CN107417906A - A kind of preparation method of light poly (arylene ether nitrile) resin - Google Patents
A kind of preparation method of light poly (arylene ether nitrile) resin Download PDFInfo
- Publication number
- CN107417906A CN107417906A CN201710700809.9A CN201710700809A CN107417906A CN 107417906 A CN107417906 A CN 107417906A CN 201710700809 A CN201710700809 A CN 201710700809A CN 107417906 A CN107417906 A CN 107417906A
- Authority
- CN
- China
- Prior art keywords
- poly
- arylene ether
- ether nitrile
- resin
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a kind of preparation method of light poly (arylene ether nitrile) resin, the present invention is using method of fractional steps synthesis poly (arylene ether nitrile) resin, bisphenol-A reacts to obtain phenol alkali salt with alkali first, then phenol alkali salt and 2, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made in 6 dichlorobenzonitriles, alkali carbonate, N crassitudes reactive ketone, poly (arylene ether nitrile) high polymer is made in the poly (arylene ether nitrile) oligomer of phenol alkali salt and chlorine end-blocking, alkali carbonate, N crassitudes reactive ketone again, final purification obtains light poly (arylene ether nitrile) resin product；Dehydrating agent is not used in preparation process and reduces the dosage of catalyst alkali carbonate, remaining salinity in poly (arylene ether nitrile) resin product, solvent and dehydration agent content is reduced, avoids because of the not high and aobvious dark color of poly (arylene ether nitrile) resin product purity；Present invention improves poly (arylene ether nitrile) resin color, improve product quality；Resulting light poly (arylene ether nitrile) resin is of light color, transparency is high, has widened the application field of poly (arylene ether nitrile) resin.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of preparation method of poly (arylene ether nitrile) resin.
Background technology
Poly (arylene ether nitrile) (PEN) is that macromolecular main chain possesses aryl oxide construction unit, and one of which aryl oxide side base is itrile group
Thermoplastic polymer；Possess good heat endurance, high mechanical properties, good insulating, chemicals-resistant corrosion and possess from anti-flammability etc.
Excellent combination property；It is widely used in the fields such as electronic apparatus, machine-building, auto parts, Aero-Space.
The poly (arylene ether nitrile) that the initial stage eighties, D.K.Mohanty etc. was prepared for having practical application performance with phenyl-dihalide formonitrile HCN
Homopolymer, afterwards poly aryl ether product achieve fast development, such as Japanese S.Matsuo in 1986 has applied for series of patents, day
This light extraction Xing Chan companies successfully develop PEN products.The research of poly (arylene ether nitrile) at home is started in the 1980s, main collection
In research synthesis technique and formula etc..Closely during the last ten years, due to the outstanding chemical property of poly (arylene ether nitrile), Physical Mechanical
Energy, high heat-resistant stability and good processing characteristics, PEN are greatly paid close attention in special engineering plastics field.Therefore it is poly-
Aryl oxide nitrile becomes most important a kind of polymer in polyarylether polymer.
At present prepare the synthetic method that poly (arylene ether nitrile) mainly uses be by by dihalo cyanophenyl and dihydric phenol in N- methyl
In pyrrolidones (NMP) polar solvent, using carbonate as catalyst, toluene is dehydrating agent, carries out synthetically prepared and obtains.Such as public affairs
The number of opening is that CN101838390B Chinese invention discloses a kind of preparation method of poly (arylene ether nitrile) resin, with 2,6- dichlorobenzonitriles
It is raw material with aromatic dicarboxylic phenol, using 1-METHYLPYRROLIDONE as solvent, under catalyst and dehydrating agent effect in reactor
Normal pressure completes reaction, and solution precipitates through diluting pressure atomization in backward precipitating reagent, and sediment has flowed back with precipitating reagent heating stirring
Enter rectifying column rectifying recycling design through centrifuge separation of solid and liquid, liquid after into solvent extraction, solid is dried after boiling water washs
Obtain poly (arylene ether nitrile) resin.Such synthetic method, need to be by its mistake because carbonate is alkalescent material using carbonate as catalyst
Amount, which adds, can just be smoothed out reaction, therefore a certain amount of unreacted carbonate in caused product be present, cause product pure
The not high and aobvious dark color of degree；Simultaneously as NMP polar solvents can react and go bad with alkali so that the PEN trees produced
Such a large amount of solvent of remaining and dehydrating agent in fat, it will be produced to color of resin and have a strong impact on, and content is higher, and color of resin is got over
Deep, transparency is lower；If poly (arylene ether nitrile) resin will limit its application in some fields in dark color.Therefore, PEN trees how to be improved
Fat quality of colour is current urgent problem to be solved.
