CN106633041B - A kind of preparation method of the modified ppta with fluorescent effect - Google Patents

A kind of preparation method of the modified ppta with fluorescent effect Download PDF

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CN106633041B
CN106633041B CN201611177783.6A CN201611177783A CN106633041B CN 106633041 B CN106633041 B CN 106633041B CN 201611177783 A CN201611177783 A CN 201611177783A CN 106633041 B CN106633041 B CN 106633041B
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ppta
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fluorescent effect
added
naphthylenediamine
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CN106633041A (en
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廖耀祖
李佳欢
秦明林
余木火
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds

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  • Polyamides (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a kind of polymerization of modified ppta with fluorescent effect, under stirring condition, p-phenylenediamine PDA and 1 is added in LiCl solution, 5- naphthylenediamine 1,5-DAN, after being completely dissolved, it is cooling, then paraphthaloyl chloride TPC is added in two portions, increases revolving speed at once to 500~3000r/min, adds sour sorbent reactions 20-40min, occur removing cooling device after rod climbing phenomenon, the reaction was continued under room temperature state 2-3h, post-processing to get.Fluorescent monomer 1, the introducing of 5- naphthylenediamine can make modified PPTA molecule have fluorescent effect, be expected to expand application of the PPTA in terms of fluorescence falsification preventing, fluorescence detection.

