CN108586955B - Modified graphene/polybutylene composite master batch material and preparation method and application thereof - Google Patents
Modified graphene/polybutylene composite master batch material and preparation method and application thereof Download PDFInfo
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- CN108586955B CN108586955B CN201810489394.XA CN201810489394A CN108586955B CN 108586955 B CN108586955 B CN 108586955B CN 201810489394 A CN201810489394 A CN 201810489394A CN 108586955 B CN108586955 B CN 108586955B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The modified graphene/polybutylene composite master batch material is characterized by being prepared from the following raw materials: 0.1-40 parts of modified graphene; 80-120 parts of polybutylene resin; 0.1-1.1 parts of antioxidant; 0.2-1.2 parts of a nucleating agent; 0.1-1.2 parts of dispersing agent. The composite material is applied to the polybutylene tubing, and the polybutylene tubing is prepared by simply adding the modified composite material components, so that the mechanical property of the polybutylene tubing can be greatly improved, the polybutylene tubing has higher heat-conducting property, and the problems of low heating efficiency and low comprehensive utilization rate of heat energy when the polybutylene tubing is used as a heating pipe are solved.
Description
Technical Field
The invention belongs to the field of plastic pipes, and particularly relates to a modified graphene/polybutylene composite master batch material, and a preparation method and application thereof.
Background
The polybutene is a semi-crystalline polyolefin high molecular polymer with a linear molecular structure, which is synthesized by taking 1-butene as a raw material under the action of a catalyst. It has the excellent characteristics of no toxicity, no smell, acid and alkali resistance, solvent resistance, high and low temperature resistance, capability of being mixed with other high molecular polymers for modification and the like, and is also praised as 'plastic gold' due to high price. In view of so many excellent characteristics of polybutene, it is widely used for piping materials requiring high heating systems and hot water, drainage pipes, seals, and compression wrap films and electric wires and cables for underground mining, etc. Although polybutene has such excellent characteristics, polybutene has many disadvantages, such as the softness of the material and general mechanical properties, compared with PP-R, crosslinked polyethylene, polybutene pipe material has low heat conductivity coefficient, which limits the use performance of polybutene pipe material as heat conduction material, and when used as a heating pipe, the heat supply efficiency and the comprehensive utilization rate of heat energy are directly influenced.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a polybutylene composite material with good mechanical properties and good thermal conductivity.
In order to achieve the purpose, the invention provides the following technical scheme:
a modified graphene/polybutylene composite master batch material is prepared from the following raw materials:
the nucleating agent is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol, 2-dimethylenebis (4, 6-di-tert-butylphenol) phosphonate, and is mixed with one of diamide compounds.
In some of these embodiments, the polybutene resin has a molecular weight of 40 to 60 ten thousand and a melt mass flow rate of 0.5 to 0.6 g/min.
In some embodiments, the mass ratio of the modified graphene to the polybutene resin is (0.1-20): 100.
in some of these embodiments, the mass ratio of the silane-based coupling agent to the graphene is (9-12): 100, respectively; or
The mass ratio of the titanate coupling agent to the graphene is (0.1-0.3): 100; or
The mass ratio of the total amount of the octadecylamine and the isocyanate to the graphene is (0.8-1.2): 100.
In some of the embodiments, the surface treatment agent is one or two of a silane coupling agent, a titanate coupling agent, octadecylamine, and isocyanate; and/or
The antioxidant is antioxidant 1010 and/or antioxidant 168; and/or
The dispersant is selected from: paraffin wax, polyethylene glycol and fatty acid.
In some of these embodiments, the ratio of the antioxidant 168 to the antioxidant 1010 is 2: (0.8 to 1).
The invention also aims to provide a preparation method of the modified graphene/polybutylene composite master batch material, and the specific technical scheme is as follows:
the preparation method of the modified graphene/polybutylene composite master batch material comprises the following steps: adding an antioxidant, a nucleating agent and a dispersing agent into the polybutene resin solution, mixing, and performing ultrasonic dispersion to obtain a blend; adding the modified graphene dispersion liquid, and precipitating to obtain a modified graphene/polybutylene composite master batch material;
the mixed solvent is a mixed solvent of one or more of isopropanol, acetone, methanol and ethanol and water;
the solvent of the polybutene resin solution is one or more of xylene, toluene and benzene.
