CN105693890B - A kind of nylon toughener, preparation method and application - Google Patents
A kind of nylon toughener, preparation method and application Download PDFInfo
- Publication number
- CN105693890B CN105693890B CN201610183903.7A CN201610183903A CN105693890B CN 105693890 B CN105693890 B CN 105693890B CN 201610183903 A CN201610183903 A CN 201610183903A CN 105693890 B CN105693890 B CN 105693890B
- Authority
- CN
- China
- Prior art keywords
- nylon
- polyolefin
- preparation
- antioxidant
- toughener
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of nylon toughener, preparation method and application, polyolefin is placed in plasma reaction device, after vacuumizing, it is passed through gas, polyolefin is surface-treated using low temperature plasma, its surface is produced hydroxyl, carboxyl isoreactivity group, so as to obtain the polyolefin of surface modification, then by reacting to obtain the polyolefin of polar compound graft modification, as nylon toughener with polar compound and antioxidant.The present invention utilizes lower temperature plasma technology, in the case where not introducing radical initiator, adds (such as hydroxyl, carboxyl, the carbonyl, amino) type of active group caused by polyolefin surfaces and concentration, improves grafting efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of tenacity increased nylon, and in particular to one kind prepares nylon with reference to low temperature plasma
Toughener and preparation method thereof.
Background technology
Nylon is that a kind of purposes is most wide, the engineering plastics of most species, and the material has good mechanical property, heat-resisting
Property, wear resistance, chemical solvent resistance, self lubricity and certain anti-flammability, while the material processing characteristics is excellent, can be integral
The complicated structure member of chemical conversion type, is widely used in the fields such as automobile, electronic apparatus, machinery, track traffic, sports apparatus.But
It is the application that the shortcomings that water imbibition is strong, low temperature impact properties are poor limits nylon material.
Polyolefin or polyolefin elastomer are mixed with nylon, can significantly improve that the material water imbibition is strong, low temperature punching
The shortcomings that hitting poor performance.It is nonpolar due to polyolefin based materials, it is difficult to be well mixed with the nylon material of polarity, using polarity
Compound carries out graft modification to polyolefin, is then uniformly divided polyolefin by the method for reaction extrusion process, In Situ Compatibilization
It is scattered in nylon material, turns into and prepare the most frequently used method of tenacity increased nylon.Dispersed polyolefin or polyolefin elastomer
The impact energy that matrix material is subject to can be effectively absorbed, scattered polyolefin particles can also effectively prevent the generation of crackle,
Therefore the impact strength of nylon material at low temperature is significantly improved, the addition of non-polar polyolefinic can also substantially reduce material
Water imbibition.
A kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof (CN 101781389A) disclose one kind
Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof, by ethylene-alpha-octylene copolymers, peroxide initiator, clothing
Health acid polar monomer is well mixed in high-speed mixer, then 160~200 DEG C, screw speed 100~400 in an extruder
Reactive extrursion is carried out under rev/min, obtains Itaconic Acid Grafted ethylene-alpha-octylene copolymers, the copolymer grafted efficiency 0.8~
Between 1.0%.
The preparation method (CN 102766239A) of Itaconic Acid Grafted ethylene-octene block copolymer particulate material discloses one
The preparation method of kind Itaconic Acid Grafted ethylene-octene block copolymer particulate material, by ethylene-octene block copolymer, peroxidating
Thing initiator dibenzoyl peroxide, itaconic acid polar monomer, antioxidant are uniformly mixed, and then pass through double screw extruder
Reactive extrursion obtains Itaconic Acid Grafted ethylene-octene block copolymer at 150~170 DEG C, and copolymer grafted efficiency is
1.35%~1.65%.
A kind of modifying agent and preparation method and application (CN 101831131B) discloses a kind of Itaconic Acid Grafted polyolefin
Elastomer copolymer, by polyolefin elastomer, peroxide initiator cumyl peroxide, itaconic acid polar monomer, poly- second
Alkene wax is well mixed in banbury, then reactive extrursion in an extruder, is prepared into the copolymer.
