CN109485846A - Photosensitive colour-changing selfreparing intelligence nylon 6 and preparation method thereof - Google Patents
Photosensitive colour-changing selfreparing intelligence nylon 6 and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a kind of photosensitive colour-changing selfreparing intelligence nylon 6 and preparation method thereof, belong to intellectual material technical field.The present invention in 6 macromolecular chain of nylon by introducing urea groups pyrimidone structure and spiro-pyrans ring structure, it can make the color of nylon material that reversible change occur using the fracture and reconstruction of spiro-pyrans ring, and easy invertibity forms Quadrupolar hydrogen bond to realize selfreparing when nylon 6 material deterioration between urea groups pyrimidone molecular structure.The preparation method that the present invention designs is more easy to operate, reaction time is short, and post-processing is simple, and yield is higher, the nylon material being prepared not only had had long service life but also color change can be presented under different illumination, had wide application prospect in photochromic material field.
Description
Technical field
The present invention relates to nylon materials, belong to intellectual material technical field, more particularly to a kind of photosensitive colour-changing selfreparing
Intelligent nylon 6 and preparation method thereof.
Background technique
Polyamide (nylon) one of as five large-engineering plastics, have tensile strength is high, elasticity modulus is big, wearability and from
Therefore the features such as lubricity is excellent obtains extensively in industries such as auto manufacturing, electronic enterprises, mechanical equipment and packagings
General application.However, when nylon material is applied to machinery industry as structural member, suffered alternate stress in use
Easily make to generate fatigue crack inside nylon material and lead to the early damage of material, shortens its service life.In addition, working as nylon material
When material inside generates fatigue crack, existing nylon material can not intuitively show its internal micro-variations to user, send out
Wave forewarning function.Therefore, a kind of novel nylon material is developed, so that it is had resisting fatigue crack propagation and from forewarning function, it is right
Accident risk is particularly important caused by improving the service life of nylon, reducing structural member damage, which will be with wide
Application market.
Currently, macromolecule self-repair material receives significant attention, importance is exactly to be to extend the use longevity of material
Life, can in the use process of material patching material, especially in the untouchable place of people such as space station or mal-condition, corruption
Under erosion, radiation environment, there is self-repair function with greater need for material.The selfreparing high molecular material of early stage focuses primarily upon micro- glue
Capsule, micro-pipe rupture cause polymerize again realize damage foreign aid's type reparation, as Chinese invention patent application (application publication number:
CN103594559A, data of publication of application: 2014-02-19) disclose a kind of preparation side of self-repair type solar battery back film
Method, that application discloses preferred epoxy adhesive, the Amino End Group in nylon molecules structure is as the solidification in epoxy resin
Agent, when nylon backboard is by external forces, self repairing agent (microcapsule product) the energy quick release for being embedded in backboard goes out core
Core, epoxy resin are reacted with the nylon end amido in nylon backboard, solidification crosslinking, can quickly the crackle caused by external force into
Row repairing is to obtain higher performance.
However this self-repairability is typically only capable to realize one twice, can not repeat to repair damage.But high molecular material has
There is adjustable chemical structure, its segmented structure is designed and then the control to polymerization process, it can be relatively easily
Realize the regulation to material property, current research, which is then focusing more on, realizes to material the structure design of high molecular material itself
Expect the Intrinsical selfreparing of damage, i.e. material itself is changed adaptive not by environmental stimuli or energy input by self structure
Realize dynamic regulation to property.
In the development process of Intrinsical self-healing polymers, hydrogen bond has played important function, has invertibity, collaboration
Property and behavioral characteristics, can polymeric inner realize the mutual phase transition of fracture-recombination, and then resist micro-crack extension, wherein
What it is with inventions such as Dutch scientist Meijer is the hydrogen bond type self-healing polymeric of end group with 2- urea -4- pyrimidone derivatives (UPy)
Object has been commercialized and (has been produced by SupraPolix company, trade name SupraB), and UPy is self-complementary to form Quadrupolar hydrogen bond dimerization
Body, UPy base hydrogen bond destroy when heated, are formed when cooling, have invertibity.The self-healing of UPy base hydrogen bond type supermolecule polymer
Conjunction behavior is to be in liquid condition by polymer under high temperature, can fill up crackle, be in solid-state in room temperature and realize selfreparing.