Description

A kind of preparation method of the modified ppta with fluorescent effect
Technical field
The invention belongs to the preparation field of fluorescent material, in particular to the preparation of a kind of modified ppta with fluorescent effect Method.
Background technique
Aramid fiber, carbon fiber and polyethylene fibre are as domestic and international widely applied three kinds of high-performance fibers at present, in fiber There is important use in terms of based composites.Committee member has trade relations in order to be different from fatty polyamide, by aromatic series polyamides in U.S. government Amine, which is named, refers to that in strand at least 85% amido bond (- CONH-) is directly connected with two aromatic rings for Aramid Linear macromolecule is exactly aromatic polyamide fibre by the fiber that it is produced, i.e. aramid fiber PPTA, is also Aramid fiber. PPTA fiber is a kind of novel high-tech synthetic fibers, it has superhigh intensity, high-modulus and high temperature resistant, light specific gravity, resistance toization It learns excellent performance, the intensity such as corrosion and is higher than 3 times of general organic fiber or more.In addition to this, PPTA fiber also has good Good insulating properties and anti-aging property is used in fields such as composite material, ballistic-resistant article, building materials, special type protection clothes, electronic equipments It is very extensive on the way.However, due to PPTA molecular structure arranged regular and with the symmetry of height, and molecule interchain exists by force Hydrogen bond action, leading to its molecule chain lengthening is the club shaped structure of rigidity, and not soluble in water and common organic solvents are only dissolve in dense In sulfuric acid.This feature causes PPTA very high to equipment requirement in process of production, and difficulty of processing is very big.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of modified ppta with fluorescent effect, one Kind N-Methyl pyrrolidone/lithium chloride (NMP/LiCl) dicyandiamide solution, and there is fluorescent effect with dicyandiamide solution synthesis The polymerization of modified ppta, by introducing fluorescent monomer 1,5- naphthylenediamine, combined polymerization in existing binary PPTA polymerization system Obtained modified ppta has fluorescent effect.
A kind of preparation method of modified ppta with fluorescent effect of the invention, comprising:
(1) under the conditions of nitrogen protection, lithium chloride LiCl and solvent are mixed, and stirring and dissolving under normal temperature condition obtains LiCl Solution；
(2) under stirring condition, it is added powdered p-phenylenediamine PDA and 1 in LiCl solution, 5- naphthylenediamine 1,5-DAN, completely It is cooling after dissolution, paraphthaloyl chloride TPC is then added in two portions, adds sour adsorbent, reacts, post-processes to get having The modified ppta of fluorescent effect；Wherein the molar ratio of 1,5- naphthylenediamine and p-phenylenediamine is 10:90~50:50；Terephthaldehyde Acyl chlorides and 1,5- naphthylenediamine and the molar ratio of p-phenylenediamine total amount are 1.009~1.012:1.
Solvent is N-Methyl pyrrolidone NMP in the step (1)；The concentration of LiCl solution is 10~20g/L.
The N-Methyl pyrrolidone NMP is N-Methyl pyrrolidone NMP after purification, specifically: NMP is placed in distillation In flask, vacuum distillation, main purpose is the moisture removed in solvent, is then stored in the container of sealing, and be put into molecule Sieve drying.
Addition p-phenylenediamine PDA and 1 in LiCl solution in step (2), 5- naphthylenediamine 1,5-DAN, after being completely dissolved, wherein The molar concentration of 1,5- naphthylenediamine is 0.035~0.176mol/L.
Paraphthaloyl chloride TPC is added in two portions in the step (2) specifically: the two of each addition TPC total amount/ One, it is added twice altogether.
Total mol concentration after TPC is added in step (2) in the reaction system is 0.2~0.5mol/L.
The type of cooling in the step (2) are as follows: be cooled to -15~-5 DEG C using constant-temperature condensation ethanol bath.
Accelerate mixing speed in the step (2) to 500~3000r/min.
Paraphthaloyl chloride TPC is added in two portions in (2) in step, adds sour adsorbent, reaction specifically: in two times plus Enter paraphthaloyl chloride TPC, increases revolving speed at once to 500~3000r/min, add sour sorbent reactions 20-40min, out Cooling device is removed after existing rod climbing phenomenon, the reaction was continued under room temperature state 2-3h.
Sour adsorbent is pyridine in the step (2), and additional amount is 10~30mL/L of overall reaction system.
Post-processing in the step (2) are as follows: repeatedly wash with water, ethyl alcohol be precipitated to be in neutrality and filter after gather what is obtained It closes object and is put into 60~120 DEG C of oven dryings.
Rod climbing phenomenon refers to that resin viscosity becomes larger, and bonds in stirring rod.
Beneficial effect
It is that the Third monomer 1 containing naphthalene nucleus, 5- naphthalene are introduced in the technique of synthesis tradition PPTA in preparation process of the present invention Diamines can destroy its original system after introducing PPTA polymerization system since the molecular structure bending of naphthalene nucleus itself, asymmetry are high Symmetry and regularity so that the crystallinity of new modified PPTA of synthesis is declined, can be dissolved in the concentrated sulfuric acid, NMP, The organic solvents such as DMF and DMSO facilitate the solubility property for improving traditional PPTA.
Meanwhile 1,5- naphthylenediamine are the monomers with fluorescence property, its introducing can make containing 1,5- naphthylenediamine group Modified ppta molecule has fluorescent effect, this achievement can have good application prospect in terms of fluorescence falsification preventing, fluorescence detection.
Detailed description of the invention
Fig. 1 be PPTA before modified after ultraviolet spectrogram；
Fig. 2 be PPTA before modified after nmr spectrum chart；
Fig. 3 be PPTA before modified after X-ray diffraction spectra figure；
Fig. 4 is influence diagram of the 1,5-DAN content to modified ppta viscosity；
Fig. 5 is the influence diagram that 1,5-DAN content crystallizes modified ppta；
Fig. 6 is the liquid crystal phenomenon figure of the modified ppta containing 20mol%1,5-DAN at different temperatures；Wherein a is 50 DEG C, b It is 95 DEG C, c is 115 DEG C；
Fig. 7 be 1,5-DAN before modified after PPTA fluorescence emission spectrogram of compound.
Note: the molar percentage mol% of 1,5-DAN is M1,5- naphthylenediamine/(MP-phenylenediamine (PDA)+M1,5- naphthylenediamine) × 100%, wherein 10mol% (embodiment 1), 20mol% (embodiment 2), 30mol% (embodiment 3), 40mol% (embodiment 4), 50mol% (embodiment 5).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology person The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims Range.
Embodiment 1