The content of the invention
The technical problems to be solved by the invention, which are to provide one kind, prevents catalyst in course of reaction, polar solvent etc. from influenceing
Poly (arylene ether nitrile) resin color, improve a kind of preparation method of light poly (arylene ether nitrile) resin of poly (arylene ether nitrile) resin quality of colour.
The technical solution adopted for the present invention to solve the technical problems is：A kind of preparation side of light poly (arylene ether nitrile) resin
Method, comprise the following steps：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and alkali as 1: 2-2.1 stock, phenol alkali salt is reacted to obtain；
(b) poly (arylene ether nitrile) oligomer is prepared：
With the mol ratio of phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, 1-METHYLPYRROLIDONE for 1: 1.1-2:
0.01-0.1: 8-15 stock, reacts the poly (arylene ether nitrile) oligomer that chlorine end-blocking is made；
(c) poly (arylene ether nitrile) high polymer is prepared
By mol ratio be 1: 1: 0.01-0.1: 8-15 phenol alkali salt, chlorine end-blocking poly (arylene ether nitrile) oligomer, alkali metal carbonic acid
Salt, 1-METHYLPYRROLIDONE input reactor, react to obtain poly (arylene ether nitrile) high polymer；
(d) purify
Poly (arylene ether nitrile) high polymer obtained by step (c) and extractant are put into extraction device, extraction is carried out after removing solvent
Dry, that is, obtain light poly (arylene ether nitrile) resin.
Preferably, in the step (a), the aqueous slkali that mass fraction is 10-50% is prepared with alkali first, puts into reactor
In, then by bisphenol-A addition aqueous slkali, controlling reaction temperature is 5-60 DEG C, reacts 1-3h；React after terminating at 20-30 DEG C
Crystallization is completed, then is dried in vacuo, obtains phenol alkali salt；
Preferably, by phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, N- crassitudes in the step (b)
Ketone puts into reactor, is warming up to 180-200 DEG C of reaction 2-3h, reactor interpolymer mucus is poured into pure water and cooled down,
Solidfied material is obtained, pure water is used after then being crushed with pulverizer, then is dried, the poly (arylene ether nitrile) oligomerisation of chlorine end-blocking is made
Thing；
Preferably, by phenol alkali salt, the poly (arylene ether nitrile) oligomer of chlorine end-blocking, alkali carbonate, N- first in the step (c)
Base pyrrolidones puts into reactor, and rise temperature to 180-200 DEG C of reaction 2-5h completes polymerisation, by reactor interpolymer
Mucus is poured into pure water and cooled down, and obtains solidfied material, and pure water is used after then being crushed with pulverizer, then is dried, i.e.,
Obtain poly (arylene ether nitrile) high polymer；
Preferably, alkali is potassium hydroxide or sodium hydroxide in the step (a).
Preferably, described alkali carbonate is potassium carbonate or sodium carbonate.
Preferably, it is 25-45 DEG C by the control of the reaction temperature of bisphenol-A and aqueous slkali in step (a).
Preferably, reactor is the reactor with nitrogen protection and agitator in step (a), (b), (c).
Preferably, the extractant is sulfolane, ethanol, methanol or ether.
Preferably, the mass ratio of the poly (arylene ether nitrile) high polymer and extractant is 1：4-20.
