CN102040733B - Method for preparing poly(terephthaloyl-p-phenylene diamine) resin - Google Patents
Method for preparing poly(terephthaloyl-p-phenylene diamine) resin Download PDFInfo
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- CN102040733B CN102040733B CN2010105403513A CN201010540351A CN102040733B CN 102040733 B CN102040733 B CN 102040733B CN 2010105403513 A CN2010105403513 A CN 2010105403513A CN 201010540351 A CN201010540351 A CN 201010540351A CN 102040733 B CN102040733 B CN 102040733B
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Abstract
The invention belongs to the field of polymer chemistry and discloses a method for preparing poly(terephthaloyl-p-phenylene diamine) resin by using a composite solvent system, which comprises the following steps: (1) completely dissolving p-phenylenediamine powder in solvent containing cosolvent and acid acceptor; (2) adding 20 to 80 percent of powdered paraphthaloyl chloride into a reaction kettle at a low temperature of -10 to 25 DEG C, adding the rest paraphthaloyl chloride powder for low-temperature polycondensation after the temperature is stable, and continuing to stirring for 1 to 6 hours at 50 to 80 DEC after the reaction system starts gelatinizing; and (3) standing the polymer obtained by reaction, washing, dewatering and drying to obtain the product. The use of the composite solvent system in the invention is more favorable for improving the molecular weight of resin. After a secondary feed adding process is adopted, the heat release during reaction is slow, so local gelatinization is avoided effectively. The logarithmic viscosity number of the poly(terephthaloyl-p-phenylene diamine) resin prepared by the method ranges from 4.5 to 6.5dl/g.
Description
Technical field
The invention belongs to chemical field; Be specifically related to a kind of at N; In N-N,N-DIMETHYLACETAMIDE and the N-Methyl pyrrolidone double solvents system, be the method for feedstock production PPTA resin (PPTA) with p-phthaloyl chloride and Ursol D.
Technical background
PPTA resins are aramid fibers and aramid paddle hectometer of raw materials, aramid fiber with high strength, high modulus, high temperature resistance and anti-corrosion properties, aramid paddle hectometer with high wear resistance and high dispersion advantages.They are widely used in fields such as aerospace, bullet resistant material, high-temperature-resistant filtering material and reinforcing rubber material, and constantly are applied in the new high-tech industry field.
The preparation method of PPTA resin reports a lot of, and main method is to be raw material with p-phthaloyl chloride and Ursol D, in the polar solvent that contains acid binding agent and solubility promoter, carries out the polymkeric substance of cryogenic fluid polycondensation preparation.CN1048710A provides with CaCl
2The method for preparing PPTA for solubility promoter.CaCl
2Large usage quantity, cause Ca residual in the PPTA resin
2+More, be prone to make the PPTA molecular degradation in the spinning stage.EP0104410 provides the method that reinforced legal system of a step is equipped with the PPTA resin.This method makes that the speed of response of Ursol D and p-phthaloyl chloride is fast, and thermal discharge is big, causes temperature of reaction too high, and a lot of side reaction generation, can not get high molecular weight polymers, finally influences the quality of rosin products.CN85100048 has reported a kind of method of synthetic PPTA resin; The churning time that adds p-phthaloyl chloride afterreaction liquid is merely 10～20 minutes; Make that the fluoropolymer resin kinetic viscosity that generates is very big; If stir insufficient, inhomogeneous then can cause local reaction, form a lot of gel particles, influence resin quality.It is the method that solvent is made the PPTA resin that CN101550231 provides with the N-Methyl pyrrolidone, and speed of reaction is lower in this method, and solvent purity requires very high.The present invention uses LiCl to make solubility promoter, and the resin ash content that makes is little; Adopt reinforced method of two steps, controlled the rate of heat release of reaction effectively; Churning time is sufficient, has guaranteed sufficient reacting; In addition, DMAC N,N and N-Methyl pyrrolidone double solvents reaction system have increased speed of reaction, have reduced the requirement to solvent purity.
Summary of the invention
The present invention is the deficiency that overcomes above-mentioned prior art, and a kind of method of using the double solvents system to prepare PPTA is provided.
