CN107541048B - A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material - Google Patents
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, block copolymerization is first carried out with the dimethyl silicone polymer that hydroxy-end capped poly (arylene ether nitrile) and chlorine block, PEN-PDMS copolymer is carried out to compound, obtained high tenacity poly (arylene ether nitrile) composite material with poly (arylene ether nitrile) resin matrix again.The method can improve dimethyl silicone polymer and PEN matrix compatibility, the performance characteristics such as its high tenacity are played simultaneously, to improve shock resistance, melt fluidity of PEN resin etc., the present invention can expand the application field of poly (arylene ether nitrile) resin, meet the needs of related fields development.
Description
Technical field
The invention belongs to thermoplas tic resin composite's technical fields, and in particular to a kind of poly (arylene ether nitrile)-poly dimethyl silicon
The preparation method of the block copolymer-toughened poly (arylene ether nitrile) composite material of oxygen alkane.
Background technique
Poly (arylene ether nitrile) (PEN) belongs to special engineering plastics field, and macromolecular main chain possesses aryl oxide structural unit, and wherein
A kind of aryl oxide side group is itrile group, combines the performance characteristics of each component.Initial stage eighties D.K.Mohanty etc. is with phenyl-dihalide first
Nitrile is prepared for the poly (arylene ether nitrile) homopolymer with practical application performance, and poly aryl ether product achieves fast development later, such as
Japan S.Matsuo in 1986 etc. has applied for series of patents, and Japanese Chu Guangxingchan company successfully develops PEN product.Poly (arylene ether nitrile)
Research at home is started in the 1980s, being concentrated mainly on research synthesis technology and formula etc..PEN product is available
In special engineering plastics, film, fiber and composite material, possess good thermal stability, high mechanical properties, good insulating, chemically-resistant
Product corrode and possess the comprehensive performance excellent from anti-flammability etc..
As the application of PEN resin is gradually expanded, it has been found that the shortcoming present in it, such as notch shock
Intensity is poor, and low-temperature flexibility is poor, causes it to be unable to satisfy the requirement in certain fields, it would be highly desirable to seek toughening technology.
Polydimethylpolysiloxane (PDMS) is Undec elastomer under high temperature, has low-surface-energy, higher use
Temperature and the performance characteristics such as fire-retardant can realize performance complement with PEN, but its compatibility is poor.If with hydroxy-end capped poly- virtue
The polydimethylpolysiloxane of ether nitrile and chlorine sealing end carries out block copolymerization, then by PEN-PDMS copolymer and poly (arylene ether nitrile) resin base
Body progress is compound, can improve itself and PEN matrix compatibility, while playing its performance characteristics, so that the low temperature for improving PEN resin is tough
Property, melt fluidity and anti-flammability etc..
Summary of the invention
The object of the present invention is to provide a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, with
Overcome defect of the existing technology, expand the application field of poly (arylene ether nitrile) resin, meets the needs of related fields development.
Technical scheme is as follows:
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, first with hydroxy-end capped polyarylether
The polydimethylpolysiloxane of nitrile and chlorine sealing end carries out block copolymerization, then poly (arylene ether nitrile)-polydimethylsiloxaneblock block is copolymerized
Object (PEN-PDMS) and the progress of poly (arylene ether nitrile) resin matrix are compound, and high tenacity poly (arylene ether nitrile) composite material is made, and the method can change
Kind dimethyl silicone polymer and PEN matrix compatibility, while the performance characteristics such as its high tenacity are played, to improve PEN resin
Erosion-resisting characteristics, melt fluidity and anti-flammability etc..
