CN110437539A - A kind of modified chlorinated graphene and high melt strength polypropylene material - Google Patents
A kind of modified chlorinated graphene and high melt strength polypropylene material Download PDFInfo
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- CN110437539A CN110437539A CN201910821194.4A CN201910821194A CN110437539A CN 110437539 A CN110437539 A CN 110437539A CN 201910821194 A CN201910821194 A CN 201910821194A CN 110437539 A CN110437539 A CN 110437539A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention discloses a kind of modified chlorinated graphene and high melt strength polypropylene material.The polypropylene material, including following components: 54-95 parts of polypropylene, 5-30 parts of polyamide, 0.5-6 parts of chloridized polyolefin, graphene 0.2-0.8 parts modified chlorinated, 0.6-0.9 parts of antioxidant, 0.1-0.4 parts of hydrotalcite.The present invention is using chloridized polyolefin as compatilizer, during melt extrusion, it can effectively improve the compatibility of polypropylene and modified chlorinated graphene, and modified chlorinated graphene is realized by the amino being grafted and bridged with polyamide macromolecular with chemical bond coupled mode.Present invention efficiently solves the compatibilities of polypropylene and polyamide.Simultaneously as graphene bigger serface lamellar structure feature, polypropylene and polyamide macromolecular can be enriched on its surface, composite material is caused to be capable of forming micro- cross-linked structure, to obtain polypropylene material with high melt strength.
Description
Technical field
The present invention relates to field of high polymer material modification, in particular to graphene is modified and polypropylene material is led
Domain.
Background technique
Polypropylene has low-density, high-melting-point, source is wide, price is low and mechanical performance is superior, chemical stability is good etc.
Feature, is widely used in packaging, light industry, building, electronics, electric appliance and automobile and other industries, and dosage is only second to PE and PVC.However often
Isotactic polypropylene belongs to semicrystalline polymeric, and after processing temperature is higher than fusing point, melt viscosity sharply declines, so as to cause polymer
Sag resistant performance it is poor, thermoformed articles wall unevenness, edge curl when Extrusion Coating, calendering is shunk, abscess when extrusion foaming
The problems such as collapsing.To improve this problem, exploitation high melt strength, propylene becomes the key breakthrough point to solve the above problems.Mesh
Before, prepare high melt strength, propylene method and be broadly divided into two major classes: one kind is that polypropylene and unsaturated monomer carry out in situ gather
Close graft modification；Another kind of is that polypropylene and other polymers carry out blending and modifying.Particular technique route mainly has: x ray irradiation x
Modified method of method, reactive extrursion method, solution grafting, melt blending etc..
The open invention such as Chinese patent CN104558424A, CN105254814A, CN104031320A uses x ray irradiation x
Branching prepares high melt strength, propylene.But the implementation of this technology needs high equipment investment and stringent process conditions control
System, and product stability control difficulty is larger, is restricted its application.Chinese patent CN109553724 A,
CN101376683B and CN101250249B uses organic peroxide and unsaturated monomer such as maleic acid anhydride, esters of acrylic acid
Deng being modified to polypropylene, situ-formed graft growth branch prepares high melt strength, propylene.Since reactive extrursion is generally in height
It is carried out under the conditions of temperature, thus easily causes polyacrylic serious and gelation problems of degrading.Chinese patent CN104945753A is used
Organic peroxide causes maleic anhydride grafted chlorinated polypropylene as initiator, and nylon 6 is connect by maleic anhydride matrix
Graft polymers is formed on branch to chlorinated polypropylene, but there are decomposition of initiator object and monomer remnants.