A kind of super-tough nylon alloy and preparation method thereof (CN 101781455A) discloses a kind of system of super-tough nylon alloy
Preparation Method, nylon, Itaconic Acid Grafted ethylene-alpha-octylene copolymers, antioxidant, lubricant are put into high-speed mixer and mixed,
Then mixture is put into double screw extruder, 250~280 DEG C of extrusion temperature, 200~400 revs/min of driving screw rotating speed,
By drawing, cooling down, pelletizing, polyolefin tenacity-increased nylon mixture is obtained.
A kind of toughening polyamide combination and preparation method thereof (CN 1480489A) discloses a kind of system of toughened polyamide
Preparation Method, first in the presence of peroxide initiator, in an extruder using polar monomer graft polyolefin elastomer, so
The graft is well mixed with nylon 6 afterwards, granulation extrusion is carried out in an extruder, obtains with excellent toughness and processing characteristics
Composition.
A kind of super-toughened nylon and preparation method thereof (CN 1445278A) discloses a kind of preparation method of super-toughened nylon, will
The POE of maleic anhydride grafting is well mixed with nylon 6, while by the way of dynamic vulcanization in an extruder
Extruded, obtain the super-toughened nylon with excellent machinability.
Tenacity nylon material and its production technology (CN 90106778.4A) disclose a kind of preparation method of tenacity increased nylon,
First in the presence of cumyl peroxide initiator, ethylene-propylene-diene monomer is grafted using maleic anhydride in an extruder
Glue, the polyolefin of graft modification is obtained, be then well mixed the graft with nylon66 fiber, carried out being granulated in an extruder and squeeze
Go out, obtained material has good insulation properties, heat-resisting and cold tolerance, can be -40 DEG C~70 during as rail insulated joint
Used in the range of DEG C.
It can see from above-mentioned patent, as the toughener of tenacity increased nylon important component, all using peroxide conduct
Initiator, prepared in an extruder by the graft reaction of polar monomer, but peroxide initiator is except that can trigger polarity
Outside the main reaction of monomer graft polyolefin, also causing the generations of numerous side reactions, (crosslinking of such as polyethylene is polyacrylic
Degraded side reaction), this significantly reduces the efficiency of polar monomer graft polyolefin, and polyolefine material melt index becomes
After change, processing characteristics when can influence subsequently to mix with nylon.When using this graft polyolefin reactive extrursion is carried out with nylon
When preparing tenacity increased nylon, can not only harmful effect be produced to expressing technique；And because polyolefin graft rate is low, it is necessary to add big
Weight polyolefin could meet toughness of material demand, and this can significantly reduce the mechanical property of nylon material.
The content of the invention
The defects of to overcome prior art, the invention provides a kind of nylon toughener, preparation method and application, add
The efficiency of polar monomer graft polyolefin, it is added into the mechanical property that nylon is also increased in nylon.
To achieve the above object, the technical scheme is that：
A kind of preparation method of nylon toughener, polyolefin is placed in plasma reaction device, after vacuumizing, is passed through
Gas, polyolefin is surface-treated using low temperature plasma, its surface is produced hydroxyl, carboxyl isoreactivity group, from
And the polyolefin of surface modification is obtained, then by reacting to obtain polar compound graft modification with polar compound and antioxidant
Polyolefin, as nylon toughener.
The present invention utilizes lower temperature plasma technology, in the case where not introducing radical initiator, adds polyolefin
(such as hydroxyl, carboxyl, the carbonyl, amino) type of active group caused by surface and concentration, improve grafting efficiency.