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, including walk as follows poly-:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
By 2,6- dichlorobenzonitrile, aromatic dicarboxylic phenol, carbonate, N-Methyl pyrrolidone, toluene by certain mole
Mixing is matched, and is put into reaction kettle, heating stirring carries out dehydration, lead to during dehydration to 120~170 DEG C
Water and dehydrating agent toluene that reflux unit separation reaction generates are crossed, reaction obtained oligomer after 2~3 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, the methylene chloride that chlorine sealing end dimethyl silicone polymer is added dropwise is molten
Liquid, after dripping, the reaction was continued at 170~220 DEG C 2~5h, the obtained PEN-PDMS block copolymer of synthesis, the production that will be obtained
Object is washed with water to neutrality, and is dried；
(3) prepared by blend
Will self-control poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, then by PEN-PDMS copolymer obtained and poly (arylene ether nitrile) tree
Rouge is added in high-speed mixer and is uniformly mixed, and carries out extruding pelletization with double screw extruder, obtains PEN-PDMS copolymer and gathers
Aryl oxide nitrile composite material.
Preferably, feed molar described in step (1) matches are as follows: 2,6- dichlorobenzonitriles: aromatic dicarboxylic phenol: carbonic acid
Salt: N-Methyl pyrrolidone: toluene=1: (1.02~1.12): (1.2~1.35): (5~10): (1~5).
The aromatic dicarboxylic phenol is bisphenol-A, in hydroquinone, phenolphthalein, resorcinol, '-biphenyl diphenol, catechol
The mixture of any one or two kinds of arbitrary proportions.
Any one of the carbonate in potassium carbonate or sodium carbonate.
Preferably, in step (2) hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine sealing end dimethyl silicone polymer molar ratio
It is 1: 1~1.2.
Preferably, raw material constituent mass percentage in step (3) are as follows: poly (arylene ether nitrile) resin: PEN-PDMS copolymer=
70%~98%:2%~30%.
Preferably, setting extrusion temperature is 310~350 DEG C in step (3).
Beneficial effect
The invention has the advantages that due to PDMS be high temperature under Undec elastomer, have low-surface-energy and compared with
The performance characteristics such as high use temperature can realize performance complement with PEN.Poly (arylene ether nitrile) composite material is in PEN-PDMS copolymer substance
When amount dosage is 20%, notch impact strength reaches 38.35J/m2, it is 4 times of pure poly (arylene ether nitrile) resin, significantly improves poly-
The toughness of aryl oxide nitrile.And heat distortion temperature does not reduce substantially, tensile strength and bending strength remain at the 90% of comparative example with
On.Melt flow rate (MFR) increases to 29.45g/10min by the 15.59g/10min of pure resin raw material, and melt fluidity is good.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but scope of the present invention is not
It is confined to range involved in embodiment.
Embodiment 1
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, includes the following steps:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
By 2,6- dichlorobenzonitrile: hydroquinone: potassium carbonate: N-Methyl pyrrolidone: toluene=1: 1.02: 1.2: 5:
1.3 molar ratio mixing, and put into reaction kettle, heating stirring is to 150 DEG C, progress dehydration, during dehydration
The water and dehydrating agent toluene that reaction generates are separated by reflux unit, reaction obtained oligomer after 2 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, chlorine is added dropwise by metering dropping funel and blocks polydimethylsiloxanes
The dichloromethane solution of alkane, after dripping, the reaction was continued at 180 DEG C 3h is synthesized and PEN-PDMS block copolymer is made, will
To product be washed with water to neutrality, and be dried；Mole of hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine endcapped siloxanes
Than being 1: 1；
(3) prepared by blend
By poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, raw material components mass percent are as follows: poly (arylene ether nitrile) resin: PEN-
PDMS copolymer=80%:20%, then PEN-PDMS copolymer obtained and poly (arylene ether nitrile) resin are added in high-speed mixer
It is uniformly mixed, carries out extruding pelletization with double screw extruder, setting extrusion temperature is 310~350 DEG C, to obtain PEN-PDMS
Copolymer and poly (arylene ether nitrile) composite material.
