CN109280372A - Polyphenyl ether/nylon alloy material product and preparation method thereof - Google Patents
Polyphenyl ether/nylon alloy material product and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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Abstract
The present invention provides a kind of polyphenyl ether/nylon alloy material products and preparation method thereof, wherein the raw material for preparing of alloy material product includes the following component being calculated in mass percent: polymerization nylon 18~70%；Polyphenylene oxide 25~60%；First auxiliary agent 2~10%；Second auxiliary agent 0.2~12%, polymerization nylon are obtained by cycloalphatic diamine, aromatic acid, lactams and synthesis of epoxy compounds, and the first auxiliary agent is compatilizer.The epoxy group of epoxide can both be reacted with amino therein or carboxyl in the polymerization nylon that the present invention uses, it can be reacted again with the hydroxyl in polyphenylene oxide, thus epoxy group can be used as bridge and be combined polymerization nylon and polyphenylene oxide and generate containing polymerization nylon-epoxide-polyphenyl ether structure copolymer, it also means that, noncrystalline nonpolar copolymer polyphenylene oxide and crystalline polar copolymer nylon is enable to carry out the compatible performance to make its polyphenyl ether/nylon alloy material obtained have both polyphenylene oxide and polymerization nylon simultaneously well.
Description
Technical field
The present invention relates to nylon products more particularly to a kind of polyphenyl ether/nylon alloy material product and preparation method thereof.
Background technique
Polyphenylene oxide, abbreviation PPO are one of big general engineering plastics in the world five, have that rigidity is big, heat resistance is high, fire retardant, strong
The advantages that spending higher, excellent electrical properties.In addition, polyphenylene oxide also has many advantages, such as wear-resisting, nontoxic, anti-pollution.Polyphenylene oxide is engineering
One of the smallest kind of dielectric constant and dielectric loss in plastics, is hardly influenced by temperature, humidity, can be used for it is low, in,
High-frequency electric field field.Polyamide is commonly called as nylon (Nylon), English name Polyamide (abbreviation PA), is contained on molecular backbone
The thermoplastic resin general name of recurring amide radical group-[NHCO]-, including amorphous nylon, aliphatic-aromatic race nylon and aromatic series Buddhist nun
Dragon.Wherein amorphous nylon is wide in variety, yield is big, is widely used, and nylon has a good comprehensive performance, including mechanical property,
Heat resistance, wear resistance, chemical resistance and self-lubrication, and coefficient of friction is low, there is certain anti-flammability, it is easy to process,
Suitable for its performance with glass fibre and other filler filling enhancing modifieds, can be improved and expand application range.Such product purpose
Extensively, it is good material to mould the metals such as Dai Gang, iron, copper, engineering plastics is important, in automobile, electronic apparatus, sport, machinery
Aspect has application.
In polyphenyl ether/nylon alloy, nylon provides good solvent resistance and processing performance, polyphenylene oxide are with higher
Heat resistance, low water absorbable, dimensional stability, while its higher heat resistance of content of polyphenylene oxide is better.Polyphenylene oxide is amorphism
Nonpolar copolymer, and nylon is crystalline polar copolymer, the two mutually has certain difficulty, at present on the market
Polyphenyl ether/nylon alloy is mostly polyphenylene oxide/styrene/nylon alloy, this allows for the thermal deformation temperature of polyphenyl ether/nylon alloy
It is not very high for spending, and has certain limitation in application aspect.
Therefore, how to improve the compatibility between polyphenylene oxide and nylon and expand the application range of polyphenyl ether/nylon alloy
As trend of the situation.
Summary of the invention
The present invention is intended to provide a kind of polyphenyl ether/nylon alloy material product and preparation method thereof, it can solve polyphenylene oxide
The performance of the various aspects of polyphenyl ether/nylon alloy can be improved to expand its application range in consistency problem between nylon.