Preferably, its step is：
(1) polyolefin is placed in plasma reaction device, vacuumized；
(2) gas is passed through to gas ions reaction unit, controls the type for being passed through gas, ratio, gas pressure intensity, electric discharge work(
Rate, discharge time to be surface-treated to polyolefin, make its surface produce hydroxyl, carboxyl isopolarity group, so as to obtain table
The polyolefin that face is modified；
(3) polyolefin, polar compound, the antioxidant being modified surface are put into extruder and reacted, extrudate warp
Traction, cooling, drying, pelletizing are crossed, obtains the polyolefin particles of polar compound graft modification, as nylon toughener.
By controlling the type for being passed through gas, ratio, gas pressure intensity, discharge power, discharge time, can further adjust
(such as hydroxyl, carboxyl, the carbonyl, amino) type of active group caused by polyolefin surfaces and concentration, can further increase grafting
Efficiency.
Preferably, in terms of mass parts, 99.89~78.0 parts of polyolefin, 0.1~18.0 part of polar compound, antioxidant
0.01~4.0 part.
It is further preferred that in the step (2) when 10~10000Pa of gas pressure intensity, 10~800W of discharge power, electric discharge
Between 0.5~30min.Active group caused by polyolefin surfaces (such as hydroxyl, carboxyl, carbonyl, amino) type is more under the conditions of being somebody's turn to do, dense
Degree is high, can further improve grafting efficiency.
It is further preferred that gas is air, oxygen, nitrogen, carbon dioxide, argon gas, helium, ammonia in the step (2)
A kind of several mixture of gas.Active group caused by polyolefin surfaces (such as hydroxyl, carboxyl, carbonyl, amino) under the conditions of being somebody's turn to do
Type is more, and concentration is high, can further improve grafting efficiency.
It is further preferred that step (3) concretely comprise the following steps, rapidly by surface improved polyalkene, polar compound,
Antioxidant is well mixed, and is put into extruder hopper, between 140 DEG C~220 DEG C, 60~400 revs/min of driving screw rotating speed,
Reacted under the conditions of 10~80 revs/min of feed screw rotating speed, extrudate obtains pole by traction, cooling, dry, pelletizing
The polyolefin particles of property compound graft modification, as nylon toughener.The condition improves polar compound and polyolefin table
The reaction efficiency of active group caused by face, so as to improve the grafting rate of polyolefin.
Preferably, the plasma reaction device is reaction of low temperature plasma device, discharge mode be glow discharge,
One kind in corona discharge, dielectric barrier discharge, radio frequency discharge or microwave discharge.
Preferably, the polyolefin is that low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), linea low density gather
Ethene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), POE (POE), ethylene propylene diene rubber
(EPDM) one or more of mixtures in.
Preferably, the polar compound be ethanedioic acid, malonic acid, tartronic acid, succinic acid, dyhydrobutanedioic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, 11 carbon diacid, dodecanedioic acid, hendecane dicarboxylic acid, ten
Four carbon diacid, pertadecane diacid, thapsic acid, 18 carbon diacid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), second
Acid anhydrides, propionic andydride, succinic anhydride, benzoyl oxide, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, clothing
Health acid anhydrides, citraconic anhydride, one or more of mixtures of crotonic anhydride.
Preferably, the antioxidant is [four (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant
1010), 3- (3,5- di-t-butyl -4- hydroxyls) propylene octadecyl ester (antioxidant 1076), N, N'- it is double-(3- (3,5- di-t-butyls -
4- hydroxy phenyls) propiono) hexamethylene diamine (antioxidant 1098), 2,6- di-t-butyl -4- cresols (antioxidant 264), 2,4,6- tri-
It is one or more of in tert-butyl phenol (antioxidant 246), (2,4- di-tert-butyl-phenyls) tris phosphite (irgasfos 168)
Mixture.
Nylon toughener prepared by a kind of above-mentioned preparation method.
A kind of application of above-mentioned nylon toughener in tenacity increased nylon is prepared.
A kind of preparation method of tenacity increased nylon, obtained after nylon, above-mentioned nylon toughener, antioxidant are carried out into hybrid reaction
Tenacity increased nylon.
