CN109722020B - Nylon composite material toughened by amino-functionalized polyolefin elastomer and preparation method thereof - Google Patents
Nylon composite material toughened by amino-functionalized polyolefin elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-tough nylon composite material toughened by amino-functional polyolefin elastomer and a preparation method thereof, wherein a peroxide cross-linking agent and a polar monomer are not required to be added in the preparation process of the composite material, so that side reactions such as cross-linking, degradation and the like in the processing process are effectively avoided, and the prepared high-toughness nylon composite material has good processing performance, better tensile strength and excellent toughness, really achieves rigidity-toughness balance, and widens the application prospect of the nylon material. The high-toughness nylon comprises the following components in parts by weight: 50-97 parts of nylon resin; 2-50 parts of amino-functionalized polyolefin elastomer and 0-0.8 part of antioxidant.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a nylon composite material toughened by an amino-functionalized polyolefin elastomer and a preparation method thereof.
Background
Nylon is the earliest developed and most widely applied variety in thermoplastic engineering plastics, and is one of the varieties with the largest yield in polyamide plastics at present. PA66 has the advantages of high mechanical strength, good electrical property, wear resistance, shock resistance, sound absorption, oil resistance, acid and alkali resistance, wider use temperature range, excellent comprehensive properties of organic solvents and the like, is widely applied to automobiles, mechanical parts, electric appliances, packages and the like, but also has the defects of low dry and low-temperature impact strength, poor toughness, large melt fluidity and the like, and greatly limits the application range of the PA 66. The polyolefin elastomer is a common toughening modifier, has the advantages of low price and good low-temperature toughening effect, but the nonpolar chain structure of the polyolefin elastomer has poor compatibility with nylon, so the application of the polyolefin elastomer serving as a nylon toughening agent is greatly limited.
The polyolefin elastomer is grafted with polar monomers such as amido, anhydride and the like, which is a common method for solving the problem of poor compatibility between a non-polar polyolefin elastomer and polar nylon. The industry generally adopts the method of grafting maleic anhydride on polyolefin elastomer to improve the compatibility of the polyolefin elastomer and nylon. Patents CN104177825A, CN103421148A, CN1480489A, CN106496610A report several methods of maleic anhydride in-situ grafting polyolefin elastomer, and further toughening nylon with it. The above patents all find that maleic anhydride on the grafted elastomer can react with nylon to generate a graft copolymer in situ, thereby greatly improving the compatibility of the polyolefin elastomer and the nylon and obtaining a good toughening effect. However, the grafting method has the problems of low grafting rate of the maleic anhydride monomer, partial compatibility, emission of toxic micromolecules in the extrusion process, environmental pollution and the like. The amino-functional polyolefin has similar polarity with nylon and better compatibility. U.S. Pat. No. 3,3755279 and J.Am.chem.Soc.1992,114,9679 both report the synthesis of amino-functionalized polyolefins, but the above cases of amino-functionalized polyolefins toughening modified nylon have not been reported.
Disclosure of Invention
Based on the research background, the invention provides an amido functionalized polyolefin elastomer toughening modified nylon composite material and a preparation method thereof. The amido-functionalized polyolefin elastomer can be directly blended with nylon to effectively improve the elongation at break and the notch impact strength of the nylon, and the toughening effect is obvious. Meanwhile, the toughening modified nylon has simple formula and process, does not have small molecular monomers in the extrusion injection molding process, is nontoxic and odorless, has no pollution to the environment, and has good application prospect.
The invention provides a nylon composite material toughened by an amino-functional polyolefin elastomer, which has the advantages of no toxicity and odor in the preparation process, simple process, excellent mechanical property, better tensile strength, rigidity and excellent toughness, and really achieves the balance of rigidity and toughness.
The invention provides a nylon composite material toughened by an amido functionalized polyolefin elastomer, which comprises the following components in parts by weight: 50-97 parts of nylon resin; 2-50 parts of amino-functionalized polyolefin elastomer and 0-0.8 part of antioxidant; preferably 75-95 parts of nylon resin, 5-25 parts of amino-functionalized polyolefin elastomer and 0.1-0.5 part of antioxidant, more preferably 85-92 parts of nylon resin, 8-15 parts of amino-functionalized polyolefin elastomer and 0.1-0.5 part of antioxidant.