The beneficial effects of the invention are as follows：
The present invention reacts to obtain phenol alkali salt using method of fractional steps synthesis poly (arylene ether nitrile) resin, first bisphenol-A with alkali, then phenol alkali
The poly (arylene ether nitrile) oligomer of chlorine end-blocking is made in salt and 2,6- dichlorobenzonitrile, alkali carbonate, 1-METHYLPYRROLIDONE reaction,
The poly (arylene ether nitrile) oligomer of phenol alkali salt and chlorine end-blocking, alkali carbonate, 1-METHYLPYRROLIDONE are reacted and polyarylether are made again
Nitrile high polymer, final purification obtain light poly (arylene ether nitrile) resin product；
Dehydrating agent is not used in preparation process and reduces the dosage of catalyst alkali carbonate, reduces polyarylether
Remaining salinity, solvent and dehydration agent content, are avoided because of the not high and aobvious depth of poly (arylene ether nitrile) resin product purity in nitrile naval stores
Color；Secondly as bisphenol-A reacts to obtain phenol alkali salt with alkali, then phenol alkali salt participates in reacting again, therefore it is molten with polarity to avoid alkali
Agent 1-METHYLPYRROLIDONE instead react and go bad by life, and then influences the color of poly (arylene ether nitrile) resin product；
Present invention improves poly (arylene ether nitrile) resin color, improve poly (arylene ether nitrile) resin product quality；Resulting light color
Poly (arylene ether nitrile) resin is of light color, transparency is high, has widened the application field of poly (arylene ether nitrile) resin.
Embodiment
A kind of preparation method of light poly (arylene ether nitrile) resin of the present invention, comprises the following steps：
(a) phenol alkali salt is prepared：Using the mol ratio of bisphenol-A and alkali as 1: 2-2.1 stock；Preparing mass fraction with alkali first is
10-50% aqueous slkali, put into reactor, then bisphenol-A is added in aqueous slkali, controlling reaction temperature is 5-60 DEG C, reaction
1-3h；Reaction completes crystallization after terminating at 20-30 DEG C, then is dried in vacuo, and obtains phenol alkali salt；Further, alkali is selected from hydroxide
Potassium or sodium hydroxide, alkali carbonate are selected from potassium carbonate or sodium carbonate；Reactor selects the reaction protected and stirred with nitrogen
Device；The mol ratio of bisphenol-A and alkali is 1: 2-2.1, and alkali is slightly excessive, reaction is carried out under alkaline environment, is advantageous to phenol alkali salt
Generation；During reaction at a temperature of 5-60 DEG C stirring reaction 1-3h, then crystallize, be dried to obtain phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：By phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, N- methylpyrroles
Alkanone put into reactor, be warming up to 180-200 DEG C reaction 2-3h, reactor interpolymer mucus is poured into pure water carry out it is cold
But, solidfied material is obtained, pure water is used after then being crushed with pulverizer, then is dried, the poly (arylene ether nitrile) that chlorine end-blocking is made is neat
Polymers；The phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1.1-2:
0.01-0.1∶8-15；Protected with nitrogen, in the reactor of agitator, phenol alkali salt, 2,6- dichlorobenzonitriles, alkali metal carbonic acid
Salt, 1-METHYLPYRROLIDONE are reacted, and reactor interpolymer mucus is poured into pure water and cooled down by reaction after terminating, and is obtained
To solidfied material, then pure water is used 3-6 times after being crushed with pulverizer, remove the impurity such as salinity and solvent therein, then dry
More than 4h, so as to get chlorine end-blocking poly (arylene ether nitrile) oligomer moisture within 5 ‰；
(c) poly (arylene ether nitrile) high polymer is prepared：Poly (arylene ether nitrile) oligomer, alkali carbonate, the N- that phenol alkali salt, chlorine are blocked
Methyl pyrrolidone puts into reactor, and rise temperature to 180-200 DEG C of reaction 2-5h is completed polymerisation, will polymerize in reactor
Thing mucus, which is poured into pure water, to be cooled down, and obtains solidfied material, and pure water is used after then being crushed with pulverizer, then is dried,
Produce poly (arylene ether nitrile) high polymer；Poly (arylene ether nitrile) oligomer, alkali carbonate, the N- methylpyrroles of the phenol alkali salt, chlorine end-blocking
The mol ratio of alkanone is 1: 1: 0.01-0.1: 8-15；Pure water is used after solidfied material is crushed with pulverizer 5-6 times, then carried out
Dry, produce the few poly (arylene ether nitrile) high polymer of impurity content, the poly (arylene ether nitrile) high polymer impurity content of gained 100ppm with
It is interior.