Under the conditions of nitrogen protection, the N-Methyl pyrrolidone (NMP) and 0.912g of 57mL are added into three-necked flask LiCl, mechanical stirring dissolves under room temperature, is made into the LiCl/NMP solution that mass concentration is 16g/L；After being completely dissolved to LiCl, The powdered p-phenylenediamine (PDA) of 1.944g and 1, the 5- naphthylenediamine of 0.316g are added under agitation, until it is completely dissolved Afterwards, -10 DEG C are cooled to constant-temperature condensation ethanol bath, paraphthaloyl chloride (TPC) is added in two portions, the one of total amount is added every time Half, the total 4.06406g of additional amount increase revolving speed to 500~3000r/min at once, 1.5mL acid absorbent pyridine (pyrrole are added immediately The concentration of pyridine is 26ml/L), reaction 30min occurs removing constant-temperature condensation ethanol bath after rod climbing phenomenon, under room temperature state after Two hours of continuous reaction.It is filtered after standing, repeatedly washs to be precipitated to water, ethyl alcohol and be in neutrality, then vacuum is dry at 120 DEG C It is dry, obtain modified ppta polymer powder.Yield is 93.0%.
Embodiment 2
Under the conditions of nitrogen protection, the N-Methyl pyrrolidone (NMP) and 0.912g of 57mL are added into three-necked flask LiCl, mechanical stirring dissolves under room temperature, is made into the LiCl/NMP solution that mass concentration is 16g/L；After being completely dissolved to LiCl, The powdered p-phenylenediamine (PDA) of 1.728g and 1, the 5- naphthylenediamine of 0.632g are added under agitation, until it is completely dissolved Afterwards, -10 DEG C are cooled to constant-temperature condensation ethanol bath, be added in two portions paraphthaloyl chloride (TPC), the total 4.06406g of additional amount, Revolving speed is increased at once to 500~3000r/min, 1.5mL acid absorbent pyridine (concentration of pyridine is 26ml/L) is added immediately, instead 30min is answered to occur removing constant-temperature condensation ethanol bath after rod climbing phenomenon, the reaction was continued under room temperature state two hours.After standing It filters, repeatedly washs to be precipitated to water, ethyl alcohol and be in neutrality, be then dried in vacuo at 120 DEG C, obtain modified ppta polymer powder End.Yield is 94.8%, and selecting wavelength is the ultraviolet light of 335nm, fluorescent emission intensity 450a.u..
Embodiment 3
Under the conditions of nitrogen protection, the N-Methyl pyrrolidone (NMP) and 0.912g of 57mL are added into three-necked flask LiCl, mechanical stirring dissolves under room temperature, is made into the LiCl/NMP solution that mass concentration is 16g/L；After being completely dissolved to LiCl, The powdered p-phenylenediamine (PDA) of 1.512g and 1, the 5- naphthylenediamine of 0.948g are added under agitation, until it is completely dissolved Afterwards, -10 DEG C are cooled to constant-temperature condensation ethanol bath, be added in two portions paraphthaloyl chloride (TPC), the total 4.06406g of additional amount, Revolving speed is increased at once to 500~3000r/min, 1.5mL acid absorbent pyridine (concentration of pyridine is 26ml/L) is added immediately, instead 30min is answered to occur removing constant-temperature condensation ethanol bath after rod climbing phenomenon, the reaction was continued under room temperature state two hours.After standing It filters, repeatedly washs to be precipitated to water, ethyl alcohol and be in neutrality, be then dried in vacuo at 120 DEG C, obtain modified ppta polymer powder End.Yield is 91.5%.
Embodiment 4
Under the conditions of nitrogen protection, the N-Methyl pyrrolidone (NMP) and 0.912g of 57mL are added into three-necked flask LiCl, mechanical stirring dissolves under room temperature, is made into the LiCl/NMP solution that mass concentration is 16g/L；After being completely dissolved to LiCl, The powdered p-phenylenediamine (PDA) of 1.296g and 1, the 5- naphthylenediamine of 1.264g are added under agitation, until it is completely dissolved Afterwards, -10 DEG C are cooled to constant-temperature condensation ethanol bath, be added in two portions paraphthaloyl chloride (TPC), the total 4.06406g of additional amount, Revolving speed is increased at once to 500~3000r/min, 1.5mL acid absorbent pyridine (concentration of pyridine is 26ml/L) is added immediately, instead 30min is answered to occur removing constant-temperature condensation ethanol bath after rod climbing phenomenon, the reaction was continued under room temperature state two hours.After standing It filters, repeatedly washs to be precipitated to water, ethyl alcohol and be in neutrality, be then dried in vacuo at 120 DEG C, obtain modified ppta polymer powder End.Yield is 89.4%.
Embodiment 5
Under the conditions of nitrogen protection, the N-Methyl pyrrolidone (NMP) and 0.912g of 57mL are added into three-necked flask LiCl, mechanical stirring dissolves under room temperature, is made into the LiCl/NMP solution that mass concentration is 16g/L；After being completely dissolved to LiCl, The powdered p-phenylenediamine (PDA) of 1.08g and 1, the 5- naphthylenediamine of 1.580g are added under agitation, until it is completely dissolved Afterwards, -10 DEG C are cooled to constant-temperature condensation ethanol bath, be added in two portions paraphthaloyl chloride (TPC), the total 4.06406g of additional amount, Revolving speed is increased at once to 500~3000r/min, 1.5mL acid absorbent pyridine (concentration of pyridine is 26ml/L) is added immediately, instead 30min is answered to occur removing constant-temperature condensation ethanol bath after rod climbing phenomenon, the reaction was continued under room temperature state two hours.After standing It filters, repeatedly washs to be precipitated to water, ethyl alcohol and be in neutrality, be then dried in vacuo at 120 DEG C, obtain modified ppta polymer powder End.Yield is 88.9%.
Detailed description of the invention: as shown in Figure 1, modified ppta not only remains the feature ultraviolet absorption peak of modified prepolymer (230nm, 265nm and), while there is new ultraviolet absorption peak (200nm), show that 1,5- naphthylenediamine monomer is introduced in In PPTA strand.
As shown in Figure 2, modified ppta occurs the feature nuclear magnetic resonance peak for belonging to naphthylenediamine in 120ppm, further demonstrates that into Be synthesized to function target product, i.e. naphthylenediamine modified ppta.
As can be seen from Figure 3, the characteristics of pure PPTA and modified ppta show typical crystalline polymer, and the knot of modified ppta Brilliant degree is declined to a certain extent, and polymer chain is made to become loose, is conducive to improve its dissolubility.
Shown in Fig. 4, reach viscosity highest point when 1,5-DAN content is 20%, and viscosity to a certain extent can be with Indicate molecular weight, i.e. molecular weight highest when 1,5-DAN content is 20%.
As can be seen from Figure 5, with the increase of 1,5-DAN content, the substantially linear downward trend of crystallinity, polymer chain Become loose, is conducive to the dissolubility for improving PPTA.
As seen from Figure 6, modified ppta-H2SO4Solution shows gorgeous color under petrographic microscope, image compared with Clearly and it can find there is apparent liquid crystal texture.The above phenomenon illustrates that the new modified PPTA of synthesis maintains the liquid crystal of pure PPTA Characteristic can carry out batch production for fiber spinning from crystalline state to such modified ppta.
The modified ppta that this patent synthesizes when with 1,5-DAN content being 20% is typical example, to illustrate its photoluminescent property. The modified PPTA fluorescence intensity of 1,5- naphthylenediamine greatly enhances it can be seen from the fluorescence emission spectrum of Fig. 7.