Graphene one kind as single layer of carbon atom it is tightly packed made of bi-dimensional cellular lattice structure, have larger conjugated body
The features such as system, unique big lamellar structure, large specific surface area and excellent mechanical property and electric property, be a kind of excellent nanometer
Filler.Graphene is introduced into the nanocomposite formed in polymer not only has the skin effect of nano material, quantum ruler
Very little effect, and the excellent properties that show excellent rigidity, dimensional stability, thermal stability etc. many.Chinese patent
CN103159952A obtains the polyamides with photoelectric properties by the way that the graphene oxide of functional modification to be introduced into polyamide
Amine/graphene oxide composite material.Chinese patent CN103588915 is in situ in such a way that catalyst loads graphene oxide
Catalytic polymerization obtains olefin polymerization nanometer composite material.The above invention is all made of graphene oxide as presoma, and complicated contains
Oxygen groups, so that graphene chemical reaction is uncontrollable, another aspect graphene grafting rate is limited, leads to the performance of composite material not
It is prominent.
Summary of the invention
The present invention is directed to the deficiency of existing technology of preparing, provides a kind of modified chlorinated graphene and high melt strength, propylene
Material.The modified chlorinated graphene can effectively improve the compatibility of polypropylene and polyamide material, the polypropylene
Material has apparent high fondant-strength feature, material compatibility good, and smell is small.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of high melt strength polypropylene material, calculates by weight, including following components: 54-95 parts of polypropylene, polyamides
5-30 parts of amine, 0.5-6 parts of chloridized polyolefin, graphene 0.2-0.8 parts modified chlorinated, 0.6-0.9 parts of antioxidant, hydrotalcite 0.1-
0.4 part.
As a preferred scheme, the high melt strength polypropylene material calculates by weight, comprising with the following group
Point: 65-90 parts of polypropylene, 8-20 parts of polyamide, 2-5 parts of chloridized polyolefin, graphene 0.3-0.6 parts modified chlorinated, antioxidant
0.7-0.8 parts, 0.2-0.3 parts of hydrotalcite.
Polypropylene of the present invention include homopolypropylene, block copolymerization polypropylene and atactic copolymerized polypropene one kind or
A variety of, melt index is 3-100g/10min (230 DEG C, 2.16kg).
Polyamide of the present invention includes nylon 6, nylon66 fiber, nylon 11, nylon 12, nylon 610, nylon 612, nylon
46, nylon 1010 etc. is one or more.
Chloridized polyolefin of the present invention is the halogen such as haloflex, chlorinated polypropylene, fluorinated polyethylene, fluorinated polypropylene
Change polyolefin one or more of them.
Preferably, chloridized polyolefin is chlorinated polypropylene, chlorinity 22-30wt%, and content is 20- under the conditions of 25 DEG C
The toluene solution viscosities of 30wt% chlorinated polypropylene are 100-3000mpas.
The preparation method of modified chlorinated graphene of the present invention, comprising the following steps:
(1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 100 DEG C -280
DEG C progress is chlorination modified, and wherein chlorine and graphene weight ratio are 0.2-1.2:1, and the chlorination reaction time is 0.5-3.5h, obtains
To chlorination graphene (chlorinity 10-48wt%)；
(2) by chlorination graphene dispersion in n,N-Dimethylformamide, it is molten that the ethyl alcohol containing amino modified reagent is added
Liquid and acid binding agent stir under nitrogen atmosphere wherein amino modified reagent and chlorination graphene weight ratio are 0.05-0.4:1
It is heated to 70-80 DEG C and carries out reaction 1-2h, separated, washed and dried later, obtain amino modified chlorination graphene；
(3) it disperses amino modified chlorination graphene uniform in n,N-Dimethylformamide, it is molten that polyamide is added later
Liquid, wherein polyamide and the control of amino modified chlorination graphene weight ratio are in 1-5:1, and 100-120 DEG C under nitrogen atmosphere
2-3h is reacted, is separated later, washing and drying, the modified chlorinated graphene for obtaining polyamide prepolymer dispersion and cladding (referred to as change
Property chlorination graphene).
Modified chlorinated graphene of the present invention, chlorinity 6wt%-32wt% are based on X-ray photoelectron spectroscopic analysis
(XPS) graphene chemical element composition result is obtained to calculate；The grafting rate of amino agents is 0.3-1.8wt%, is based on X-ray light
Electron spectroscopy analysis (XPS) obtains nitrogen ratio in graphene chemical element composition result and calculates.