(d) purify：Poly (arylene ether nitrile) high polymer obtained by step (c) is added after extractant extraction removes solvent and dried, i.e.,
Obtain light poly (arylene ether nitrile) resin；Further, the extractant is selected from sulfolane, ethanol, methanol or ether；Poly (arylene ether nitrile) is high
The mass ratio of polymers and extractant is 1：4-20；
Poly (arylene ether nitrile) high polymer prepared by (c) step is put into Soxhlet extractor, extractant is added, by extraction temperature
50-300 DEG C is arranged to, extraction is stripped after being heated to extractant boiling, repeats to extract 2-24h, removes residual solvents, take out
More than 4h is dried, that is, obtains light poly (arylene ether nitrile) resin product.
With reference to embodiment, the present invention is further described.
Embodiment 1：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and potassium hydroxide as 1: 2.02 stock；Preparing mass fraction with potassium hydroxide first is
10% potassium hydroxide solution, put into reactor, then bisphenol-A is added in aqueous slkali, controlling reaction temperature is 25 DEG C, reaction
1h；Reaction completes crystallization after terminating at 20 DEG C, then is dried in vacuo, and obtains phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：
By phenol alkali salt, 2,6- dichlorobenzonitriles, sodium carbonate, 1-METHYLPYRROLIDONE input reactor, 180 DEG C are warming up to instead
2h is answered, reactor interpolymer mucus is poured into pure water and cooled down, obtains solidfied material, with pure after then being crushed with pulverizer
Water washing, then be dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made；The phenol alkali salt, 2,6- dichlorobenzonitriles, carbonic acid
Sodium, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1.1: 0.01: 8；
(c) poly (arylene ether nitrile) high polymer is prepared：
Poly (arylene ether nitrile) oligomer, sodium carbonate, the 1-METHYLPYRROLIDONE input reactor that phenol alkali salt, chlorine are blocked, rise
Temperature completes polymerisation to 180 DEG C of reaction 2h, and reactor interpolymer mucus is poured into pure water and cooled down, is solidified
Thing, pure water is used after then being crushed with pulverizer, then be dried, produce poly (arylene ether nitrile) high polymer；The phenol alkali salt, chlorine envelope
The poly (arylene ether nitrile) oligomer at end, sodium carbonate, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1: 0.01: 8；
(d) purify：
Poly (arylene ether nitrile) high polymer obtained by step (c) is added after extractant extraction removes solvent and dried, that is, obtains light color
Poly (arylene ether nitrile) resin.
The test of poly (arylene ether nitrile) resin color：Obtained light poly (arylene ether nitrile) resin powder is prepared as standard with injection machine
Colour table, then yellow value degree test is carried out to it with to color instrument, transparent test is carried out to it with mist degree instrument, is as a result yellowing 80, mist
Degree 14.
Embodiment 2：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and potassium hydroxide as 1: 2.1 stock；It is 50% to prepare mass fraction with potassium hydroxide first
Potassium hydroxide solution, put into reactor in, then by bisphenol-A add aqueous slkali in, controlling reaction temperature be 30 DEG C, react 3h；
Reaction completes crystallization after terminating at 25 DEG C, then is dried in vacuo, and obtains phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：
By phenol alkali salt, 2,6- dichlorobenzonitriles, potassium carbonate, 1-METHYLPYRROLIDONE input reactor, 200 DEG C are warming up to instead
3h is answered, reactor interpolymer mucus is poured into pure water and cooled down, obtains solidfied material, with pure after then being crushed with pulverizer
Water washing, then be dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made；The phenol alkali salt, 2,6- dichlorobenzonitriles, carbonic acid
Potassium, the mol ratio of 1-METHYLPYRROLIDONE are 1: 2: 0.1: 15；
(c) poly (arylene ether nitrile) high polymer is prepared：
Poly (arylene ether nitrile) oligomer, potassium carbonate, the 1-METHYLPYRROLIDONE input reactor that phenol alkali salt, chlorine are blocked, rise
Temperature completes polymerisation to 200 DEG C of reaction 5h, and reactor interpolymer mucus is poured into pure water and cooled down, is solidified
Thing, pure water is used after then being crushed with pulverizer, then be dried, produce poly (arylene ether nitrile) high polymer；The phenol alkali salt, chlorine envelope
The poly (arylene ether nitrile) oligomer at end, potassium carbonate, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1: 0.1: 15；
(d) purify：
Obtained 50g poly (arylene ether nitrile) high polymers are placed in extractor, add 500g ethanol, repeats to extract 14h, takes out
Light poly (arylene ether nitrile) resin is produced after sample drying.
