CN110437539B - Modified chlorinated graphene and high-melt-strength polypropylene material - Google Patents
Modified chlorinated graphene and high-melt-strength polypropylene material Download PDFInfo
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- CN110437539B CN110437539B CN201910821194.4A CN201910821194A CN110437539B CN 110437539 B CN110437539 B CN 110437539B CN 201910821194 A CN201910821194 A CN 201910821194A CN 110437539 B CN110437539 B CN 110437539B
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- 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
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Abstract
The invention discloses modified chlorinated graphene and a high-melt-strength polypropylene material. The polypropylene material comprises the following components: 54-95 parts of polypropylene, 5-30 parts of polyamide, 0.5-6 parts of chlorinated polyolefin, 0.2-0.8 part of modified chlorinated graphene, 0.6-0.9 part of antioxidant and 0.1-0.4 part of hydrotalcite. According to the invention, chlorinated polyolefin is used as a compatilizer, the compatibility of polypropylene and modified chlorinated graphene can be effectively improved in the melt extrusion process, and the modified chlorinated graphene is bridged with polyamide macromolecules in a chemical bond coupling manner through grafted amino groups. The invention effectively solves the compatibility of polypropylene and polyamide. Meanwhile, due to the characteristic of a lamellar structure with large specific surface area of graphene, polypropylene and polyamide macromolecules can be enriched on the surface of the graphene, so that the composite material can form a micro-crosslinking structure, and the polypropylene composite material with high melt strength is obtained.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to the field of graphene modification and polypropylene materials.
Background
The polypropylene has the characteristics of low density, high melting point, wide source, low price, excellent mechanical property, good chemical stability and the like, is widely applied to the industries of packaging, light industry, building, electronics, electric appliances, automobiles and the like, and has the use amount second to PE and PVC. However, the conventional polypropylene belongs to a semi-crystalline polymer, and the melt viscosity is rapidly reduced after the processing temperature is higher than the melting point, so that the problems of poor anti-sagging performance of the polymer, uneven wall thickness of a hot forming product, edge curling and shrinkage during extrusion coating and calendering, collapse of foam holes during extrusion foaming and the like are caused. To ameliorate this problem, the development of high melt strength polypropylene has become a key breakthrough in solving the above problem. At present, the methods for preparing high melt strength polypropylene are mainly divided into two main categories: one is in-situ polymerization grafting modification of polypropylene and unsaturated monomer; the other is the blending modification of polypropylene with other polymers. The specific technical route mainly comprises: ray irradiation method, reaction extrusion method, solution grafting method, melt blending modification method and the like.
Chinese patents CN104558424A, CN105254814A, CN104031320A and the like disclose the invention that the high melt strength polypropylene is prepared by adopting ray irradiation branching. However, the implementation of this technology requires high equipment investment and strict process condition control, and the difficulty of controlling the product stability is large, so that the application thereof is limited. Chinese patents CN 109553724A, CN101376683B and CN101250249B adopt organic peroxide and unsaturated monomers such as maleic anhydride, acrylate and the like to modify polypropylene, and prepare high-melt-strength polypropylene by in-situ grafting and growing branched chains. Since reactive extrusion is generally carried out under high temperature conditions, severe degradation and gelation problems of polypropylene are easily caused. The Chinese patent CN104945753A adopts organic peroxide as an initiator to initiate maleic anhydride grafting chlorinated polypropylene, and nylon 6 is grafted to the chlorinated polypropylene through a maleic anhydride matrix to form a graft polymer, but the problems of initiator decomposition products and monomer residues exist.
The graphene is a two-dimensional honeycomb lattice structure formed by tightly stacking single-layer carbon atoms, has the characteristics of a large conjugated system, a unique large-sheet structure, a large specific surface area, excellent mechanical properties and electrical properties and the like, and is an excellent nano filler. The nano composite material formed by introducing the graphene into the polymer not only has the surface effect and the quantum size effect of the nano material, but also shows a plurality of excellent performances such as excellent rigidity, excellent size stability, excellent thermal stability and the like. Chinese patent CN103159952A obtains a polyamide/graphene oxide composite material with photoelectric properties by introducing functionalized modified graphene oxide into polyamide. The Chinese patent CN103588915 adopts a mode of loading graphene oxide by a catalyst to obtain the polyolefin nano composite material by in-situ catalytic polymerization. In the invention, graphene oxide is used as a precursor, and the complex oxygen-containing group of the graphene oxide enables the chemical reaction of graphene to be uncontrollable, and on the other hand, the grafting rate of graphene is limited, so that the performance of the composite material is not outstanding.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified chlorinated graphene and a high-melt-strength polypropylene material. The modified chlorinated graphene can effectively improve the compatibility of polypropylene and polyamide materials, and the polypropylene material has the advantages of obvious high melt strength characteristic, good material compatibility and small smell.