Technical scheme of the present invention is following:
A kind of preparation method who prepares the PPTA resin may further comprise the steps:
(1) under 70～80 ℃, the solubility promoter adding is contained in the main solvent of acid binding agent, stir 0.5～5h, under 25～35 ℃, Ursol D is dissolved in the above-mentioned reaction solution then; Stir 0.5～1h; Be cooled under the coldcondition 20～80% of the p-phthaloyl chloride total amount of the reaction of adding participation for the first time Powdered p-phthaloyl chloride in reaction solution;
Wherein said main solvent comprises DMAC N,N, N-Methyl pyrrolidone, 1, any two kinds of double solventss in 3-dimethyl--2-imidazolone or the N-methylmorpholine;
Described solubility promoter comprises LiCl, CaCl
2, MgCl
2, Ca (SCN)
2In one or more; Solubility promoter and total solvent and weight ratio be 0.02:1～0.10:1;
Described acid binding agent is a tertiary amine bases acid binding agent, and the weight ratio of acid binding agent and total solvent is 0.05:1～0.10:1;
Need dehydration before described solvent and acid binding agent use, solubility promoter needed 300～500 ℃ of following activation 5～8h before dropping into, and the water ratio of control reaction solution is in 300ppm.Can avoid the p-phthaloyl chloride hydrolysis like this, influence two kinds of monomeric mol ratios.
After the Ursol D dissolving, cooling makes the low-temperature polycondensation temperature be-15～25 ℃.
(2) behind the 5min, in-5～15 ℃ of downhill reaction liquid, add remainder p-phthaloyl chloride powder, strengthen mixing speed, reaction system gets into the gelation post curing;
Described mixing speed is 2000～4000rpm,
Described curing temperature scope is 50～90 ℃,
Churning time is 2～5h in the maturing process;
The mol ratio of p-phthaloyl chloride total amount and Ursol D is 1:1～1.01:1, and the concentration of Ursol D is 0.20～0.50mol/L in the total solvent.
(3) product that makes at room temperature leaves standstill 5～20h, with obtaining Powdered polymer after deionized water agitator treating, dehydration 4 times and the drying.
Wherein step (1) contains the solubility promoter adding in the main solvent of acid binding agent, preferably stirs 0.5～3h; Preferred temperature is under 25～30 ℃ Ursol D to be dissolved in the above-mentioned reaction solution; The Powdered p-phthaloyl chloride add-on that preferably in reaction solution, adds the p-phthaloyl chloride total amount of participating in reaction for the first time is 35～65%;
Wherein the main solvent described in the step (1) is preferably from the mixed solvent of DMAC N,N and N-Methyl pyrrolidone; Described solubility promoter is preferably from LiCl or CaCl
2Solubility promoter and total solvent and weight ratio be preferably 0.02:1～0.05:1.
Wherein the acid binding agent described in the step (1) is preferably from pyridine, α-Jia Jibiding, 2; 6-lutidine, triethylamine, tripropyl amine or Tributylamine; The weight ratio of acid binding agent and total solvent is preferred 0.06:1～0.08:1, and the water ratio of control reaction solution is preferably in 100ppm, after the Ursol D dissolving; Cooling makes the low-temperature polycondensation temperature preferably from-10～5 ℃.
Wherein the mixing speed described in the step (2) is preferably 2000～3000rpm,
Described curing temperature scope is preferably 70～80 ℃,
Churning time is preferably 3h in the maturing process;
The mol ratio of p-phthaloyl chloride total amount and Ursol D is preferably from 1:1～1.005:1; The concentration of Ursol D is preferably from 0.24～0.30mol/L in the total solvent.
Wherein the product that makes of step (3) preferably at room temperature leaves standstill 15～20h.
Advantage of the present invention:The present invention uses the double solvents system to prepare the method for PPTA, and than traditional single solvent system, the double solvents system that the present invention uses more helps improving the molecular weight of PPTA resin.In addition, traditional once reinforced method exists that exothermic heat of reaction is fast, heat is difficult to problems such as transfer in time, very easily causes topical gelization.Adopt the heat release of secondary charging method afterreaction slow, effectively avoided topical gelization.The viscosity of the obtained PPTA resin of the present invention can reach 4.5～6.5dl/g.
Description of drawings
The process flow sheet for preparing PPTA for low-temperature solution polycondensation of the present invention shown in Figure 1.