The test of poly (arylene ether nitrile) resin color：Obtained light poly (arylene ether nitrile) resin powder is prepared as standard with injection machine
Colour table, then yellow value degree test is carried out to it with to color instrument, transparent test is carried out to it with mist degree instrument, is as a result yellowing 62, mist
Degree 9.
Embodiment 3：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and potassium hydroxide as 1: 2.05 stock；Preparing mass fraction with potassium hydroxide first is
20% potassium hydroxide solution, put into the reactor with stirring, then bisphenol-A is added in potassium hydroxide solution, control reaction
Temperature is 50 DEG C, reacts 2h；Reaction completes crystallization after terminating at 25 DEG C, then is dried in vacuo, and obtains phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：
Phenol alkali salt, 2,6- dichlorobenzonitriles, potassium carbonate, 1-METHYLPYRROLIDONE are put into the protection of band nitrogen, agitator, divided
The reactor of hydrophone, 190 DEG C of reaction 2.5h are warming up to, reactor interpolymer mucus is poured into pure water and cooled down, is obtained
Solidfied material, pure water is used after then being crushed with pulverizer, then be dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made；Institute
It is 1: 1.5: 0.05: 10 to state phenol alkali salt, 2,6- dichlorobenzonitriles, potassium carbonate, the mol ratio of 1-METHYLPYRROLIDONE；
(c) poly (arylene ether nitrile) high polymer is prepared：
By phenol alkali salt, chlorine block poly (arylene ether nitrile) oligomer, potassium carbonate, 1-METHYLPYRROLIDONE input band nitrogen protection,
The reactor of agitator, water knockout drum, rise temperature to 190 DEG C of reaction 3h completes polymerisation, by reactor interpolymer mucus
Pour into pure water and cooled down, obtain solidfied material, pure water is used after then being crushed with pulverizer, then be dried, produce poly-
Aryl oxide nitrile high polymer；The phenol alkali salt, the poly (arylene ether nitrile) oligomer of chlorine end-blocking, potassium carbonate, the mol ratio of 1-METHYLPYRROLIDONE
For 1: 1: 0.05: 10；
(d) purify：
Poly (arylene ether nitrile) high polymer is added after extractant sulfolane extraction removes solvent and dried, the poly (arylene ether nitrile) high polymer
Mass ratio with extractant is 1：4, that is, obtain light poly (arylene ether nitrile) resin.
The test of poly (arylene ether nitrile) resin color：Obtained light poly (arylene ether nitrile) resin powder is prepared as standard with injection machine
Colour table, then yellow value degree test is carried out to it with to color instrument, transparent test is carried out to it with mist degree instrument, is as a result yellowing 67, mist
Degree 12.
Embodiment 4：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and sodium hydroxide as 1: 2.02 stock；Preparing mass fraction with sodium hydroxide first is
30% aqueous slkali, put into reactor, then bisphenol-A is added in sodium hydroxide solution, controlling reaction temperature is 40 DEG C, reaction
2.5h；Reaction completes crystallization after terminating at 30 DEG C, then is dried in vacuo, and obtains phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：
By phenol alkali salt, 2,6- dichlorobenzonitriles, potassium carbonate, 1-METHYLPYRROLIDONE input reactor, 200 DEG C are warming up to instead
2.2h is answered, reactor interpolymer mucus is poured into pure water and cooled down, obtains solidfied material, is used after then being crushed with pulverizer
Pure water, then be dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made；The phenol alkali salt, 2,6- dichlorobenzonitriles, carbonic acid
Potassium, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1.8: 0.06: 12；
(c) poly (arylene ether nitrile) high polymer is prepared：
Poly (arylene ether nitrile) oligomer, potassium carbonate, the 1-METHYLPYRROLIDONE input reactor that phenol alkali salt, chlorine are blocked, rise
Temperature completes polymerisation to 200 DEG C of reaction 4h, and reactor interpolymer mucus is poured into pure water and cooled down, is solidified
Thing, pure water is used after then being crushed with pulverizer, then be dried, produce poly (arylene ether nitrile) high polymer；The phenol alkali salt, chlorine envelope
The poly (arylene ether nitrile) oligomer at end, potassium carbonate, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1: 0.06: 12；
(d) purify：
Obtained 40g poly (arylene ether nitrile) high polymers are placed in extractor, add 400g ether, repeats to extract 18h, takes out
Light poly (arylene ether nitrile) resin is produced after sample drying.