The nylon is one or a mixture of two or more of nylon 66, nylon 1010, nylon 6, nylon 46, nylon 612, nylon 1212, nylon 12 and nylon 9.
The amino-functionalized polyolefin elastomer of the present invention is a random copolymer prepared by copolymerization of ethylene, alpha-olefin, amino-functionalized monomer under the action of metallocene catalyst, and can be prepared according to the method disclosed in U.S. Pat. No. 3755279 and document J.Am.chem.Soc.1992,114,9679. Wherein the alpha-olefin is one or more of octene, hexene and butene, the random copolymer has the following structure,
wherein M is an alkylene group derived from an α -olefin such as butene, hexene, octene, etc., R1, R2 are each independently H, alkyl, aryl or aralkyl; preferably C1-C10 alkyl, C5-C10 aryl, C6-C15 aralkyl, as C1-C10 alkyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl, etc.; examples of the C5-C10 aryl group include phenyl, indenyl and the like; examples of the aralkyl group include benzyl, benzhydryl, trityl, phenethyl, phenylpropyl, and the like, (x + y)/z is 1:10000 to 10000:1, and n is 1 to 10. The amine-functional polyolefin elastomer has a number average molecular weight Mw of 1000-400000, and may be a random or block polymer having a multiplicity of amine-based monomer contents of 0.1 wt% to 80wt%, preferably 15 wt% to 25 wt%, for example 20wt%, ethylene contents of 0.01 wt% to 90wt%, preferably 65 wt% to 75 wt%, for example 70wt%, and alpha-olefin contents of 0.1 wt% to 70wt%, preferably 5 wt% to 15 wt%, for example 10 wt%. The metallocene catalyst may be one or more of a non-bridged bis-metallocene, a bridged half-metallocene, a non-bridged half-metallocene catalyst. The copolymerization reaction temperature is 90-200 ℃, and the reaction pressure is 0.1-6 MPa. The reaction time is 5-100 min.
The invention describes an amino-functionalized polyolefin elastomer, characterized in that the amino-functionalized monomer has the following structural features:
wherein n is a positive integer of 1 to 10, R1, R2 are each independently H, alkyl, aryl, or aralkyl, etc.; preferably C1-C10 alkyl, C5-C10 aryl, C6-C15 aralkyl, C1-C10 alkyl including methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl, and the like; examples of the C5-C10 aryl group include phenyl, indenyl and the like; examples of the C6-C15 aralkyl group include a benzyl group, a benzhydryl group, a trityl group, a phenethyl group, a diphenylethyl group, a phenylpropyl group, and a phenylbutyl group.
The antioxidant comprises one or a mixture of more of an antioxidant 1010, an antioxidant 168, an antioxidant 1076, an antioxidant 1035 and an antioxidant 264.
The preparation method of the amido functionalized polyolefin elastomer toughened nylon composite material comprises the following steps: the nylon resin, the amido functional polyolefin elastomer and the optional antioxidant are evenly mixed in a high-speed mixer, the mixed materials are added into a double-screw extruder for melt mixing, and the mixture is extruded from the head of the screw extruder for granulation.
In one embodiment, the method comprises mixing the nylon resin, the amino-functionalized polyolefin elastomer and the optional antioxidant uniformly in a high-speed mixer (for example, at the rotation speed of 100-, finally drying in drying equipment at 50-150 deg.C for 1-24 hr, preferably 80 deg.C for 5 hr to obtain the final product.
The nylon composite material toughened by the amido-functionalized polyolefin elastomer solves the problem of poor toughness of nylon materials, is nontoxic and tasteless in preparation process, simple in process and suitable for mass production. The composite material has excellent mechanical property, better tensile strength, rigidity and excellent toughness, and widens the application field of nylon.
