CN107857989A - A kind of polyethylene/polypropylene alloy for toughening nylon and preparation method thereof - Google Patents
A kind of polyethylene/polypropylene alloy for toughening nylon and preparation method thereof Download PDFInfo
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- CN107857989A CN107857989A CN201711024714.6A CN201711024714A CN107857989A CN 107857989 A CN107857989 A CN 107857989A CN 201711024714 A CN201711024714 A CN 201711024714A CN 107857989 A CN107857989 A CN 107857989A
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- polyethylene
- polypropylene
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- nylon
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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
- C08L77/02—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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
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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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of polyethylene/polypropylene alloy for toughening nylon and preparation method thereof, include the raw material of following parts by weight：50~80 parts of polythene PE, 5~40 parts of polypropylene PP, 1~20 part of bulking agent, the first 0.5~5 part of grafted monomers, the second 0.1~5 part of grafted monomers, 0.01~0.5 part of initiator, 0.1~2 part of diluent.Preparation method includes：Raw material is stirred, added in 80~220 DEG C of extruder, fusion plastification, kneading mixing, is extruded, is granulated, is cooled down, is dehydrated, dries, produces.The present invention produces PE/PP alloys by twin-screw extrusion method, improve PE/PP compatibilities by adding bulking agent, the alloy toughener is compounded with elastic body toughening and organic rigid-particle toughening mechanism, can be while nylon toughness be improved, the rigidity of tenacity increased nylon is preferably kept, while the raw material of its low price can reduce the cost of downstream modification of nylon enterprise.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of polyethylene/polypropylene alloy for toughening nylon
And preparation method thereof.
Background technology
Nylon is one of five big general engineering plastics, and nylon yield is big, purposes is wide, has an excellent mechanical strength, heat-resisting,
Oil resistant, weak acid resistant, alkaline-resisting and common solvent, nontoxic, odorless, electrical insulating property is good, good weatherability.The shortcomings that nylon is notch shock
Performance is general, and its product needs later stage conditioning to improve toughness, while the water absorption rate of nylon is larger, influences the size of product
Stability, production cost is added, significantly limit its application.In order to solve the problems, such as nylon toughness deficiency, typically by adding
Toughener is added to be improved.
The toughness reinforcing of nylon is based on elastic body toughening at present, i.e., by the chemical modification method of grafting in soft polyolefin
Chemical reaction or the suitable function monomer of polarity can occur with nylon molecules for grafting in elastomer molecules, make polyolefin elastomer with
Molecule is evenly dispersed in nylon matrix and forms firm boundary layer with nylon, soft when by foreign impacts
Polyolefin elastomer absorb energy first, produce Voiding and surrender, and then transmitted by interface and trigger crazing and shear band,
A large amount of consumed energies, macroscopically play the effect for improving material impact intensity.But polyolefin elastomer is flexible polymer,
The rigidity of material is considerably reduced while improving nylon toughness.And for the elastomer such as ethylene-alpha-octylene of toughener
The prices such as copolymer p OE, ethylene-propylene-dicyclopentadiene terpolymers EPDM are higher, add Nylon In Toughening By Blending into
This.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of polyethylene/polypropylene alloy for toughening nylon and its
Preparation method, the present invention are used for Nylon In Toughening By Blending using PE/PP alloys, and flexible PE is as elastic body toughening reason in alloy
Toughness reinforcing main body in assigns nylon toughness；The good PP of rigidity then meets organic rigid-particle toughening mechanism to be risen in toughened system
Acted on to coordination plasticizing.
A kind of polyethylene/polypropylene alloy for toughening nylon of the present invention, include the raw material of following parts by weight：Poly- second
5~40 parts of 50~80 parts of alkene PE, polypropylene PP, 1~20 part of bulking agent, the first 0.5~5 part of grafted monomers, the second grafting are single
0.1~5 part of body, 0.01~0.5 part of initiator, 0.1~2 part of diluent.
The polypropylene is LLDPE, low density polyethylene (LDPE), ultra-low density polyethylene, the poly- second of Midst density
One or more in alkene, high density polyethylene (HDPE) and metallocene PE.
The polypropylene is the one or more in homo-polypropylene, block copolymerization polypropylene, atactic copolymerized polypropene.
The bulking agent is ethylene-propylene-dicyclopentadiene terpolymers EPDM, ethylene propylene copolymer EPM, acrylic
One or more in elastomer POP.
