mechanical property of the nylon material is damaged due to long-term illumination, the internal quadruple hydrogen bonds are broken to cause obvious cracks on the surface of the material, and the internal quadruple hydrogen bonds can be formed again after the external acting force disappears or the illumination disappears, thereby avoiding the further expansion of external microcracks caused by external force or illumination and improving the service life of the nylon 6 material, on the other hand, the nylon 6 material increases the interaction force between polymer chains and the chains due to the formation of a plurality of quadruple hydrogen bonds inside the nylon 6 material, improves the mechanical property of the nylon 6, wherein, the quadruple hydrogen bonding force formed among 2 ureido pyrimidone molecular structures is shown as the following formula II (taking the formula I-1 as an example):
the principle that the intelligent nylon 6 prepared by the invention has photochromic function is as follows:
the spiropyran ring is introduced into a molecule of the nylon 6 material, the surface of the spiropyran ring can generate color change under the condition of light breakage, and reversible color change is generated on the surface of the nylon 6 material when the light disappears, wherein the photochromic process of the spiropyran ring is shown as the following formula III:
the beneficial effects of the invention are mainly embodied in the following aspects:
1. the preparation method designed by the invention is easy to operate, short in reaction time, simple in post-treatment and high in yield;
2. the intelligent nylon 6 designed by the invention can firstly change color under the illumination condition so as to enrich the practicability of the material, and meanwhile, the invention introduces the color-changing spiropyran ring into the macromolecular chain of the nylon material, which is different from the prior art that introduces the color-changing powder, so that the durability of the color-changing performance is improved;
3. when the mechanical property of the material is damaged and the surface of the material cracks due to long-term illumination, reversible fracture and recombination of quadruple hydrogen bonds in a macromolecular chain of the nylon material can realize the repair of microcracks in the material and the surface cracks of the material, thereby ensuring that the nylon material has longer service life. Therefore, the nylon material prepared by the invention has sensitive color-changing performance and self-repairing performance, and has important application value in the fields of functional garment materials, military camouflage, package anti-counterfeiting, information storage and the like;
4. the intelligent nylon 6 material designed by the invention introduces the ureido pyrimidone structure which can form a plurality of intramolecular or intermolecular hydrogen bonds into a macromolecular chain, thereby further enhancing the stress capability of the material.
Drawings
FIG. 1 is a HNMR map of a compound of formula A, an intermediate product prepared in example 1 of the present invention;
FIG. 2 is a DSC curve of the compound of formula I-1 prepared in example 1 of the present invention.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
1) 1.50g of pyrimidone derivative, 3.1g of hexamethylene diisocyanate and 12mg of dibutyltin dilaurate were weighed and reacted at 70 ℃ for 12 hours in a nitrogen atmosphere to obtain 4.1g of diisocyanate containing a ureido pyrimidone structure.
The pyrimidone derivative adopted in this embodiment is a structural formula shown in formula a of the specification and a specific synthetic route disclosed in the specification, and fig. 1 in the drawing of the specification gives a data characterization map thereof, and it can be known from fig. 1 that various hydrogen atoms in the molecular structural formula shown in formula a are correspondingly characterized on the map, which also indicates that the pyrimidone derivative of this embodiment is prepared by using the synthetic route of the specification.
2) 0.57g of spiropyran derivative, 4.1g of diisocyanate containing a ureido pyrimidone structure, 5.1mg of dibutyltin dilaurate and 10ml of nitrogen-nitrogen dimethylformamide are weighed, the reaction temperature is 25 ℃, and after 1 hour of reaction, the product is purified to be 3.9 g.
3) Weighing 40g of caprolactam, 0.44g of deionized water and 0.4g of concentrated phosphoric acid (85 wt%), adding the caprolactam into a three-neck flask, introducing nitrogen to remove oxygen in the system, heating to 250 ℃, changing a condensing device into a vacuumizing device after reacting for 3 hours, closing the nitrogen, vacuumizing for 10 minutes at 250 ℃ and at a rotating speed of 250r/min, wherein the melt in the three-neck flask has obvious rod climbing phenomenon and is transparent, bubbles are few, vacuumizing is finished, and then introducing nitrogen into the system to obtain the molten nylon 6.
