CN100551949C - Manufacture method with the monomer modified polyaramide resin of fragrant heterocycle, chloro - Google Patents
Manufacture method with the monomer modified polyaramide resin of fragrant heterocycle, chloro Download PDFInfo
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- CN100551949C CN100551949C CNB200610022083XA CN200610022083A CN100551949C CN 100551949 C CN100551949 C CN 100551949C CN B200610022083X A CNB200610022083X A CN B200610022083XA CN 200610022083 A CN200610022083 A CN 200610022083A CN 100551949 C CN100551949 C CN 100551949C
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- phthaloyl chloride
- ursol
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Abstract
The invention discloses a kind of manufacture method with the monomer modified polyaramide resin of fragrant heterocycle, chloro, with p-phthaloyl chloride, Ursol D and 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines is monomer, wherein p-phthaloyl chloride and Ursol D drop into material by calculating equivalent, 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines drop into material by calculating normal 20-80%, at NMP/CaCl
2Adopt the two-step process synthetic resin solution in the solvent system, described two step method is meant and allows part p-phthaloyl chloride and whole Ursol D react in solvent system earlier, forms with the end capped low-molecular-weight oligomer of amido; Allow remaining p-phthaloyl chloride further react the resin of the son amount that finally secures satisfactory grades then with the end capped low-molecular-weight oligomer of amido.It is good that the product that present method is produced has flame retardant properties, physical strength height, and the relatively low advantage of cost.
Description
Affiliated technical field
The invention belongs to the specialty synthetic fibre production field.
Background technology
Adopting p-phthaloyl chloride and Ursol D is the raw material production aromatic polyamide resin, and is well-known technology with this resin as the presoma of preparation aramid fiber, film, and has a large amount of patents to deliver.But this aromatic polyamide resin is a powdered, need further be dissolved in just can be used for spinning, system film in the vitriol oil and make fibrid.Simultaneously, the fiber made from this resin does not also satisfy the needs of some purposes at aspects such as tensile strength, tensile modulus, flame retardant properties, resistance to fatigues.Therefore, above-mentioned resin synthetic carried out a large amount of study on the modification.
Japan Supreme Being people company is by introducing the 3rd monomer-3, and 4 '-diaminodiphenyl oxide has obtained the resin of solution shape, can directly carry out spinning with this resin and prepare the Tehnora fiber, has improved the intensity (3.8GPa) and the elongation at break (5-6%) of fiber.
Russia then introduces the resin that fragrant heterocyclic monomer [2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines] has obtained the solution shape, and carries out wet-spinning with this resin and obtained tensile strength and the higher Armos fiber fibre of tensile modulus.The intensity of dimension is 4.5-5.5Gpa, elongation at break 1.5-2.5%.
In addition, in Russ P (RU2143504), disclosed the method for preparing modifying aramid fiber with 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines, 2-chlorine Ursol D.Tensile strength, tensile modulus height have been obtained, the fiber of good flame resistance.
When Russia introduced fragrant heterocyclic monomer [2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines] synthetic resins in p-phthaloyl chloride and Ursol D, the solvent system of employing was lithium chloride/N,N-DIMETHYLACETAMIDE (LiCl/DMAC) system.Because lithium chloride price height, toxicity be big, reclaim relatively difficulty, is unfavorable for reducing cost.In addition, in Russ P, do not relate to the synthesis technique equipment of resin, when implementing, be difficult to guarantee to obtain molecular weight height, the resin solution of even molecular weight distribution.
Summary of the invention
The present invention, a kind of manufacture method with the monomer modified polyaramide resin of fragrant heterocycle, chloro, with p-phthaloyl chloride, Ursol D and 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines is monomer, wherein p-phthaloyl chloride and Ursol D drop into material by calculating equivalent, 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines drop into material by calculating normal 20-80%, at NMP/CaCl
2Adopt the two-step process synthetic resin solution in the solvent system, described two step method is meant and allows part p-phthaloyl chloride and whole Ursol D react in solvent system earlier, forms with the end capped low-molecular-weight oligomer of amido; Allow remaining p-phthaloyl chloride further react the resin of the son amount that finally secures satisfactory grades then with the end capped low-molecular-weight oligomer of amido; The coefficient of dynamic viscosity of gained resin solution is the 400-1200 pool, can be directly used in spinning, system film, coating and making fibrid.