First grafted monomers are maleic anhydride, maleic acid, fumaric acid, acrylic acid, O-phthalic
One or more in acid anhydrides, GMA.
Second grafted monomers are the one or more in styrene, pyridine, caprolactam.
The initiator is the bis(t-butylperoxy) hexane of 2,5- dimethyl -2,5, double (tert-butyl peroxides) 3 of 1,1-,
3,5- trimethyl-cyclohexanes, cumyl peroxide DCP, dibenzoyl peroxide BPO, double (2- t-butylperoxyisopropyls)
Double (the t-amyl peroxy)-fourths of benzene, t-butylcumylperoxide, di-tert-butyl peroxide, benzylhydroperoxide tert-pentyl ester, 2,2-
Alkane, two t-amyl peroxy compounds, tert butyl peroxy benzoate, tert-butyl hydroperoxide -2 ethyl hexanoic acid ester, t-butyl peroxy
One or more in change -3,5,5 Trimethylhexanoic acid ester, dibenzoyl peroxide.
The diluent is the one or more in acetone, butanone, ethanol, ethyl acetate.
A kind of preparation method of polyethylene/polypropylene alloy for toughening nylon of the present invention, including：Raw material is stirred
Mixing, add in 80~220 DEG C of extruder, fusion plastification, kneading mixing, extrude, be granulated, cool down, be dehydrated, dry, produce
Polyethylene/polypropylene alloy for toughening nylon.
The extruder is double screw extruder, the temperature in the area of extruder 1 to 12nd area be respectively set to 80 DEG C, 180 DEG C,
200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, head is 200 DEG C.
The technological parameter that is stirred is：Speed of agitator is 75~85rpm；Mixing time is 20~30min.
The granulation is water ring pelletizing.
The drying is forced air drying.
Beneficial effect
(1) present invention prepares toughener by base material of PE/PP alloys, the toughness of nylon is greatly improved,
And nylon is rigidly kept as more preferably for elastic body toughening, so as to obtain preferable rigidity-toughness balanced, have excellent
Toughening effect.
(2) present invention be combined with each other by the way that elastic body toughening theory and organic rigid-particle toughness reinforcing are theoretical, is closed with PE/PP
Gold does nylon toughener, and it is reduced while can improving nylon toughness and is rigidly lost, and reduces the cost of Nylon In Toughening By Blending.
(3) raw material PE, PP of the invention are universal polymer, and ample supply of commodities on the market is cheap, can drop well
The cost of low nylon product, obtain preferable economic benefit.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Weigh the raw material of following parts by weight：60 parts of PE resins (Zhenghai refinery, 7042), PP resins (Yangtze petrochemical industry, J340)
25 parts, 15 parts of bulking agent EPDM (Tao Shi, 3725P), the first 2 parts of grafted monomers maleic anhydride, the second grafted monomers styrene 1
Part, 0.1 part of initiator DCP, dissolved dilution is carried out with 1 part of acetone of diluent.
20min is blended in the low-speed mixer that rotating speed is 80rpm in above-mentioned supplementary material, is added to double screw extruder
In, the area of extruder 1 to 12 area's temperature settings be 80 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, head is 200 DEG C, and mixed material is through fusion plastification, kneading mixing, head extrusion, water ring
Pelletizing, cooling, dehydration, forced air drying, produce the polyethylene/polypropylene alloy for toughening nylon.
Embodiment 2
Weigh the raw material of following parts by weight：70 parts of PE resins (Exxon-Mobil, 3518CB), PP resins (Yangtze petrochemical industry,
K8003) 25 parts, 5 parts of bulking agent POP (Exxon-Mobil, VM3000), the first 2 parts of grafted monomers maleic anhydride, the second grafting
1 part of monomer caprolactam, initiator B PO and DCP press 1:2 ratios form 0.15 part, with 1.5 parts of butanone of diluent dissolve dilute
Release.
20min is blended in the low-speed mixer that rotating speed is 80rpm in above-mentioned supplementary material, is added to double screw extruder
In, the area of extruder 1 to 12 area's temperature settings be 80 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, head is 200 DEG C, and mixed material is through fusion plastification, kneading mixing, head extrusion, water ring
Pelletizing, cooling, dehydration, forced air drying, produce the polyethylene/polypropylene alloy for toughening nylon.
