CN105693890A - Nylon toughener, and preparation method and application thereof - Google Patents
Nylon toughener, and preparation method and application thereof Download PDFInfo
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- CN105693890A CN105693890A CN201610183903.7A CN201610183903A CN105693890A CN 105693890 A CN105693890 A CN 105693890A CN 201610183903 A CN201610183903 A CN 201610183903A CN 105693890 A CN105693890 A CN 105693890A
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- 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
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- 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
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- 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
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Abstract
The invention discloses a nylon toughener, and a preparation method and application thereof. The preparation method comprises the following steps: putting polyolefins in a plasma reactor, vacuumizing, introducing gas, and carrying out surface treatment on the polyolefins by using low-temperature plasma so as to generate hydroxyl, carboxyl and other active groups on the surface, thereby obtaining the surface-modified polyolefins; and carrying out reaction on the surface-modified polyolefins, a polar compound and an antioxidant to obtain the polar-compound-graft-modified polyolefins, which are the nylon toughener. The low-temperature plasma technique is utilized to increase the types and concentration of the active groups (such as hydroxyl, carboxyl, carbonyl and amino) generated on the polyolefin surface on the premise of not introducing any free-radical initiator, thereby enhancing the grafting efficiency.
Description
Technical field
The preparation method that the present invention relates to a kind of tenacity increased nylon, is specifically related to a kind of preparation method and application preparing nylon toughener and tenacity increased nylon in conjunction with low temperature plasma。
Background technology
Nylon is that a kind of purposes is the widest, the engineering plastics of most species, this material has good mechanical property, thermostability, mar proof, chemical solvent resistance, self lubricity and certain anti-flammability, this materials processing function admirable simultaneously, can the complicated structure member of integrated molding, be widely used in the fields such as automobile, electronic apparatus, machinery, track traffic, sports apparatus。But the shortcoming that water absorption is strong, low temperature impact properties is poor limits the range of application of nylon material。
Polyolefin or polyolefin elastomer are mixed with nylon, it is possible to the shortcoming significantly improving this material water absorption being strong, low temperature impact properties is poor。Nonpolar due to polyolefin based materials, it is difficult to mix homogeneously with the nylon material of polarity, adopt polar compound that polyolefin is carried out graft modification, then pass through reaction extrusion process, polyolefin is evenly spread in nylon material by the method for In Situ Compatibilization, becomes and prepares tenacity increased nylon most common method。Homodisperse polyolefin or polyolefin elastomer can effectively absorb matrix material impact energy, scattered polyolefin particles can also effectively stop the generation of crackle, therefore significantly improving nylon material impact strength at low temperatures, the addition of non-polar polyolefinic can also substantially reduce the water absorption of material。
A kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof (CN101781389A) discloses a kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof, by ethylene-alpha-octylene copolymers, peroxide initiator, itaconic acid polar monomer mix homogeneously in high-speed mixer, then in an extruder 160～200 DEG C, react extrusion under screw speed 100～400 revs/min, obtaining Itaconic Acid Grafted ethylene-alpha-octylene copolymers, this copolymer grafted efficiency is between 0.8～1.0%。
The preparation method that the preparation method (CN102766239A) of Itaconic Acid Grafted ethylene-octene block copolymer particulate material discloses a kind of Itaconic Acid Grafted ethylene-octene block copolymer particulate material, ethylene-octene block copolymer, peroxide initiator dibenzoyl peroxide, itaconic acid polar monomer, antioxidant are uniformly mixed, then passing through double screw extruder reactive extrursion at 150～170 DEG C and obtain Itaconic Acid Grafted ethylene-octene block copolymer, copolymer grafted efficiency is 1.35%～1.65%。
A kind of modifying agent and preparation method thereof and application (CN101831131B) disclose a kind of Itaconic Acid Grafted polyolefin elastic precursor copolymer, by polyolefin elastomer, peroxide initiator cumyl peroxide, itaconic acid polar monomer, Tissuemat E mix homogeneously in banbury, then reactive extrursion in an extruder, prepares into described copolymer。