As Chinese invention patent application (application publication number: CN106221100A, data of publication of application: 2016-12-14) is open
A kind of preparation method of the optical drive selfreparing film based on ethylene-butylene copolymer comprising by 2- amino-4-hydroxy -6-
Methylpyrimidine and hexamethylene diisocyanate synthesize UPy-NCO, then product and poly- (Ethylene/Butylene) and 4 '-two (hydroxyl first
Base) azobenzene reaction, the progress of both materials is compound, and obtaining can be with the block copolymer of selfreparing under ultraviolet lighting；For another example
It is poly- that Chinese invention patent application (application publication number: CN107325256A, data of publication of application: 2017-11-07) discloses selfreparing
Object material and preparation method thereof is closed, the preparation method of this application discloses prepares urea groups pyrimidone type end-capping reagent or chain extension first
Then agent prepares side chain and end group containing four using oligomer dihydric alcohol, chain extender and the first diisocyanate random copolymerization reaction
Deuterium bond group can the quick self-healing polymers material of low temperature.Compared to traditional self-repair material, such self-repair material exists
The multiplicating selfreparing of same position under lower temperature can be realized without additional renovation agent for breakage, and repair ability is high, power
It is good to learn performance, material filming and transparent good, simple process and low cost.
Photosensitive colour-changing polymer material is that one kind can change with light source and generate performance change " intelligence " material, in army
Thing camouflage, protective materials, daily necessities, extraordinary photosensitive material and information storing material, packaging material etc. fields have played important work
With.Spiro-pyrans is a kind of optical Response group well, has photochromic effect.By the design of molecular structure, it is polymerizeing
Such spiro-pyrans is accessed in object chain backbone can prepare optical Response polymer material.
However, not had been reported that at present by introducing spiro-pyrans structure and urea groups pyrimidone structure in nylon macromolecular chain
(UPy), production, which is prepared, display color to change under different illumination and deteriorate generation selfreparing to the performance of material to prolong
The high molecular material of slow material aging.
Summary of the invention
In order to solve the above technical problems, the invention discloses one kind both to have had photosensitive colour-changing function, but also with reviewing one's lessons by oneself reactivation
Photosensitive colour-changing selfreparing intelligence nylon 6 of power and preparation method thereof.
To achieve the above object, the invention discloses a kind of photosensitive colour-changing selfreparing intelligence nylon 6, the intelligence nylon 6
Color change can occur when material is irradiated by different light sources, and material property can be delayed to deteriorate by selfreparing, its point
It include the derivative for having urea groups pyrimidone structure, spiro-pyrans structure, the molecular structural formula of urea groups pyrimidone derivatives in subchain
As shown in following formula A, the molecular structural formula of spiropyran derivatives is as shown in following formula B:
Wherein, the specific preparation process of urea groups pyrimidone derivatives shown in formula A is as follows:
Reagent in said synthesis route marked as 1 and 2 is Aladdin reagent, No. CAS be respectively 517-23-7,
593-85-1。
And spiropyran derivatives shown in formula B are also Aladdin reagent (CAS16111-07-2).