Reaction is carried out in two steps, can prevent implode; Can help various monomers and when condensation, form needed sequential structure.In the present invention, polycondensation is carried out in a kind of ascending, descending formula reactor of particular design.During stirring, stir shaft can move up and down.Material is subjected to intensive simultaneously and axially mixes intensive radially mixes except being subjected in this agitator.Therefore conduct heat, mass transfer effect is good, the molecular resin amount height of gained, even molecular weight distribution.In addition, the resin deaeration is carried out in the falling film evaporator of particular design, can deviate from the bubble in the resin at short notice, for follow-up spinning work provides the spinning that meets the requirements slurry.It is good that the product that present method is produced has flame retardant properties, physical strength height, and the relatively low advantage of cost.
Description of drawings
Fig. 1 is the structure sectional view of the ascending, descending formula reactor of this process using.
Fig. 2 is the structure sectional view of the falling film evaporator of this process using.
Embodiment
Solvent system is: NMP/CaCl
2CaCl
2Concentration in NMP is 4-8%, and monomer is at NMP/CaCl
2In concentration be 4-5%.
Elder generation is with the CaCl of 35-50%
2The aqueous solution of the aqueous solution and 93-97%NMP is pressed CaCl
2Concentration in NMP (4-8%) is made into the aqueous solution, anhydrates through decompression, and getting concentration is the CaCl of 4-8%
2/ nmp solution, water content≤150ppm.
Ursol D and chloro Ursol D are dissolved in the CaCl of calculated amount
2In/the nmp solution, cool to 4-8 ℃.Adding chloro p-phthaloyl chloride or p-phthaloyl chloride (it is little by 0.5 that the mol ratio of diamines and diacid chloride is wanted) under violent stirring forms and gives aggressiveness (low-molecular-weight oligomer).To give again after aggressiveness is cooled to 2-5 ℃, add the p-phthaloyl chloride or the chloro p-phthaloyl chloride of residual content, coefficient of dynamic viscosity be the resin solution of 400-1200 pool.This resin solution is deviate to deliver to behind the bubble relevant workshop section (spinning, make film, make fibrid and pulp) in falling film evaporator use.
Can introduce or not introduce the azines tertiary amine compounds when carrying out polycondensation, as pyridine or α-Jia Jibiding, introduction azines tertiary amine compounds can reduce the requirement to material purity and water-content, helps reaction and carries out.
The structure of ascending, descending formula reactor as shown in Figure 1.(1) is transmission mechanism, by the variable frequency regulating speed control mixing speed.(2) be hydraulic lift, allow stir shaft by certain frequency lifting.(3) be agitating vane, not only can scrape wall when stirring, favourable and material surface is brought in constant renewal in, and agitating vane can be strengthened axial mixed effect in the process of moving up and down, help material heat transfer, mass transfer, thereby obtain the molecular weight height, the resin solution of even molecular weight distribution.
Falling film evaporator as shown in Figure 2.Material is extruded slivering through divider (6) under pressure by pipeline (4), and this resin streak falls downwards along light gage wire, enters in the V-shaped groove (7) of the second layer to converge.Resin flows out by aperture from the bottom of V-shaped groove again then, and falls downwards along light gage wire, enters into trilaminar V-shaped groove and converges.The number of plies of flowing through is determined as required.Its objective is material is fully exchanged, prolong the time of falling downwards, thereby increased degasifying effect.(9) use spiral tube for heating, make the still wall keep certain temperature, prevent that condensed gas from condensing on wall.(5) be vacuum interface, (8) are visor.