To achieve the above object, first aspect present invention provides a kind of polyphenyl ether/nylon alloy material product, preparation
Raw material includes the following component being calculated in mass percent:
The polymerization nylon is obtained by cycloalphatic diamine, aromatic acid, lactams and synthesis of epoxy compounds,
First auxiliary agent is compatilizer.
The polymerization nylon that the present invention uses is that cycloalphatic diamine, aromatic acid, lactams and epoxide are poly-
It closes and obtains, be a kind of semi-aromatic nylon class material, have the characteristics that high temperature resistant, low water absorption, intensity are high；In polymerization nylon
The epoxy group of epoxide can not only be reacted with amino therein or carboxyl, but also can be reacted with the hydroxyl in polyphenylene oxide,
Thus epoxy group can be used as bridge and be combined polymerization nylon and polyphenylene oxide and generate containing polymerization nylon-epoxy compound
Object-polyphenyl ether structure copolymer, also means that, makes noncrystalline nonpolar copolymer polyphenylene oxide and crystalline polarity
Copolymer nylon carries out compatible to enable its polyphenyl ether/nylon alloy material obtained to have both polyphenylene oxide simultaneously and gather well
Close the performance of nylon；Compatilizer can also further promote the compatibility between polyphenylene oxide and polymerization nylon simultaneously, especially solve
The uneven problem of the bad dispersion of resulting product local consistency can to sum up make polyphenyl ether/nylon alloy material obtained simultaneously
Have both the excellent properties of polyphenylene oxide and polymerization nylon, i.e., heat resistance, lower water absorption rate and dimensional stability with higher.
Its fusing point of polymerization nylon produced by the present invention is up to 235~305 DEG C, and saturated water absorption is 4.5~6.5%, meaning
It has higher high temperature resistance and lower water absorption rate.
Further, the mass percent of polymerization nylon can for 18%, 20%, 25%, 30%, 35%, 40%, 45%,
50%, 55%, 60%, 65%, 70%, the mass percent of polyphenylene oxide can be 25%, 30%, 35%, 40%, 45%, 50%,
55%, 60%, the mass percent of compatilizer can be 2%, 4%, 5%, 8%, 10%, and the mass percent of the second auxiliary agent can be
0.2%, 0.4%, 0.5%, 0.8%, 1%, 2%, 4%, 6%, 8%, 10%, 12%.Further second auxiliary agent, which is selected from, to be increased
Tough dose, antioxidant, one of lubricant and light stabilizer or a variety of, it is preferred that the second auxiliary agent includes at least toughener, and increases
The 50~100% of the tough dose of quality for accounting for the second auxiliary agent, it is furthermore preferred that the second auxiliary agent includes toughener, antioxidant, lubricant and light
Stabilizer, and to account for the mass percentage for preparing raw material of polyphenyl ether/nylon alloy material product, toughener is 2~10%,
Antioxidant is 0.2~0.5%, lubricant is 0.2~0.6%, and light stabilizer is 0.2~0.6%.Polyphenyl can be improved in toughener
Ether/nylon alloy material toughness can be Styrene-Butadiene-Styrene Block Copolymer, styrene-ethylene-butadiene-benzene
One of ethylene block copolymer and maleic anhydride grafted ethene-octene copolymer are a variety of, preferably styrene-ethylene-
Butylene-styrene block copolymer.Antioxidant can reduce the volatilization of each substance under high temperature, can be selected from N, and N'- is bis--(3- (3,5- bis-
Tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and/or three [2.4- di-tert-butyl-phenyl] phosphite esters.Lubricant can be hard
Resin acid calcium, modified one of ethylene bis-fatty acid amides and ethylene bis stearamide or a variety of, can enhance the table of alloy material
Face makes resulting product surface-brightening.Light stabilizer can prevent polyphenyl ether/nylon alloy material product color due to illumination oxidation from sending out
Huang, preferably ultraviolet absorbing agent, such as benzophenone, benzotriazole.
