CN109438697A - A kind of preparation method of aromatic amides - Google Patents
A kind of preparation method of aromatic amides Download PDFInfo
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- CN109438697A CN109438697A CN201811131114.4A CN201811131114A CN109438697A CN 109438697 A CN109438697 A CN 109438697A CN 201811131114 A CN201811131114 A CN 201811131114A CN 109438697 A CN109438697 A CN 109438697A
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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
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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Abstract
The invention discloses a kind of preparation methods of aromatic amides, comprising the following steps: and under the protection of inert gas, 4,4 '-diaminodiphenyl sulfides are added into p-phenylenediamine solution and stir to dissolution, it is cooling, hydrogenation calcium powder is added；(2,5- dihydroxy paraphthaloyl chloride is added portionwise again to be reacted；Then lithium hydroxide powder is added, stirring, reacting when the pH value of reaction system is 6~7 terminates；Finally by reaction product freezing, crush, washing, it is dry to get arriving the aromatic amides.During preparation method of the invention, polymeric system viscosity is lower, conducive to the growth of molecular weight, and polymeric reaction condition is mild, polymerization unit and control are required relatively low, can obtain that molecular weight distribution is relatively narrow, the higher polymer of molecular weight, commercial viability is high；The aromatic amides of generation not only have with performance similar in aramid fiber, and make up its bending and torsional fatigue, the disadvantages of anti-ultraviolet ageing is poor.
Description
Technical field
The invention belongs to polymeric material field more particularly to a kind of preparation methods of aromatic amides.
Background technique
Poly(p-phenylene terephthalamide) is mainly used for high-performance aramid fiber and film, has high-strength and high-modulus, heat-resisting, resistance to
The a series of excellent performances such as chemical attack, the low, dimensionally stable of density, in multiple fields such as aerospace industry, auto industrys
It is widely used.However, current surface activity of aramid fiber group is less, inertia is stronger, cause compression strength it is low,
Surface and resin-bonded power it is weak the defects of, cause aramid fiber using potential constraint；Aramid fiber fiber table under uv radiation
The macromolecular chain end in face aoxidizes in air, and the crystal structure of fiber surface is reset, and fiber surface is caused to corrode,
This effect causes products machinery performance that can be gradually reduced, generation becomes fragile, is cracked so that material generation degradation, aging and deterioration
And yellowing phenomenon, it even completely destroys and is not available.And aramid fiber molecule chain rigidity is big, and strand is closely piled up and height
Degree crystallization, so dissolubility is very poor, is difficult to dissolve in common organic solvents, when preparing aramid fiber, it is necessary to by aramid fiber resin
Dissolution carries out fiber spinning from crystalline state in concentrated sulfuric acid, and process flow is complicated, more demanding to the resistance to strong acid corrosivity of equipment, and operation is relatively more tired
It is difficult.And solve these technical problems is the raw material aromatic amides resin needed from aramid fiber is prepared at all, fragrance
The performance of race's amide resin directly affects the performance and preparation flow of aramid fiber.
And preparing aromatic amides resin methods at present is mainly interfacial polymerization and low temperature solution polymerization.Interfacial polymerization needs
By dissolution of raw material in two kinds of immiscible two kind solvents, then by being gathered under the conditions of high-speed stirred in contact interface
It closes, this method needs a large amount of solvent dissolutions, requires height for the measuring accuracy of raw material in production process, leads to production cost
It is high.The main method of low temperature solution polymerization is by dissolution of raw material in NMP/CaCl2, LiCl composition polymer solvent in, in low temperature
Under the conditions of polymerize, be generally that low temperature solution polymerization reaction is carried out using mixer and screw reactor, in the mistake of reaction
It needs the inlet amount to reaction raw materials, reaction condition accurately to be controlled in journey, causes production equipment investment larger；Using
CaCl2, LiCl as cosolvent can improve the dissolubility of polymer in a solvent, but the HCl constantly generated in the reaction, still
The viscosity that will lead to reaction system constantly increases, and influences mass transfer, the heat transfer of system, so that molecular weight is difficult to continue increase, molecule
Amount distribution broadens.