Preferably, concretely comprise the following steps and nylon, above-mentioned nylon toughener, antioxidant are put into extruder hopper, at 180 DEG C
Between~290 DEG C, 60~400 revs/min of driving screw rotating speed, reacted under the conditions of 10~80 revs/min of feed screw rotating speed,
Extrudate obtains tenacity increased nylon particle by traction, cooling, dry, pelletizing.
Preferably, in terms of mass parts, 4.99~56.0 parts of nylon 9,5.0~40.0 parts of above-mentioned nylon toughener, antioxidant
0.01~4.0 part.
Preferably, the nylon is nylon 6, nylon66 fiber, nylon 46, NYLON610, nylon 612, nylon 9, nylon 11, Buddhist nun
One or more of mixtures in dragon 12, nylon 1010, Nylon 1012, nylon 1212.
Preferably, the antioxidant is [four (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant
1010), 3- (3,5- di-t-butyl -4- hydroxyls) propylene octadecyl ester (antioxidant 1076), N, N'- it is double-(3- (3,5- di-t-butyls -
4- hydroxy phenyls) propiono) hexamethylene diamine (antioxidant 1098), 2,6- di-t-butyl -4- cresols (antioxidant 264), 2,4,6- tri-
It is one or more of in tert-butyl phenol (antioxidant 246), (2,4- di-tert-butyl-phenyls) tris phosphite (irgasfos 168)
Mixture.
Compared with prior art, it is an advantage of the invention that：
1st, the present invention does not use radical initiator, can effectively reduce the crosslinking and degraded side reaction of polyolefin, polyene
Significant changes will not occur for hydrocarbon toughener fluidity of molten, and grafting efficiency is higher.
Processing characteristics is excellent when the 2nd, nylon toughener of the present invention and nylon being blended in an extruder, is meeting toughness of material
In the case of, toughener addition is fewer than toughener addition prepared by conventional method, can reduce nylon material to a greater extent
Expect the decline of mechanical property.
Brief description of the drawings
Fig. 1 is the schematic device of corona treatment polyolefin.
Embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further described.
Embodiment 1：Comparative example
Weigh 81.9 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 0.1 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, maleic anhydride is dissolved in 10.0 parts of absolute ethyl alcohols,
Dibenzoyl peroxide is dissolved in 5.0 parts of absolute ethyl alcohols, by LDPE, dibenzoyl peroxide solution, maleic anhydride solution, anti-
Oxygen agent 1010 is well mixed in high-speed mixer, said mixture is added in extruder hopper, each area's temperature of extruder exists
Between 150 DEG C~180 DEG C, 60 revs/min of driving screw rotating speed, 10 revs/min of feed screw rotating speed, extrudate, which passes through, to be drawn, is cold
But, dry, pelletizing, obtain maleic anhydride grafting LDPE particles.Weigh 6 85.0 parts of nylon, maleic anhydride grafting LDPE12.0
Part, 3.0 parts of antioxidant 1010, in high-speed mixer be well mixed, be put into extruder hopper, 200 DEG C~260 DEG C it
Between, 80 revs/min of driving screw rotating speed, reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain tenacity increased nylon particle.
Embodiment 2：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through argon gas, gas
Pressure 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxidant
1010 mixing 30min, mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed,
Reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate obtains maleic acid by traction, cooling, dry, pelletizing
Acid anhydride is grafted LDPE particles.6 85.0 parts of nylon, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed, in height
It is well mixed, is put into extruder hopper in fast mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed, is fed
Reacted under the conditions of 40 revs/min of screw speed of material, extrudate obtains tenacity increased nylon by traction, cooling, dry, pelletizing
Particle.