Amino modified reagent of the present invention includes ethylenediamine, hexamethylene diamine, heptamethylene diamine, nonamethylene diamine, decamethylene diamine, benzene two
It is one or more in amine, 4,4- diaminodiphenylmethane and amino acid etc..
Acid binding agent of the present invention includes but is not limited to triethylamine, pyridine etc..
Antioxidant of the present invention includes primary antioxidant and auxiliary anti-oxidant, and the primary antioxidant includes hindered phenol and hindered amine
One of kind antioxidant is a variety of；The auxiliary anti-oxidant includes one of thioesters class and phosphite ester antioxidant or more
Kind.
Primary antioxidant of the present invention is preferably N, and N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono)
Hexamethylene diamine (antioxidant 1098), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076),
N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazines (antioxidant 1024) and four (β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid) one of pentaerythrite (antioxidant 1010) or a variety of.
Auxiliary anti-oxidant of the present invention is preferably three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168), double
One of (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites (antioxidant 626) and the double octadecyls of thio-2 acid
Or it is a variety of.
The preparation of high melt strength, propylene of the present invention can be preferably double to carry out in equipment known in the art
Screw extruder.The following steps are included: proportionally, by polypropylene, polyamide, chloridized polyolefin, modified chlorinated graphene, resisting
Oxygen agent, hydrotalcite etc. are uniformly mixed in high mixer, are then added to double screw extruder by spout, and melting extrusion is granulated,
By water cooling, pelletizing, i.e. acquisition high melt strength, propylene.
The revolution of the double screw extruder is set as 150~300 revs/min, and extrusion temperature is 180~220 DEG C, preferably
, revolution is 180~250 revs/min, 190-210 DEG C of extrusion temperature.
Compared with the prior art, the present invention has the following beneficial effects:
The present invention provides a kind of preparation method of high grafting rate Graphene derivative, compared to the complicated chemical of graphene oxide
Structure, the chlorination graphene that the present invention uses chemical structure single is as modified feedstock, it is advantageous that big on graphene skeleton
The carbon chlorine key of amount provides a large amount of reactivity site for graft modification, not only simplifies grafting chemical reaction process, more has
Conducive to the control to reaction process, while additionally providing a kind of preparation method of high grafting rate modified graphene.
The present invention carries out pre-dispersed and coats amino modified chlorination graphene using polyamide, the amino being grafted by it
It realizes and polyamide molecule is bridged with chemical bond form, and then improve the compatibility between polyamide and chlorination graphene.
The present invention is using chloridized polyolefin as compatilizer, during melt extrusion, improves polypropylene and modified chlorinated
Graphene compatibility, and modified chlorinated graphene carries out bridge by the amino and polyamide of grafting with chemical bond coupled mode
It connects.
The present invention efficiently solves the compatibility of polypropylene and polyamide, has evaded and having been made using maleic anhydride inoculated polypropylene
The problem that grafting rate is low when for compatilizer, material smell is big and two phase material interfacial bonding property is poor.
The present invention, as the micro- crosslinking agent of composite material, utilizes its bigger serface lamellar structure using modified chlorinated graphene
The characteristics of, polypropylene and polyamide macromolecular can be enriched on its surface, and composite material is caused to be capable of forming micro- crosslinking knot
Structure, to obtain polypropylene material with high melt strength.
The present invention obtains high melt strength, propylene, the tradition evaded on the basis of not attacking material bulk properties
Technique peroxide initiator and monomer residue, this method is easy to implement, is easy to implement industrialization.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not limited solely to implement
Example should also include other any well known changes in scope of the presently claimed invention.
Double screw extruder: (Nanjing) Machinery Co., Ltd. grand again, section, model C TE35 PLUS.
Polypropylene: middle sandstone EP548RQ, melting means 28-32g/10min.