Further, the molecular structural formula of the intelligent nylon 6 is as shown in following formula I:
Further, the R is one of hexa-methylene, diphenyl methane, methane phenyl, molecular structural formula such as following formula
A, described in formula b and formula c:
Formula a:
Formula b:
Formula c:
Therefore, photosensitive colour-changing selfreparing intelligence nylon 6 disclosed by the invention includes following several molecular structural formulas:
In order to preferably realize technical purpose of the invention, the invention also discloses above-mentioned photosensitive colour-changing selfreparing intelligence Buddhist nuns
The preparation method of dragon 6, including following preparation step:
1) two isocyanides comprising urea groups pyrimidone structure are prepared in urea groups pyrimidone derivatives and di-isocyanate reaction
Acid esters, molecular structural formula is as shown in following formula I-a；
2) under the action of catalyst, spiropyran derivatives are reacted with the Formulas I-a of step 1) be prepared it is phonetic comprising urea groups
The substance of pyridine ketone and spiro-pyrans structure, molecular structural formula is as shown in following formula I-b；
3) caprolactam hydrolyzes to obtain end amido polycaprolactam, and molecular structural formula is as shown in following formula I-c；
4) Formulas I-c of step 3) is reacted with Formulas I-b, photosensitive colour-changing selfreparing intelligence nylon 6, molecule knot is prepared
Structure formula is as shown in formula I above；
Further, the specific reaction process of the step 1) is as follows:
Take pyrimidone derivatives with diisocyanate according to the mass ratio of the material 1:(2.05~2.1) mix, in catalyst and
12h, which is reacted, under inert gas shielding atmosphere, at 70 DEG C obtains the diisocyanate of the structure of pyrimidone containing urea groups.
Preferably, the mass ratio of the material is 1:2.05 between pyrimidone derivatives and diisocyanate.
Preferably, the mass ratio of the material is 1:2.07 between pyrimidone derivatives and diisocyanate.
Preferably, the mass ratio of the material is 1:2.1 between pyrimidone derivatives and diisocyanate.
Further, the dosage (amount of substance) of catalyst described in step 1) be diisocyanate 0.1~
0.5mol%.
Preferably, the dosage of catalyst dibutyltin dilaurylate described in step 1) is diisocyanate
0.3mol%.
Preferably, step 1) and step 2) are reacted under nitrogen protection atmosphere.
Further, in the step 2), between spiropyran derivatives and Formulas I-a the mass ratio of the material be 1:(5.05~
5.1), reaction temperature is 25 DEG C, reaction time 1h.
Preferably, the mass ratio of the material is 1:5.05 between spiropyran derivatives and Formulas I-a.
Preferably, the mass ratio of the material is 1:5.06 between spiropyran derivatives and Formulas I-a.
Preferably, the mass ratio of the material is 1:5.07 between spiropyran derivatives and Formulas I-a.
Preferably, the mass ratio of the material is 1:5.08 between spiropyran derivatives and Formulas I-a.
Preferably, the mass ratio of the material is 1:5.09 between spiropyran derivatives and Formulas I-a.
Preferably, the mass ratio of the material is 1:5.1 between spiropyran derivatives and Formulas I-a.
Further, the dosage (amount of substance) of catalyst described in step 2) is 0.1~0.5mol% of Formulas I-a.
Preferably, the dosage of catalyst dibutyltin dilaurylate described in step 2) is the 0.3mol% of Formulas I-a.
Further, the specific reaction process of the step 4) are as follows: when Formulas I-c is in a molten state, by step 2) institute
It obtains product Formulas I-b to be added thereto, reaction to solid matter all disappears, and obtains target product photosensitive colour-changing selfreparing intelligence nylon
6, and discoloration to target product and self-repairability can be carried out test.
Preferably, the reaction temperature of the step 4) is 190~250 DEG C.
Further, in the step 3), the molecular weight of Formulas I-c is 15000~50000g/mol, and molecular weight is too big, end
Base content is relatively fewer, will affect the discoloration and self-reparing capability of the reaction efficiency and later period material of end group.
