CN102924711A - Preparation method for aromatic copolyamide - Google Patents
Preparation method for aromatic copolyamide Download PDFInfo
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- CN102924711A CN102924711A CN2011102275823A CN201110227582A CN102924711A CN 102924711 A CN102924711 A CN 102924711A CN 2011102275823 A CN2011102275823 A CN 2011102275823A CN 201110227582 A CN201110227582 A CN 201110227582A CN 102924711 A CN102924711 A CN 102924711A
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Abstract
The present invention relates to a preparation method for aromatic copolyamide. According to the preparation method, p-phenylenediamine, one or two diamine monomers and terephthaloyl chloride are adopted to carry out a low temperature solution polymerization reaction in a cosolvent-containing amide solvent system to prepare an aromatic copolyamide solution with a solid content of 2-10%, wherein dynamic viscosity of the solution is 50-500 thousand cP, logarithmic viscosity number of the polymer is 4-7.5, and the solution can be subjected to a spinning process control to prepare aromatic polyamide fibers with characteristics of high strength, high modulus and high temperature resistance.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic series copolyamide.By in the polymerization process of different solvents system, regulating kind and the ratio of copolymerized diamine monomer, control aromatic series copolyamide macromolecular chain structure, the aromatic series copolyamide solution that obtains can be used for directly spinning high strength, high-modulus, resistant to elevated temperatures aromatic coplyamide fibre.
Background technology
The aromatic series copolyamide is the raw material of preparation high strength, high-modulus, resistant to elevated temperatures special fibre, the fiber specific tenacity that makes with it be steel wire 5-6 doubly, specific modulus be steel wire 2-3 doubly, can anti-400 ℃ high temperature.Because its outstanding performance becomes the body material of the preferred matrix materials in field such as space flight and aviation, military project just gradually.Its epoxy composite material is successfully applied to the aspects such as solid rocket motor case, tank armor plate.Russia produces
Fiber is exactly a kind of aromatic coplyamide fibre of performance brilliance, and its tensile strength is 4.2～5.5GPa, modulus 120～145GPa.
The at present preparation of aromatic series copolyamide mainly is to change the character such as structure, regularity, degree of crystallinity of macromolecular chain by the kind that changes diamine monomer, thereby changes the mechanical property of its fiber.
US Patent No. P4 discloses a kind of preparation method of aromatic series copolyamide in 018,735.This patent adopts the mixed solvent system of NMP and hexamethylphosphoric acid triamide (HMPA), and the Ursol D of different ratios and 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline and p-phthaloyl chloride reaction obtain the aromatic series copolyamide.Because the HMPA solvent has carcinogenesis and is not suitable for using in industrialization.
The preparation method who discloses a kind of aromatic coplyamide fibre among a kind of preparation method of aromatic series copolyamide and the CN101787582 is disclosed among the Chinese patent CN1480479.These two patents all adopt the DMAC-LiCl solvent system, the reaction of the Ursol D of different ratios and 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline and p-phthaloyl chloride obtains the aromatic series copolyamide, the aromatic coplyamide fibre good mechanical properties that obtains by spinning.
Relate to the method that adopts simultaneously adjacent chlorine Ursol D, 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline to prepare the aromatic series copolyamide as the 3rd, the 4th monomer there are no patent or document.
Summary of the invention:
The present invention aims to provide a kind of preparation method of aromatic series copolyamide, and the polymer that obtains can be prepared high strength, high-modulus, resistant to elevated temperatures aromatic polyamide fibre.
In order to realize the foregoing invention purpose, the present invention by the following technical solutions:
A kind of preparation method of aromatic series copolyamide, Ursol D and copolymerization diamine monomer and p-phthaloyl chloride to be carried out the low temperature solution polymerization reaction be prepared from containing the amide solvent system of solubility promoter, it is characterized in that described copolymerized diamine monomer is one or both mixing of adjacent chlorine Ursol D, 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline.
In a preferred embodiment of the invention, mixing and the mol ratio between the Ursol D of one or both of described adjacent chlorine Ursol D, 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline are 10～90: 90～10.
In a preferred embodiment of the invention, the mol ratio between described adjacent chlorine Ursol D and 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline is 0～100: 100～0.
The molar ratio of described Ursol D and copolymerized diamine monomer sum and p-phthaloyl chloride is 1～1.005: 1～1.005.