4) Adding the product obtained in the step 2) into the nylon 6 (with the molecular weight of 16000g/mol) in the molten state obtained in the step 3), reacting for 0.5h to obtain the photosensitive color-changing self-repairing nylon 6, and then measuring the self-repairing and color-changing performances of the photosensitive color-changing self-repairing nylon 6;
the characterization data of the photochromic self-repairing nylon 6 prepared in the above way is shown in fig. 2, and it can be known from fig. 2 that the target product is obtained in the preparation of this embodiment.
Example 2
1) 1.80g of pyrimidone derivative, 3.7g of hexamethylene diisocyanate and 16.7mg of dibutyltin dilaurate were weighed and reacted at 70 ℃ for 12 hours in a nitrogen atmosphere to obtain 4.9g of diisocyanate containing a ureido pyrimidone structure.
2) 0.67g of spiropyran derivative, 4.9g of diisocyanate containing a ureido pyrimidone structure, 7.3mg of dibutyltin dilaurate and 12ml of nitrogen-nitrogen dimethylformamide are weighed, the reaction temperature is 25 ℃, and after 1 hour of reaction, the product is purified to be 4.5 g.
3) Weighing 40g of caprolactam, 0.44g of deionized water and 0.4g of concentrated phosphoric acid (85 wt%), adding the caprolactam into a three-neck flask, introducing nitrogen to remove oxygen in the system, heating to 250 ℃, changing a condensing device into a vacuumizing device after reacting for 3 hours, closing the nitrogen, vacuumizing for 10 minutes at 250 ℃ and at a rotating speed of 250r/min, wherein the melt in the three-neck flask has obvious rod climbing phenomenon and is transparent, bubbles are few, vacuumizing is finished, and then introducing nitrogen into the system to obtain the molten nylon 6.
4) Adding the product obtained in the step 2) into the molten nylon 6 (with the molecular weight of 16200g/mol) obtained in the step 3), reacting for 0.5h to obtain the photochromic self-repairing nylon 6, and then measuring the self-repairing and color-changing performances of the photochromic self-repairing nylon 6.
Example 3
1) Weighing 2.0g of pyrimidone derivative, 4.1g of hexamethylene diisocyanate and 20mg of dibutyltin dilaurate, and reacting at 70 ℃ for 12h in a nitrogen atmosphere to obtain 5.4g of diisocyanate containing a ureido pyrimidone structure.
2) 0.75g of spiropyran derivative, 5.4g of diisocyanate containing a ureido pyrimidone structure, 8.8mg of dibutyltin dilaurate and 14ml of nitrogen-nitrogen dimethylformamide are weighed, the reaction temperature is 25 ℃, and after 1 hour of reaction, the product is purified to be 5.1 g.
3) Weighing 40g of caprolactam, 0.44g of deionized water and 0.4g of concentrated phosphoric acid (85 wt%), adding the caprolactam into a three-neck flask, introducing nitrogen to remove oxygen in the system, heating to 250 ℃, changing a condensing device into a vacuumizing device after reacting for 3 hours, closing the nitrogen, vacuumizing for 10 minutes at 250 ℃ and at a rotating speed of 250r/min, wherein the melt in the three-neck flask has obvious rod climbing phenomenon and is transparent, bubbles are few, vacuumizing is finished, and then introducing nitrogen into the system to obtain the molten nylon 6.
4) Adding the product obtained in the step 2) into the molten nylon 6 (with the molecular weight of 16500g/mol) obtained in the step 3), reacting for 0.5h to obtain the photochromic self-repairing nylon 6, and then measuring the self-repairing and color-changing performances of the photochromic self-repairing nylon 6.