Embodiment
The logarithmic viscosity number of PPTA resin is to be solvent with 95～98% the vitriol oil among the present invention, adopt Ubbelodhe viscometer, mensuration under 30 ℃ of constant temperature.Concrete steps are following:
With the 0.125gPPTA resin dissolves of complete drying in the vitriol oil of 25ml 98%, with Ubbelohde viscometer (30
+0.2) ℃ water bath with thermostatic control in measure logarithm viscosity.Be calculated as follows:
η
inh=In(t/t
0)/C
In the formula, t-the effusive time of PPTA resin solution;
t
0-the effusive time of neat solvent;
C-the gram number of PPTA resin in the 100mL solvent, g/dl.
Embodiment 1
At N
2Protection is injected 50mL DMAC N,N, 2.40mL α-Jia Jibiding and 0.94g Ca (SCN) down in polymerization reaction kettle
2Reaction solution is stirred 0.5h down at 80 ℃, make Ca (SCN)
2All be dissolved in the solvent.Reaction solution is cooled to 25 ℃, adds 0.54g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.Reaction solution is cooled to-10 ℃ with the cryosel bath, adds 0.66g p-phthaloyl chloride powder, add 0.38g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 3000rpm, and after reaction system got into gelation, at 80 ℃ of slaking 5h, reaction system left standstill 5h.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 5h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 5.60dl/g.
Embodiment 2
At N
2Protection is injected the 40mL DMAC N,N down in polymerization reaction kettle, 10mL 1,3-dimethyl-imidazolinone, 2.64mL2,6-lutidine and 1.08g CaCl
2Reaction solution is stirred 1h down at 80 ℃, make CaCl
2All be dissolved in the solvent.Reaction solution is cooled to 28 ℃, adds 1.08g Ursol D powder, stirring reaction liquid 1.5h all is dissolved in the reaction solution Ursol D.Reaction solution is cooled to-5 ℃ with the cryosel bath, adds 1.23g p-phthaloyl chloride powder, add 0.84g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 2500rpm, after reaction system gets into gelation, at 70 ℃ of slaking 4h.At N
2Protection is left standstill 5h with reaction system down.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 10h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 5.91dl/g.
Embodiment 3
At N
2Protection is injected 40mL DMAC N,N, 5mLN-methylmorpholine, 2.88mL triethylamine and 1.23gLiCl down in polymerization reaction kettle.Reaction solution is stirred 2h down at 80 ℃, LiCl all is dissolved in the solvent.Reaction solution is cooled to 30 ℃, adds 1.19g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.Reaction solution is cooled to-5 ℃ with the cryosel bath, adds 0.89g p-phthaloyl chloride powder.Add 1.39g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 2000rpm, after reaction system gets into gelation, at 60 ℃ of slaking 3h.At N
2Protection is left standstill 5h with reaction system down.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 15h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 6.04dl/g.
Embodiment 4
At N
2Protection is injected 47mLN, N-N,N-DIMETHYLACETAMIDE, 3mLN-SL 1332,3.13mL pyridine and 1.32gLiCl down in polymerization reaction kettle.Reaction solution is stirred 3h down at 80 ℃, LiCl all is dissolved in the solvent.Reaction solution is cooled to 30 ℃, adds 1.35g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.Reaction solution is cooled to-5 ℃ with the cryosel bath, adds 0.91g p-phthaloyl chloride powder.Add 1.68g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 2000rpm.After reaction solution becomes milk yellow, with reaction solution at 60 ℃ of following slaking 3h.。Reaction system is left standstill 15h.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 15h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 6.5dl/g.
Embodiment 5
At N
2Protection is injected 47mLN, N-N,N-DIMETHYLACETAMIDE, 3mLN-SL 1332,3.36mL pyridine and 1.89gCaCl down in polymerization reaction kettle
2Reaction solution is stirred 3h down at 80 ℃, LiCl all is dissolved in the solvent.Reaction solution is cooled to 30 ℃, adds 2.70g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.With the cryosel bath reaction solution is cooled to 3 ℃, adds 1.82g p-phthaloyl chloride powder.Add 3.36g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 2500rpm.After reaction solution becomes milk yellow, with reaction solution at 60 ℃ of following slaking 3.5h.Reaction system is left standstill 15h.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 15h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 6.12dl/g.