Embodiment 3：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through argon gas/oxygen
(volume ratio 4/1) mixed gas, gas pressure intensity 100Pa, radio frequency discharge power 20W, discharge time 10min, then surface is changed
Property LDPE, maleic anhydride, antioxidant 1010 mixing 30min, mixture is put into extruder hopper, 150~180 DEG C it
Between, 60 revs/min of driving screw rotating speed, reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain maleic anhydride grafting LDPE particles.Weigh 6 85.0 parts of nylon, maleic anhydride grafting LDPE 12.0
Part, 3.0 parts of antioxidant 1010, in high-speed mixer be well mixed, be put into extruder hopper, 200 DEG C~260 DEG C it
Between, 80 revs/min of driving screw rotating speed, reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain tenacity increased nylon particle.
Embodiment 4：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through air, gas
Pressure 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxidant
1010 mixing 30min, mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed,
Reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate obtains maleic acid by traction, cooling, dry, pelletizing
Acid anhydride is grafted LDPE particles.6 85.0 parts of nylon, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed, in height
It is well mixed, is put into extruder hopper in fast mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed, is fed
Reacted under the conditions of 40 revs/min of screw speed of material, extrudate obtains tenacity increased nylon by traction, cooling, dry, pelletizing
Particle.
Embodiment 5：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through carbon dioxide,
Gas pressure intensity 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxygen
Agent 1010 mixes 30min, and mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed
Clock, reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate by traction, cooling, dry, pelletizing, obtain Malaysia
Acid anhydrides is grafted LDPE particles.6 85.0 parts of nylon, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed,
It is well mixed, is put into extruder hopper in high-speed mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed,
Reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate obtains toughness reinforcing Buddhist nun by traction, cooling, dry, pelletizing
Imperial particle.
Embodiment 6：Comparative example
Weigh 81.9 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 0.1 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, maleic anhydride is dissolved in 10.0 parts of absolute ethyl alcohols,
Dibenzoyl peroxide is dissolved in 5.0 parts of absolute ethyl alcohols, by LDPE, dibenzoyl peroxide solution, maleic anhydride solution, anti-
Oxygen agent 1010 is well mixed in high-speed mixer, said mixture is added in extruder hopper, each area's temperature of extruder exists
Between 150 DEG C~180 DEG C, 60 revs/min of driving screw rotating speed, 10 revs/min of feed screw rotating speed, extrudate, which passes through, to be drawn, is cold
But, dry, pelletizing, obtain maleic anhydride grafting LDPE particles.Weigh 85.0 parts of nylon66 fiber, maleic anhydride grafting LDPE 12.0
Part, 3.0 parts of antioxidant 1010, in high-speed mixer be well mixed, be put into extruder hopper, 200 DEG C~260 DEG C it
Between, 80 revs/min of driving screw rotating speed, reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain tenacity increased nylon particle.
Embodiment 7：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through argon gas, gas
Pressure 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxidant
1010 mixing 30min, mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed,
Reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate obtains maleic acid by traction, cooling, dry, pelletizing
Acid anhydride is grafted LDPE particles.85.0 parts of nylon66 fiber, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed,
It is well mixed, is put into extruder hopper in high-speed mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed,
Reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate obtains toughness reinforcing Buddhist nun by traction, cooling, dry, pelletizing
Imperial particle.
Embodiment 8：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through argon gas/oxygen
(volume ratio 4/1) mixed gas, gas pressure intensity 100Pa, radio frequency discharge power 20W, discharge time 10min, then surface is changed
Property LDPE, maleic anhydride, antioxidant 1010 mixing 30min, mixture is put into extruder hopper, 150~180 DEG C it
Between, 60 revs/min of driving screw rotating speed, reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain maleic anhydride grafting LDPE particles.Weigh 85.0 parts of nylon66 fiber, maleic anhydride grafting LDPE 12.0
Part, 3.0 parts of antioxidant 1010, in high-speed mixer be well mixed, be put into extruder hopper, 200 DEG C~260 DEG C it
Between, 80 revs/min of driving screw rotating speed, reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate is by traction, cold
But, dry, pelletizing, obtain tenacity increased nylon particle.