The test of poly (arylene ether nitrile) resin color：Obtained light poly (arylene ether nitrile) resin powder is prepared as standard with injection machine
Colour table, then yellow value degree test is carried out to it with to color instrument, transparent test is carried out to it with mist degree instrument, is as a result yellowing 75, mist
Degree 16.
Embodiment 5：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and sodium hydroxide as 1: 2.1 stock；It is 50% to prepare mass fraction with sodium hydroxide first
Sodium hydroxide solution, put into reactor in, then by bisphenol-A add sodium hydroxide solution in, controlling reaction temperature be 45 DEG C, instead
Answer 3h；Reaction completes crystallization after terminating at 30 DEG C, then is dried in vacuo, and obtains phenol alkali salt；
(b) poly (arylene ether nitrile) oligomer is prepared：
By phenol alkali salt, 2,6- dichlorobenzonitriles, sodium carbonate, 1-METHYLPYRROLIDONE input reactor, 180 DEG C are warming up to instead
2h is answered, reactor interpolymer mucus is poured into pure water and cooled down, obtains solidfied material, with pure after then being crushed with pulverizer
Water washing, then be dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made；The phenol alkali salt, 2,6- dichlorobenzonitriles, carbonic acid
Sodium, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1.6: 0.05: 10；
(c) poly (arylene ether nitrile) high polymer is prepared：
Poly (arylene ether nitrile) oligomer, sodium carbonate, the 1-METHYLPYRROLIDONE input reactor that phenol alkali salt, chlorine are blocked, rise
Temperature completes polymerisation to 180 DEG C of reaction 2h, and reactor interpolymer mucus is poured into pure water and cooled down, is solidified
Thing, pure water is used after then being crushed with pulverizer, then be dried, produce poly (arylene ether nitrile) high polymer；The phenol alkali salt, chlorine envelope
The poly (arylene ether nitrile) oligomer at end, sodium carbonate, the mol ratio of 1-METHYLPYRROLIDONE are 1: 1: 0.05: 10；
(d) purify：
Obtained 50g poly (arylene ether nitrile) high polymers are placed in extractor, add 800g ether, repeats to extract 24h, takes out
Light poly (arylene ether nitrile) resin is produced after sample drying.
The test of poly (arylene ether nitrile) resin color：Toner is prepared as Standard colour board with injection machine, then with to color instrument pair
It carries out yellow value degree test, carries out transparent test to it with mist degree instrument, as a result yellowing 58, mist degree 11.
The poly (arylene ether nitrile) resin color of table 1
| Color characteristics | Yellowing | Mist degree |
| Embodiment 1 | 80 | 14 |
| Embodiment 2 | 62 | 9 |
| Embodiment 3 | 67 | 12 |
| Embodiment 4 | 75 | 16 |
| Embodiment 5 | 58 | 11 |
| Control group 1 | 426 | 82 |
| Control group 2 | 378 | 75 |
Control group 1,2 is for raw material, with N- first with 2,6- dichlorobenzonitriles in the prior art and aromatic dicarboxylic phenol in table 1
Base pyrrolidones is solvent, and normal pressure completes reaction in reactor under catalyst and dehydrating agent effect, is dried after removal of impurities, washing
Obtain poly (arylene ether nitrile) resin, 1-5 of the embodiment of the present invention prepare light poly (arylene ether nitrile) resin compared with control group 1,2, yellowing and
Mist degree is greatly lowered, due to less yellowing and mist degree so that light poly (arylene ether nitrile) resin color prepared by the present invention
It is shallow, transparency is high, widened the application field of poly (arylene ether nitrile) resin.