Example 4
1) Weighing 2.0g of pyrimidone derivative, 4.1g of hexamethylene diisocyanate and 20.0mg of dibutyltin dilaurate, and reacting at 70 ℃ for 12h in a nitrogen atmosphere to obtain 5.4g of diisocyanate containing a ureido pyrimidone structure.
2) 0.74g of spiropyran derivative, 5.4g of diisocyanate containing a ureido pyrimidone structure, 8.8mg of dibutyltin dilaurate and 12ml of nitrogen-nitrogen dimethylformamide are weighed, the reaction temperature is 25 ℃, and after 1 hour of reaction, the product is purified to be 5.2 g.
3) Weighing 40g of caprolactam, 0.5g of deionized water and 0.4g of concentrated phosphoric acid (85 wt%), adding the caprolactam into a three-neck flask, introducing nitrogen to remove oxygen in the system, heating to 250 ℃, changing a condensing device into a vacuumizing device after reacting for 3 hours, closing the nitrogen, vacuumizing for 10 minutes at 250 ℃ and at a rotating speed of 250r/min, wherein the melt in the three-neck flask has obvious rod climbing phenomenon and is transparent, bubbles are few, vacuumizing is finished, and then introducing nitrogen into the system to obtain the molten nylon 6.
4) Adding the product obtained in the step 2) into the molten nylon 6 (with the molecular weight of 16800g/mol) obtained in the step 3), reacting for 0.5h to obtain the photochromic self-repairing nylon 6, and then measuring the self-repairing and color-changing performances of the photochromic self-repairing nylon 6.
Among them, the above examples use hexamethylene diisocyanate as a chain extender, and the present invention can also use diphenylmethane diisocyanate and methane phenyl diisocyanate as chain extenders, and the preparation process and principle are similar to those of the examples, so the present invention is not exemplified.
The performance test method of the photochromic self-repairing nylon 6 obtained in the above embodiments 1 to 4 is as follows:
processing the photochromic self-repairing nylon 6 into a dumbbell standard sample bar, bending the sample bar for 100 times, testing the retention rate of the tensile strength of the sample bar, and comparing the retention rate with the retention rate of the tensile strength of the nylon material (comparative example) obtained in the step 3) of bending treatment under the same condition. In addition, scratches with the depth of less than or equal to 0.2mm are engraved on the surfaces of the photochromic nylon and the nylon material obtained in the step 3), then the scratches are subjected to illumination heating treatment by an infrared lamp at room temperature, and the scratch depth change is observed after 12 hours. The performance results are shown in table 1.
TABLE 1 list of photochromic nylon 6 and comparative examples
| Test items | Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 |
| Retention of tensile strength | 75％ | 80％ | 82％ | 83％ | 86％ |
| Variation of depth of scratch | Slightly shallow | Slightly shallow | Become shallow | Become shallow | Disappearance of scratch |
As can be seen from table 1, the mechanical properties of the modified nylon 6 of the present invention are enhanced to some extent, and the color of the modified nylon 6 can be changed from purple to light yellow after being irradiated by sunlight. When the sample is placed indoors away from the sunlight, the color of the sample can change back to purple. Therefore, the material prepared by the invention can be applied to the technical fields of photochromic functional materials and the like, such as photochromic nylon fibers and textiles, and the durability of the photochromic function is improved because the photochromic group is bonded in the high molecular chain segment through a covalent bond. In addition, the existence of the self-repairing functional group is beneficial to delaying the deterioration of the mechanical property of the photochromic nylon material caused by illumination and improving the service life of the material.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (6)
1. The utility model provides a photochromic selfreparing intelligence nylon 6 which characterized in that: the intelligent nylon 6 generates reversible color change under different illumination and realizes self-repairing of the material when the material is degraded, a molecular chain of the intelligent nylon 6 comprises derivatives with ureido pyrimidone structures and spiropyran structures, the molecular structural formula of the ureido pyrimidone derivatives is shown as a formula A, and the molecular structural formula of the spiropyran derivatives is shown as a formula B:
wherein, the molecular structural formula of the intelligent nylon 6 is shown as the following formula I:
and R in the formula I is one of hexamethylene, diphenylmethane or tolyl;
and the photochromic self-repairing intelligent nylon 6 comprises the following preparation steps:
1) reacting the ureido pyrimidone derivative with diisocyanate to prepare diisocyanate containing a ureido pyrimidone structure, wherein the molecular structural formula is shown as the following formula I-a;
2) under the action of a catalyst, reacting a spiropyran derivative with the formula I-a in the step 1) to prepare a substance containing ureidopyrimidone and a spiropyran structure, wherein the molecular structural formula is shown as the following formula I-b;
3) hydrolyzing caprolactam to obtain terminal amino polycaprolactam, wherein the molecular structural formula is shown as the following formula I-c;
in the step 3), the molecular weight of the formula I-c is 15000-50000 g/mol;
4) and (3) reacting the formula I-c in the step 3) with the formula I-b in the step 2) to prepare the photochromic self-repairing intelligent nylon 6.