Preferably, the molecular weight of Formulas I-c is 15000,17000,20000,35000,40000,45000 or 50000g/
mol。
Preferably, the hydrolytic process of step 3) specifically:
Using caprolactam as raw material, using deionized water as hydrolytic reagent, concentrated phosphoric acid is catalyst, wherein control deionized water
Dosage be caprolactam 1~2wt%, the dosage of concentrated phosphoric acid is 1~2wt% of caprolactam, and to entire reaction system
Controlled at 220~300 DEG C after vacuumizing.
The principle that intelligence nylon 6 prepared by the present invention has selfreparing is as follows:
The present invention is using easily reversible formation Quadrupolar hydrogen bond between 2 urea groups pyrimidone molecular structures to realize nylon 6
The process of material selfreparing, it is on the one hand larger by external influence in nylon 6 or long-term illumination leads to nylon material mechanical property
When impaired, internal Quadrupolar hydrogen bond fracture causes material surface obvious crackle occur, and disappears in external forces disappearance or illumination
It is internal to re-form Quadrupolar hydrogen bond again after mistake, so that external micro-crack caused by external force or illumination is avoided to further expand,
The service life of nylon 6 material is improved, on the other hand, nylon 6 material is increased since inside forms several Quadrupolar hydrogen bonds
Interaction force between polymer chain and chain improves the mechanical property of nylon 6, wherein 2 urea groups pyrimidone molecular structures
Between the Quadrupolar hydrogen bond active force that is formed as shown in Formula Il (by taking Formulas I -1 as an example):
The principle that intelligence nylon 6 prepared by the present invention has photosensitive colour-changing is as follows:
Spiro-pyrans ring is introduced in nylon 6 material molecule of the present invention, fracture of the spiro-pyrans ring under illumination condition makes its table
Color change can occur for face, and when illumination disappears, reversible color change occurs for nylon 6 material surface, wherein spiro-pyrans
Shown in the following formula III of photosensitive colour-changing process of ring:
The beneficial effects are mainly reflected as follows following aspects:
1, the preparation method that the present invention designs is more easy to operate, and the reaction time is short, and post-processing is simple, and yield is higher；
2, under illumination condition color change can occur for the intelligent nylon 6 that the present invention designs first, to enrich the reality of material
With property, meanwhile, present invention design introduces discoloration spiro-pyrans ring in nylon material macromolecular chain, different from introducing in the prior art
Change colour powder, and the durability of discoloration will increase；
3, the intelligent nylon that the present invention designs causes the mechanical property of material impaired and material table occurs in long-term illumination
When facial cleft line, the reversible fracture of Quadrupolar hydrogen bond inside nylon material macromolecular chain is with recombination to realize material internal micro-crack
And the reparation of material surface crackle, and then guarantee that nylon material has long service life.Therefore, nylon material prepared by the present invention
Material has more sensitive discoloration and self-healing properties, this kind of material is anti-in functional clothing fabric, camouflage, packaging
The fields such as pseudo-, information storage have significant application value；
4, the intelligent nylon 6 material that the present invention designs introduces in macromolecular chain can form several intramoleculars or intermolecular
The urea groups pyrimidone structure of hydrogen bond, further enhances the stress-bearing capability of material.
Detailed description of the invention
Fig. 1 is the HNMR map of compound shown in the intermediate product formula A of the preparation of the embodiment of the present invention 1；
Fig. 2 is the DSC curve of compound shown in the Formulas I -1 of the preparation of the embodiment of the present invention 1.
Specific embodiment
In order to better explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to following embodiment.
Embodiment 1
1) pyrimidone derivatives 1.50g, hexamethylene diisocyanate 3.1g, dibutyl tin dilaurate 12mg are weighed,
12h, which is reacted, under nitrogen atmosphere, at 70 DEG C obtains the diisocyanate 4.1g of the structure of pyrimidone containing urea groups.
Wherein, the pyrimidone derivatives that the present embodiment uses is disclosed in specification structural formula shown in formula A and specifications
Specific synthetic route, and Fig. 1 of Figure of description gives its data characterization map, in conjunction with Fig. 1 it is found that molecule knot shown in formula A
Various hydrogen atoms in structure formula have all obtained corresponding characterization on map, and this also illustrates the synthetic route systems using specification
It is standby to have obtained the pyrimidone derivatives of the present embodiment.
