CN106967215A - A kind of new light degradable triazenes polymer - Google Patents
A kind of new light degradable triazenes polymer Download PDFInfo
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- CN106967215A CN106967215A CN201710207168.3A CN201710207168A CN106967215A CN 106967215 A CN106967215 A CN 106967215A CN 201710207168 A CN201710207168 A CN 201710207168A CN 106967215 A CN106967215 A CN 106967215A
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- triazenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/22—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond containing chains of three or more nitrogen atoms with one or more nitrogen-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/22—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond containing chains of three or more nitrogen atoms with one or more nitrogen-to-nitrogen double bonds
- C07C245/24—Chains of only three nitrogen atoms, e.g. diazoamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
Abstract
The application belongs to induced with laser forward transfer technical field, and in particular to a kind of new light degradable triazenes polymer.Triazenes polymer architecture novelty provided by the present invention can photodissociation, its optical absorption peak wavelength is in more than 380nm, damage of the ultraviolet source to cell can be prevented effectively from, the potential demand that induced with laser forward transfer technology is applied to biomedical science experimental study is met；Meanwhile, such triazenes polymer purity is high, solubility is good, occurs uniformly resolve into fractionlet during photodissociation, gaseous products are resolved into ablation plume, not only will not contamination of cells layer, but also can take away cellular layer remained on surface solid ablation product, without extra cleaning step.
Description
Technical field
The invention belongs to induced with laser forward transfer technical field, and in particular to a kind of new light degradable triazenes polymerization
Thing.
Background technology
It is attached that induced with laser forward transfer technology (LIFT) focuses on material film using high energy beam laser light residuite
Closely, the effect of strong laser field near focusing is passed through so that material film flies away from matrix and is attached to receptor surface, realizes thin-film material
Deposition.Because the thermic load of laser is acted on, damage usually is caused to the material of sedimentary.Accordingly, it would be desirable in residuite and sink
Set an intermediate layer between lamination to absorb laser, this intermediate layer is referred to as sacrifice layer (DRL).
Mainly there are the metals such as titanium, gold and Triazenes polymer currently used as the material of sacrifice layer.Metal is to laser
No wavelength limitation is absorbed, but its heat produced damages big with solid particle to sedimentary.Existing triazenes polymer
Optical absorption peak is 280-350nm, and the absorbance that wavelength is more than 380nm is drastically declined, and transmission effect is poor.LIFT is applied to life
When thing medical science is tested, if cellular damage in sedimentary can be caused even as light source using about 300nm ultraviolet light
Death, result in existing triazenes polymer and cannot be widely applied in biomedicine experiment.In addition, existing triazenes polymer
Solubility it is relatively low, solution easily sticky or even gel.This sticky polymers are spun on film, laser pulse effect
Micro-nano granules are easily formed when sacrifice layer, after sacrifice layer gasification to pollute.
The content of the invention
In view of this, the invention provides the new light degradable triazenes polymer of one kind, its optical absorption peak wavelength exists
More than 380nm, effectively prevent damage of the ultraviolet source to cell.
Specific embodiments of the present invention are as follows：
The invention provides the new light degradable triazenes polymer of one kind, shown in its structure such as formula (I) or formula (II)：
Wherein, R1, R3 are each independently selected from carbonyl, aryl or substituted aryl；
R2 is selected from C1~12Alkyl；
N=1~106。
It is preferred that, n=1~104；More preferably n=1~102；Most preferably n=1~20.
It is preferred that, R1 and R3 are each independently selected from：
It is preferred that, R2 is selected from ethyl, methyl, n- propyl group or isopropyl.
It is preferred that, the triazenes polymer is：
Wherein, the R2 is ethyl.
Present invention also offers a kind of light degradation material, the light degradation material includes foregoing triazenes polymer.
Present invention also offers foregoing triazenes polymer or foregoing light degradation material in induced with laser forward transfer technology
In application.