Summary of the invention
It is less the technical problem to be solved by the present invention is to improve surface activity of aramid fiber group, with resin-bonded power
The problem of weak, the problems such as compression strength is low, fatigue resistance is low, UV radiation is poor, it one kind be provided can reduce spinning and set
For requirement, the preparation method of spinning aromatic amides easy to operate.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of aromatic amides, comprising the following steps:
(1) under the protection of inert gas, 4,4 '-diaminodiphenyl sulfides is added into p-phenylenediamine solution and stir to molten
Solution, it is cooling, hydrogenation calcium powder is added；
(2) 2,5- dihydroxy paraphthaloyl chloride is added portionwise into the solution after step (1) to be reacted；
(3) lithium hydroxide powder is added into the reaction system after step (2), quickly stirs, the pH value to reaction system
Reacting at 6~7 terminates；
(4) by the freezing of step (3) resulting reaction product, crush, washing, it is dry to get arriving the aromatic amides.
Hydrogenation calcium powder is added in the present invention during preparation method, following reaction can occur with the HCl generated is reacted:
CaH2+2HCl→CaCl2+2H2↑；
HCl is the product of polycondensation reaction, on the one hand the presence of HCl increases the apparent viscosity of reaction system constantly, makes
The mixing for obtaining reaction system becomes difficult, and increases the reaction time；On the other hand can also occur with the intermediate product of polycondensation reaction anti-
Salt should be generated, to make its inactivation, prevents the further growth of polymer molecular chain.The present invention is added during preparation method
Calcium hydride has both eliminated the undesirable substance HCl in reaction, and the moisture content that can also contain in removing system is conducive to polymerization reaction
Progress；Moreover, reaction product CaCl2It is also used as cosolvent, is conducive to polycondensation product in the dissolution of dicyandiamide solution.
4,4 '-diaminodiphenyl sulfides are added into p-phenylenediamine solution during preparation method of the invention to stir to molten
Xie Hou adds 2,5- dihydroxy paraphthaloyl chloride and reacts, it is ensured that 4,4 '-diaminodiphenyl sulfide of Third monomer
It can more be evenly distributed in entire macromolecular chain, achieve the purpose that modified resin, enable to fiber after subsequent spinning
It is whole that there is uniform performance；Otherwise, Third monomer can not be evenly distributed in entire macromolecular chain, cannot reach modified resin
Purpose.
In step (3) of the invention, lithium hydroxide is cheap, can be used as the HCl in acid binding agent and generated.
Above-mentioned preparation method, it is preferred that in the step (1), p-phenylenediamine solution is the N- methyl pyrrole of p-phenylenediamine
Pyrrolidone solution, concentration are 0.5~0.8mol/L；
Be added 4,4 '-diaminodiphenyl sulfides after, in solution the concentration of 4,4 '-diaminodiphenyl sulfides be 0.2~
0.3mol/L；
Hydrogenation calcium powder is added, the hydrogenation calcium concentration in solution is 0.15mol/L~0.25mol/L.
Above-mentioned preparation method, it is preferred that in the step (1), cooling refers to that ice salt bath is cooled to -10 DEG C~5 DEG C.
Above-mentioned preparation method, it is preferred that in the step (2), a part 2,5- dihydroxy paraphenylene terephthalamide is first added
Chlorine is reacted, and control reaction temperature is at 10 DEG C~30 DEG C, 10~30min of reaction time；Reaction temperature is excessively high, is on the one hand easy
It generates gel reaction and is unfavorable for molecule chain growth, another aspect product is easy to happen degradation.Reaction temperature is too low, reaction rate
It is too low, influence reaction efficiency.It adds remaining 2,5- dihydroxy paraphthaloyl chloride to be reacted, controls reaction temperature 55
DEG C~65 DEG C, 40~50min of reaction time；Reaction temperature is excessively high, is on the one hand easy to produce gel reaction and is unfavorable for strand increasing
Long, another aspect product is easy to happen degradation.Reaction temperature is too low, and reaction rate is too low, influences reaction efficiency.Reaction time
Too long, reaction efficiency is low；Reaction time is short, reacts insufficient, influences the growth of strand.It is advantageous to control different reaction temperatures
In the growth of polymerization reaction molecular weight and the homogeneous distribution of molecular weight.
Above-mentioned preparation method, it is preferred that the amount that 2,5- dihydroxy paraphthaloyl chloride is first added accounts for p-phenylenediamine addition
The 50%~85% of amount；Again be added 2,5- dihydroxy paraphthaloyl chloride amount account for p-phenylenediamine additive amount 15%~
50%；Total additional amount of 2,5- dihydroxy paraphthaloyl chloride is identical with the additional amount of p-phenylenediamine.