The preparation method that a kind of super-tough nylon alloy and preparation method thereof (CN101781455A) discloses a kind of super-tough nylon alloy, nylon, Itaconic Acid Grafted ethylene-alpha-octylene copolymers, antioxidant, lubricant are put in high-speed mixer and mixed, then mixture is put in double screw extruder, extrusion temperature 250～280 DEG C, driving screw rotating speed 200～400 revs/min, through traction, cooling, pelletizing, obtain polyolefin tenacity-increased nylon mixture。
The preparation method that a kind of toughening polyamide combination and preparation method thereof (CN1480489A) discloses a kind of toughened polyamide, first under the effect of peroxide initiator, adopt polar monomer graft polyolefin elastomer in an extruder, then this graft is mixed homogeneously with nylon 6, carry out pelletize extrusion in an extruder, obtain the compositions with excellent toughness and processing characteristics。
The preparation method that a kind of super-toughened nylon and preparation method thereof (CN1445278A) discloses a kind of super-toughened nylon, the POE of maleic anhydride graft is mixed homogeneously with nylon 6, the mode simultaneously adopting dynamic vulcanization is extruded in an extruder, obtains the super-toughened nylon with excellent machinability。
The preparation method that tenacity nylon material and production technology (CN90106778.4A) thereof disclose a kind of tenacity increased nylon, first under the effect of cumyl peroxide initiator, adopt maleic anhydride grafting ethylene propylene diene rubber in an extruder, obtain the polyolefin of graft modification, then this graft is mixed homogeneously with nylon66 fiber, carry out pelletize extrusion in an extruder, the material obtained has good insulation properties, heat-resisting and cold tolerance, can use during as rail insulated joint within the scope of-40 DEG C～70 DEG C。
From above-mentioned patent it can be seen that, toughener as tenacity increased nylon important component, all adopt peroxide as initiator, prepared by the graft reaction of polar monomer in an extruder, but peroxide initiator is except causing the polyolefinic primary response of polar monomer graft, also can cause the generation (crosslinking or polyacrylic degraded side reaction such as polyethylene) of numerous side reaction, this significantly reduces the polyolefinic efficiency of polar monomer graft, and after polyolefine material melt index changes, follow-up processing characteristics when mixing can be affected with nylon。When use this graft polyolefin and nylon react extrusion prepare tenacity increased nylon time, not only expressing technique can be produced harmful effect；And owing to polyolefin graft rate is low, it is necessary to adding big weight polyolefin and could meet toughness of material demand, this can significantly reduce the mechanical property of nylon material。
Summary of the invention
For overcoming the defect of prior art, the invention provides a kind of nylon toughener, preparation method and application, improve the polyolefinic efficiency of polar monomer graft, be added in nylon to also improve the impact property of nylon。
For achieving the above object, the technical scheme is that
A kind of preparation method of nylon toughener, polyolefin is placed in plasma reaction device, after evacuation, pass into gas, utilize low temperature plasma that polyolefin is carried out surface treatment so that it is surface produces hydroxyl, carboxyl isoreactivity group, thus obtaining the polyolefin of surface modification, then pass through and be obtained by reacting the polyolefin of polar compound graft modification with polar compound and antioxidant, be nylon toughener。
The present invention utilizes lower temperature plasma technology, when not introducing radical initiator, adds active group (such as hydroxyl, carboxyl, carbonyl, amino) type and concentration that polyolefin surfaces produces, improves grafting efficiency。
Preferably, the steps include:
(1) polyolefin is placed in plasma reaction device, evacuation；
(2) gas is passed into gas ions reaction unit, control to pass into the type of gas, ratio, gas pressure intensity, discharge power, discharge time so that polyolefin is carried out surface treatment, its surface is made to produce hydroxyl, carboxyl isopolarity group, thus obtaining the polyolefin of surface modification；
(3) polyolefin of surface modification, polar compound, antioxidant being put in extruder and reacted, extrudate, through traction, cooling, dry, pelletizing, obtains the polyolefin particles of polar compound graft modification, is nylon toughener。