Further, the cycloalphatic diamine and the aromatic acid are equimolar ratio, and the lactams accounts for institute
The 1~30% of cycloalphatic diamine and the aromatic acid quality sum is stated, the epoxide accounts for described alicyclic
The proportion of the 0.2~4% of diamine and the aromatic acid quality sum, lactams and epoxide it is less because
And have no effect on the mechanical performance of the main structure of polymerization nylon.
Further, cycloalphatic diamine is selected from 4,4 '-diamino-dicyclohexyl methanes and isophorone diamine
One or two, aromatic acid are selected from one or both of M-phthalic acid and terephthalic acid (TPA), and lactams selects oneself
One or both of lactams and lauryl lactan.
Further, the epoxide is N, N, N', N'- four glycidyl group -4,4'- diamino hexichol first
Alkane, epoxy group is more, thus may make under equal volume between polyphenylene oxide and polymerization nylon it is compatible more preferably.
Further, the compatilizer is maleic anhydride grafted polyphenylene ether or citric acid, preferably citric acid, due to lemon
The meeting of lemon acid so that final products performance declines, thus needs for citric acid and polyphenylene oxide to be grafted so that polymerization nylon degradation
Polyphenylene oxide-citric acid graft copolymer is formed, and the citric acid after being grafted can also react to form acyl with carboxyl in polymerization nylon
Amine or sub- acid amide-grafted copolymer, are also equivalent to, and citric acid equally plays bridge work between polyphenylene oxide and polymerization nylon
With, thus improve the compatibility between polyphenylene oxide and polymerization nylon.
Second aspect of the present invention provides a kind of preparation method of copolymer nylon product, including following step successively:
1) preparation of polymerization nylon
Under nitrogen atmosphere, the cycloalphatic diamine of formula ratio, aromatic acid, lactams and epoxide are added
Enter in polymeric kettle, and heating stirring, then draining is exhausted, cooling and dicing obtains the polymerization nylon after the molding of Cast Strip；
2) preparation of compatilizer grafted polyphenylene ether
By the compatilizer and polyphenylether blending of formula ratio, dries and can obtain after extrusion；
3) preparation of polyphenyl ether/nylon alloy material product
The polymerization nylon of formula ratio, the compatilizer grafted polyphenylene ether and the second auxiliary agent are uniformly mixed, shearing is squeezed
Out, and granulated and dried can obtain.
In preparation method of the invention by compatilizer first with polyphenylether blending be made compatilizer grafted polyphenylene ether after again with
Polymerization nylon is blended, and can prevent compatilizer from polymerization nylon being made to degrade and the performance of influence alloy material product obtained.Meanwhile by
In the compatibility of polymerization nylon and polyphenylene oxide preferably without the melting extrusion of high temperature, to alloy material when can avoid high-temperature fusion
The performance of material influences.
Further, in the preparation of step 3) polyphenyl ether/nylon alloy material product, the revolving speed for shearing use is more than or equal to
250r/min, to be conducive to the dispersion of polyphenylene oxide.
Further, the preparation method of polyphenyl ether/nylon alloy material product is specific can include:
1) preparation of polymerization nylon
Under the conditions of nitrogen protection, by the cycloalphatic diamine of formula ratio, aromatic acid, lactams and epoxy compound
Object is soluble in water, is warming up to 80~180 DEG C, reacts 2~4h, up to reaction solution is at limpid or uniform aaerosol solution, by solution
It being transferred in polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure starts to be vented when being promoted to 10~20bar,
Temperature is increased to 300~340 DEG C in exhaust process, then forms after moisture removal is gone down in nitrogen effect through die head Cast Strip, cooling
Polymerization nylon is made in pelletizing；
2) preparation of compatilizer grafted polyphenylene ether
By the polyphenylether blending of the compatilizer of formula ratio and formula ratio, dried after double screw extruder squeezes out
It can obtain；
3) preparation of polyphenyl ether/nylon alloy material product
By the polymerization nylon of formula ratio, the compatilizer grafted polyphenylene ether of formula ratio and the second auxiliary agent of formula ratio
It is uniformly mixed, is added in the main feeding hopper of extruder and is squeezed out using the rotating speed cutting of 250~300r/min, through twin-screw extrusion
Machine extrusion, pelletizing, drying and obtain.