In order to solve the technical problems, the invention adopts the following technical scheme:
the high melt strength polypropylene material comprises the following components in parts by weight: 54-95 parts of polypropylene, 5-30 parts of polyamide, 0.5-6 parts of chlorinated polyolefin, 0.2-0.8 part of modified chlorinated graphene, 0.6-0.9 part of antioxidant and 0.1-0.4 part of hydrotalcite.
As a preferred scheme, the high melt strength polypropylene material comprises the following components in parts by weight: 65-90 parts of polypropylene, 8-20 parts of polyamide, 2-5 parts of chlorinated polyolefin, 0.3-0.6 part of modified chlorinated graphene, 0.7-0.8 part of antioxidant and 0.2-0.3 part of hydrotalcite.
The polypropylene comprises one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene, and the melt index of the polypropylene is 3-100g/10min (230 ℃, 2.16 kg).
The polyamide of the invention comprises one or more of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 46, nylon 1010 and the like.
The chlorinated polyolefin is one or more of halogenated polyolefins such as chlorinated polyethylene, chlorinated polypropylene, fluorinated polyethylene, fluorinated polypropylene and the like.
Preferably, the chlorinated polyolefin is chlorinated polypropylene, the chlorine content is 22-30 wt%, and the toluene solution of the chlorinated polypropylene with the chlorine content of 20-30 wt% at 25 ℃ has a viscosity of 100-3000 mpa-s.
The preparation method of the modified chlorinated graphene comprises the following steps:
(1) heating graphene, vacuumizing to remove moisture, and heating to 100-280 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 0.2-1.2:1, and the chlorination reaction time is 0.5-3.5h, so that chlorinated graphene (with the chlorine content of 10-48 wt%) is obtained;
(2) dispersing chlorinated graphene in N, N-dimethylformamide, adding an ethanol solution containing an amino modification reagent and an acid-binding agent, wherein the weight ratio of the amino modification reagent to the chlorinated graphene is 0.05-0.4:1, stirring and heating to 70-80 ℃ in a nitrogen atmosphere to react for 1-2h, and then separating, washing and drying to obtain amino modified chlorinated graphene;
(3) uniformly dispersing amino modified chlorinated graphene in N, N-dimethylformamide, then adding a polyamide solution, controlling the weight ratio of polyamide to amino modified chlorinated graphene to be 1-5:1, reacting for 2-3h at the temperature of 120 ℃ in the nitrogen atmosphere, and then separating, washing and drying to obtain the modified chlorinated graphene (modified chlorinated graphene for short) pre-dispersed and coated by polyamide.
According to the amino modified chlorinated graphene, the chlorine content is 6 wt% -32 wt%, and the calculation is carried out based on the composition result of graphene chemical elements obtained by X-ray photoelectron spectroscopy (XPS); the grafting ratio of the amino reagent is 0.3-1.8 wt%, calculated based on the nitrogen element ratio in the composition result of graphene chemical elements obtained by X-ray photoelectron spectroscopy (XPS).
The amino modification reagent comprises one or more of ethylenediamine, hexamethylenediamine, heptamethylenediamine, nonanediamine, decanediamine, phenylenediamine, 4-diaminodiphenylmethane, amino acid and the like.
The acid-binding agent of the invention includes but is not limited to triethylamine, pyridine and the like.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant comprises one or more of hindered phenol and hindered amine antioxidants; the auxiliary antioxidant comprises one or more of thioesters and phosphite antioxidants.
The main antioxidant is preferably one or more of N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (antioxidant 1024) and tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol (antioxidant 1010).
The auxiliary antioxidant is preferably one or more of tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626) and dioctadecyl thiodipropionate.