The type of gas, ratio, gas pressure intensity, discharge power, discharge time is passed into by control, active group (such as hydroxyl, carboxyl, carbonyl, amino) type and concentration that polyolefin surfaces produces can be adjusted further, grafting efficiency can be further increased。
Preferably, in mass parts, polyolefin 99.89～78.0 parts, polar compound 0.1～18.0 part, 0.01～4.0 part of antioxidant。
It is further preferred that gas pressure intensity 10～10000Pa in described step (2), discharge power 10～800W, discharge time 0.5～30min。Active group (such as hydroxyl, carboxyl, carbonyl, the amino) type that under this condition, polyolefin surfaces produces is many, and concentration is high, it is possible to further improve grafting efficiency。
It is further preferred that gas is a kind of several mixture of air, oxygen, nitrogen, carbon dioxide, argon, helium, ammonia in described step (2)。Active group (such as hydroxyl, carboxyl, carbonyl, the amino) type that under this condition, polyolefin surfaces produces is many, and concentration is high, it is possible to further improve grafting efficiency。
It is preferred that, concretely comprising the following steps of described step (3), rapidly by surface modification polyolefin, polar compound, antioxidant mix homogeneously, put in extruder hopper, between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, react under 10～80 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains the polyolefin particles of polar compound graft modification, is nylon toughener。This condition improves the reaction efficiency of the active group that polar compound produces with polyolefin surfaces, thus improve polyolefinic percent grafting。
Preferably, described plasma reaction device is reaction of low temperature plasma device, and discharge mode is the one in glow discharge, corona discharge, dielectric barrier discharge, radio-frequency discharge or microwave discharge。
Preferably, described polyolefin is the mixture of one or more in Low Density Polyethylene (LDPE), high density polyethylene (HDPE) (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), POE (POE), ethylene propylene diene rubber (EPDM)。
Preferably, described polar compound is ethanedioic acid, malonic acid, hydroxymalonic acid., succinic acid, dyhydrobutanedioic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, 11 carbon diacid, dodecanedioic acid, hendecane dicarboxylic acid, 14 carbon diacid, pertadecane diacid, thapsic acid, 18 carbon diacid, phthalic acid, M-phthalic acid, p-phthalic acid, acetic anhydride, propionic andydride, succinic anhydride, benzoyl oxide, maleic acid, fumaric acid, itaconic acid, citraconic acid, .beta.-methylacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, the mixture of one or more of crotonic anhydride。
Preferably, described antioxidant is [four (3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), 3-(3, 5-di-t-butyl-4-hydroxyl) propylene octadecyl ester (antioxidant 1076), N, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), 2, 6-di-t-butyl-4-cresol (antioxidant 264), 2, 4, 6-tri-butyl-phenol (antioxidant 246), (2, 4-di-tert-butyl-phenyl) mixture of one or more in tris phosphite (irgasfos 168)。
Nylon toughener prepared by a kind of above-mentioned preparation method。
The application in preparing tenacity increased nylon of a kind of above-mentioned nylon toughener。
The preparation method of a kind of tenacity increased nylon, obtains tenacity increased nylon by nylon, above-mentioned nylon toughener, antioxidant after carrying out hybrid reaction。
Preferably, concretely comprise the following steps and nylon, above-mentioned nylon toughener, antioxidant are put in extruder hopper, between 180 DEG C～290 DEG C, driving screw rotating speed 60～400 revs/min, react under 10～80 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Preferably, in mass parts, nylon 9 4.99～56.0 parts, above-mentioned nylon toughener 5.0～40.0 parts, 0.01～4.0 part of antioxidant。
Preferably, described nylon is the mixture of one or more in nylon 6, nylon66 fiber, Stanyl (DSM)., NYLON610, nylon 612, nylon 9, nylon 11, nylon 12, nylon 1010, Nylon 1012, nylon 1212。
Preferably, described antioxidant is [four (3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), 3-(3, 5-di-t-butyl-4-hydroxyl) propylene octadecyl ester (antioxidant 1076), N, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), 2, 6-di-t-butyl-4-cresol (antioxidant 264), 2, 4, 6-tri-butyl-phenol (antioxidant 246), (2, 4-di-tert-butyl-phenyl) mixture of one or more in tris phosphite (irgasfos 168)。
Compared with prior art, the invention have the advantage that
1, the present invention does not adopt radical initiator, it is possible to effectively reducing polyolefinic crosslinking and degraded side reaction, notable change will not occur polyolefine toughener fluidity of molten, and grafting efficiency is higher。