Polyamide PA12: win wound industrial group, low viscosity model L2140, melt index be 2-3g/10min (230 DEG C,
2.16kg)。
Chlorinated polypropylene (CPP), Nippon Paper company, model；14-LWP, chlorinity 27wt%, 30wt% chlorination are poly-
The toluene solution viscosities of propylene are 200mpas.
Hydrotalcite: Japanese Kyowa Chemical Industry Co., Ltd, model DHT-4A.
Antioxidant: Ciba fine chemicals, model antioxidant 1010, antioxidant 1098, irgasfos 168.
Polypropylene grafted maleic anhydride, Chemtura, model Polybond3200.
Graphene: the hexa-atomic cellulosic material Co., Ltd in Changzhou, model SE1133.
Graphene oxide: the hexa-atomic cellulosic material Co., Ltd in Changzhou, model SE2430W (oxygen carbon molar ratio: 0.5-0.6).
Rotational rheometer: instrument, TA (U.S.), model ARES G2,200 DEG C of test temperature.
Fusion index instrument: INSTRON CEAST (U.S.), model MF30.
Oder levels test: test method, PV3900,6 grades of grade classification.
X-ray photoelectron spectroscopic analysis (XPS) instrument: model Kratos ASAM 800, producer: Kratos
Analytical Ltd。
Material compatibility characterization: material compatibility can be characterized by material melting means and viscosity, material of the invention
Compatibility is that the chlorination graphene designed based on chlorinated polypropylene and structure improves the degree realization that reacts to each other between different materials
's.Extent of reaction increase causes material molecule amount to improve between material, and the melting means so as to cause material reduces and viscosity increases.
Embodiment 1
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 100 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 2:10, reaction time 0.5h, obtain chlorination graphene (chlorinity
10wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 0.5:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 70 DEG C under nitrogen atmosphere and carries out reaction 1h,
It filtered, washed and is dried later, obtaining the modified chlorination graphene of decamethylene diamine, (chlorinity 6wt%, diamines grafting rate are
0.3wt%).
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio control is 1:1, and carries out reaction 2h under the conditions of 100 DEG C, nitrogen atmosphere, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) 95 parts of polypropylene, 5 parts, 0.5 part chlorinated polypropylene of polyamide, 0.2 part of modified chlorinated graphite are weighed by weight
Alkene, 0.2 part of antioxidant 1010,0.1 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.1 part of hydrotalcite, in high-speed mixer and mixing 2
Minute, it is uniformly mixed.Later, uniformly mixed material is poured into twin-screw extrusion machine inlet, in 180 DEG C of temperature and revolving speed
Melting extrusion under conditions of being 150 revs/min, is extruded into the initial material of strip, through cooling in water-carrying groove and air, then by pelletizing machine-cut
At plastic pellet.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Embodiment 2
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 150 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 4:10, reaction time 1.0h, obtain chlorination graphene (chlorinity
18wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 1:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 70 DEG C under nitrogen atmosphere and carries out reaction 2h, obtains
The chlorination graphene (chlorinity 9wt%, diamines grafting rate 0.5wt%) modified to decamethylene diamine.
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 2:1, and under the conditions of 100 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) weigh by weight 90 parts of polypropylene, 8 parts, 2 parts chlorinated polypropylenes of polyamide, 0.3 part of modified chlorinated graphene,
0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.2 part of hydrotalcite, divide in high-speed mixer and mixing 2
Clock is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in 190 DEG C of temperature and is turned
Speed is melting extrusion under conditions of 180 revs/min, is extruded into the initial material of strip.Through cooling in water-carrying groove and air, then by pelleter
It is cut into plastic pellet.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Embodiment 3
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine and be heated to 200 DEG C of progress chlorinations and change
Property, wherein chlorine and graphene weight ratio are 6:10, reaction time 1.5h, obtain chlorination graphene (chlorinity
32wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 2:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 80 DEG C under nitrogen atmosphere, reacts 1h, obtain
The modified chlorination graphene (chlorinity 18wt%, diamines grafting rate 1.0wt%) of decamethylene diamine.