Embodiment 6
At N
2Protection is injected 47mLN, N-N,N-DIMETHYLACETAMIDE, 3mLN-SL 1332,3.60mL Tributylamine, 1.72gLiCl and 0.31gAlCl down in polymerization reaction kettle
3Reaction solution is stirred 2h down at 80 ℃, make LiCl and AlCl
3All be dissolved in the solvent.Reaction solution is cooled to 30 ℃, adds 3.24g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.With the cryosel bath reaction solution is cooled to 5 ℃, adds 3.36g p-phthaloyl chloride powder, add 2.86g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 3000rpm.After reaction solution becomes milk yellow, with reaction solution at 65 ℃ of following slaking 4.5h.
Reaction system is left standstill 15h.The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 15h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 5.41dl/g.
Embodiment 7
At N
2Protection is injected 47mLN, N-N,N-DIMETHYLACETAMIDE, 3mLN-SL 1332,3.84mL tripropyl amine and 4.71gMgCl down in polymerization reaction kettle
2Reaction solution is stirred 1h down at 80 ℃, make MgCl
2All be dissolved in the solvent.Reaction solution is cooled to 30 ℃, adds 4.33g Ursol D powder, stirring reaction liquid 0.5h all is dissolved in the reaction solution Ursol D.With the cryosel bath reaction solution is cooled to 5 ℃, adds 3.14g p-phthaloyl chloride powder.Add 5.16g p-phthaloyl chloride powder after 5 minutes again.The rotating speed of telo merization still is to 3000rpm.After reaction solution becomes milk yellow, reaction solution is stirred 5h down at 70 ℃, reaction system is left standstill 15h.
The resin that makes is steeped in the 1000mL deionized water, stirred 20 minutes, the suction filtration dehydration.Repeated washing and dehydration 4 times.Under 80 ℃, the resin of producing is vacuumized the toner that dry 15h obtains faint yellow corn pasty state.The logarithmic viscosity number that records resin is 4.52dl/g.
Claims (5)
1. preparation method who prepares the PPTA resin may further comprise the steps:
(1) under 70～80 ℃, the solubility promoter adding is contained in the main solvent of acid binding agent, stir 0.5～5h, under 25～35 ℃, Ursol D is dissolved in the above-mentioned reaction solution then, stir 0.5～1h; Be cooled under the coldcondition, 20～80% of the p-phthaloyl chloride total amount of the reaction of adding participation for the first time Powdered p-phthaloyl chloride in reaction solution,
Wherein said main solvent comprises DMAC N,N, N-Methyl pyrrolidone, 1, any two kinds of double solventss in 3-dimethyl--2-imidazolone or the N-methylmorpholine;
Described solubility promoter comprises LiCl, CaCl
2, MgCl
2, Ca (SCN)
2In one or more; The weight ratio of solubility promoter and total solvent is 0.02:1～0.10:1;
Described acid binding agent is a tertiary amine bases acid binding agent, and the weight ratio of acid binding agent and total solvent is 0.05:1～0.10:1;
Need dehydration before described solvent and acid binding agent use, solubility promoter needed 300～500 ℃ of following activation 5～8h before dropping into, and the water ratio of control reaction solution is in 300ppm;
After the Ursol D dissolving, cooling makes the low-temperature polycondensation temperature be-15～25 ℃;
(2) behind the 5min, in-5～15 ℃ of downhill reaction liquid, add remainder p-phthaloyl chloride powder, strengthen mixing speed, reaction system gets into the gelation post curing;
Described mixing speed is 2000～4000rpm,
Described curing temperature scope is 50～90 ℃,
Churning time is 2～5h in the maturing process;
The mol ratio of p-phthaloyl chloride total amount and Ursol D is 1:1～1.01:1, and the concentration of Ursol D is 0.20～0.50mol/L in the total solvent,
(3) product that makes at room temperature leaves standstill 5～20h, with obtaining Powdered polymer after deionized water agitator treating, dehydration 4 times and the drying.
2. according to the said a kind of preparation method who prepares the PPTA resin of claim 1, it is characterized in that wherein the main solvent described in the step (1) is the mixed solvent of DMAC N,N and N-Methyl pyrrolidone; Described solubility promoter is LiCl or CaCl
2The weight ratio of solubility promoter and total solvent is 0.02:1～0.05:1.