In a preferred embodiment of the invention, concrete steps are:
(1) described Ursol D and described copolymerized diamine monomer added contain in the amide solvent system of solubility promoter, cool after the dissolving to-15 ℃～10 ℃ two amine aqueous solutions;
(2) p-phthaloyl chloride and gained two amine aqueous solutions with 30～70wt% carry out making in prepolymerization reaction 1-2 hour performed polymer at-15 ℃～10 ℃; Gained performed polymer and remain to such an extent that the p-phthaloyl chloride of 70～30wt% carries out making in polycondensation 1-3 hour aromatic series copolyamide solution at-10 ℃～80 ℃.
In a preferred embodiment of the invention, described step (1) is to be to contain in the amide solvent system of solubility promoter 0～38 ℃ of lower adding with described Ursol D and described copolymerized diamine monomer.
In a preferred embodiment of the invention, in the described step (1), in the described amide solvent system that contains solubility promoter, the mass percent of described solubility promoter is 5～12%.
In a preferred embodiment of the invention, in the described step (2), p-phthaloyl chloride and gained two amine aqueous solutions of 30～70wt% are carried out making in prepolymerization reaction 1-2 hour performed polymer at-15 ℃～0 ℃
In a preferred embodiment of the invention, the aromatic series copolyamide solution adding double-screw reactor of described step (2) preparation further improves molecular weight 20%-30% and obtains spinning solution, wherein the screw diameter of double-screw reactor is that φ 25～65mm, length-to-diameter ratio are 1: 14～70, and rotating speed is 90～200rpm.
In a preferred embodiment of the invention, the kinetic viscosity of described spinning solution is 5～500,000, and the logarithmic viscosity number of aromatic series copolyamide is between 4～7.5, and solid content is 2～10wt%.
In a preferred embodiment of the invention, the described residence time of aromatic series copolyamide solution in described twin screw extruder is 0.5～15 minute, and temperature is 10 ℃～60 ℃.
In a preferred embodiment of the invention, the described amide solvent system that contains solubility promoter is one or both or the two or more mixing in the N-ethyl pyrrolidone (NEP) that is selected from the N,N-DIMETHYLACETAMIDE (DMAC) that contains solubility promoter, the N-Methyl pyrrolidone (NMP) that contains solubility promoter, contains solubility promoter; Wherein said solubility promoter is the muriate of basic metal or alkaline-earth metal.
Described solubility promoter is one or more the mixing that is selected from calcium chloride, lithium chloride, magnesium chloride and the tin chloride.
In a preferred embodiment of the invention, the mixing of one or more that the reinforced form of p-phthaloyl chloride is that solution is reinforced, powder reinforced, melting is reinforced.
Adopt the aromatic series copolyamide solution of aforesaid method preparation, its solid content is 2～10%, and kinetic viscosity is 5～500,000 centipoises, and logarithmic viscosity number is between 4～7.5.This aromatic series copolyamide solution is controlled through spinning technique can prepare breaking tenacity 25～35cN/detx, the aromatic polyamide fibre of Young's modulus 950～1350cN/detx.
Embodiment:
The present invention will be further described in detail below in conjunction with specific embodiment, but the invention is not restricted to these embodiment.
Following examples are selected the kinetic viscosity of the digital viscometer determining aromatic series of NDJ-8S copolyamide solution according to GB10247-88 " viscosity test method ".
The 0.125g aromatic series copolyamide of complete drying is dissolved in 98% the vitriol oil of 25mL AR, in the water bath with thermostatic control of (30 ± 0.2) ℃, measures logarithm viscosity with Ubbelohde viscometer.
Embodiment 1
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 5 (6)-amino of 63g-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continues stirring reaction and obtained aromatic series copolyamide solution in 60 minutes; it is φ 25mm that aromatic series copolyamide solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtain the spinning solution that kinetic viscosity is 80,000 centipoises, the logarithmic viscosity number of aromatic series copolyamide is 6.3.
Embodiment 2
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 15.12g; 58.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 8.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.38.
Embodiment 3
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 21.6g; 5 (6)-amino of 45g-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 90,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.43.
Embodiment 4
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 31.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; 20.09g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 9.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.6.
Embodiment 5
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 5 (6)-amino of 18g-2-(4-aminophenyl) benzoglyoxaline; 28.7g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 9.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.5.
Embodiment 6
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-Methyl pyrrolidone (NMP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 5 (6)-amino of 45g-2-(4-aminophenyl) benzoglyoxaline; 11.48g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 90,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.52.