Claims (10)
1. a kind of preparation method of light poly (arylene ether nitrile) resin, it is characterised in that comprise the following steps：
(a) phenol alkali salt is prepared：
Using the mol ratio of bisphenol-A and alkali as 1: 2-2.1 stock, phenol alkali salt is reacted to obtain；
(b) poly (arylene ether nitrile) oligomer is prepared：
With the mol ratio of phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, 1-METHYLPYRROLIDONE for 1: 1.1-2:
0.01-0.1: 8-15 stock, reacts the poly (arylene ether nitrile) oligomer that chlorine end-blocking is made；
(c) poly (arylene ether nitrile) high polymer is prepared
By mol ratio be 1: 1: 0.01-0.1: 8-15 phenol alkali salt, chlorine end-blocking poly (arylene ether nitrile) oligomer, alkali carbonate,
1-METHYLPYRROLIDONE puts into reactor, reacts to obtain poly (arylene ether nitrile) high polymer；
(d) purify
Poly (arylene ether nitrile) high polymer obtained by step (c) and extractant are put into extraction device, extraction is dried after removing solvent,
Obtain light poly (arylene ether nitrile) resin.
A kind of 2. preparation method of light poly (arylene ether nitrile) resin according to claim 1, it is characterised in that the step
(a) in, the aqueous slkali that mass fraction is 10-50% is prepared with alkali first, is put into reactor, then bisphenol-A is added into aqueous slkali
In, controlling reaction temperature is 5-60 DEG C, reacts 1-3h；Reaction completes crystallization after terminating at 20-30 DEG C, then is dried in vacuo, and obtains
Phenol alkali salt.
A kind of 3. preparation method of light poly (arylene ether nitrile) resin according to claim 1, it is characterised in that the step
(b) phenol alkali salt, 2,6- dichlorobenzonitriles, alkali carbonate, 1-METHYLPYRROLIDONE are put into reactor in, are warming up to 180-
200 DEG C of reaction 2-3h, reactor interpolymer mucus is poured into pure water and cooled down, solidfied material is obtained, then uses pulverizer
Pure water is used after crushing, then is dried, the poly (arylene ether nitrile) oligomer of chlorine end-blocking is made.
A kind of 4. preparation method of light poly (arylene ether nitrile) resin according to claim 1, it is characterised in that the step
(c) poly (arylene ether nitrile) oligomer, alkali carbonate, the 1-METHYLPYRROLIDONE for blocking phenol alkali salt, chlorine in put into reactor, rise
High-temperature completes polymerisation to 180-200 DEG C of reaction 2-5h, and reactor interpolymer mucus is poured into pure water and cooled down,
Solidfied material is obtained, pure water is used after then being crushed with pulverizer, then is dried, produces poly (arylene ether nitrile) high polymer.
A kind of 5. preparation method of light poly (arylene ether nitrile) resin according to claim 1 or 2, it is characterised in that the step
Suddenly alkali is potassium hydroxide or sodium hydroxide in (a).
6. the preparation method of a kind of light poly (arylene ether nitrile) resin according to claim 1 or 3, it is characterised in that described
Alkali carbonate is potassium carbonate or sodium carbonate.
7. the preparation method of a kind of light poly (arylene ether nitrile) resin according to claim 2, it is characterised in that in step (a)
It it is 25-45 DEG C by the control of the reaction temperature of bisphenol-A and aqueous slkali.
A kind of 8. preparation method of light poly (arylene ether nitrile) resin according to claim any one of 2-4, it is characterised in that step
Suddenly reactor is the reactor with nitrogen protection and agitator in (a), (b), (c).
A kind of 9. preparation method of light poly (arylene ether nitrile) resin according to claim 1, it is characterised in that the extractant
For sulfolane, ethanol, methanol or ether.