The preparation of the high melt strength polypropylene according to the present invention may be carried out in equipment known in the art, preferably a twin screw extruder. The method comprises the following steps: according to the proportion, polypropylene, polyamide, chlorinated polyolefin, modified chlorinated graphene, an antioxidant, hydrotalcite and the like are uniformly mixed in a high-speed mixer, then the mixture is added into a double-screw extruder through a feeding port, and the mixture is subjected to melt extrusion granulation, water cooling and grain cutting to obtain the high-melt-strength polypropylene.
The rotation speed of the double-screw extruder is set to be 150-300 r/min, the extrusion temperature is 180-220 ℃, and preferably, the rotation speed is 180-250 r/min, and the extrusion temperature is 190-210 ℃.
Compared with the prior art, the invention has the following beneficial effects:
compared with the complex chemical structure of graphene oxide, the chlorinated graphene with a single chemical structure is used as a modification raw material, and the preparation method has the advantages that a large number of carbon-chlorine bonds on a graphene skeleton provide a large number of reactive sites for grafting modification, so that the grafting chemical reaction process is simplified, the control on the reaction process is facilitated, and meanwhile, the preparation method of the modified graphene with the high grafting rate is also provided.
According to the invention, polyamide is adopted for pre-dispersing and amino-modified chlorinated graphene coating, and the grafted amino realizes bridging with polyamide molecules in a chemical bond form, so that the compatibility between polyamide and chlorinated graphene is improved.
According to the invention, chlorinated polyolefin is used as a compatilizer, the compatibility of polypropylene and modified chlorinated graphene is improved in the melt extrusion process, and the modified chlorinated graphene is bridged with polyamide in a chemical bond coupling mode through a grafted amino group.
The invention effectively solves the compatibility of polypropylene and polyamide and avoids the problems of low grafting rate, large material odor and poor interfacial bonding property of two-phase materials when maleic anhydride grafted polypropylene is used as a compatilizer.
According to the invention, the modified chlorinated graphene is used as the composite material micro-crosslinking agent, and by utilizing the characteristic of a lamellar structure with a large specific surface area, polypropylene and polyamide macromolecules can be enriched on the surface of the modified chlorinated graphene, so that the composite material can form a micro-crosslinking structure, and the high-melt-strength polypropylene composite material is obtained.
The invention obtains the polypropylene with high melt strength on the basis of not damaging the performance of the material body, avoids the residual of peroxide initiator and monomer in the traditional process, and is easy to implement and convenient to realize industrialization.
Detailed Description
The invention is further described in the following with reference to examples, but the scope of protection of the invention is not limited to the examples only, but also includes any other known variations within the scope of the claims of the invention.
A double-screw extruder: cobolon (Nanjing) machinery, Inc., model CTE35 PLUS.
Polypropylene: the medium sand petrochemical EP548RQ has a melt index of 28-32g/10 min.
Polyamide PA 12: winning industrial group, low viscosity model L2140, and melt index of 2-3g/10min (230 deg.C, 2.16 kg).
Chlorinated polypropylene (CPP), japan paper company, model number; 14-LWP with a chlorine content of 27% by weight and a 30% by weight chlorinated polypropylene with a toluene solution viscosity of 200 mpa.s.
Hydrotalcite: japan Synechol chemical industry Co., Ltd, model DHT-4A.
Antioxidant: ciba, Switzerland, model 1010, antioxidant 1098, antioxidant 168.
Polypropylene grafted maleic anhydride, kepi, model Polybond 3200.
Graphene: heizhou sixth element materials, Inc., model number SE 1133.
And (3) graphene oxide: hezhou Hexa materials Ltd, model No. SE2430W (molar ratio of oxygen to carbon: 0.5-0.6).
Rotating the rheometer: the instrument, TA (USA), model ARES G2, test temperature 200 ℃.
Melt index meter: INSTRON center (usa), model MF 30.
And (3) testing the odor grade: test method, PV3900, grade 6.
X-ray photoelectron spectroscopy (XPS) instrument: the model is Kratos ASAM 800, manufacturer: kratos Analytical Ltd.
And (3) material compatibility characterization: the material compatibility can be characterized by material melt index and viscosity, and the material compatibility is realized by improving the mutual reaction degree of different materials based on chlorinated polypropylene and chlorinated graphene with a structural design. The increased degree of reaction between the materials results in an increase in the molecular weight of the materials, thereby causing a decrease in the melt index and an increase in the viscosity of the materials.