2) spiropyran derivatives 0.57g, the diisocyanate 4.1g of the structure of pyrimidone containing urea groups, two fourth of tin dilaurate are weighed
Base tin 5.1mg, N,N-Dimethylformamide 10ml, reaction temperature is 25 DEG C, and purification waits until product 3.9g after reacting 1h.
3) caprolactam 40g, deionized water 0.44g are weighed, concentrated phosphoric acid (85wt%) 0.4g adds it to three-necked flask
In, nitrogen is passed through with the oxygen in removing system, is heated to 250 DEG C, reacts and condensing unit is changed to vacuum evacuation device after 3h, close
Nitrogen is closed, vacuumizes 10min under conditions of 250 DEG C, revolving speed 250r/min, it is existing apparent pole-climbing occur for melt in three-necked flask
As, and melt is transparence, bubble is less, that is, terminates to vacuumize, and is passed through nitrogen in backward system, obtains the nylon of molten condition
6。
4) product obtained in step 2) is added to (the molecular weight 16000g/ of nylon 6 of the molten condition of step 3)
Mol in), reaction 0.5h photosensitive colour-changing selfreparing nylon 6 can be obtained, after its selfreparing and discoloration are measured；
Wherein, the characterize data of the photosensitive colour-changing selfreparing nylon 6 of above-mentioned preparation is as shown in Fig. 2, in conjunction with Fig. 2 it is found that originally
Target product has been prepared in embodiment.
Embodiment 2
1) pyrimidone derivatives 1.80g, hexamethylene diisocyanate 3.7g, dibutyl tin dilaurate are weighed
16.7mg reacts 12h under nitrogen atmosphere, at 70 DEG C and obtains the diisocyanate 4.9g of the structure of pyrimidone containing urea groups.
2) spiropyran derivatives 0.67g, the diisocyanate 4.9g of the structure of pyrimidone containing urea groups, two fourth of tin dilaurate are weighed
Base tin 7.3mg, N,N-Dimethylformamide 12ml, reaction temperature is 25 DEG C, and purification waits until product 4.5g after reacting 1h.
3) caprolactam 40g, deionized water 0.44g are weighed, concentrated phosphoric acid (85wt%) 0.4g adds it to three-necked flask
In, nitrogen is passed through with the oxygen in removing system, is heated to 250 DEG C, reacts and condensing unit is changed to vacuum evacuation device after 3h, close
Nitrogen is closed, vacuumizes 10min under conditions of 250 DEG C, revolving speed 250r/min, it is existing apparent pole-climbing occur for melt in three-necked flask
As, and melt is transparence, bubble is less, that is, terminates to vacuumize, and is passed through nitrogen in backward system, obtains the nylon of molten condition
6。
4) product obtained in step 2) is added to (the molecular weight 16200g/ of nylon 6 of the molten condition of step 3)
Mol in), reaction 0.5h photosensitive colour-changing selfreparing nylon 6 can be obtained, after its selfreparing and discoloration are measured.
Embodiment 3
1) pyrimidone derivatives 2.0g, hexamethylene diisocyanate 4.1g, dibutyl tin dilaurate 20mg, nitrogen are weighed
12h, which is reacted, under atmosphere is enclosed, at 70 DEG C obtains the diisocyanate 5.4g of the structure of pyrimidone containing urea groups.
2) spiropyran derivatives 0.75g, the diisocyanate 5.4g of the structure of pyrimidone containing urea groups, two fourth of tin dilaurate are weighed
Base tin 8.8mg, N,N-Dimethylformamide 14ml, reaction temperature is 25 DEG C, and purification waits until product 5.1g after reacting 1h.