Claims (10)

1. a kind of preparation method of the modified ppta with fluorescent effect, comprising:
(1) under the conditions of nitrogen protection, lithium chloride LiCl and solvent are mixed, and stirring and dissolving under normal temperature condition obtains LiCl solution；
(2) under stirring condition, p-phenylenediamine PDA and 1 is added in nitrogen protection in LiCl solution, 5- naphthylenediamine 1,5-DAN, completely It is cooling after dissolution, paraphthaloyl chloride TPC is then added in two portions, adds sour adsorbent, reacts, post-processes to get having The modified ppta of fluorescent effect；Wherein the molar ratio of 1,5- naphthylenediamine and p-phenylenediamine is 10:90~50:50；Terephthaldehyde Acyl chlorides and 1,5- naphthylenediamine and the molar ratio of p-phenylenediamine total amount are 1.009~1.012:1.
2. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: described Solvent is N-Methyl pyrrolidone NMP in step (1)；The concentration of LiCl solution is 10~20g/L.
3. a kind of preparation method of modified ppta with fluorescent effect according to claim 2, it is characterised in that: described N-Methyl pyrrolidone NMP is N-Methyl pyrrolidone NMP after purification, specifically: NMP is placed in distilling flask, is depressurized Distillation, is then stored in the container of sealing, and it is dry to be put into molecular sieve.
4. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: step (2) addition p-phenylenediamine PDA and 1 in LiCl solution in, 5- naphthylenediamine 1,5-DAN, after being completely dissolved, mole of 1,5- naphthylenediamine Concentration is 0.035~0.176mol/L.
5. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: described Paraphthaloyl chloride TPC is added in two portions in (2) in step specifically: the half of TPC total amount is added every time, adds twice altogether Enter.
6. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: step (2) after the completion of TPC is added in, the total mol concentration of TPC is 0.2~0.5mol/L.
7. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: described It is cooling in step (2) are as follows: to be cooled to -15~-5 DEG C using constant-temperature condensation ethanol bath.
8. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: described Paraphthaloyl chloride TPC is added in two portions in (2) in step, adds sour adsorbent, reaction specifically: be added in two portions to benzene two Formyl chloride TPC increases revolving speed to 500~3000r/min at once, adds sour sorbent reactions 20-40min, it is existing pole-climbing occur As removing cooling device later, the reaction was continued under room temperature state 2-3h.
9. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: described Sour adsorbent is pyridine in step (2), and additional amount is 10~30mL/L.
10. a kind of preparation method of modified ppta with fluorescent effect according to claim 1, it is characterised in that: institute State post-processing in step (2) are as follows: repeatedly washed with water, ethyl alcohol be precipitated to be in neutrality and filter after obtained polymer is put into 60 ~120 DEG C of oven dryings.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1082634A (en) * 1992-05-28 1994-02-23 住友化学工业株式会社 Low polymerization degree is right-the polyarylamide spinning solution
CN103467736A (en) * 2013-09-13 2013-12-25 东华大学 Polymerization method capable of effectively controlling phase transformation in PPTA (poly-p-phenylene terephthamide) synthesis process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1082634A (en) * 1992-05-28 1994-02-23 住友化学工业株式会社 Low polymerization degree is right-the polyarylamide spinning solution
CN103467736A (en) * 2013-09-13 2013-12-25 东华大学 Polymerization method capable of effectively controlling phase transformation in PPTA (poly-p-phenylene terephthamide) synthesis process

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