Example 1
1) Heating and vacuumizing graphene to remove moisture, and then heating to 100 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 2: 10, and the reaction time is 0.5h, so that chlorinated graphene (with the chlorine content of 10 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 0.5: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere for reaction for 1 hour, and then carrying out suction filtration, washing and drying to obtain the decamethylenediamine modified chlorinated graphene (the chlorine content is 6 wt%, and the diamine grafting rate is 0.3 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 1: 1, reacting for 2 hours at 100 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 95 parts of polypropylene, 5 parts of polyamide, 0.5 part of chlorinated polypropylene, 0.2 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.1 part of hydrotalcite in parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 180 ℃ and 150 r/min of rotating speed, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Example 2
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 150 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 4: 10, and the reaction time is 1.0h, so that chlorinated graphene (with the chlorine content of 18 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 1: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 2 hours to obtain decamethylenediamine modified chlorinated graphene (the chlorine content is 9 wt%, and the diamine grafting rate is 0.5 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 2:1, reacting for 3 hours at 100 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of chlorinated polypropylene, 0.3 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite in parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Example 3
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 200 ℃ under chlorine gas to perform chlorination modification, wherein the weight ratio of the chlorine gas to the graphene is 6: 10, and the reaction time is 1.5h, so that chlorinated graphene (with the chlorine content of 32 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 2: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 80 ℃ in a nitrogen atmosphere, and reacting for 1h to obtain decamethylenediamine modified chlorinated graphene (the chlorine content is 18 wt%, and the diamine grafting rate is 1.0 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 3: 1, reacting for 2 hours at 120 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 76 parts of polypropylene, 20 parts of polyamide, 4.0 parts of chlorinated polypropylene, 0.5 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.3 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.3 part of hydrotalcite in parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. The uniformly mixed raw materials are taken out, poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 210 ℃ and 250 revolutions per minute, extruded into strip-shaped primary materials, cooled in a water tank and air, cut into plastic particles by a granulator, and subjected to melt index, extensional viscosity and odor tests, and the results are shown in table 1.
Example 4
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 250 ℃ under chlorine gas to perform chlorination modification, wherein the weight ratio of the chlorine gas to the graphene is 10: 10, and the reaction time is 3h, so that chlorinated graphene (with a chlorine content of 42 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 3: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, and then carrying out suction filtration, washing and drying to obtain the decamethylenediamine modified chlorinated graphene (the chlorine content is 26 wt%, and the diamine grafting rate is 1.5 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 4:1, reacting for 3 hours at 120 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 65 parts of polypropylene, 30 parts of polyamide, 5 parts of chlorinated polypropylene, 0.6 part of modified chlorinated graphene, 0.1 part of antioxidant 1010, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 168 and 0.4 part of hydrotalcite DHT-4A according to parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, performing melt extrusion at the temperature of 210 ℃ and the rotating speed of 250 revolutions per minute, extruding the raw materials into strip-shaped primary materials, cooling the primary materials in a water tank and air, and cutting the primary materials into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Example 5
1) Heating and vacuumizing graphene to remove moisture, and then heating to 280 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 12: 10, and the reaction time is 3.5h, so that chlorinated graphene (with the chlorine content of 48 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 4: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, and then carrying out suction filtration, washing and drying to obtain the decamethylenediamine modified chlorinated graphene (the chlorine content is 32 wt%, and the diamine grafting rate is 1.8 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled at 5:1, reacting for 3 hours at 120 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 54 parts of polypropylene, 40 parts of polyamide, 6 parts of chlorinated polypropylene, 0.8 part of modified chlorinated graphene, 0.1 part of antioxidant 1010, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 168 and 0.4 part of hydrotalcite DHT-4A according to parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, performing melt extrusion at the temperature of 220 ℃ and the rotating speed of 300 r/min, extruding the raw materials into strip-shaped primary materials, cooling the primary materials in a water tank and air, and cutting the primary materials into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Comparative example 1
1) Dispersing graphene oxide in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to chlorinated graphene is 1: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 2 hours to obtain decamethylenediamine-modified graphene oxide (the diamine grafting rate is 0.2 wt%).