2, by excellent for processing characteristics time blended in an extruder to nylon toughener of the present invention and nylon, when meeting toughness of material, toughener addition is fewer than toughener addition prepared by traditional method, it is possible to reduce the decline of nylon material mechanical property to a greater extent。
Accompanying drawing explanation
Fig. 1 is the polyolefinic device schematic diagram of Cement Composite Treated by Plasma。
Detailed description of the invention
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described。
Embodiment 1: comparative example
Weigh LDPE81.9 part (weight portion, lower same, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, dibenzoyl peroxide 0.1 part, antioxidant 1010 3.0 parts, maleic anhydride is dissolved in 10.0 parts of dehydrated alcohol, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by LDPE, dibenzoyl peroxide solution, maleic anhydride solution, antioxidant 1010 is mix homogeneously in high-speed mixer, said mixture is added in extruder hopper, extruder each district temperature is between 150 DEG C～180 DEG C, driving screw rotating speed 60 revs/min, feed screw rotating speed 10 revs/min, extrudate is through traction, cooling, dry, pelletizing, obtain maleic anhydride graft LDPE granule。Weigh nylon 685.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 2:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into argon, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon 685.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 3:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, pass into argon/oxygen (volume ratio 4/1) mixing gas, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon 685.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 4:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into air, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon 685.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 5:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into carbon dioxide, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon 685.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 6: comparative example
Weigh LDPE81.9 part (weight portion, lower same, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, dibenzoyl peroxide 0.1 part, antioxidant 1010 3.0 parts, maleic anhydride is dissolved in 10.0 parts of dehydrated alcohol, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by LDPE, dibenzoyl peroxide solution, maleic anhydride solution, antioxidant 1010 is mix homogeneously in high-speed mixer, said mixture is added in extruder hopper, extruder each district temperature is between 150 DEG C～180 DEG C, driving screw rotating speed 60 revs/min, feed screw rotating speed 10 revs/min, extrudate is through traction, cooling, dry, pelletizing, obtain maleic anhydride graft LDPE granule。Weigh nylon66 fiber 85.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 7:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into argon, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon66 fiber 85.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 8:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, pass into argon/oxygen (volume ratio 4/1) mixing gas, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon66 fiber 85.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 9:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into air, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon66 fiber 85.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment 10:
Weigh LDPE82.0 part (weight portion, lower to, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic anhydride 15.0 parts, antioxidant 1010 3.0 parts。LDPE is placed in plasma reaction device, after evacuation, passes into carbon dioxide, gas pressure intensity 100Pa, radio-frequency discharge power 20W, discharge time 10min, then by surface modification LDPE, adipic acid, antioxidant 1010 mixing 30min, mixture is put in extruder hopper, between 150～180 DEG C, driving screw rotating speed 60 revs/min, react under 10 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains maleic anhydride graft LDPE granule。Weigh nylon66 fiber 85.0 parts, maleic anhydride graft LDPE12.0 part, antioxidant 1010 3.0 parts, mix homogeneously in high-speed mixer, put in extruder hopper, between 200 DEG C～260 DEG C, driving screw rotating speed 80 revs/min, reacting under 40 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
Embodiment plasma processes polyolefinic device as shown in Figure 1。
Embodiment 1～10 polar compound graft-modified polyolefin result is as shown in table 1:
Table 1