3. according to the said a kind of preparation method who prepares the PPTA resin of claim 1; It is characterized in that wherein the acid binding agent described in the step (1) is pyridine, α-Jia Jibiding, 2,6-lutidine, triethylamine, tripropyl amine or Tributylamine, the weight ratio of acid binding agent and total solvent is 0.06:1～0.08:1; The water ratio of control reaction solution is in 100ppm; After the Ursol D dissolving, cooling makes the low-temperature polycondensation temperature be-10～5 ℃.
4. according to the said a kind of preparation method who prepares the PPTA resin of claim 1, it is characterized in that wherein the mixing speed described in the step (2) is 2000～3000rpm,
Described curing temperature scope is 70～80 ℃,
Churning time is 3h in the maturing process;
The mol ratio of p-phthaloyl chloride total amount and Ursol D is 1:1～1.005:1; The concentration of Ursol D is 0.24～0.30mol/L in the total solvent.
5. according to the said a kind of preparation method who prepares the PPTA resin of claim 1, it is characterized in that the product that step (3) wherein makes at room temperature leaves standstill 15～20h.
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|---|---|---|---|
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| CN2010105403513A CN102040733B (en) | 2010-11-12 | 2010-11-12 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532529B (en) * | 2012-01-06 | 2014-01-29 | 东华大学 | Method for preparing terephthaloyl phenylenediamine resin through low-temperature solution out-of-phase polycondensation |
| CN102649842B (en) * | 2012-05-11 | 2013-10-30 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
| CN107653508A (en) * | 2017-10-17 | 2018-02-02 | 蓝星（成都）新材料有限公司 | A kind of preparation method of high intensity Fanglun l414 fiber |
| CN112201903A (en) * | 2019-11-26 | 2021-01-08 | 中蓝晨光化工研究设计院有限公司 | High-performance polyaramide lithium battery diaphragm coating based polymerization solution and preparation method and application thereof |
| CN111704715B (en) * | 2020-04-29 | 2023-04-07 | 常州瑞华化工工程技术股份有限公司 | Preparation method of all-para-aromatic polyamide |
| CN114230786B (en) * | 2021-11-23 | 2023-09-22 | 烟台泰和兴材料科技股份有限公司 | Preparation method and application of superfine poly-p-phenylene terephthamide powder |
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|---|---|---|---|---|
| EP0104410A2 (en) * | 1982-08-30 | 1984-04-04 | Korea Advanced Institute Of Science And Technology | Highly oriented aromatic polyamide short fiber |
| CN1048710A (en) * | 1990-08-15 | 1991-01-23 | 化学工业部成都有机硅应用研究技术服务中心 | The preparation method of high viscosity PPTA |
| CN101215376A (en) * | 2007-12-29 | 2008-07-09 | 中蓝晨光化工研究院有限公司 | Material mixer used for high temperature difference quick reaction |
| CN101220148A (en) * | 2007-01-08 | 2008-07-16 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
| CN101550231A (en) * | 2008-04-03 | 2009-10-07 | 中国神马集团有限责任公司 | Industrial method and polycondensation reactor for continuously preparing poly-p-phenylene terephthamide resin with high viscosity |
-
2010
- 2010-11-12 CN CN2010105403513A patent/CN102040733B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104410A2 (en) * | 1982-08-30 | 1984-04-04 | Korea Advanced Institute Of Science And Technology | Highly oriented aromatic polyamide short fiber |
| CN1048710A (en) * | 1990-08-15 | 1991-01-23 | 化学工业部成都有机硅应用研究技术服务中心 | The preparation method of high viscosity PPTA |
| CN101220148A (en) * | 2007-01-08 | 2008-07-16 | 江苏昊诚皮革新材料有限公司 | Novel preparation technique for poly (p-phenylene terephthalamide) |
| CN101215376A (en) * | 2007-12-29 | 2008-07-09 | 中蓝晨光化工研究院有限公司 | Material mixer used for high temperature difference quick reaction |
| CN101550231A (en) * | 2008-04-03 | 2009-10-07 | 中国神马集团有限责任公司 | Industrial method and polycondensation reactor for continuously preparing poly-p-phenylene terephthamide resin with high viscosity |
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