In summary, the present invention uses the higher benzene compound of diaminourea two of conjugated degree as reaction substrate, with amine
Compound is reacted, and has synthesized a kind of new light degradable triazenes polymer using diazonium reactant salt, successfully will be sacrificial
Moved after the optical absorption peak of domestic animal layer material.The triazenes polymer obtained by technical scheme, structure novelty can photodissociation,
Its optical absorption peak wavelength can be prevented effectively from damage of the ultraviolet source to cell in more than 380nm, meet induced with laser is positive
Transfer techniques are applied to the potential demand of biomedical science experimental study；Meanwhile, such triazenes polymer purity is high, dissolving
Spend, occur uniformly resolve into fractionlet during photodissociation, gaseous products are resolved into ablation plume, will not only pollute thin
Born of the same parents' layer, but also the solid ablation product of cellular layer remained on surface can be taken away, without extra cleaning step.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is existing triazenes polymer TP-6d ultra-violet absorption spectrum；
Fig. 2 is the ultra-violet absorption spectrum for the triazenes polymer 1 that embodiment 1 is synthesized；
Fig. 3 be embodiment it is 2-in-1 into triazenes polymer 2 ultra-violet absorption spectrum；
Fig. 4 is as sacrifice layer to carry out the obtained cellular layer table of induced with laser forward transfer using Titanium in embodiment 4
The micrograph in face；
Fig. 5 be in embodiment 4 using Titanium as sacrifice layer carry out the obtained cellular layer of induced with laser forward transfer by
Damage the micrograph of cell；
Fig. 6 carries out induced with laser forward direction for the triazenes polymer synthesized in embodiment 4 using embodiment 1 as sacrifice layer
Shift the micrograph of obtained cell layer surface.
Embodiment
For current existing triazenes polymer as the deficiency present in sacrificial layer material, the present invention is using conjugation journey
The Du Genggao benzene compound of diaminourea two and diamines as reaction substrate, using diazonium reactant salt synthesized it is a kind of it is new can light
The triazenes polymer of solution, successfully by the optical absorption peak red shift of sacrificial layer material so that the optical absorption peak of tri azene compound
Wavelength is more than 380nm, compensate for the deficiencies in the prior art, it is to avoid damage of the light source to cell.
Technical scheme is clearly and completely described below in conjunction with description of the invention accompanying drawing, it is clear that
Described embodiment is a part of embodiment of the invention, rather than whole embodiments.Those skilled in the art should manage
Solution, modifies to the specific embodiment of the present invention or some technical characteristics is replaced on an equal basis, without departing from the present invention
The spirit of technical scheme, all should cover in the scope of protection of the invention.
Embodiment 1
1) by 0.015mol diaminobenzophenones, 30mL water and 7.5mL 37% mixed in hydrochloric acid, it is slowly stirred at room temperature
- 5 DEG C are cooled to after 2h, mixed solution 1 is obtained；In the RO water that 0.03mol natrium nitrosums are added to 20mL, sodium nitrate is obtained molten
Liquid, is cooled to after -5 DEG C sodium nitrate solution being added dropwise to progress reaction 1h in mixed solution 1, and reaction temperature is -5 DEG C, is obtained
To first kind solution 1；
2) by 0.015mol N, Novoldiamine, the 37% mixed in hydrochloric acid reaction of 3- propane diamine, 50mL water and 3.5mL,
- 5 DEG C are cooled to, Equations of The Second Kind solution is obtained；
3) 1.5g/mL mixed proportion is pressed, trash ice is added in n-hexane, mixing obtains the 3rd class solution；Then by institute
State first kind solution 1 and Equations of The Second Kind solution is alternately added in the 3rd class solution dropwise, stirring reaction 0.5h, obtain intermediate product 1；
4) toward step 3) intermediate product in add 60mL 2mol/L K2HPO4.3H2(- 5 DEG C) mixing of O, adjust pH value to 7
~8；Then, 60mL 2mol/L K is added3PO4.3H2(- 5 DEG C) mixing of O, adjust pH value to 8.5~9；Finally, 60mL is added
2mol/L (- 5 DEG C) mixing of KOH, adjust pH value to 10~11, continue to stir 3h at room temperature, obtain crude product 1.