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 3:1, and under the conditions of 120 DEG C, nitrogen atmosphere and carries out reaction 2h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) 76 parts of polypropylene, 20 parts, 4.0 parts chlorinated polypropylenes of polyamide, 0.5 part of modified chlorinated graphite are weighed by weight
Alkene, 0.2 part of antioxidant 1010,0.3 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.3 part of hydrotalcite, in high-speed mixer and mixing 2
Minute, it is uniformly mixed.Raw material after mixing takes out, and pours into twin-screw extrusion machine inlet, in 210 DEG C of temperature and turns
Speed is melting extrusion under conditions of 250 revs/min, is extruded into the initial material of strip, through cooling in water-carrying groove and air, then by pelleter
It is cut into plastic pellet, melting means, tensile viscosity and smell test is carried out, the results are shown in Table 1.
Embodiment 4
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine and be heated to 250 DEG C of progress chlorinations and change
Property, wherein chlorine and graphene weight ratio are 10:10, reaction time 3h, obtain chlorination graphene (chlorinity 42wt%).
By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), it is molten that decamethylene diamine ethyl alcohol is added
Liquid (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio are 3:
10, acid binding agent and amino modified reagent weight ratio are 1:10, are heated to 80 DEG C under nitrogen atmosphere, carry out reaction 2h, it is laggard
Row suction filtration, washing and drying obtain the modified chlorination graphene (chlorinity 26wt%, diamines grafting rate 1.5wt%) of decamethylene diamine.
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 4:1, and under the conditions of 120 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) 65 parts of polypropylene, 0 part, 5 parts chlorinated polypropylenes of kymene, 0.6 part of modified chlorinated graphite, are weighed by weight
Alkene, 0.1 part of antioxidant 1010,0.4 part of antioxidant, 1098,0.4 parts of irgasfos 168s, 0.4 part of hydrotalcite DHT-4A, in high mixer
Middle mixing 2 minutes, is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in temperature
210 DEG C and revolving speed are melting extrusion under conditions of 250 revs/min, are extruded into the initial material of strip, through cooling in water-carrying groove and air,
Plastic pellet is cut by pelleter again.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Embodiment 5
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 280 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 12:10, reaction time 3.5h, obtain chlorination graphene (chlorinity
48wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 4:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 80 DEG C under nitrogen atmosphere, carries out reaction 2h,
It filtered, washed and is dried later, obtain decamethylene diamine modified chlorination graphene (chlorinity 32wt%, diamines grafting rate
1.8wt%).
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 5:1, and under the conditions of 120 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) 54 parts of polypropylene, 40 parts, 6 parts chlorinated polypropylenes of polyamide, 0.8 part of modified chlorinated graphite, are weighed by weight
Alkene, 0.1 part of antioxidant 1010,0.4 part of antioxidant, 1098,0.4 parts of irgasfos 168s, 0.4 part of hydrotalcite DHT-4A, in high mixer
Middle mixing 2 minutes, is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in temperature
220 DEG C and revolving speed are melting extrusion under conditions of 300 revs/min, are extruded into the initial material of strip, through cooling in water-carrying groove and air,
Plastic pellet is cut by pelleter again.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Comparative example 1
1) graphene oxide is dispersed in n,N-Dimethylformamide (solution concentration 2.0wt%), decamethylene diamine second is added
Alcoholic solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent is with chlorination graphene weight ratio
1:10, acid binding agent and amino modified reagent weight ratio are 1:10, are heated to 70 DEG C under nitrogen atmosphere, carry out reaction 2h, obtain
The modified graphene oxide (diamines grafting rate 0.2wt%) of decamethylene diamine.
2) the modified graphene oxide of above-mentioned decamethylene diamine is dispersed in N,N-dimethylformamide (solution concentration
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified graphene oxide weight ratio controls in 2:1, and under the conditions of 100 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified graphene oxide.