Detailed Description
In order to facilitate the researchers in the field to better understand the nylon composite toughened by the amino functionalized polyolefin elastomer prepared by the present invention and the properties thereof, the present invention will be further described by using specific examples, which are only described in further detail and are not intended to limit the scope of the present invention. The content and kind of the antioxidant have little influence on the mechanical properties of the nylon composite material toughened by the amino-functionalized polyolefin elastomer prepared by the present invention, so the antioxidant 1010 and the antioxidant 1035 are exemplified in the following examples, which are not illustrated.
Preparation example 1
Amino-functionalized polyolefin elastomer synthesis step: adding 80g of octene and 30g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10wt% of cocatalyst are added into a reaction kettle for stirring and reaction for 15min to obtain a reactant solution, the reaction solution is transferred into absolute ethyl alcohol to obtain solid precipitate, and the solid precipitate is filtered and dried to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 5 wt% of the amino-functionalized monomer used in the embodiments 1 to 5.
Preparation example 2
Amino-functionalized polyolefin elastomer synthesis step: adding 90g of octene and 10g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. Adding 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10wt% of cocatalyst into a reaction kettle, stirring and reacting for 15min to obtain a reactant solution, transferring the reaction solution into absolute ethyl alcohol to obtain solid precipitate, filtering and drying to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 2 wt% of the amino-functionalized monomer used in the embodiment 6.
Preparation example 3
Amino-functionalized polyolefin elastomer synthesis step: adding 75g of octene and 25g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10wt% of cocatalyst are added into a reaction kettle for stirring and reaction for 15min to obtain a reactant solution, the reaction solution is transferred into absolute ethyl alcohol to obtain solid precipitate, and the solid precipitate is filtered and dried to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 4 wt% of the amino-functionalized monomer used in the embodiment 7.
Preparation example 4
Amino-functionalized polyolefin elastomer synthesis step: adding 55g of octene and 45g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10 weight percent of cocatalyst are added into a reaction kettle for stirring and reaction for 15min to obtain a reactant solution, the reaction solution is transferred into absolute ethyl alcohol to obtain solid precipitate, and the solid precipitate is filtered and dried to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 6 weight percent of the amino-functionalized monomer used in the embodiment 8.
Preparation example 5
Amino-functionalized polyolefin elastomer synthesis step: adding 50g of octene and 50g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10 weight percent of cocatalyst are added into a reaction kettle for stirring and reaction for 15min to obtain a reactant solution, the reaction solution is transferred into absolute ethyl alcohol to obtain solid precipitate, and the solid precipitate is filtered and dried to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 8 weight percent of the amino-functionalized monomer used in the embodiment 9.
Preparation example 6
Amino-functionalized polyolefin elastomer synthesis step: adding 30g of octene and 70g of allylamine into 1L of alkane mixed solvent by adopting a cationic metallocene coordination polymerization mode to prepare 1g/10ml of solution, adding the solution into a reaction kettle, heating to 120 ℃, introducing ethylene gas, and controlling the pressure in the kettle to be 2.5 MPa. Adding 1mg of dimethylsilyl tert-butylamine indenyl titanium dichloride as a main catalyst and 0.25ml of methylaluminoxane solution with 10wt% of cocatalyst into a reaction kettle, stirring and reacting for 15min to obtain a reactant solution, transferring the reaction solution into absolute ethyl alcohol to obtain solid precipitate, filtering and drying to obtain the amino-functionalized polyolefin elastomer with the insertion rate of 10wt% of the amino-functionalized monomer used in the embodiment 10.
Example 1
97 parts (by weight, the same below) of nylon 66 (the mark is BASF A3K BK, the same below) and 3 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 5 w%) are mixed for 15 minutes at the rotating speed of 500rpm by a high-speed mixer, then the mixture is uniformly mixed with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, the mixture is added into a hopper in a double-screw extruder, the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, the mixture is melt-extruded, and the mixture is pulled, cooled, granulated by a cutting machine and dried by a double-screw extruder to obtain a final product.