Below the invention will be further described by embodiment
Embodiment 1: with 100 parts of (weight) content is that 97% NMP and 17.7 parts of content are 35% CaCl
2After mixing, be heated to 200 ℃, be input to then and remove moisture content in the rectifying tower, get 103.2 parts of CaCl through preheater
2Content is 6% nmp solution (water-content≤150ppm) make solvent to use.Then 40% mole of 2-5 ' dichloro Ursol D and 60% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 6% (weight) CaCl
2Nmp solvent in (concentration of diamines in NMP is 5%).To dissolve two good amine aqueous solutions subsequently and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 700 pools.
Resin solution outgases in 60-80 ℃ falling film evaporator after filtering, promptly gets the spinning slurry of using for spinning.The fibre property that spinning slurry obtains after spinning is as follows:
Filament strength 5.5GPa
Fracture specific elongation 1.4%;
Young's modulus 210GPa,
Density 1.45 grams per milliliters; Limiting oxygen index(LOI) 43%
Embodiment 2:CaCl
2Content is that (preparation method of water-content≤150ppm) is with embodiment 1 for 6% nmp solution.
40% mole of 2-chlorine Ursol D and 60% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 6% (weight) CaCl by the method for embodiment 1
2Nmp solvent in.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 900 pools.
The fibre property that resin solution outgases in falling film evaporator, obtain after the spinning is as follows:
Filament strength 6.0GPa
Fracture specific elongation 1.9%;
Young's modulus 172GPa,
Density 1.45 grams per milliliters; Limiting oxygen index(LOI) 40%
Embodiment 3:CaCl
2Content is that (preparation method of water-content≤150ppm) is with embodiment 1 for 6% nmp solution.
80% mole of 2-chlorine Ursol D and 20% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 6% (weight) CaCl by the method for embodiment 1
2Nmp solvent in.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 800 pools.
The fibre property that resin solution outgases in falling film evaporator, obtain after the spinning is as follows:
Filament strength 6.0GPa
Fracture specific elongation 1.6%;
Young's modulus 180GPa,
Density 1.46 grams per milliliters;
Limiting oxygen index(LOI) 45%
Embodiment 4:CaCl
2Content is that (preparation method of water-content≤150ppm) is with embodiment 1 for 6% nmp solution.
80% mole of Ursol D and 20% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 6% (weight) CaCl by the method for embodiment 1
2Nmp solvent in.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of 2-chlorine p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of 2-chlorine p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 430 pools.
The fibre property that resin solution outgases in falling film evaporator, obtain after the spinning is as follows:
Filament strength 4.5GPa
Fracture specific elongation 2.6%;
Young's modulus 130GPa,
Density 1.45 grams per milliliters;
Limiting oxygen index(LOI) 40%
Embodiment 5: with 2,3,5,6-tetrachloro-p-phenylene dimethyl chloride replaces 2-chlorine p-phthaloyl chloride, and all the other are with embodiment 4, and obtaining coefficient of dynamic viscosity is the resin solution of 410 pools.
The fibre property that resin solution obtains after spinning is:
Filament strength 4.3Pa
Fracture specific elongation 2.3%;
Young's modulus 145G, limiting oxygen index(LOI) 43%.
Embodiment 6:CaCl
2Content is that (preparation method of water-content≤300ppm) is with embodiment 1 for 6% nmp solution.
The pyridine of 80% mole of Ursol D and 20% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines and 2% (quantity of solvent) is dissolved in 6% (weight) CaCl by the method for embodiment 1
2Nmp solvent in.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of 2-chlorine p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of 2-chlorine p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 430 pools.
The fibre property that resin solution outgases in falling film evaporator, obtain after the spinning is as follows:
Filament strength 4.7GPa
Fracture specific elongation 2.5%;
Young's modulus 135GPa,
Density 1.45 grams per milliliters;
Limiting oxygen index(LOI) 42%
Comparative example 1:CaCl
2Content is that (preparation method of water-content≤150ppm) is with embodiment 1 for 6% nmp solution.
50% mole of Ursol D and 50% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 3% (in the DMAC solvent of weight LiCl.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and under violent stirring, add 50% mole of p-phthaloyl chloride and form with the end capped low-molecular-weight oligomer of amido.Low-molecular-weight oligomer is cooled to 2-5 ℃ then, progressively adds 50% mole of p-phthaloyl chloride of residual content again, obtaining coefficient of dynamic viscosity is the resin solution of 560 pools.