3) weigh by weight 90 parts of polypropylene, 8 parts, 2 parts chlorinated polypropylenes of polyamide, 0.3 part of modified graphene oxide,
0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.2 part of hydrotalcite, divide in high-speed mixer and mixing 2
Clock is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in 190 DEG C of temperature and is turned
Speed is melting extrusion under conditions of 180 revs/min, is extruded into the initial material of strip.Through cooling in water-carrying groove and air, then by pelleter
It is cut into plastic pellet.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Comparative example 2
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 150 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 4:10, reaction time 1.0h, obtain chlorination graphene (chlorinity
18wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 1:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 70 DEG C under nitrogen atmosphere and carries out reaction 2h, obtains
The chlorination graphene (chlorinity 9wt%, diamines grafting rate 0.5wt%) modified to decamethylene diamine.
2) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 2:1, and under the conditions of 100 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
3) 8 parts, 2 parts 90 parts of polypropylene, polyamide polypropylene grafted maleic anhydrides are weighed by weight
(Polybond3200), 0.3 part of modified chlorinated graphene, 0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of antioxygens
168,0.2 parts of hydrotalcites of agent were uniformly mixed at high-speed mixer and mixing 2 minutes.Raw material after mixing is taken out,
Enter twin-screw extrusion machine inlet, melting extrusion under conditions of 190 DEG C of temperature and revolving speed are 180 revs/min is extruded into strip
Initial material.Plastic pellet is cut into through cooling in water-carrying groove and air, then by pelleter.Melting means, tensile viscosity and smell test are carried out,
It the results are shown in Table 1.
Comparative example 3
1) take 97 parts of chlorinated polypropylene, 3 parts of maleic anhydride in dimethylbenzene, be stirred and heated to 60 DEG C under nitrogen atmosphere
It is completely dissolved chlorinated polypropylene and maleic anhydride；After being continuously heating to 120 DEG C, it is added dropwise into reaction kettle dissolved with benzoyl peroxide first
Rear insulation reaction 1.0h is added dropwise in the xylene solution of acyl 1.5wt%；Above-mentioned reactant acetone-dehydrated alcohol is mixed
Solution is washed repeatedly, is dried under vacuum to constant weight under the conditions of 60 DEG C, is obtained maleic anhydride grafted chlorinated polypropylene.
2) reaction kettle is vacuumized and is filled with nitrogen, the triethylamine of nylon 6 and 0.3ml, agitating and heating liter are added into reaction
Temperature is completely dissolved nylon 6 to 150 DEG C, and the xylene solution of above-mentioned maleic anhydride grafted chlorinated polypropylene is added at 110 DEG C,
Insulation reaction 10h later；Above-mentioned reactant is washed repeatedly with n,N-Dimethylformamide, and is carried out under the conditions of 90 DEG C
It is dried under vacuum to constant weight, obtains grafted chlorinated polypropylene polymer.
3) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 150 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 4:10, reaction time 1.0h, obtain chlorination graphene (chlorinity
18wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 1:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 70 DEG C under nitrogen atmosphere and carries out reaction 2h, obtains
The chlorination graphene (chlorinity 9wt%, diamines grafting rate 0.5wt%) modified to decamethylene diamine.
4) (solution concentration is dispersed in N,N-dimethylformamide by the modified chlorination graphene uniform of above-mentioned decamethylene diamine
2.0wt%), later be added contain polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide with
Amino modified chlorination graphene weight ratio controls in 2:1, and under the conditions of 100 DEG C, nitrogen atmosphere and carries out reaction 3h, later
It is filtered, washed and dried, obtains modified chlorinated graphene.