Above-mentioned preparation method, it is preferred that in the step (3), stirring rate is 800r/min~1500r/min, is stirred
Mixing the time is 60~70min.
Above-mentioned preparation method, it is preferred that the addition again of 2, the 5- dihydroxy paraphthaloyl chloride is to add in batches
Enter.
Above-mentioned preparation method, it is preferred that in the step (4), freezing refers to be freezed in liquid nitrogen；Using liquid nitrogen frozen
It can be rapidly frozen reaction product, be conducive to the crushing of next step.It is dry to refer to dry 5h~6h at 100~120 DEG C.
Above-mentioned preparation method, it is preferred that the inert gas is nitrogen.
Compared with the prior art, the advantages of the present invention are as follows:
(1) solubility property of the invention in order to improve aromatic amides, uses low-temperature solution polycondensation during the preparation process
It is prepared, 4,4 '-diaminodiphenyl sulfide of Third monomer is introduced in aramid fiber rigidity Chain System, is not changing aramid fiber substantially
On the basis of the original excellent performance of resin, third component flexible is introduced in strand, improves its dissolubility, it can
It is dissolved in common polar solvent, so as to prepare full-bodied spinning solution, can directly carry out wet spinning, this side
Method is easy to operate, greatly reduces the cost for preparing aramid fiber spinning equipment.
(2) the shortcomings that present invention is in order to improve aramid fiber performance itself, selects raw material (2, the 5- dihydroxy pair of polyhydroxy
Phthalyl chloride), the high molecular polymer containing polyhydroxy can be made by polycondensation reaction, macromolecule during spinning
Hydroxyl in polymer is interacted in the form of hydrogen bond, on the one hand improves surface activity of aramid fiber, be conducive to it is other
Material be combined with each other；On the other hand, be conducive to absorption ultraviolet light and achieve the purpose that energy converts, can effectively resist ultraviolet light
Erosion damage.This method is compared to carrying out physical chemistry processing to fiber itself and be added during synthesis ultraviolet
The mode of light absorbers, effect is more preferable, also relatively simple.
(3) during the preparation method of aromatic amides of the invention, polymeric system viscosity is lower, conducive to molecular weight
Increase, and polymeric reaction condition is mild, polymerization unit and control are required it is relatively low, can obtain molecular weight distribution it is relatively narrow,
The higher polymer of molecular weight, commercial viability are high；The aromatic amides of generation not only have with performance similar in aramid fiber, and
And make up its bending and torsional fatigue, the disadvantages of anti-ultraviolet ageing is poor.In addition, polymerizate both can be used as full-bodied spinning
Stoste, directly progress wet spinning, are greatly reduced the cost of spinning equipment, can be film-made, be had excellent performance with stoste
Film has opened up the application field of aramid fiber material.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of aromatic amides of the invention.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The logarithmic viscosity number measuring method of Inventive polymers is as follows:
Dry 0.125g copolymer sample is dissolved in the concentrated sulfuric acid (95%~98%) of 25mL, Ubbelohde viscometer is used
The estimated viscosity in the water bath with thermostatic control of (30 ± 0.5) DEG C, is calculated as follows out the reduced inherent viscosity of copolymer:
ηinh=ln (t/t0)/C；
In formula: t is the time of solution outflow, s；T0 is the time of pure solvent outflow, s；C is copolymer in 100mL solvent
Grams, g/dL.
Describe fiber dynamic bending fatigue performance using repeated flex number (test condition --- swing angle: 120 °,
Tension: 3.0cN/dtex, corner frequency: 1Hz)；
Describe fiber dynamic torsional fatigue performance using repeat number of torsions (test condition --- torsional angle: 45 °, tension:
0.2cN/dtex accommodates length: 6.8mm).
Logarithmic viscosity number more high molecular weight is higher；And endurance test can characterize the width of molecular weight distribution indirectly
Narrow, fatigue performance is good, and molecular weight distribution is relatively narrow.