The fibre property that resin solution outgases in falling film evaporator, obtain after the spinning is as follows:
Filament strength 4.5GPa
Fracture specific elongation 2.6%;
Young's modulus 140GPa, limiting oxygen index(LOI) 30%
Comparative example 2:CaCl
2Content is that (preparation method of water-content≤150ppm) is with embodiment 1 for 6% nmp solution.
50% mole of Ursol D and 50% mole of 2-(4 aminophenyl)-5 (6) aminophenyl benzoglyoxalines are dissolved in 3% (in the DMAC solvent of weight LiCl.To dissolve two good amine aqueous solutions then and be cooled to 2-5 ℃, and in common enamel still, under the 85rpm stirring velocity, once add 100% mole of p-phthaloyl chloride, obtaining coefficient of dynamic viscosity is the resin solution of 360 pools.
The fibre property that resin solution outgases in common enamel still, obtain after the spinning is as follows:
Filament strength 3.7GPa
Fracture specific elongation 3.0%;
Young's modulus 120GPa,
Head is many during spinning, easily stifled spinning jet.
Claims (7)
1, a kind of manufacture method with the monomer modified polyaramide resin of fragrant heterocycle, chloro, with p-phthaloyl chloride, Ursol D and 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines is monomer, wherein p-phthaloyl chloride and Ursol D drop into material by calculating equivalent, 2-(4-aminophenyl)-5 (6) aminophenyl benzoglyoxalines drop into material by calculating normal 20-80%, at NMP/CaCl
2Adopt the two-step process synthetic resin solution in the solvent system, synthetic being meant of described two step method allows part p-phthaloyl chloride and whole Ursol D react in solvent system earlier, forms with the end capped low-molecular-weight oligomer of amido; Allow remaining p-phthaloyl chloride further react then, finally obtain the high-molecular weight resin with the end capped low-molecular-weight oligomer of amido; Polycondensation is carried out in the ascending, descending formula reactor that stir shaft can move up and down, and the coefficient of dynamic viscosity of gained resin solution is the 400-1200 pool, can be directly used in spinning, system film, coating and making fibrid.
2, the manufacture method with fragrant heterocycle, chloro monomer modified polyaramide resin according to claim 1 is characterized in that Ursol D can be the chloro Ursol D.
3, the manufacture method with fragrant heterocycle, chloro monomer modified polyaramide resin according to claim 2 is characterized in that described chloro Ursol D can be 2-chlorine Ursol D and 2, one of 5-dichloro Ursol D.
4, the manufacture method with fragrant heterocycle, chloro monomer modified polyaramide resin according to claim 1 is characterized in that described p-phthaloyl chloride can be the chloro p-phthaloyl chloride.
5, the manufacture method with fragrant heterocycle, chloro monomer modified polyaramide resin according to claim 4 is characterized in that described chloro p-phthaloyl chloride can be 2-chlorine p-phthaloyl chloride, 2,5-dichloro p-phthaloyl chloride and 2,3,5, the 6-tetrachloro is for one of p-phthaloyl chloride.
6, in the manufacture method described in the claim 1, it is characterized in that CaCl with the monomer modified polyaramide resin of fragrant heterocycle, chloro
2Concentration in NMP (weight) is 4-8%, water-content≤150ppm.
7, in the manufacture method described in the claim 1, it is characterized in that, when carrying out polycondensation, can introduce the azines tertiary amine compounds with the monomer modified polyaramide resin of fragrant heterocycle, chloro.
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Assignee: Sichuan Deyang Technology Co., Ltd. Assignor: Huatong Sichuan Research Center For Special Engineering Plastics Contract record no.: 2011510000238 Denomination of invention: Method for preparing polyaramide resin modified by aromatic heterocycle and chloromonomer Granted publication date: 20091021 License type: Exclusive License Open date: 20080423 Record date: 20110831 |
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