5) 90 parts of polypropylene, 8 parts, 2 parts grafted chlorinated polypropylene polymer of polyamide, 0.3 part of modification are weighed by weight
Chlorination graphene, 0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.2 part of hydrotalcite, it is mixed in height
It mixes 2 minutes, is uniformly mixed in machine.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in temperature
190 DEG C of degree and revolving speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip.Through cold in water-carrying groove and air
But, then by pelleter it is cut into plastic pellet.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Comparative example 4
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 150 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 4:10, reaction time 1.0h, obtain chlorination graphene (chlorinity
18wt%).By above-mentioned chlorination graphene dispersion in n,N-Dimethylformamide (solution concentration 2.0wt%), the last of the ten Heavenly stems two is added
Amine ethanol solution (10wt%) and acid binding agent (triethylamine, 0.1wt%), wherein amino modified reagent and chlorination graphene weight ratio
Example is 1:10, and acid binding agent and amino modified reagent weight ratio are 1:10, is heated to 70 DEG C under nitrogen atmosphere and carries out reaction 2h, obtains
The chlorination graphene (chlorinity 9wt%, diamines grafting rate 0.5wt%) modified to decamethylene diamine.
2) the modified chlorine of 90 parts of polypropylene, 8 parts, 2 parts chlorinated polypropylenes of polyamide, 0.3 part of decamethylene diamine is weighed by weight
Graphite alkene, 0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.2 part of hydrotalcite, in high mixer
Middle mixing 2 minutes, is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in temperature
190 DEG C and revolving speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip.Through cooling in water-carrying groove and air,
Plastic pellet is cut by pelleter again.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
Comparative example 5
1) graphene is heated and is vacuumized after removing moisture, be placed under chlorine atmosphere and be heated to 150 DEG C of progress chlorine
Change and be modified, wherein chlorine and graphene weight ratio are 4:10, reaction time 1.0h, obtain chlorination graphene (chlorinity
18wt%).
2) (solution concentration 2.0wt%) is dispersed in n,N-Dimethylformamide by above-mentioned chlorination graphene uniform, later
It is added and contains polyamide n,N-Dimethylformamide solution (solution concentration 5.0wt%), wherein polyamide and chlorination graphene weight
The control of amount ratio carries out reaction 3h in 2:1, and under the conditions of 100 DEG C, nitrogen atmosphere, is filtered, washed and dried, is changed later
Property chlorination graphene.
3) weigh by weight 90 parts of polypropylene, 8 parts, 2 parts chlorinated polypropylenes of polyamide, 0.3 part of modified chlorinated graphene,
0.2 part of antioxidant 1010,0.2 part of antioxidant, 1098,0.3 parts of irgasfos 168s, 0.2 part of hydrotalcite, divide in high-speed mixer and mixing 2
Clock is uniformly mixed.Raw material after mixing is taken out, twin-screw extrusion machine inlet is poured into, in 190 DEG C of temperature and is turned
Speed is melting extrusion under conditions of 180 revs/min, is extruded into the initial material of strip.Through cooling in water-carrying groove and air, then by pelleter
It is cut into plastic pellet.Melting means, tensile viscosity and smell test are carried out, the results are shown in Table 1.
The melt index and melt viscosity of each embodiment of table 1 and comparative example polypropylene material
The melt index and melt viscosity of each embodiment of 1 (Continued) of table and comparative example polypropylene material
*: value when rotational shear rate is 0.1s.It is that reaction material melt strength changes intuitive index.
Above embodiments are only described to the preferred embodiment of the present invention, rather than to the limit of the scope of the present invention
System, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should understand that, to this hair
Bright technical solution is modified or replaced equivalently all variations and modifications made, and should all fall into claim of the invention
In the protection scope that book determines.
Claims (10)
1. a kind of modified chlorinated graphene, which is characterized in that the preparation method of the modified chlorinated graphene, including following step
It is rapid:
(1) dry graphene is placed under chlorine atmosphere to be heated to 100 DEG C of -280 DEG C of progress chlorination modified, obtains chlorination stone
Black alkene；
(2) chlorination graphene and amino modified reagent are subjected to reaction 1-2h at 70-80 DEG C, are separated, washed and is done later
It is dry, obtain amino modified chlorination graphene；
(3) polyamide solution is added in solvent in amino modified chlorination graphene dispersion later, in 100-120 DEG C of reaction 2-
3h, separation later, washing and dry, the modified chlorinated graphene for obtaining polyamide prepolymer dispersion and coating.