The present invention also provides the preparation methods that another does not need to carry out graft reaction in advance for compatilizer, including
Following step successively:
1) preparation of polymerization nylon
Under nitrogen atmosphere, polymeric kettle is added in cycloalphatic diamine, aromatic acid, lactams and epoxide
In, and heating stirring, then draining is exhausted, cooling and dicing obtains the polymerization nylon after the molding of Cast Strip；
2 ') preparation of polyphenyl ether/nylon alloy material product
The second of the polymerization nylon of formula ratio, the polyphenylene oxide of formula ratio, the compatilizer of formula ratio and formula ratio is helped
Agent is uniformly mixed, shear extrusion, and granulated and dried can obtain.
Further, the preparation method of polyphenyl ether/nylon alloy material product is specific can include:
1) preparation of polymerization nylon
Under the conditions of nitrogen protection, by the cycloalphatic diamine of formula ratio, aromatic acid, lactams and epoxy compound
Object is soluble in water, is warming up to 80~180 DEG C, reacts 2~4h, up to reaction solution is at limpid or uniform aaerosol solution, by solution
It being transferred in polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure starts to be vented when being promoted to 10~20bar,
Temperature is increased to 300~340 DEG C in exhaust process, then forms after moisture removal is gone down in nitrogen effect through die head Cast Strip, cooling
Polymerization nylon is made in pelletizing；
2 ') preparation of polyphenyl ether/nylon alloy material product
The second of the polymerization nylon of formula ratio, the polyphenylene oxide of formula ratio, the compatilizer of formula ratio and formula ratio is helped
Agent is uniformly mixed, and is added in the main feeding hopper of extruder and is squeezed out using the rotating speed cutting of 250~300r/min, is squeezed through twin-screw
Out machine extrusion, pelletizing, drying and obtain.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention, involved in the embodiment of the present invention
Raw material can be obtained by commercially available.
For convenience's sake, the moieties being referred to herein, using being referred to as described, specifically include in specification:
Polyphenyl ether/nylon (PPO/PA), polyphenylene oxide (PPO), nylon (PA), polymerization nylon (HPA), isophorone diamine (IPDA), 4,
4 '-diamino-dicyclohexyl methanes (DDCM), M-phthalic acid (IPA), terephthalic acid (TPA) (TPA), citric acid (CA), N, N,
N', N'- four glycidyl group -4,4'- diaminodiphenylmethane (TGDDM), lauryl lactan (LL), caprolactam (CPL),
Maleic anhydride grafted polyphenylene ether (PPO-g-MAH), citric acid grafted polyphenylene ether (PPO-co-CA), styrene-butadiene-benzene second
Alkene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride grafted ethene-are pungent
Alkene copolymer (POE-g-MAH), N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant
1098), three [2.4- di-tert-butyl-phenyl] phosphite esters (antioxidant TH-168), modified ethylene bis-fatty acid amides (TAF), second
Support bis-stearamides (EBS), nylon66 fiber (PA66).
Embodiment 1
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer CA, toughener SEBS, antioxygen
Agent is antioxidant 1098, and lubricant TAF, light stabilizer is benzophenone ultraviolet absorbent.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and TPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
By the HPA of formula ratio, the PPO-co-CA of formula ratio, the SEBS of formula ratio, the antioxidant 1098 of formula ratio, formula
The TAF of amount and the benzophenone ultraviolet absorbent of formula ratio are uniformly mixed, and are added in the main feeding hopper of extruder and are used
The rotating speed cutting of 300r/min squeezes out, through double screw extruder extrusion, pelletizing, drying and obtain.