Embodiment 7
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N-Methyl pyrrolidone (NMP) the solution 2760g of 240g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 19.44g; 94.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 60.9g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 60.9g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 110,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.32.
Embodiment 8
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N-Methyl pyrrolidone (NMP) the solution 2760g of 240g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 19.44g; 47.25g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; 30.13g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 60.9g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 60.9g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 120,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.45.
Embodiment 9
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N,N-DIMETHYLACETAMIDE (DMAC) the solution 2880g of 120g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 5 (6)-amino of 63g-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 80,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.35.
Embodiment 10
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N,N-DIMETHYLACETAMIDE (DMAC) the solution 2880g of 120g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 21.6g; 5 (6)-amino of 45g-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 90,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.5.
Embodiment 11
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N,N-DIMETHYLACETAMIDE (DMAC) the solution 2880g of 120g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 31.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; 20.09g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 9.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.7.
Embodiment 12
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-ethyl pyrrolidone (NEP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 5 (6)-amino of 63g-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 80,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.36.
Embodiment 13
The preparation method of aromatic series copolyamide, specific as follows: as in the stainless steel cauldron of 5000L with chuck, to inject 240g calcium chloride (CaCl
2) N-ethyl pyrrolidone (NEP) solution 2760g; at 15 ℃ of lower Ursol D (PPDA) that add 12.96g; 31.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; 20.09g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 40.6g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 40.6g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 90,000 centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.59.
Embodiment 14
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N-ethyl pyrrolidone (NEP) the solution 2760g of 240g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 19.44g; 94.5g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 60.9g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 60.9g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 11.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.4.
Embodiment 15
The preparation method of aromatic series copolyamide; specific as follows: in the stainless steel cauldron of 5000L with chuck; inject N-ethyl pyrrolidone (NEP) the solution 2760g of 240g lithium chloride (LiCl); at 15 ℃ of lower Ursol D (PPDA) that add 19.44g; 47.25g 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline; 30.13g adjacent chlorine Ursol D; it is fully dissolved; be cooled to-15 ℃; the p-phthaloyl chloride (TPC) that slowly adds 60.9g; stirring reaction formed performed polymer in 60 minutes under nitrogen protection; the TPC that adds 60.9g in 0 ℃ performed polymer continued stirring reaction 60 minutes; it is φ 25mm that this solution is added diameter; length-to-diameter ratio is 1: 48; rotating speed is to proceed polycondensation in the in the same way extruding machine with two screw rods engaging of 90rpm under 30 ℃; obtaining kinetic viscosity is the aromatic series copolyamide solution of 12.5 ten thousand centipoises, and the logarithmic viscosity number of aromatic series copolyamide is 6.53.
Claims (14)
1. the preparation method of an aromatic series copolyamide, Ursol D and copolymerization diamine monomer and p-phthaloyl chloride to be carried out the low temperature solution polymerization reaction be prepared from containing the amide solvent system of solubility promoter, it is characterized in that described copolymerized diamine monomer is one or both mixing of adjacent chlorine Ursol D, 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline.
2. the preparation method of aromatic series copolyamide as claimed in claim 1, it is characterized in that mixing and the mol ratio between the Ursol D of one or both of described adjacent chlorine Ursol D, 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline are 10～90: 90～10.
3. the preparation method of aromatic series copolyamide as claimed in claim 1 is characterized in that, the mol ratio between described adjacent chlorine Ursol D and 5 (6)-amino-2-(4-aminophenyl) benzoglyoxaline is 0～100: 100～0.
4. the preparation method of aromatic series copolyamide as claimed in claim 1 is characterized in that, the molar ratio of described Ursol D and copolymerized diamine monomer sum and p-phthaloyl chloride is 1～1.005: 1～1.005.
5. such as the preparation method of the described aromatic series copolyamide of each claim of claim 1 to 4, it is characterized in that concrete steps are:
(1) described Ursol D and described copolymerized diamine monomer added contain in the amide solvent system of solubility promoter, cool after the dissolving to-15 ℃～10 ℃ two amine aqueous solutions;
(2) p-phthaloyl chloride and gained two amine aqueous solutions with 30～70wt% carry out making in prepolymerization reaction 1-2 hour performed polymer at-15 ℃～10 ℃; Gained performed polymer and remain to such an extent that the p-phthaloyl chloride of 70～30wt% carries out making in polycondensation 1-3 hour aromatic series copolyamide solution at-10 ℃～80 ℃.