Embodiment 2
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, includes the following steps:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
By 2,6- dichlorobenzonitrile: bisphenol-A: sodium carbonate: N-Methyl pyrrolidone: toluene=1: 1.12: 1.34: 10: 1.5
Molar ratio mixing, and put into reaction kettle, heating stirring carries out dehydration, pass through during dehydration to 140 DEG C
The water and dehydrating agent toluene that reflux unit separation reaction generates, reaction obtained oligomer after 2 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, chlorine is added dropwise by metering dropping funel and blocks polydimethylsiloxanes
The dichloromethane solution of alkane, after dripping, the reaction was continued at 190 DEG C 3h is synthesized and PEN-PDMS block copolymer is made, will
To product be washed with water to neutrality, and be dried；Mole of hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine endcapped siloxanes
Than being 1: 1.2；
(3) prepared by blend
By poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, raw material components mass percent are as follows: poly (arylene ether nitrile) resin: PEN-
PDMS copolymer=90%:10%, then PEN-PDMS copolymer obtained and poly (arylene ether nitrile) resin are added in high-speed mixer
It is uniformly mixed, carries out extruding pelletization with double screw extruder, setting extrusion temperature is 310~350 DEG C, to obtain PEN-PDMS
Copolymer and poly (arylene ether nitrile) composite material.
Embodiment 3
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, includes the following steps:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
By 2,6- dichlorobenzonitrile: resorcinol: potassium carbonate: N-Methyl pyrrolidone: toluene=1: 1.08: 1.2: 10: 5
Molar ratio mixing, and put into reaction kettle, heating stirring carries out dehydration, pass through during dehydration to 150 DEG C
The water and dehydrating agent toluene that reflux unit separation reaction generates, reaction obtained oligomer after 2 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, chlorine is added dropwise by metering dropping funel and blocks polydimethylsiloxanes
The dichloromethane solution of alkane, after dripping, the reaction was continued at 200 DEG C 3h is synthesized and PEN-PDMS block copolymer is made.Will
To product be washed with water to neutrality, and be dried；Mole of hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine endcapped siloxanes
Than being 1: 1.1；
(3) prepared by blend
By poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, raw material components mass percent are as follows: poly (arylene ether nitrile) resin: PEN-
PDMS copolymer=95%:5%, then PEN-PDMS copolymer obtained and poly (arylene ether nitrile) resin are added in high-speed mixer and mixed
It closes uniformly, carries out extruding pelletization with double screw extruder, setting extrusion temperature is 310~350 DEG C, so that it is total to obtain PEN-PDMS
Polymers and poly (arylene ether nitrile) composite material.
Embodiment 4
A kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, includes the following steps:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
By 2,6- dichlorobenzonitrile: bisphenol-A: sodium carbonate: N-Methyl pyrrolidone: toluene=1: 1.1: 1.3: 5: 2.5
Molar ratio mixing, and put into reaction kettle, heating stirring carries out dehydration, passes through back during dehydration to 140 DEG C
Water and dehydrating agent toluene that device separation reaction generates are flowed, reaction obtained oligomer after 2 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, chlorine is added dropwise by metering dropping funel and blocks polydimethylsiloxanes
The dichloromethane solution of alkane, after dripping, the reaction was continued at 180 DEG C 3h is synthesized and PEN-PDMS block copolymer is made, will
To product be washed with water to neutrality, and be dried；Mole of hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine endcapped siloxanes
Than being 1: 1.2；
(3) prepared by blend
By poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, raw material components mass percent are as follows: poly (arylene ether nitrile) resin: PEN-
PDMS copolymer=98%:2%, then PEN-PDMS copolymer obtained and poly (arylene ether nitrile) resin are added in high-speed mixer and mixed
It closes uniformly, carries out extruding pelletization with double screw extruder, setting extrusion temperature is 310~350 DEG C, so that it is total to obtain PEN-PDMS
Polymers and poly (arylene ether nitrile) composite material.