Embodiment 2
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer CA, toughener SEBS, antioxygen
Agent is antioxidant 1098, and lubricant TAF, light stabilizer is benzophenone ultraviolet absorbent.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and TPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
By the HPA of formula ratio, the PPO-co-CA of formula ratio, the SEBS of formula ratio, the antioxidant 1098 of formula ratio, formula
The TAF of amount and the benzophenone ultraviolet absorbent of formula ratio are uniformly mixed, and are added in the main feeding hopper of extruder and are used
The rotating speed cutting of 300r/min squeezes out, through double screw extruder extrusion, pelletizing, drying and obtain.
Embodiment 3
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer CA, toughener SEBS, antioxygen
Agent is antioxidant 1098, and lubricant TAF, light stabilizer is benzophenone ultraviolet absorbent.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and TPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
By the HPA of formula ratio, the PPO-co-CA of formula ratio, the SEBS of formula ratio, the antioxidant 1098 of formula ratio, formula
The TAF of amount and the benzophenone ultraviolet absorbent of formula ratio are uniformly mixed, and are added in the main feeding hopper of extruder and are used
The rotating speed cutting of 300r/min squeezes out, through double screw extruder extrusion, pelletizing, drying and obtain.
Embodiment 4
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that DDCM, IPA, CPL and TGDDM polymerize and obtain, compatilizer CA, toughener SBS, antioxygen
Agent is antioxidant TH-168, and lubricant EBS, light stabilizer is Benzotriazole Ultraviolet Stabilizer.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar DDCM and IPA, account for DDCM and IPA quality sum be 18% CPL and
It is soluble in water to account for the TGDDM that DDCM and IPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
By the HPA of formula ratio, the PPO-co-CA of formula ratio, the SBS of formula ratio, the antioxidant TH-168 of formula ratio, formula
The EBS of amount and the Benzotriazole Ultraviolet Stabilizer of formula ratio are uniformly mixed, and are added in the main feeding hopper of extruder and are used
The rotating speed cutting of 300r/min squeezes out, through double screw extruder extrusion, pelletizing, drying and obtain.
Embodiment 5
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer PPO-g-MAH, and toughener is
SEBS, antioxidant are antioxidant 1098, and lubricant TAF, light stabilizer is benzophenone ultraviolet absorbent.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and TPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2 ') preparation of PPO/PA alloy material product
By the HPA of formula ratio, the PPO-g-MAH of formula ratio, the SEBS of formula ratio, the antioxidant 1098 of formula ratio, formula
The TAF of amount and the benzophenone ultraviolet absorbent of formula ratio are uniformly mixed, and are added in the main feeding hopper of extruder and are used
The rotating speed cutting of 300r/min squeezes out, through double screw extruder extrusion, pelletizing, drying and obtain.
Embodiment 6
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer CA, toughener SEBS, antioxygen
Agent is antioxidant 1098.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and TPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
The antioxidant 1098 of the HPA of formula ratio, the PPO-co-CA of formula ratio, the SEBS of formula ratio, formula ratio is mixed
It is even, it is added in the main feeding hopper of extruder and is squeezed out using the rotating speed cutting of 300r/min, squeeze out, cut through double screw extruder
Grain is dried and is obtained.
Embodiment 7
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Polymerization nylon HPA is that IPDA, TPA, LL and TGDDM polymerize and obtain, compatilizer CA, toughener SEBS.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
1) preparation of HPA
Under the conditions of nitrogen protection, by equimolar IPDA and TPA, account for IPDA and TPA quality sum be 18% LL and
It is soluble in water to account for the TGDDM that IPDA and IPA quality sum is 2%, is warming up to 120 DEG C, reacts 3h, until reaction solution at limpid or
Uniform aaerosol solution, transfers the solution into polymeric kettle, lasting stirring and heating, reaches 240 DEG C to temperature, air pressure promotion is arrived
Start to be vented when 15bar, temperature is increased to 320 DEG C in exhaust process, then casts after moisture removal is gone down in nitrogen effect through die head
Polymerization nylon is made in band molding, cooling and dicing；
2) preparation of PPO-co-CA
The CA of formula ratio is blended with the PPO of formula ratio, drying after double screw extruder squeezes out can obtain；
3) preparation of PPO/PA alloy material product
The SEBS of the HPA of formula ratio, the PPO-co-CA of formula ratio, formula ratio is uniformly mixed, the master that extruder is added feeds
In hopper and using 300r/min rotating speed cutting squeeze out, through double screw extruder extrusion, pelletizing, drying and obtain.