Embodiment 3
Weigh the raw material of following parts by weight：50 parts of PE resins (Yangtze petrochemical industry, 2426H), PP resins (Zhenghai refinery, T30S)
30 parts, 10 parts of bulking agent EPM (Exxon-Mobil, 8900), the first 3 parts of grafted monomers maleic anhydride, the second grafted monomers benzene second
1 part of alkene, 1 part of caprolactam, initiator 2,5- dimethyl -2,5- is double -0.2 part of (t-butylperoxy) hexane, with 2 parts of diluent
Ethanol carries out dissolved dilution.
20min is blended in the low-speed mixer that rotating speed is 80rpm in above-mentioned supplementary material, is added to double screw extruder
In, the area of extruder 1 to 12 area's temperature settings be 80 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C,
210 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, head is 200 DEG C, and mixed material is through fusion plastification, kneading mixing, head extrusion, water ring
Pelletizing, cooling, dehydration, forced air drying, produce the polyethylene/polypropylene alloy for toughening nylon.
Comparative example 1
Weigh the raw material of following parts by weight：100 parts of POE resin (DOW, ENGAGE 8150), grafted monomers maleic anhydride 2
Part, 0.1 part of initiator DCP, dissolved dilution, 0.2 part of white oil are carried out with 1 part of acetone of diluent..
20min is blended in the low-speed mixer that rotating speed is 80rpm in above-mentioned supplementary material, is added to double screw extruder
In, the area of extruder 1 to 12 area's temperature settings be 80 DEG C, 160 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 190 DEG C,
180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C, head is 150 DEG C, and mixed material is through fusion plastification, kneading mixing, head extrusion, drawing
Bar, cooling, pelletizing, drying, produce the common toughener in market.
Toughener made from embodiment 1~3 and comparative example 1 is separately to carry out in PA6 (Ube, 1013B)
Performance test.Toughener made from 15 parts of embodiments 1~3 and comparative example 1 is added in PA6 respectively, performance is as shown in table 1.
The toughener performance comparison of the embodiment 1~3 of table 1 and comparative example 1
It was found from data above contrast, embodiment 1~3 is being added compared with comparative example 1 (the common toughener of Vehicles Collected from Market)
In the case that amount is 15%, using tensile strength, bending strength and the bending modulus of the tenacity increased nylon product of embodiment 1~3
It is better than the common toughener in market of comparative example 1, and the notch impact strength of the tenacity increased nylon product using embodiment 1~3
Meets the needs of market super-toughened nylon, combination property is better than commercially available common toughener, and its cheap price makes it have
Competitive advantage economically, meet Patent design requirement.
Claims (10)
- A kind of 1. polyethylene/polypropylene alloy for toughening nylon, it is characterised in that：Include the raw material of following parts by weight：It is poly- 5~40 parts of 50~80 parts of ethene PE, polypropylene PP, 1~20 part of bulking agent, the first 0.5~5 part of grafted monomers, the second grafting 0.1~5 part of monomer, 0.01~0.5 part of initiator, 0.1~2 part of diluent.
- A kind of 2. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described Polypropylene is LLDPE, low density polyethylene (LDPE), ultra-low density polyethylene, medium density polyethylene, high-density polyethylene One or more in alkene and metallocene PE.
- A kind of 3. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described Polypropylene is the one or more in homo-polypropylene, block copolymerization polypropylene, atactic copolymerized polypropene.
- A kind of 4. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described Bulking agent is in ethylene-propylene-dicyclopentadiene terpolymers EPDM, ethylene propylene copolymer EPM, propylene-based elastomeric POP One or more.
- A kind of 5. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described First grafted monomers are maleic anhydride, maleic acid, fumaric acid, acrylic acid, phthalic anhydride, metering system One or more in acid glycidyl ester；Second grafted monomers are the one or more in styrene, pyridine, caprolactam.
- A kind of 6. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described Initiator is the bis(t-butylperoxy) hexane of 2,5- dimethyl -2,5, double (tert-butyl peroxide) 3,3,5- front three basic rings of 1,1- Hexane, cumyl peroxide DCP, dibenzoyl peroxide BPO, double (2- t-butylperoxyisopropyls) benzene, peroxidating uncle Butyl isopropylbenzene, di-tert-butyl peroxide, benzylhydroperoxide tert-pentyl ester, 2,2- double (t-amyl peroxy)-butane, two tertiary pentyl mistakes Oxide, tert butyl peroxy benzoate, tert-butyl hydroperoxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide -3,5,5- front threes One or more in base capronate, dibenzoyl peroxide.