2) Uniformly dispersing the decamethylenediamine-modified graphene oxide in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), controlling the weight ratio of the polyamide to the amino-modified graphene oxide to be 2:1, reacting for 3 hours at 100 ℃ in a nitrogen atmosphere, and filtering, washing and drying to obtain the modified graphene oxide.
3) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of chlorinated polypropylene, 0.3 part of modified graphene oxide, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite according to parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Comparative example 2
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 150 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 4: 10, and the reaction time is 1.0h, so that chlorinated graphene (with the chlorine content of 18 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 1: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 2 hours to obtain decamethylenediamine modified chlorinated graphene (the chlorine content is 9 wt%, and the diamine grafting rate is 0.5 wt%).
2) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 2:1, reacting for 3 hours at 100 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of polypropylene grafted maleic anhydride (Polybond3200), 0.3 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite according to parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Comparative example 3
1) 97 parts of chlorinated polypropylene and 3 parts of maleic anhydride are taken and put in dimethylbenzene, stirred under the atmosphere of nitrogen and heated to 60 ℃ to completely dissolve the chlorinated polypropylene and the maleic anhydride; continuously heating to 120 ℃, dropwise adding a dimethylbenzene solution dissolved with 1.5 wt% of benzoyl peroxide into the reaction kettle, and keeping the temperature for reaction for 1.0h after dropwise adding; and repeatedly washing the reactant by using an acetone-absolute ethyl alcohol mixed solution, and drying the reactant in vacuum at the temperature of 60 ℃ to constant weight to obtain the maleic anhydride grafted chlorinated polypropylene.
2) Vacuumizing the reaction kettle, filling nitrogen, adding nylon 6 and 0.3ml of triethylamine into the reaction kettle, stirring, heating to 150 ℃ to completely dissolve the nylon 6, adding the dimethylbenzene solution of the maleic anhydride grafted chlorinated polypropylene at 110 ℃, and then carrying out heat preservation reaction for 10 hours; and repeatedly washing the reactants by using N, N-dimethylformamide, and drying the reactants in vacuum at the temperature of 90 ℃ to constant weight to obtain the chlorinated polypropylene graft polymer.
3) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 150 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 4: 10, and the reaction time is 1.0h, so that chlorinated graphene (with the chlorine content of 18 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 1: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 2 hours to obtain decamethylenediamine modified chlorinated graphene (the chlorine content is 9 wt%, and the diamine grafting rate is 0.5 wt%).
4) Uniformly dispersing the decamethylenediamine-modified chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), then adding a solution containing polyamide N, N-dimethylformamide (the solution concentration is 5.0 wt%), wherein the weight ratio of the polyamide to the amino-modified chlorinated graphene is controlled to be 2:1, reacting for 3 hours at 100 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
5) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of chlorinated polypropylene graft polymer, 0.3 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite according to parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Comparative example 4
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 150 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 4: 10, and the reaction time is 1.0h, so that chlorinated graphene (with the chlorine content of 18 wt%) is obtained. Dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a decamethylenediamine ethanol solution (10 wt%) and an acid-binding agent (triethylamine, 0.1 wt%), wherein the weight ratio of an amino modification reagent to the chlorinated graphene is 1: 10, the weight ratio of the acid-binding agent to the amino modification reagent is 1: 10, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 2 hours to obtain decamethylenediamine modified chlorinated graphene (the chlorine content is 9 wt%, and the diamine grafting rate is 0.5 wt%).
2) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of chlorinated polypropylene, 0.3 part of decamethylenediamine-modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite in parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
Comparative example 5
1) Heating and vacuumizing graphene to remove moisture, and then heating the graphene to 150 ℃ in a chlorine atmosphere to perform chlorination modification, wherein the weight ratio of chlorine to graphene is 4: 10, and the reaction time is 1.0h, so that chlorinated graphene (with the chlorine content of 18 wt%) is obtained.
2) Uniformly dispersing the chlorinated graphene in N, N-dimethylformamide (the solution concentration is 2.0 wt%), adding a polyamide-containing N, N-dimethylformamide solution (the solution concentration is 5.0 wt%), controlling the weight ratio of polyamide to chlorinated graphene to be 2:1, reacting for 3 hours at 100 ℃ under the nitrogen atmosphere, and then filtering, washing and drying to obtain the modified chlorinated graphene.