Comparative example 1
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Toughener is SEBS, and antioxidant is antioxidant 1098, and lubricant TAF, light stabilizer is benzophenone type ultraviolet
Light absorbers.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
(1) in PA66, PPO of formula ratio, SEBS, antioxidant 1098, TAF, the mixing of benzophenone ultraviolet absorbent
Uniformly；
(2) material will be blended obtained by step (1) and puts into double screw extruder, be mixed it is even after, melting extrusion, temperature is 290
DEG C, revolving speed 300r/min, pelletizing screening can obtain after cooling.
Comparative example 2
A kind of polyphenyl ether/nylon alloy material product, preparing raw material includes the following component being calculated in mass percent:
Compatilizer is PPO-g-MAH, and toughener SEBS, antioxidant is antioxidant 1098, lubricant TAF, light stabilization
Agent is benzophenone ultraviolet absorbent.
This polyphenyl ether/nylon alloy material the preparation method comprises the following steps:
(1) in PA66, PPO of formula ratio, PPO-g-MAH, SEBS, antioxidant 1098, TAF, benzophenone ultraviolet
Absorbent is uniformly mixed；
(2) material will be blended obtained by step (1) and puts into double screw extruder, be mixed it is even after, melting extrusion, temperature is 290
DEG C, revolving speed 300r/min, pelletizing screening can obtain after cooling.
The polyphenyl ether/nylon alloy material product of Examples 1 to 7 and comparative example 1~2 is subjected to various mechanicalnesses respectively
The detection of energy, heat-resisting quantity and shrinking percentage, concrete operations are as follows, and test result is as shown in table 1.
Mechanical performance detection: tensile strength is tested using GB/T 1040-2006 standard, and bending strength uses GB/T
9341-2008 standard is tested, and notch impact strength is tested using GB/T 1843-2008 standard；
Heat-resisting quantity: heat-resisting quantity is characterized using heat distortion temperature, heat distortion temperature using ASTM D648 standard into
Row test；
Shrinking percentage: shrinking percentage detection is carried out using ASTMD955 standard.
Every test result of 1 Examples 1 to 7 of table and comparative example 1~2
Examples 1 to 7 and comparative example 1~2 based on table 1 are it is found that substitute common nylon with polymerization nylon of the invention
Polyphenyl ether/nylon alloy material product prepared by material has excellent high temperature resistance, mechanical strength and dimensional stability,
It is a kind of polyphenyl ether/nylon alloy material product of high thermal deformation of low warpage, illustrates polyphenyl ether/nylon alloy material of the invention
The compatibility of polyphenylene oxide and nylon is fine in product.
Based on embodiment 3 and embodiment 5 it is found that using citric acid as compatilizer, properties are more preferably.
It should be pointed out that embodiments above is only illustrative of the invention and is not intended to limit the scope of the invention, readding
After having read the present invention, those skilled in the art each fall within right appended by the present invention to the modification of various equivalent forms of the invention
It is required that the range limited.
Claims (10)
1. a kind of polyphenyl ether/nylon alloy material product, which is characterized in that its prepare raw material include be calculated in mass percent as
Lower component:
The polymerization nylon is obtained by cycloalphatic diamine, aromatic acid, lactams and synthesis of epoxy compounds,
First auxiliary agent is compatilizer.
2. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the cycloalphatic diamine
It is equimolar ratio with the aromatic acid, the lactams accounts for the cycloalphatic diamine and the aromatic acid matter
The 1~30% of the sum of amount, the epoxide account for the cycloalphatic diamine and the aromatic acid quality sum
0.2~4%.
3. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the cycloalphatic diamine
Selected from one or both of 4,4 '-diamino-dicyclohexyl methanes and isophorone diamine.
4. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the aromatic acid
Selected from one or both of M-phthalic acid and terephthalic acid (TPA).
5. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the lactams selects oneself
One or both of lactams and lauryl lactan.
6. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the epoxide is
N, N, N', N'- four glycidyl group -4,4'- diaminodiphenylmethane.
7. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that the compatilizer is Malaysia
Acid anhydrides grafted polyphenylene ether or citric acid.
8. polyphenyl ether/nylon alloy material product according to claim 1, which is characterized in that second auxiliary agent is selected from
One of toughener, antioxidant, lubricant and light stabilizer are a variety of.
9. a kind of preparation method of polyphenyl ether/nylon alloy material product, including following step successively:
1) preparation of polymerization nylon
Under nitrogen atmosphere, the cycloalphatic diamine of formula ratio, aromatic acid, lactams and epoxide are added poly-
It closes in kettle, and heating stirring, then draining is exhausted, cooling and dicing obtains the polymerization nylon after the molding of Cast Strip；
2) preparation of compatilizer grafted polyphenylene ether
By the compatilizer and polyphenylether blending of formula ratio, dries and can obtain after extrusion；
3) preparation of polyphenyl ether/nylon alloy material product
The polymerization nylon of formula ratio, the compatilizer grafted polyphenylene ether and the second auxiliary agent are uniformly mixed, shear extrusion, and
Granulated and dried can obtain.
10. a kind of preparation method of polyphenyl ether/nylon alloy material product, including following step successively:
1) preparation of polymerization nylon
Under nitrogen atmosphere, cycloalphatic diamine, aromatic acid, lactams and epoxide are added in polymeric kettle,
And heating stirring, then draining is exhausted, cooling and dicing obtains the polymerization nylon after the molding of Cast Strip；
2 ') preparation of polyphenyl ether/nylon alloy material product
Second auxiliary agent of the polymerization nylon of formula ratio, the polyphenylene oxide of formula ratio, the compatilizer of formula ratio and formula ratio is mixed
It closes uniformly, shear extrusion, and granulated and dried can obtain.
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| CN115466506A (en) * | 2022-09-15 | 2022-12-13 | 河南天海电器有限公司 | Polyphenyl ether/nylon resin composite material for new energy electric appliance box, preparation method of polyphenyl ether/nylon resin composite material and new energy electric appliance box |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN103923314A (en) * | 2014-04-10 | 2014-07-16 | 东莞市意普万尼龙科技股份有限公司 | High temperature resistant copolymer nylon with low hygroscopicity and preparation method thereof |
| CN104212161A (en) * | 2013-05-29 | 2014-12-17 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenyl ether/polyamide alloy material and preparation method |
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| CN104212161A (en) * | 2013-05-29 | 2014-12-17 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenyl ether/polyamide alloy material and preparation method |
| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN103923314A (en) * | 2014-04-10 | 2014-07-16 | 东莞市意普万尼龙科技股份有限公司 | High temperature resistant copolymer nylon with low hygroscopicity and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115466506A (en) * | 2022-09-15 | 2022-12-13 | 河南天海电器有限公司 | Polyphenyl ether/nylon resin composite material for new energy electric appliance box, preparation method of polyphenyl ether/nylon resin composite material and new energy electric appliance box |
| CN115466506B (en) * | 2022-09-15 | 2023-10-20 | 河南天海电器有限公司 | Polyphenyl ether/nylon resin composite material for new energy electric appliance box, preparation method of polyphenyl ether/nylon resin composite material and new energy electric appliance box |
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