A kind of 10. preparation method of light poly (arylene ether nitrile) resin according to claim 9, it is characterised in that the poly- virtue
The mass ratio of ether nitrile high polymer and extractant is 1：4-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710700809.9A CN107417906A (en) | 2017-08-16 | 2017-08-16 | A kind of preparation method of light poly (arylene ether nitrile) resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710700809.9A CN107417906A (en) | 2017-08-16 | 2017-08-16 | A kind of preparation method of light poly (arylene ether nitrile) resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107417906A true CN107417906A (en) | 2017-12-01 |
Family
ID=60438111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710700809.9A Pending CN107417906A (en) | 2017-08-16 | 2017-08-16 | A kind of preparation method of light poly (arylene ether nitrile) resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107417906A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283310A (en) * | 2019-06-10 | 2019-09-27 | 宜宾天原集团股份有限公司 | A kind of preparation method of light color poly (arylene ether nitrile) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60147439A (en) * | 1984-01-10 | 1985-08-03 | Idemitsu Kosan Co Ltd | Novel polymer and its production |
| US4812507A (en) * | 1986-03-25 | 1989-03-14 | Idemitsu Kosan Company Limited | Reinforced resinous composition comprising polycyano arylene ether |
-
2017
- 2017-08-16 CN CN201710700809.9A patent/CN107417906A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60147439A (en) * | 1984-01-10 | 1985-08-03 | Idemitsu Kosan Co Ltd | Novel polymer and its production |
| US4812507A (en) * | 1986-03-25 | 1989-03-14 | Idemitsu Kosan Company Limited | Reinforced resinous composition comprising polycyano arylene ether |
Non-Patent Citations (7)
| Title |
|---|
| 杨建 等: "双酚A型聚芳醚腈共聚物的合成与性能", 《塑料工业》 * |
| 杨建: "官能侧基化聚芳醚腈的合成与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 程振华 等: "NMP萃取精馏系统防结焦技术的研究与应用", 《石油炼制与化工》 * |
| 蒋荣海: "《药物化学基础》", 31 May 2001, 中国医药科技出版社 * |
| 蒲泽军 等: "聚芳醚腈结构与性能的研究进展", 《中国材料进展》 * |
| 陈兰: "新型聚芳醚腈的合成与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 高建峰 等: "双酚A在碱中的氧化及其防止", 《华北工学院学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283310A (en) * | 2019-06-10 | 2019-09-27 | 宜宾天原集团股份有限公司 | A kind of preparation method of light color poly (arylene ether nitrile) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103180367A (en) | Polyarylene sulfide production method and polyarylene sulfide | |
| CN106633034B (en) | A kind of preparation method of polyether-ether-ketone resin and polyether-ether-ketone resin obtained | |
| CN103275320B (en) | Front desalination process prepares the method for linear high molecular weight polyphenylene sulfide | |
| CN113683772B (en) | Low-molecular-weight functionalized star-shaped polyphenyl ether and preparation method thereof | |
| CN107417906A (en) | A kind of preparation method of light poly (arylene ether nitrile) resin | |
| CN107417907A (en) | A kind of preparation method of high crystalline poly (arylene ether nitrile) | |
| CN112851942B (en) | Preparation method of polyether sulfone | |
| CN101864077B (en) | Polyarylene sulfide ketone and preparation method thereof | |
| CN104870519B (en) | The manufacture method of ring type polyphenylene ether ether one compositions and wire polyphenylene ether ether ketone, the manufacture method of polyphenylene ether ether ketone | |
| CN107141477A (en) | A kind of method of the high low molecule separation of polyphenylene sulfide | |
| CN114149586B (en) | Chain-extended polysulfate and preparation method thereof | |
| US4719259A (en) | Process for producing ethylene/vinyl alcohol copolymers | |
| CN113999394B (en) | Sulfone polymer and preparation method and application thereof | |
| CN101492381B (en) | Method of preparing 2,2-di(3-amino-4-hydroxyl phenyl) hexafluoroacetore | |
| CN108129654A (en) | A kind of readily soluble flame retardant type fluorinated poly arylene ether nitrile resin of high temperature resistant and preparation method thereof | |
| CN105175714B (en) | A kind of process for preparing cyano group ketone-grouped resin | |
| CN115010926A (en) | Polysulfone resin and preparation method thereof | |
| CN111410746B (en) | Hyperbranched polysulfone with controllable branching degree and preparation method thereof | |
| CN114479011A (en) | Epoxy glass polymer material based on dynamic reversible covalent bond and preparation method thereof | |
| CN110272546B (en) | Method for synthesizing polyether sulfone resin | |
| CN105778093A (en) | Halogen-free catalytic polyphenylene sulfide and preparation method thereof | |
| CN117510854B (en) | Polysulfone resin and preparation method thereof | |
| CN107501553A (en) | A kind of preparation method of the polyphenylene sulfide of no catalyst | |
| CN114437338B (en) | Synthesis method of polyether-ether-ketone | |
| CN107722203A (en) | A kind of solvent-free method for preparing polyether-ether-ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171201 |