2. modified chlorinated graphene according to claim 1, which is characterized in that chlorine and graphene in the step (1)
Weight ratio is 0.2-1.2:1, and the chlorination reaction time is 0.5-3.5h, and the chlorinity of chlorination graphene is 10-48wt%.
3. modified chlorinated graphene according to claim 1, which is characterized in that amino modified reagent in the step (2)
It is 0.05-0.4:1 with chlorination graphene weight ratio；The amino modified reagent includes ethylenediamine, hexamethylene diamine, heptamethylene diamine, nonyl
It is one or more in diamines, decamethylene diamine, phenylenediamine, 4,4- diaminodiphenylmethane and amino acid.
4. modified chlorinated graphene according to claim 1, which is characterized in that in the step (3), polyamide and amino
Modified chlorination graphene weight ratio is 1-5:1.
5. modified chlorinated graphene according to claim 1, which is characterized in that chlorinity 6wt%-32wt% is based on X
Ray photoelectron spectroscopic analysis obtains graphene chemical element composition result and calculates；The grafting rate of amino modified reagent is 0.3-
1.8wt% obtains nitrogen ratio in graphene chemical element composition result based on X-ray photoelectron spectroscopic analysis and calculates.
6. a kind of high melt strength polypropylene material, calculates by weight, including following components: 54-95 parts of polypropylene, polyamide
5-30 parts, 0.5-6 parts of chloridized polyolefin, modified chlorinated graphene 0.2-0.8 parts described in claim 1, antioxidant 0.6-0.9
Part, 0.1-0.4 parts of hydrotalcite.
7. polypropylene material according to claim 6, it is characterised in that: calculate by weight, include following components: poly- third
65-90 parts of alkene, 8-20 parts of polyamide, 2-5 parts of chloridized polyolefin, modified chlorinated graphene 0.3-0.6 described in claim 1
Part, 0.7-0.8 parts of antioxidant, 0.2-0.3 parts of hydrotalcite.
8. polypropylene material according to claim 6, it is characterised in that: the polypropylene includes homopolypropylene, block
Copolymer polypropylene and atactic copolymerized polypropene it is one or more, melt index be 3-100g/10min (230 DEG C,
2.16kg)。
9. polypropylene material according to claim 6, it is characterised in that: the chloridized polyolefin is haloflex, chlorine
Change one of polypropylene, fluorinated polyethylene, fluorinated polypropylene or a variety of.
10. polypropylene material according to claim 6, it is characterised in that: the chloridized polyolefin is chlorinated polypropylene, chlorine
Content is 22-30wt%, and it is 100- that content, which is the toluene solution viscosities of 20-30wt% chlorinated polypropylene, under the conditions of 25 DEG C
3000mpa·s。
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| CN111019240A (en) * | 2019-12-11 | 2020-04-17 | 万华化学（宁波）有限公司 | Polypropylene composite material for injection molding foaming and preparation method thereof |
| CN115322461A (en) * | 2022-07-21 | 2022-11-11 | 青岛橡六胶管有限公司 | Rubber tube suitable for hydraulic transmission under mine and preparation method thereof |
| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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| CN111019240A (en) * | 2019-12-11 | 2020-04-17 | 万华化学（宁波）有限公司 | Polypropylene composite material for injection molding foaming and preparation method thereof |
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| CN115322461A (en) * | 2022-07-21 | 2022-11-11 | 青岛橡六胶管有限公司 | Rubber tube suitable for hydraulic transmission under mine and preparation method thereof |
| CN115322461B (en) * | 2022-07-21 | 2023-08-08 | 青岛橡六胶管有限公司 | Rubber tube suitable for hydraulic transmission under mine and preparation method thereof |
| CN115821420A (en) * | 2022-11-24 | 2023-03-21 | 江苏江山红化纤有限责任公司 | Graphene modified polyamide 6 composite fiber and preparation method thereof |
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