Embodiment 9：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through air, gas
Pressure 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxidant
1010 mixing 30min, mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed,
Reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate obtains maleic acid by traction, cooling, dry, pelletizing
Acid anhydride is grafted LDPE particles.85.0 parts of nylon66 fiber, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed,
It is well mixed, is put into extruder hopper in high-speed mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed,
Reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate obtains toughness reinforcing Buddhist nun by traction, cooling, dry, pelletizing
Imperial particle.
Embodiment 10：
Weigh 82.0 parts of LDPE (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
15.0 parts of acid anhydride, 3.0 parts of antioxidant 1010.LDPE is placed in plasma reaction device, after vacuumizing, is passed through carbon dioxide,
Gas pressure intensity 100Pa, radio frequency discharge power 20W, discharge time 10min, surface is then modified LDPE, maleic anhydride, antioxygen
Agent 1010 mixes 30min, and mixture is put into extruder hopper, between 150~180 DEG C, 60 revs/min of driving screw rotating speed
Clock, reacted under the conditions of 10 revs/min of feed screw rotating speed, extrudate by traction, cooling, dry, pelletizing, obtain Malaysia
Acid anhydrides is grafted LDPE particles.85.0 parts of nylon66 fiber, 12.0 parts of LDPE of maleic anhydride grafting, 3.0 parts of antioxidant 1010 are weighed,
It is well mixed, is put into extruder hopper in high-speed mixer, between 200 DEG C~260 DEG C, 80 revs/min of driving screw rotating speed
Clock, reacted under the conditions of 40 revs/min of feed screw rotating speed, extrudate by traction, cooling, dry, pelletizing, obtain toughness reinforcing
Nylon particles.
The device of embodiment plasma processing polyolefin is as shown in Figure 1.
The polar compound graft-modified polyolefin result of embodiment 1~10 is as shown in table 1：
Table 1
It can see, treated by different plasma atmosphere poly- from the LDPE graft modification results of embodiment 2~5
Alkene, the efficiency for carrying out graft reaction with polar compound in an extruder are above 5.0%, and grafting efficiency is apparently higher than freedom
Result (as described in Example 1) under base initiation conditions, LDPE is after grafting, and its melt index fall is again smaller than freedom
Result (as described in Example 1) under base initiation conditions, illustrates that LDPE crosslinking side reaction is suppressed well.
The tenacity increased nylon result of embodiment 1~10 is as shown in table 2：
Table 2
It can see from the result of the maleic anhydride grafts toughened Nylon 6 of embodiment 2~5, using low temperature plasma
The toughener of preparation is because grafting efficiency is high, and in the case of same toughness reinforcing agent content, material impact intensity is significantly higher than using biography
Toughener result (as described in Example 1) prepared by system method, also there is class during toughener Toughed nylon66 (embodiment 7~10)
Like effect.
Above-mentioned although the embodiment of the present invention is described with reference to accompanying drawing, not to invention protection domain
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
Pay various modifications that creative work can make or deformation is still within the scope of the present invention.
Claims (9)
1. a kind of preparation method of nylon toughener, it is characterized in that, its step is：
(1) polyolefin is placed in plasma reaction device, vacuumized；
(2) it is passed through gas to gas ions reaction unit, control is passed through the type of gas, ratio, gas pressure intensity, discharge power, put
The electric time to be surface-treated to polyolefin, makes its surface produce hydroxyl, carboxyl, so as to obtain the polyolefin of surface modification；
(3) polyolefin, polar compound, the antioxidant being modified surface are put into extruder and reacted, and extrudate is by leading
Draw, cool down, drying, pelletizing, obtaining the polyolefin particles of polar compound graft modification, as nylon toughener；
The polyolefin is low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), LLDPE
(LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), POE (POE), ethylene propylene diene rubber (EPDM)
In one or more of mixtures；
The polar compound is maleic anhydride.