Example 2
Mixing 88 parts of nylon 66 and 12 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 5 wt%) by a high-speed mixer at the rotating speed of 500rpm for 15 minutes, then uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 3
Mixing 75 parts of nylon 66 and 25 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 5 wt%) by a high-speed mixer at the rotating speed of 500rpm for 15 minutes, then uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 4
68 parts of nylon 66 and 32 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 5 wt%) are mixed for 15 minutes at the rotating speed of 500rpm by a high-speed mixer, then the mixture is uniformly mixed with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, the mixture is added into a hopper in a double-screw extruder, the temperature of each area of the extruder is between 150 ℃ and 220 ℃, wherein the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, the mixture is melted and extruded, and the final product is obtained by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 5
Mixing 58 parts of nylon 66 and 42 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 5 wt%) by a high-speed mixer at the rotating speed of 500rpm for 15 minutes, then uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 6
Mixing 90 parts of nylon 66 and 10 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 2 wt%) by a high-speed mixer at the rotating speed of 500rpm for 15 minutes, then uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 7
Mixing 90 parts of nylon 66 and 10 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 4 wt%) at the rotating speed of 500rpm for 15 minutes by using a high-speed mixer, uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 8
Mixing 90 parts of nylon 66 and 10 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 6 wt%) at the rotating speed of 500rpm for 15 minutes by using a high-speed mixer, uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 9
Mixing 90 parts of nylon 66 and 10 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 8 wt%) at the rotating speed of 500rpm for 15 minutes by using a high-speed mixer, uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Example 10
Mixing 90 parts of nylon 66 and 10 parts of amino-functionalized polyolefin elastomer (the insertion rate of the amino-functionalized monomer is 10 wt%) at the rotating speed of 500rpm for 15 minutes by using a high-speed mixer, uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, granulation by a cutting machine and drying equipment of the double-screw extruder.
Comparative example 1
100 parts of nylon 66, 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035 are uniformly mixed and then added into a hopper in a double-screw extruder, the temperature of each area of the extruder is between 150 and 220 ℃, wherein the rotating speed of a main screw is 70 revolutions per minute, the rotating speed of a main feeding rod is 60 revolutions per minute, a side feeding device is not used, the mixture is melted and extruded, and the final product is obtained by traction, cooling, granulation by a cutting machine and drying of equipment of the double-screw extruder.
Comparative example 2
Mixing 90 parts of nylon 66 and 10 parts of polyolefin elastomer (the insertion rate of the amino functional monomer is 0 wt%) by a high-speed mixer at the rotating speed of 500rpm for 15 minutes, uniformly mixing the mixture with 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 1035, adding the mixture into a hopper in a double-screw extruder, wherein the temperature of each area of the extruder is between 150 ℃ and 220 ℃, the rotating speed of a main screw is 70 r/min, the rotating speed of a main feeding rod is 60 r/min, a side feeding device is not used, melting and extruding the mixture, and obtaining a final product by traction, cooling, cutting machine granulation and drying equipment of the double-screw extruder.
TABLE 1
As can be seen from Table 1, the performance advantages of the nylon composite toughened by the amino-functionalized polyolefin elastomer prepared by the invention are outstanding compared with pure nylon resin. With the increase of the content of the amido-functionalized polyolefin elastomer in the composite material, the nylon composite material obviously increases the toughness of the material while keeping the better rigidity of the nylon, thereby achieving the balance of rigidity and toughness.
TABLE 2
As can be seen from Table 2, compared with the nylon composite toughened by the common polyolefin elastomer, the nylon composite toughened by the amino-functionalized polyolefin elastomer prepared by the invention has very obvious mechanical property advantages, and the nylon composite toughened by the amino-functionalized polyolefin elastomer is superior to the nylon composite toughened by the common polyolefin elastomer in both rigidity and toughness of the material. And along with the increase of the insertion rate of the amino functionalized monomer in the composite material, the toughening effect of the material is more obvious.
The above-mentioned examples are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all direct or indirect structural equivalents and substitutions made to the present disclosure are included in the scope of the present invention without departing from the inventive concept of the present invention.