From the LDPE graft modification result of embodiment 2～5 it can be seen that, through the polyolefin that different plasma atmosphere processed, the efficiency carrying out graft reaction in an extruder with polar compound is above 5.0%, grafting efficiency is apparently higher than the result (as described in Example 1) under free radical initiation conditions, LDPE is after grafting, its melt index fall, again smaller than the result (as described in Example 1) under free radical initiation conditions, illustrates that the crosslinking side reaction of LDPE is well suppressed。
Embodiment 1～10 tenacity increased nylon result is as shown in table 2:
Table 2
From the result of the maleic anhydride grafts toughened Nylon 6 of embodiment 2～5 it can be seen that, adopt toughener prepared by low temperature plasma due to grafting efficiency height, in same toughener content situation, material impact intensity is significantly higher than the toughener result (as described in Example 1) using traditional method to prepare, and also has similar effect during this toughener Toughed nylon66 (embodiment 7～10)。
The specific embodiment of the present invention is described in conjunction with accompanying drawing although above-mentioned; but the not restriction to invention protection domain; one of ordinary skill in the art should be understood that; on the basis of technical scheme, those skilled in the art need not pay various amendments or deformation that creative work can make still in protection scope of the present invention。
Claims (10)
1. the preparation method of a nylon toughener, it is characterized in that, polyolefin is placed in plasma reaction device, after evacuation, pass into gas, utilize low temperature plasma that polyolefin is carried out surface treatment, its surface is made to produce hydroxyl, carboxyl isoreactivity group, thus obtaining the polyolefin of surface modification, then passing through and being obtained by reacting the polyolefin of polar compound graft modification with polar compound and antioxidant, being nylon toughener。
2. the preparation method of a kind of nylon toughener as claimed in claim 1, is characterized in that, the steps include:
(1) polyolefin is placed in plasma reaction device, evacuation；
(2) gas is passed into gas ions reaction unit, control to pass into the type of gas, ratio, gas pressure intensity, discharge power, discharge time so that polyolefin is carried out surface treatment, its surface is made to produce hydroxyl, carboxyl isopolarity group, thus obtaining the polyolefin of surface modification；
(3) polyolefin of surface modification, polar compound, antioxidant being put in extruder and reacted, extrudate, through traction, cooling, dry, pelletizing, obtains the polyolefin particles of polar compound graft modification, is nylon toughener。
3. the preparation method of a kind of nylon toughener as claimed in claim 1, is characterized in that, in mass parts, polyolefin 99.89～78.0 parts, polar compound 0.1～18.0 part, 0.01～4.0 part of antioxidant。
4. the preparation method of a kind of nylon toughener as claimed in claim 2, is characterized in that, gas pressure intensity 10～10000Pa in described step (2), discharge power 10～800W, discharge time 0.5～30min。
5. the preparation method of a kind of nylon toughener as claimed in claim 2, is characterized in that, in described step (2), gas is a kind of several mixture of air, oxygen, nitrogen, carbon dioxide, argon, helium, ammonia。
6. the preparation method of a kind of nylon toughener as claimed in claim 2, it is characterized in that, concretely comprising the following steps of described step (3), rapidly by surface modification polyolefin, polar compound, antioxidant mix homogeneously, put in extruder hopper, between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, react under 10～80 revs/min of conditions of feed screw rotating speed, extrudate is through traction, cooling, dry, pelletizing, obtain the polyolefin particles of polar compound graft modification, be nylon toughener。
7. one kind as arbitrary in claim 1-6 as described in the nylon toughener prepared of preparation method。
8. a nylon toughener as claimed in claim 7 application in preparing tenacity increased nylon。
9. a preparation method for tenacity increased nylon, is characterized in that, after carrying out hybrid reaction, nylon, nylon toughener as claimed in claim 7, antioxidant are obtained tenacity increased nylon。
10. the preparation method of a kind of tenacity increased nylon as claimed in claim 9, it is characterized in that, concretely comprise the following steps, nylon, nylon toughener as claimed in claim 7, antioxidant are put in extruder hopper, between 180 DEG C～290 DEG C, driving screw rotating speed 60～400 revs/min, react under 10～80 revs/min of conditions of feed screw rotating speed, extrudate, through traction, cooling, dry, pelletizing, obtains tenacity increased nylon granule。
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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 |
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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 |