2. a kind of preparation method of nylon toughener as claimed in claim 1, it is characterized in that, in terms of mass parts, polyolefin
99.89~78.0 parts, 0.1~18.0 part of polar compound, 0.01~4.0 part of antioxidant.
3. a kind of preparation method of nylon toughener as claimed in claim 1, it is characterized in that, gas pressure in the step (2)
Strong 10~10000Pa, 10~800W of discharge power, 0.5~30min of discharge time.
4. a kind of preparation method of nylon toughener as claimed in claim 1, it is characterized in that, gas is in the step (2)
Air, oxygen, nitrogen, carbon dioxide, argon gas, helium, a kind of several mixture of ammonia.
5. a kind of preparation method of nylon toughener as claimed in claim 1, it is characterized in that, the specific step of the step (3)
Suddenly it is that surface improved polyalkene, polar compound, antioxidant are well mixed rapidly, are put into extruder hopper, at 140 DEG C
Between~220 DEG C, 60~400 revs/min of driving screw rotating speed, reacted under the conditions of 10~80 revs/min of feed screw rotating speed,
Extrudate obtains the polyolefin particles of polar compound graft modification, as toughening nylon by traction, cooling, dry, pelletizing
Agent.
A kind of 6. nylon toughener prepared by preparation method as described in claim 1-5 is any.
A kind of 7. application of the nylon toughener in tenacity increased nylon is prepared as claimed in claim 6.
8. a kind of preparation method of tenacity increased nylon, it is characterized in that, by nylon, nylon toughener as claimed in claim 6, antioxygen
Agent obtains tenacity increased nylon after carrying out hybrid reaction.
9. a kind of preparation method of tenacity increased nylon as claimed in claim 8, it is characterized in that, concretely comprise the following steps, by nylon, such as weigh
Profit requires that nylon toughener, antioxidant described in 6 are put into extruder hopper, between 180 DEG C~290 DEG C, driving screw rotating speed
60~400 revs/min, reacted under the conditions of 10~80 revs/min of feed screw rotating speed, extrudate is by traction, cooling, dry
Dry, pelletizing, obtain tenacity increased nylon particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610183903.7A CN105693890B (en) | 2016-03-28 | 2016-03-28 | A kind of nylon toughener, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610183903.7A CN105693890B (en) | 2016-03-28 | 2016-03-28 | A kind of nylon toughener, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105693890A CN105693890A (en) | 2016-06-22 |
| CN105693890B true CN105693890B (en) | 2018-01-23 |
Family
ID=56231856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610183903.7A Active CN105693890B (en) | 2016-03-28 | 2016-03-28 | A kind of nylon toughener, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693890B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496610B (en) * | 2016-10-26 | 2018-08-14 | 山东省科学院能源研究所 | A kind of tenacity increased nylon and nylon toughener and preparation method |
| CN107674444B (en) * | 2017-10-17 | 2020-12-08 | 嘉兴华维新能源有限公司 | Method for recycling recycled plastic for cable sheath material |
| CN111849154A (en) * | 2020-07-23 | 2020-10-30 | 江苏恒峰线缆有限公司 | Preparation method of novel nylon |
| CN112830997B (en) * | 2020-12-31 | 2022-08-09 | 石家庄联合石化有限公司 | Preparation method of graft modified polypropylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526753A (en) * | 2003-03-04 | 2004-09-08 | 後晓淮 | Apparatus and method for plasma modification of polymer material surface |
| CN101792515A (en) * | 2010-04-02 | 2010-08-04 | 上海理工大学 | Preparation method for grafting maleic anhydride onto plasma activated carbon nano tube |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1303559A4 (en) * | 2000-07-14 | 2004-06-30 | Mimotopes Pty Ltd | Activated modular grafted polymeric surfaces |
| JP2002179068A (en) * | 2000-12-20 | 2002-06-26 | Toppan Printing Co Ltd | Vessel with barrier property |
-
2016