Claims (13)
1. The nylon composite material toughened by the amino-functionalized polyolefin elastomer is characterized by comprising the following raw materials in parts by mass: 50-97 parts of nylon resin; 2-50 parts of amino-functionalized polyolefin elastomer and 0-0.8 part of antioxidant;
the amino-functionalized polyolefin elastomer has the following structural formula:
wherein M is an alkylene group derived from an α -olefin, R1, R2 are each independently H, an alkyl group, an aryl group or an aralkyl group, (x + y)/z =1:10000 to 10000:1, n =1 to 10, Mw =1000-400000, the content of the amine-based monomer is 0.1 to 80wt%, the content of ethylene is 0.01 to 90wt%, and the content of the α -olefin is 0.1 to 70 wt%.
2. The nylon composite material of claim 1, wherein the nylon resin comprises 75 to 95 parts, the amino-functionalized polyolefin elastomer comprises 5 to 25 parts, the antioxidant comprises 0.1 to 0.5 part, the amino monomer content is 20wt%, the ethylene content is 70wt%, and the alpha-olefin content is 10 wt%.
3. The nylon composite material of claim 2, wherein the nylon resin comprises 85-92 parts, the amino-functionalized polyolefin elastomer comprises 8-15 parts, and the antioxidant comprises 0.1-0.5 part.
4. The nylon composite material of claim 1, wherein the nylon resin is one or a mixture of two or more of nylon 66, nylon 1010, nylon 6, nylon 46, nylon 612, nylon 1212, nylon 12, and nylon 9.
5. The nylon composite of any of claims 1-4, wherein the amine-functionalized polyolefin elastomer is a random copolymer prepared by copolymerization of ethylene, an α -olefin, and an amine-functionalized monomer in the presence of a metallocene catalyst.
6. The nylon composite of claim 5, wherein the amine-functional polyolefin elastomer has a number average Mw = 1000-400000.
7. The nylon composite of any of claims 1-4, wherein R1, R2 are each independently selected from C1-C10 alkyl, C5-C10 aryl, C6-C15 aralkyl.
8. The nylon composite of claim 7, wherein the C1-C10 alkyl group is selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl; C5-C10 aryl is selected from phenyl, indenyl; the C6-C15 aralkyl group is selected from benzyl, benzhydryl, trityl, phenethyl, phenylpropyl.
9. The nylon composite of any of claims 1-4, wherein the amine-functional monomer has the structure:
wherein n is a positive integer from 1 to 10, R1, R2 are each independently alkyl, aryl or aralkyl.
10. The nylon composite of claim 9, wherein R1, R2 are each independently C1-C10 alkyl, C5-C10 aryl, C6-C15 aralkyl, C1-C10 alkyl is selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, isohexyl, t-hexyl, n-heptyl; C5-C10 aryl is selected from phenyl, indenyl; C6-C15 aralkyl is selected from benzyl, benzhydryl, trityl, phenethyl, diphenylethyl, phenylpropyl, phenylbutyl.
11. The nylon composite of any of claims 1-3, wherein the antioxidant comprises one or a mixture of antioxidants 1010, 168, 1076, 1035, and 264.
12. A method of preparing an amine-functionalized polyolefin elastomer toughened nylon composite of any of claims 1-11 comprising: the nylon resin, the amido functional polyolefin elastomer and the optional antioxidant are evenly mixed in a high-speed mixer, the mixed materials are added into a double-screw extruder for melt mixing, and the mixture is extruded from the head of the screw extruder for granulation.
13. The preparation method according to claim 12, wherein the method comprises the steps of uniformly mixing the nylon resin, the amino-functionalized polyolefin elastomer and the optional antioxidant in a high-speed mixer at the rotation speed of 100-, drying for 1-24h to obtain the final product.
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| US3755279A (en) * | 1965-06-25 | 1973-08-28 | Exxon Research Engineering Co | Copolymerization of alpha olefins with sterically hindered alkenyl amines using ziegler catalysts |
| CN1390234A (en) * | 1999-10-19 | 2003-01-08 | 埃克森化学专利公司 | Amine-containing graft polymers, a method for making same, and their use |
| CN103502282A (en) * | 2011-03-25 | 2014-01-08 | 埃克森美孚化学专利公司 | Amine functionalized polyolefin and methods for preparation thereof |
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