Embodiment 1:
The preparation method of aromatic amides of the invention, process flow chart are as shown in Figure 1, comprising the following steps:
(1) in the environment of drying nitrogen protection, p-phenylenediamine powder is dissolved in N-Methyl pyrrolidone at room temperature
(NMP) in, make the concentration 0.8mol/L of p-phenylenediamine, after p-phenylenediamine is completely dissolved, add a certain amount of 4,4 '-two
Diaminodiphenyl sulfide is stirred to being completely dissolved, and makes its concentration 0.3mol/L, is cooled to -10 DEG C with ice salt bath, calcium hydride is added
Powder stirs evenly, and the hydrogenation calcium concentration in solution is 0.2mol/L；
(2) the 2,5- dihydroxy paraphenylene terephthalamide of p-phenylenediamine additive amount 85% is first added into the solution after step (1)
Chlorine reacts 40min, controls reaction temperature at 25 DEG C；The 2,5- dihydroxy of p-phenylenediamine additive amount 15% is added in three batches again to benzene
Dimethyl chloride controls reaction temperature at 65 DEG C, reacts 20min；
(3) it is slowly added to lithium hydroxide powder into the system after step (2), quickly stirs (stirring rate 1000r/
Min, mixing time 60min), make reaction system gelation, reaction to pH value 6~7 terminates；
(4) reaction product after step (3) is placed in liquid nitrogen and is freezed, and crushed with pulverizer；Then spend from
The sub- multiple repeated flushing of water, the dry 5h at 120 DEG C, obtaining powder is aromatic amides.
The logarithmic viscosity number for testing aromatic amides resin manufactured in the present embodiment is 4.50.
Aromatic amides dissolubility manufactured in the present embodiment is preferable, is dissolved in usual vehicle N-Methyl pyrrolidone
In, so that it may full-bodied spinning solution is prepared, can directly carry out wet spinning, the long stapled performance that spinning is formed is such as
Shown in table 1.
1 embodiment 1 of table and the long stapled performance comparison of Fanglun l414
Embodiment 2:
The preparation method of aromatic amides of the invention, process flow chart are as shown in Figure 1, comprising the following steps:
(1) in the environment of drying nitrogen protection, p-phenylenediamine powder is dissolved in N-Methyl pyrrolidone at room temperature
(NMP) in, make the concentration 0.5mol/L of p-phenylenediamine, after p-phenylenediamine is completely dissolved, add a certain amount of 4,4 '-two
Diaminodiphenyl sulfide is stirred to being completely dissolved, and makes its concentration 0.25mol/L, is cooled to -5 DEG C with ice salt bath, calcium hydride is added
Powder stirs evenly, and the hydrogenation calcium concentration in solution is 0.2mol/L；
(2) the 2,5- dihydroxy paraphenylene terephthalamide of p-phenylenediamine additive amount 50% is first added into the solution after step (1)
Chlorine reacts 1h, controls reaction temperature at 20 DEG C；The 2,5- dihydroxy of p-phenylenediamine additive amount 50% is added in five batches again to benzene two
Formyl chloride controls reaction temperature at 60 DEG C, reacts 30min；
(3) it is slowly added to lithium hydroxide powder into the system after step (2), quickly stirs (stirring rate 1000r/
Min, mixing time 70min), make reaction system gelation, reaction to pH value 6~7 terminates；
(4) reaction product after step (3) is placed in liquid nitrogen and is freezed, and crushed with pulverizer；Then spend from
The sub- multiple repeated flushing of water, the dry 6h at 120 DEG C, obtaining powder is aromatic amides.
The logarithmic viscosity number for testing aromatic amides resin manufactured in the present embodiment is 4.25.
Aromatic amides dissolubility manufactured in the present embodiment is preferable, is dissolved in usual vehicle DMF, so that it may prepare
Full-bodied spinning solution out, can directly carry out wet spinning, and the long stapled performance that spinning is formed is as shown in table 2.