- 2016-03-28 CN CN201610183903.7A patent/CN105693890B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526753A (en) * | 2003-03-04 | 2004-09-08 | 後晓淮 | Apparatus and method for plasma modification of polymer material surface |
| CN101792515A (en) * | 2010-04-02 | 2010-08-04 | 上海理工大学 | Preparation method for grafting maleic anhydride onto plasma activated carbon nano tube |
Non-Patent Citations (2)
| Title |
|---|
| 原生态聚乙烯等离子体接枝甲基丙烯酸甲酯;林晓，等;《科学通报》;19930731;第38卷(第14期);第1286页第1节 * |
| 尼龙6/马来酸酐接枝聚乙烯共混物力学性能的研究;俞强，等;《塑料工业》;19930531(第5期);第142页右栏第1.1节，第1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105693890A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105693890B (en) | A kind of nylon toughener, preparation method and application | |
| CN106496610B (en) | A kind of tenacity increased nylon and nylon toughener and preparation method | |
| CN103421148B (en) | A kind of Cold-resistant nylon flexibilizer and preparation method thereof | |
| CN102993556B (en) | Polypropylene composite, its preparation method and application thereof | |
| CN106432614B (en) | A method of promoting polyolefin graft reaction | |
| CN102391431B (en) | Nylon toughener and preparation method and application thereof | |
| US20120149845A1 (en) | Polypropylene resin compositions having high melt tension and method for preparing the same | |
| CN105440438A (en) | Polypropylene composite material with high paint adhesion and preparation method thereof | |
| CN102516655B (en) | Strengthening and toughening polypropylene composite and preparation method thereof | |
| CN102070833A (en) | Filler masterbatch used for increasing polarity of polypropylene and preparation method thereof | |
| CN105859970A (en) | Method for increasing polyolefin grafting efficiency | |
| CN107501923B (en) | Solvent-resistant foaming material and forming method thereof | |
| CN110684344B (en) | Halogen-free flame-retardant nylon composite material and preparation method and application thereof | |
| CN104592450A (en) | Nanoparticle-maleic anhydride composite grafted polyolefin elastomer and preparation method thereof | |
| CN106750347A (en) | A kind of nylon toughener and its preparation method and application | |
| CN101591416B (en) | Environmental-friendly polypropylene compatilizer preparation method | |
| CN110684342B (en) | Glass fiber reinforced nylon composite material and preparation method and application thereof | |
| CN106928624B (en) | Core-shell nylon toughening agent based on extruder process, and preparation method and application thereof | |
| CN104513429A (en) | Wear-resistant PP (propene polymer) material and preparation method thereof | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN104710692A (en) | Solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber and preparation method thereof | |
| CN110627958B (en) | Polyethylene composition, method for improving grafting efficiency of polyethylene and application of polyethylene composition | |
| KR20030030591A (en) | Composition for Polyolefin Elastomer Modified by Chemical | |
| CN1164663C (en) | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process | |
| CN110256753A (en) | A kind of corrosion-resistant polyethylene communication tube and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Jiang Bo Inventor after: Cai Feipeng Inventor after: Wang Zhaobo Inventor after: Xie Yongguang Inventor after: Li Xiaoyu Inventor after: Guo Yanchao Inventor after: Yang Gai Inventor after: Wang Bo Inventor before: Jiang Bo Inventor before: Cai Feipeng Inventor before: Yang Gai Inventor before: Wang Bo |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180412 Address after: 250014 Shandong Province, Lixia District, Ji'nan City Hospital Road, No. 19 Co-patentee after: KELONG, Shandong, new materials, Limited by Share Ltd Patentee after: Inst. of Energy, Shandong Prov. Academy Address before: 250014 Shandong Province, Lixia District, Ji'nan City Hospital Road, No. 19 Patentee before: Inst. of Energy, Shandong Prov. Academy |
|
| TR01 | Transfer of patent right |