6. the preparation method of aromatic series copolyamide as claimed in claim 5 is characterized in that, described step (1) is to be to contain in the amide solvent system of solubility promoter 0～38 ℃ of lower adding with described Ursol D and described copolymerized diamine monomer.
7. the preparation method of aromatic series copolyamide as claimed in claim 5 is characterized in that, in the described step (1), in the described amide solvent system that contains solubility promoter, the mass percent of described solubility promoter is 5～12%.
8. the preparation method of aromatic series copolyamide as claimed in claim 7, it is characterized in that the described amide solvent system that contains solubility promoter is one or both or the two or more mixing in the N-ethyl pyrrolidone (NEP) that is selected from the N,N-DIMETHYLACETAMIDE (DMAC) that contains solubility promoter, the N-Methyl pyrrolidone (NMP) that contains solubility promoter, contains solubility promoter; Wherein said solubility promoter is the muriate of basic metal or alkaline-earth metal.
9. the preparation method of aromatic series copolyamide as claimed in claim 7 is characterized in that, described solubility promoter is one or more the mixing that is selected from calcium chloride, lithium chloride, magnesium chloride and the tin chloride.
10. the preparation method of aromatic series copolyamide as claimed in claim 5 is characterized in that, the mixing of one or more that the reinforced form of p-phthaloyl chloride is that solution is reinforced, powder reinforced, melting is reinforced.
11. the preparation method of aromatic series copolyamide as claimed in claim 5 is characterized in that, in the described step (2), p-phthaloyl chloride and gained two amine aqueous solutions of 30～70wt% is carried out making in prepolymerization reaction 1-2 hour performed polymer at-15 ℃～0 ℃
12. the preparation method of aromatic series copolyamide as claimed in claim 5, it is characterized in that, the aromatic series copolyamide solution adding double-screw reactor of described step (2) preparation is further carried polymkeric substance high molecular 20-30% and is obtained spinning solution, wherein the screw diameter of double-screw reactor is that φ 25～65mm, length-to-diameter ratio are 1: 14～70, and rotating speed is 90～200rpm.
13. the preparation method of aromatic series copolyamide as claimed in claim 12 is characterized in that, the kinetic viscosity of described spinning solution is 5～500,000, and the logarithmic viscosity number of aromatic series copolyamide is between 4～7.5, and solid content is 2～10wt%.
14. the preparation method of aromatic series copolyamide as claimed in claim 12 is characterized in that, the described residence time of aromatic series copolyamide solution in described twin screw extruder is 0.5～15 minute, and temperature is 10 ℃～60 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231261A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Method for synthesizing chlor-poly(p-phenylene terephthalamide) solution |
| CN106496547A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of poly- paraphenylene terephthalamide to diphenylamines |
| CN110103552A (en) * | 2019-06-13 | 2019-08-09 | 青岛甜昊新材料科技有限公司 | A kind of high intensity tarpaulin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018735A (en) * | 1974-07-10 | 1977-04-19 | Teijin Limited | Anisotropic dopes of aromatic polyamides |
| CN101165078A (en) * | 2006-10-20 | 2008-04-23 | 四川华通特种工程塑料研究中心有限公司 | Method for preparing polyaramide resin modified by aromatic heterocycle and chloromonomer |
| CN101787582A (en) * | 2010-02-10 | 2010-07-28 | 中蓝晨光化工研究院有限公司 | Preparation method of high-tensile high-model heterocycle aramid fiber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018735A (en) * | 1974-07-10 | 1977-04-19 | Teijin Limited | Anisotropic dopes of aromatic polyamides |
| CN101165078A (en) * | 2006-10-20 | 2008-04-23 | 四川华通特种工程塑料研究中心有限公司 | Method for preparing polyaramide resin modified by aromatic heterocycle and chloromonomer |
| CN101787582A (en) * | 2010-02-10 | 2010-07-28 | 中蓝晨光化工研究院有限公司 | Preparation method of high-tensile high-model heterocycle aramid fiber |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231261A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Method for synthesizing chlor-poly(p-phenylene terephthalamide) solution |
| CN106496547A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of poly- paraphenylene terephthalamide to diphenylamines |
| CN110103552A (en) * | 2019-06-13 | 2019-08-09 | 青岛甜昊新材料科技有限公司 | A kind of high intensity tarpaulin and preparation method thereof |
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