- A kind of 7. polyethylene/polypropylene alloy for toughening nylon according to claim 1, it is characterised in that：It is described Diluent is the one or more in acetone, butanone, ethanol, ethyl acetate.
- 8. a kind of a kind of preparation method of polyethylene/polypropylene alloy for toughening nylon as claimed in claim 1, bag Include：Raw material is stirred, added in 80~220 DEG C of extruder, fusion plastification, kneading mixing, is extruded, is granulated, is cooled down, is taken off Water, dry, produce the polyethylene/polypropylene alloy for toughening nylon.
- 9. a kind of preparation method of polyethylene/polypropylene alloy for toughening nylon according to claim 8, its feature It is：The extruder is double screw extruder, the temperature in the area of extruder 1 to 12nd area be respectively set to 80 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, head be 200 DEG C.
- 10. a kind of preparation method of polyethylene/polypropylene alloy for toughening nylon according to claim 8, it is special Sign is：The technological parameter that is stirred is：Speed of agitator is 75~85rpm, and mixing time is 20~30min；It is described It is granulated as water ring pelletizing；The drying is forced air drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711024714.6A CN107857989A (en) | 2017-10-27 | 2017-10-27 | A kind of polyethylene/polypropylene alloy for toughening nylon and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711024714.6A CN107857989A (en) | 2017-10-27 | 2017-10-27 | A kind of polyethylene/polypropylene alloy for toughening nylon and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330787A (en) * | 2019-07-04 | 2019-10-15 | 四川轻化工大学 | A kind of preparation method of linear low density polyethylene graft modification of nylon 6 |
| CN112430391A (en) * | 2020-11-23 | 2021-03-02 | 山东星达新材料有限公司 | Super-tough super-low temperature-resistant super-wear-resistant flexible nylon alloy material and preparation method thereof |
| CN113563660A (en) * | 2021-09-23 | 2021-10-29 | 北京能之光科技有限公司 | Toughening agent for automobile engineering plastics |
| CN114957851A (en) * | 2022-03-29 | 2022-08-30 | 武汉金发科技有限公司 | Polypropylene composite material easy to absorb plastic and preparation method thereof |
| CN116120669A (en) * | 2023-03-22 | 2023-05-16 | 得力集团有限公司 | Anti-drop high-stiffness file box material and preparation method thereof |
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| CN102558837A (en) * | 2010-12-21 | 2012-07-11 | 上海日之升新技术发展有限公司 | Low temperature impact resistant nylon flexibilizer and preparation method of low temperature impact resistant nylon flexibilizer |
| CN103421148A (en) * | 2012-09-07 | 2013-12-04 | 宁波能聚工程塑料有限公司 | Cold-resistant nylon flexibilizer and preparation method thereof |
| US20160319117A1 (en) * | 2014-05-07 | 2016-11-03 | Falcone Specialties AG | Silane vulcanized thermoplastic elastomers |
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2017
- 2017-10-27 CN CN201711024714.6A patent/CN107857989A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558837A (en) * | 2010-12-21 | 2012-07-11 | 上海日之升新技术发展有限公司 | Low temperature impact resistant nylon flexibilizer and preparation method of low temperature impact resistant nylon flexibilizer |
| CN103421148A (en) * | 2012-09-07 | 2013-12-04 | 宁波能聚工程塑料有限公司 | Cold-resistant nylon flexibilizer and preparation method thereof |
| US20160319117A1 (en) * | 2014-05-07 | 2016-11-03 | Falcone Specialties AG | Silane vulcanized thermoplastic elastomers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330787A (en) * | 2019-07-04 | 2019-10-15 | 四川轻化工大学 | A kind of preparation method of linear low density polyethylene graft modification of nylon 6 |
| CN112430391A (en) * | 2020-11-23 | 2021-03-02 | 山东星达新材料有限公司 | Super-tough super-low temperature-resistant super-wear-resistant flexible nylon alloy material and preparation method thereof |
| CN113563660A (en) * | 2021-09-23 | 2021-10-29 | 北京能之光科技有限公司 | Toughening agent for automobile engineering plastics |
| CN114957851A (en) * | 2022-03-29 | 2022-08-30 | 武汉金发科技有限公司 | Polypropylene composite material easy to absorb plastic and preparation method thereof |
| CN116120669A (en) * | 2023-03-22 | 2023-05-16 | 得力集团有限公司 | Anti-drop high-stiffness file box material and preparation method thereof |
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Application publication date: 20180330 |