2. A preparation method of the photochromic self-repairing intelligent nylon 6 as claimed in claim 1, which is characterized in that: the preparation method comprises the following preparation steps:
1) reacting the ureido pyrimidone derivative with diisocyanate to prepare diisocyanate containing a ureido pyrimidone structure, wherein the molecular structural formula is shown as the following formula I-a;
2) under the action of a catalyst, reacting a spiropyran derivative with the formula I-a in the step 1) to prepare a substance containing ureidopyrimidone and a spiropyran structure, wherein the molecular structural formula is shown as the following formula I-b;
3) hydrolyzing caprolactam to obtain terminal amino polycaprolactam, wherein the molecular structural formula is shown as the following formula I-c;
in the step 3), the molecular weight of the formula I-c is 15000-50000 g/mol;
4) and (3) reacting the formula I-c in the step 3) with the formula I-b in the step 2) to prepare the photochromic self-repairing intelligent nylon 6.
3. The preparation method of the photochromic self-repairing smart nylon 6 as claimed in claim 2, wherein the preparation method comprises the following steps: the specific reaction process of the step 1) is as follows:
mixing the ureido pyrimidone derivative with diisocyanate according to the mass ratio of 1 (2.05-2.1), and reacting for 12h at 70 ℃ in the presence of a catalyst and under the protection of inert gas to obtain the diisocyanate containing the ureido pyrimidone structure.
4. The preparation method of the photochromic self-repairing smart nylon 6 as claimed in claim 2 or 3, wherein the preparation method comprises the following steps: the catalyst is dibutyltin dilaurate.
5. The preparation method of the photochromic self-repairing smart nylon 6 as claimed in claim 2 or 3, wherein the preparation method comprises the following steps: in the step 2), the mass ratio of the spiropyran derivative to the substance shown in the formula I-a is 1 (5.05-5.1), the reaction temperature is 25 ℃, and the reaction time is 1 h.
6. The preparation method of the photochromic self-repairing smart nylon 6 as claimed in claim 5, wherein the preparation method comprises the following steps: the specific reaction process of the step 4) is as follows: when the formula I-c is in a molten state, adding the product I-b obtained in the step 2) into the molten state, and reacting until all solid substances disappear to obtain the target product photochromic self-repairing intelligent nylon 6.
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| WO2012068573A2 (en) * | 2010-11-19 | 2012-05-24 | Henkel Corporation | Adhesive compositions and use thereof |
| US9708199B2 (en) * | 2011-09-28 | 2017-07-18 | King Abdullah University Of Science And Technology | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
| CN105017698B (en) * | 2015-06-11 | 2017-06-30 | 付国东 | A kind of photothermal response type intelligent power saving composite membrane |
| CN107033535A (en) * | 2017-03-20 | 2017-08-11 | 浙江森之物工艺品有限责任公司 | A kind of environment-friendly resin artwork and its handicraft preparation method with long-acting aromatic |
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