2 embodiment 2 of table and the long stapled performance comparison of Fanglun l414
Embodiment 3:
The preparation method of aromatic amides of the invention, process flow chart are as shown in Figure 1, comprising the following steps:
(1) in the environment of drying nitrogen protection, p-phenylenediamine powder is dissolved in N-Methyl pyrrolidone at room temperature
(NMP) in, make the concentration 0.6mol/L of p-phenylenediamine, after p-phenylenediamine is completely dissolved, add a certain amount of 4,4 '-two
Diaminodiphenyl sulfide is stirred to being completely dissolved, and makes its concentration 0.3mol/L, is cooled to -10 DEG C with ice salt bath, calcium hydride is added
Powder stirs evenly, and the hydrogenation calcium concentration in solution is 0.2mol/L；
(2) the 2,5- dihydroxy paraphenylene terephthalamide of p-phenylenediamine additive amount 75% is first added into the solution after step (1)
Chlorine reacts 50min, controls reaction temperature at 30 DEG C；The 2,5- dihydroxy of p-phenylenediamine additive amount 25% is added in four batches again to benzene
Dimethyl chloride controls reaction temperature at 55 DEG C, reacts 25min；
(3) it is slowly added to lithium hydroxide powder into the system after step (2), quickly stirs (stirring rate 1000r/
Min, mixing time 60min), make reaction system gelation, reaction to pH value 6~7 terminates；
(4) reaction product after step (3) is placed in liquid nitrogen and is freezed, and crushed with pulverizer；Then spend from
The sub- multiple repeated flushing of water, the dry 5h at 120 DEG C, obtaining powder is aromatic amides.
The logarithmic viscosity number for testing aromatic amides resin manufactured in the present embodiment is 4.36.
Aromatic amides dissolubility manufactured in the present embodiment is preferable, is dissolved in usual vehicle dimethyl acetamide,
Full-bodied spinning solution can be prepared, wet spinning, the long stapled performance such as table 3 that spinning is formed can be directly carried out
It is shown.
3 embodiment 3 of table and the long stapled performance comparison of Fanglun l414
Claims (9)
1. a kind of preparation method of aromatic amides, which comprises the following steps:
(1) under the protection of inert gas, 4,4 '-diaminodiphenyl sulfides is added into p-phenylenediamine solution and stir to dissolution,
It is cooling, hydrogenation calcium powder is added；
(2) 2,5- dihydroxy paraphthaloyl chloride is added portionwise into the solution after step (1) to be reacted；
(3) lithium hydroxide powder, stirring, when the pH value of reaction system is 6~7 are added into the reaction system after step (2)
Reaction terminates；
(4) by the freezing of step (3) resulting reaction product, crush, washing, it is dry to get arriving the aromatic amides.
2. preparation method as described in claim 1, which is characterized in that in the step (1), p-phenylenediamine solution is to benzene two
The N-Methyl pyrrolidone solution of amine, concentration are 0.5~0.8mol/L；
After 4,4 '-diaminodiphenyl sulfides are added, the concentration of 4,4 '-diaminodiphenyl sulfides is 0.2~0.3mol/L in solution；
Hydrogenation calcium powder is added, the hydrogenation calcium concentration in solution is 0.15mol/L~0.25mol/L.
3. preparation method as described in claim 1, which is characterized in that cooling to refer to that ice salt bath is cooling in the step (1)
To -10 DEG C~5 DEG C.
4. preparation method as described in claim 1, which is characterized in that in the step (2), a part 2,5- dihydroxy is first added
Base paraphthaloyl chloride is reacted, and for control reaction temperature at 10 DEG C~30 DEG C, the reaction time is 10~30min；It adds surplus
Under 2,5- dihydroxy paraphthaloyl chloride reacted, control reaction temperature at 55 DEG C~65 DEG C, the reaction time 40~
50min。
5. preparation method as claimed in claim 4, which is characterized in that the amount that 2,5- dihydroxy paraphthaloyl chloride is first added accounts for
The 50%~85% of p-phenylenediamine additive amount；The amount that 2,5- dihydroxy paraphthaloyl chloride is added again accounts for p-phenylenediamine additive amount
15%~50%；Total additional amount of 2,5- dihydroxy paraphthaloyl chloride is identical with the additional amount of p-phenylenediamine.
6. preparation method as claimed in claim 5, which is characterized in that 2, the 5- dihydroxy paraphthaloyl chloride adds again
Enter and is added in batches.
7. preparation method as described in any one of claims 1 to 6, which is characterized in that in the step (3), stirring rate is
800r/min~1500r/min, mixing time are 60~70min.
8. preparation method as described in any one of claims 1 to 6, which is characterized in that in the step (4), freezing refers to
It is freezed in liquid nitrogen；It is dry to refer to dry 5h~6h at 100~120 DEG C.
9. preparation method as described in any one of claims 1 to 6, which is characterized in that the inert gas is nitrogen.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118292136A (en) * | 2024-06-05 | 2024-07-05 | 烟台泰和新材高分子新材料研究院有限公司 | Modified meta-aramid fiber capable of improving light fastness and preparation method thereof |
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