3) caprolactam 40g, deionized water 0.44g are weighed, concentrated phosphoric acid (85wt%) 0.4g adds it to three-necked flask
In, nitrogen is passed through with the oxygen in removing system, is heated to 250 DEG C, reacts and condensing unit is changed to vacuum evacuation device after 3h, close
Nitrogen is closed, vacuumizes 10min under conditions of 250 DEG C, revolving speed 250r/min, it is existing apparent pole-climbing occur for melt in three-necked flask
As, and melt is transparence, bubble is less, that is, terminates to vacuumize, and is passed through nitrogen in backward system, obtains the nylon of molten condition
6。
4) product obtained in step 2) is added to (the molecular weight 16500g/ of nylon 6 of the molten condition of step 3)
Mol in), reaction 0.5h photosensitive colour-changing selfreparing nylon 6 can be obtained, after its selfreparing and discoloration are measured.
Embodiment 4
1) pyrimidone derivatives 2.0g, hexamethylene diisocyanate 4.1g, dibutyl tin dilaurate 20.0mg are weighed,
12h, which is reacted, under nitrogen atmosphere, at 70 DEG C obtains the diisocyanate 5.4g of the structure of pyrimidone containing urea groups.
2) spiropyran derivatives 0.74g, the diisocyanate 5.4g of the structure of pyrimidone containing urea groups, two fourth of tin dilaurate are weighed
Base tin 8.8mg, N,N-Dimethylformamide 12ml, reaction temperature is 25 DEG C, and purification waits until product 5.2g after reacting 1h.
3) caprolactam 40g, deionized water 0.5g are weighed, concentrated phosphoric acid (85wt%) 0.4g adds it to three-necked flask
In, nitrogen is passed through with the oxygen in removing system, is heated to 250 DEG C, reacts and condensing unit is changed to vacuum evacuation device after 3h, close
Nitrogen is closed, vacuumizes 10min under conditions of 250 DEG C, revolving speed 250r/min, it is existing apparent pole-climbing occur for melt in three-necked flask
As, and melt is transparence, bubble is less, that is, terminates to vacuumize, and is passed through nitrogen in backward system, obtains the nylon of molten condition
6。
4) product obtained in step 2) is added to (the molecular weight 16800g/ of nylon 6 of the molten condition of step 3)
Mol in), reaction 0.5h photosensitive colour-changing selfreparing nylon 6 can be obtained, after its selfreparing and discoloration are measured.
Wherein, for above-described embodiment using hexamethylene diisocyanate as chain extender, the present invention can be with diphenyl methane two
Isocyanates and methane phenyl diisocyanate are chain extender, and preparation process is close with embodiment with principle, therefore of the invention
Do not enumerate.
The performance test methods of gained photosensitive colour-changing selfreparing nylon 6 are as follows in above-described embodiment 1~4:
Photosensitive colour-changing selfreparing nylon 6 is processed as dumbbell shape standard batten, after curving it 100 times, tests its stretching
The conservation rate of intensity, and the resulting nylon material of step 3) (comparative example) tensile strength with progress bending process under the same terms
Conservation rate compares.In addition, scribing depth≤0.2mm in photosensitive colour-changing nylon and the resulting nylon material surface of step 3)
Scratch, after illumination heat treatment is carried out to scratch using infrared lamp at room temperature, observation scratch depth variation after 12h.Its performance
As a result as described in Table 1.
1 photosensitive colour-changing nylon 6 of table and comparative example capabilities list
| Test item | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stretching strength retentivity | 75% | 80% | 82% | 83% | 86% |
| Scratch depth variation | Slightly shoal | Slightly shoal | It shoals | It shoals | Scratch disappears |
By above-mentioned table 1 it is found that the present invention by being modified to nylon 6 after, mechanical property obtains to a certain extent
Enhancing, in addition, the modified nylon 6 is after sunlight irradiation, color can change, become faint yellow from aubergine.