5) crude product 1 is washed with water after once being washed twice afterwards using n-hexane and be washed with water once, fallen every time after centrifugation
Go out solvent, finally carry out lucifuge drying process, obtain triazenes polymer 1.
Embodiment 2
1) by the 2 of 0.015mol, 6- diamino-anthraquinones, 30mL water and 7.5mL 37% mixed in hydrochloric acid, it is stirred at room temperature
1h, is cooled to -5 DEG C, obtains mixed solution 2；In the RO water that 0.03mol natrium nitrosums are added to 20mL, sodium nitrate solution is obtained,
It is cooled to after -5 DEG C and sodium nitrate solution is added dropwise in mixed solution 2 progress reaction 1h, reaction temperature is -5 DEG C, obtains the
One class solution 2；
2) by 0.015mol N, Novoldiamine, the 37% mixed in hydrochloric acid reaction of 3- propane diamine, 50mL water and 3.5mL,
- 5 DEG C are cooled to, Equations of The Second Kind solution is obtained；
3) 1.5g/mL mixed proportion is pressed, trash ice is added in n-hexane, mixing obtains the 3rd class solution；Then by institute
State first kind solution 2 and Equations of The Second Kind solution is alternately added in the 3rd class solution dropwise, stirring reaction 1h, obtain intermediate product 2；
4) toward step 3) intermediate product in add 60mL 2mol/L K2HPO4.3H2(- 5 DEG C) mixing of O, adjust pH value to 7
~8；Then, 60mL 2mol/L K is added3PO4.3H2(- 5 DEG C) mixing of O, adjust pH value to 8.5~9；Finally, 60mL is added
2mol/L (- 5 DEG C) mixing of KOH, adjust pH value to 10~11, continue to stir 2h at room temperature, obtain crude product 2.
5) crude product 2 is washed with water after once being washed twice afterwards using n-hexane and washed again once, poured out every time after centrifugation
Solvent, finally carries out lucifuge drying process, obtains triazenes polymer 2.
Embodiment 3
1) by 0.015mol basic fuchsin, 30mL water and 7.5mL 37% mixed in hydrochloric acid, 2h is stirred at room temperature, it is cold
But to -5 DEG C, mixed solution 3 is obtained；In the RO water that 0.03mol natrium nitrosums are added to 20mL, sodium nitrate solution is obtained, is cooled down
Sodium nitrate solution is added dropwise to progress reaction 1h in mixed solution 3 after to -5 DEG C, reaction temperature is -5 DEG C, obtains the first kind
Solution 3；
2) 0.015mol diethylamine, 50mL water and 3.5mL 37% mixed in hydrochloric acid are reacted, is cooled to -5 DEG C, obtains
Equations of The Second Kind solution 3；
3) 1.5g/mL mixed proportion is pressed, trash ice is added in n-hexane, mixing obtains the 3rd class solution；Then by institute
State first kind solution 3 and Equations of The Second Kind solution 3 is alternately added in the 3rd class solution dropwise, stirring reaction 1h, obtain intermediate product 3；
4) toward step 3) intermediate product 3 in add 60mL 2mol/L K2HPO4.3H2(- 5 DEG C) mixing of O, adjust pH value extremely
7~8；Then, 60mL 2mol/L K is added3PO4.3H2(- 5 DEG C) mixing of O, adjust pH value to 8.5~9；Finally, 60mL is added
2mol/L (- 5 DEG C) mixing of KOH, adjust pH value to 10~11, continue to stir 4h at room temperature, obtain crude product 3.
5) crude product 3 is washed with water after once being washed twice afterwards using n-hexane and be washed with water once, fallen every time after centrifugation
Go out solvent, finally carry out lucifuge drying process, obtain triazenes polymer 3.