3) Weighing 90 parts of polypropylene, 8 parts of polyamide, 2 parts of chlorinated polypropylene, 0.3 part of modified chlorinated graphene, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 1098, 0.3 part of antioxidant 168 and 0.2 part of hydrotalcite in parts by weight, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Taking out the uniformly mixed raw materials, pouring the raw materials into a feed inlet of a double-screw extruder, and performing melt extrusion at the temperature of 190 ℃ and the rotating speed of 180 r/min to obtain a strip-shaped primary material. Cooling in a water tank and air, and cutting into plastic particles by a granulator. The melt index, extensional viscosity and odor tests were performed and the results are shown in table 1.
TABLE 1 melt index and melt viscosity of the Polypropylene materials of the examples and comparative examples
TABLE 1 (continuation) melt index and melt viscosity of Polypropylene materials for each of the examples and comparative examples
*: the rotational shear rate was 0.1 s. Is an index for directly showing the change of the melt strength of the reaction material.
Although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the modified chlorinated graphene is characterized by comprising the following steps:
(1) heating the dried graphene to 100-280 ℃ in a chlorine atmosphere for chlorination modification to obtain chlorinated graphene;
(2) reacting chlorinated graphene with an amino modified reagent at 70-80 ℃ for 1-2h, and then separating, washing and drying to obtain amino modified chlorinated graphene;
(3) dispersing amino modified chlorinated graphene in a solvent, then adding a polyamide solution, reacting at the temperature of 100-120 ℃ for 2-3h, then separating, washing and drying to obtain the modified chlorinated graphene pre-dispersed and coated by polyamide.
2. The modified chlorinated graphene of claim 1, wherein in the step (1), the weight ratio of chlorine to graphene is 0.2-1.2:1, the chlorination reaction time is 0.5-3.5h, and the chlorine content of the chlorinated graphene is 10-48 wt%.
3. The modified chlorinated graphene of claim 1, wherein the weight ratio of the amino modification reagent to the chlorinated graphene in step (2) is 0.05-0.4: 1; the amino modifying reagent comprises one or more of ethylenediamine, hexamethylenediamine, heptamethylenediamine, nonanediamine, decanediamine, phenylenediamine, 4-diaminodiphenylmethane and amino acids.
4. The modified chlorinated graphene of claim 1, wherein in step (3), the weight ratio of polyamide to amino-modified chlorinated graphene is 1-5: 1.
5. The modified chlorinated graphene according to claim 1, wherein the chlorine content of the amino-modified chlorinated graphene is 6 wt% to 32 wt%, calculated based on the results of obtaining graphene chemical element composition by X-ray photoelectron spectroscopy; the grafting ratio of the amino modification reagent of the amino modified chlorinated graphene is 0.3-1.8 wt%, and the proportion of nitrogen elements in the composition result of graphene chemical elements is calculated based on X-ray photoelectron spectroscopy analysis.
6. The high melt strength polypropylene material comprises the following components in parts by weight: 54-95 parts of polypropylene, 5-30 parts of polyamide, 0.5-6 parts of chlorinated polyolefin, 0.2-0.8 part of modified chlorinated graphene according to claim 1, 0.6-0.9 part of antioxidant and 0.1-0.4 part of hydrotalcite.
7. The polypropylene material according to claim 6, wherein: the coating comprises the following components in parts by weight: 65-90 parts of polypropylene, 8-20 parts of polyamide, 2-5 parts of chlorinated polyolefin, 0.3-0.6 part of modified chlorinated graphene according to claim 1, 0.7-0.8 part of antioxidant and 0.2-0.3 part of hydrotalcite.
8. The polypropylene material according to claim 6, wherein: the polypropylene comprises one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene, and the melt index of the polypropylene is 3-100g/10min under the conditions of 230 ℃ and 2.16kg load.
9. The polypropylene material according to claim 6, wherein: the chlorinated polyolefin is one or more of chlorinated polyethylene and chlorinated polypropylene.
10. The polypropylene material according to claim 6, wherein: the chlorinated polyolefin is chlorinated polypropylene, the chlorine content is 22-30 wt%, and the viscosity of a toluene solution of the chlorinated polypropylene with the content of 20-30 wt% at 25 ℃ is 100-3000mPa & s.
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