Comparative example
Comparative example of the present invention is not mix the poly (arylene ether nitrile) pure resin of PEN-PDMS copolymer, with the matrix used resin of embodiment
It is identical.
The pure resin raw material comparative example note of PEN-PDMS is not mixed poly (arylene ether nitrile) composite material prepared by embodiment 1-4 and
It is moulded into standard testing batten, notch impact strength is tested by 1843 standard of GB/T, and tensile property presses 1040 standard of GB/T
It is tested, bending property is tested by 9341 standard of GB/T, and heat distortion temperature is tested by GB/T1634 standard, is melted
Body flow rate is tested by GB/T3682 standard.Test result such as table 1.
1 embodiment of table and comparative example test performance table
As shown in Table 1, PEN-PDMS copolymer and poly (arylene ether nitrile) composite material of the present invention are in PEN-PDMS copolymer quality
When dosage is 20%, notch impact strength reaches 38.35J/m2, significantly improve the toughness of poly (arylene ether nitrile), and thermal deformation temperature
Degree does not reduce substantially, and tensile strength and bending strength remain at 90% of comparative example or more, and comprehensive performance is good.
Claims (7)
1. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material, which is characterized in that including walking as follows
It is rapid:
(1) preparation of hydroxy-end capped poly (arylene ether nitrile) oligomer
2,6- dichlorobenzonitrile, aromatic dicarboxylic phenol, carbonate, N-Methyl pyrrolidone, toluene are pressed into certain mol ratio
Mixing, and put into reaction kettle, heating stirring carries out dehydration, passes through back during dehydration to 120~170 DEG C
Water and dehydrating agent toluene that device separation reaction generates are flowed, reaction obtained oligomer after 2~3 hours；
(2) preparation of poly (arylene ether nitrile)-polydimethylsiloxaneblock block copolymers (PEN-PDMS)
Into hydroxy-end capped poly (arylene ether nitrile) oligomer obtained, the dichloromethane solution of chlorine sealing end dimethyl silicone polymer is added dropwise,
After dripping, the reaction was continued at 170~220 DEG C 2~5h is synthesized and PEN-PDMS block copolymer, the product that will be obtained is made
It is washed with water to neutrality, and is dried；
(3) prepared by blend
By poly (arylene ether nitrile) resin in 160 DEG C of dry 4h, then PEN-PDMS block copolymer obtained and poly (arylene ether nitrile) resin added
Enter in high-speed mixer and be uniformly mixed, carries out extruding pelletization with double screw extruder, obtain PEN-PDMS copolymer and polyarylether
Nitrile composite material.
2. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
It is characterized in that: the proportion of feed molar described in step (1) are as follows: 2,6- dichlorobenzonitriles: aromatic dicarboxylic phenol: carbonate: N-
Methyl pyrrolidone: toluene=1: (1.02~1.12): (1.2~1.35): (5~10): (1~5).
3. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
Be characterized in that: the aromatic dicarboxylic phenol is bisphenol-A, in hydroquinone, phenolphthalein, resorcinol, '-biphenyl diphenol, catechol
The mixture of any one or two kinds of arbitrary proportions.
4. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
It is characterized in that: any one of the carbonate in potassium carbonate or sodium carbonate.
5. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
Be characterized in that, in step (2) hydroxy-end capped poly (arylene ether nitrile) oligomer and chlorine sealing end dimethyl silicone polymer molar ratio be 1: 1~
1.2。
6. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
It is characterized in that, raw material constituent mass percentage in step (3) are as follows: poly (arylene ether nitrile) resin: PEN-PDMS block copolymer=70%
~98%:2%~30%.
7. a kind of preparation method of dimethyl silicone polymer toughening poly (arylene ether nitrile) composite material according to claim 1,
Be characterized in that: setting extrusion temperature is 310~350 DEG C in step (3).
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| CN101838390A (en) * | 2010-05-28 | 2010-09-22 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin |
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