Embodiment 4
To triazenes polymer TP-6d ((C20H26N6O the triazenes polymer) n), and in embodiment 1 to 3 obtained is adopted
It is coated on quartz glass, sacrificial layer thickness is 70nm, is then irradiated using mercury lamp with spin-coating method, and utilizes ultraviolet spectrometry light
The analysis that degree meter carries out optical absorption spectra obtains absorbance of each polymer with wavelength change, as a result as shown in Figure 1 to Figure 3.With
Existing triazenes polymer TP-6d (280~350nm) is compared, and that embodiment 1 is synthesized into embodiment 3 is new light degradable
The light absorption wavelength of triazenes polymer is all higher than 380nm, and such triazenes polymer can be prevented effectively from ultraviolet light to cell
Damage, compensate for the deficiencies in the prior art.Moreover, the triazenes polymer of embodiment 1 to embodiment 3 is using Hg lamp irradiation
After 20min, its absorbance is decreased obviously, and illustrates that triazenes polymer of the present invention is easy to photodissociation, can be used as a kind of good light
Solve materials application technical in LIFT.
The triazenes polymer of titanium and embodiment 1 is respectively adopted as the material of sacrifice layer and is spin-coated on quartz glass substrate
On bottom, then using the yeast cells in induced with laser forward transfer technology separation cellular layer, finally seen using light microscope
The cell in receiving element is examined, is taken pictures.As shown in Figures 4 to 6, particle residue can be produced thin by preparing sacrifice layer using metal material
The surface of born of the same parents' layer, and the damage of separation cell is also created, and triazenes polymer purity synthesized by the present invention is high, dissolving
Spend, it can uniformly resolve into fractionlet as sacrifice layer when occurring photodissociation, and gaseous products are resolved into ablation plume,
Not only will not contamination of cells layer surface, but also can take away cellular layer remained on surface solid ablation product, without extra
Cleaning step.
Claims (6)
1. a kind of new light degradable triazenes polymer, shown in its structure such as formula (I) or formula (II)：
Wherein, R1, R3 are each independently selected from carbonyl, aryl or substituted aryl；
R2 is selected from C1~12Alkyl；
N=1~106。
2. triazenes polymer according to claim 1, it is characterised in that R1 and R3 are each independently selected from：
3. triazenes polymer according to claim 1, it is characterised in that R2 is selected from ethyl, methyl, n- propyl group or isopropyl
Base.
4. triazenes polymer according to claim 1, it is characterised in that the triazenes polymer is：
Wherein, the R2 is ethyl.
5. a kind of light degradation material, it is characterised in that include the triazenes polymer described in Claims 1-4 any one.
6. the light degradation material as described in triazenes polymer or claim 5 as described in Claims 1-4 any one is swashing
Application in photoinduction forward transfer technology.
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| CN201710207168.3A CN106967215B (en) | 2017-03-31 | 2017-03-31 | A kind of light degradable triazenes polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148619A (en) * | 2019-06-25 | 2019-08-20 | 京东方科技集团股份有限公司 | A kind of preparation method of display base plate, display base plate and display device |
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| EP1331104A2 (en) * | 2002-01-25 | 2003-07-30 | Fuji Photo Film Co., Ltd. | Heat sensitive recording material and recording method |
| US20120231253A1 (en) * | 2011-03-10 | 2012-09-13 | Battelle Energy Alliance, Llc | Polymer compositions, polymer films and methods and precursors for forming same |
| US20130089703A1 (en) * | 2011-10-11 | 2013-04-11 | Sungkyunkwan University Foundation For Corporate Collaboration | Solder resist composition, board for package comprising solder resist opening using the composition, and method for preparing the board for package |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1331104A2 (en) * | 2002-01-25 | 2003-07-30 | Fuji Photo Film Co., Ltd. | Heat sensitive recording material and recording method |
| US20120231253A1 (en) * | 2011-03-10 | 2012-09-13 | Battelle Energy Alliance, Llc | Polymer compositions, polymer films and methods and precursors for forming same |
| US20130089703A1 (en) * | 2011-10-11 | 2013-04-11 | Sungkyunkwan University Foundation For Corporate Collaboration | Solder resist composition, board for package comprising solder resist opening using the composition, and method for preparing the board for package |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148619A (en) * | 2019-06-25 | 2019-08-20 | 京东方科技集团股份有限公司 | A kind of preparation method of display base plate, display base plate and display device |
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