When again by sample, far from sunlight, disposed within, color can become aubergine again.Therefore, material prepared by the present invention can be applied
In technical fields such as photosensitive colour-changing functional materials, it such as can be used for preparing photosensitive colour-changing nylon fiber and textile, and due to discoloration
Through covalent bond keyed in polymer segment, the durability of colour change function will increase group.In addition, self-repair function
The presence of group helps to delay the deterioration of photosensitive colour-changing nylon material mechanical property due to caused by illumination, helps to improve
The service life of the material.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection scope.
Claims (10)
1. a kind of photosensitive colour-changing selfreparing intelligence nylon 6, it is characterised in that: the intelligence nylon 6 generates face under different illumination
Color reversible change and the selfreparing that material is realized in material degradation, include in its strand have urea groups pyrimidone structure,
The derivative of spiro-pyrans structure, the molecular structural formula of urea groups pyrimidone derivatives is as shown in following formula A, the molecule of spiropyran derivatives
Structural formula is as shown in following formula B:
2. photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 1, it is characterised in that: the molecule of the intelligence nylon 6
Structural formula is as shown in following formula I:
3. photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 2, it is characterised in that: the R in the Formulas I is six sub-
One of methyl, diphenyl methane or tolyl.
4. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 described in a kind of claim 1, it is characterised in that: including as follows
Preparation step:
1) diisocyanate comprising urea groups pyrimidone structure is prepared in urea groups pyrimidone derivatives and di-isocyanate reaction
Ester, molecular structural formula is as shown in following formula I-a；
2) spiropyran derivatives are reacted with the Formulas I-a of step 1) under the action of catalyst, and are prepared comprising urea groups pyrimidone
And the substance of spiro-pyrans structure, molecular structural formula is as shown in following formula I-b；
3) caprolactam hydrolyzes to obtain end amido polycaprolactam, and molecular structural formula is as shown in following formula I-c；
4) Formulas I-c of step 3) is reacted with the Formulas I-b of step 2), photosensitive colour-changing selfreparing intelligence nylon 6 is prepared.
5. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 4, it is characterised in that: the step
1) specific reaction process is as follows:
Take urea groups pyrimidone derivatives with diisocyanate according to the mass ratio of the material 1:(2.05~2.1) mix, in catalyst and
12h, which is reacted, under inert gas shielding atmosphere, at 70 DEG C obtains the diisocyanate of the structure of pyrimidone containing urea groups.
6. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 4 or 5, it is characterised in that: described to urge
Agent is dibutyl tin dilaurate.
7. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 4 or 5, it is characterised in that: the step
It is rapid 2) in, the mass ratio of the material is 1:(5.05~5.1 between spiropyran derivatives and Formulas I-a), reaction temperature is 25 DEG C, when reaction
Between be 1h.
8. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 7, it is characterised in that: the step
4) specific reaction process are as follows: when Formulas I-c is in a molten state, step 2) products therefrom Formulas I-b is added thereto, reaction is extremely
Solid matter all disappears, and obtains target product photosensitive colour-changing selfreparing intelligence nylon 6.
9. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 4, it is characterised in that: the step
3) in, the molecular weight of Formulas I-c is 15000~50000g/mol.
10. the preparation method of photosensitive colour-changing selfreparing intelligence nylon 6 according to claim 4, it is characterised in that: the R is
One of hexa-methylene, diphenyl methane, tolyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690131A (en) * | 2020-02-16 | 2020-09-22 | 武汉纺织大学 | Force-induced color-changing high-toughness nylon 6 and preparation method thereof |
| CN113004513A (en) * | 2021-03-01 | 2021-06-22 | 深圳市华盈新材料有限公司 | Stress response type high-temperature resistant polyamide and synthesis method thereof |
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| CN113004513A (en) * | 2021-03-01 | 2021-06-22 | 深圳市华盈新材料有限公司 | Stress response type high-temperature resistant polyamide and synthesis method thereof |
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