In some embodiments, the modified graphene dispersion liquid is prepared by dispersing a surface treatment agent and graphene in a mixed solvent, stirring at a high speed, and then performing ultrasonic dispersion;
the power of ultrasonic dispersion is 100-500W, and the time is 2-3 h.
In some of the embodiments, the mixing and dispersing are mixing and dispersing by using an internal mixer, a Z-shaped kneader or an open mill; and/or
The granulation is carried out by using a planetary screw extruder, a single screw extruder or a double screw extruder; the plasmid temperature is 160-230 ℃, and the rotating speed is 10-40 r/min.
The invention also aims to provide a polybutylene pipe, and the raw materials of the polybutylene pipe comprise the modified graphene/polybutylene composite master batch material and pipe grade polybutylene resin.
Based on the technical scheme, the invention has the following beneficial effects:
according to the invention, a large amount of creative labor is provided by the inventor, the modified graphene and the polybutene resin are adopted, and the nucleating agent is reasonably selected to prepare the modified graphene/polybutene composite master batch material. The graphene is modified by the surface modifier, so that the compatibility and the dispersibility of the graphene and the polybutylene are improved; aromatic rings are arranged in the molecular structure of the nucleating agent, pi-pi conjugation is formed between the nucleating agent and the modified graphene, so that the uniform dispersibility and the interface bonding force among the components are enhanced, and meanwhile, the nucleating agent promotes the thin graphene in the polybutylene crystallization process to be uniformly inserted into a polybutylene crystal sheet layer to form tight coating. The graphene is used as a heterogeneous phase, and also plays a certain nucleation role, so that the polybutene crystallization growth is further promoted. The composite material is applied to the polybutylene tubular product, and the modified composite material component is added into the polybutylene tubular product, so that the mechanical property of the polybutylene tubular product can be greatly improved, the polybutylene tubular product has higher heat-conducting property, and the problems of low heating efficiency and low comprehensive utilization rate of heat energy when the polybutylene tubular product is used as a heating pipe are solved.
The molecular weight and the melt flow rate of the polybutene resin in the composite material are further optimized, so that the polybutene resin has better compatibility with the modified graphene and is easier to disperse uniformly, and the mechanical property of the polybutene pipe prepared finally is ensured. According to the invention, the modified graphene is prepared by selecting an alcohol-containing solvent, the alcohol-containing solvent and the solvent capable of dissolving polybutene resin are immiscible, and the polybutene-coated graphene obtained by precipitation after mixing the alcohol-containing solvent and the solvent can be uniformly dispersed, so that the prepared modified graphene/polybutene composite master batch material is uniformly mixed, and the mechanical property and the heat conductivity of the finally prepared pipe are more stable.
According to the polybutylene tubing, the modified graphene/polybutylene composite master batch material is prepared by mixing graphene and a small amount of polybutylene resin, and then the composite master batch material is mixed with the polybutylene resin serving as a main component of the tubing, so that the compatibility of the graphene and the polybutylene resin is further improved, the mixing is more uniform, the preparation method is simple and easy to operate, and the polybutylene tubing is suitable for large-scale production, overcomes the defects of mechanical property and thermal conductivity, and is suitable for wide application.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
This example provides 6 different modified graphene/polybutylene composite masterbatch materials 1 to 6, which are prepared from the following raw materials in parts by weight.
TABLE 1
The master batch material 4 and the master batch material 1 have basically the same components and preparation methods, and are different only in that the raw material of the material 4 does not contain a nucleating agent.
The nucleating agent is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol, 2-dimethylidene bis (4, 6-tert-butyl phenol) phosphonate and derivatives thereof, and is mixed with one of diamide compounds, the preferable ratio of the dibenzylidene sorbitol, the di (p-methylbenzylidene) sorbitol, the 2, 2-dimethylidene bis (4, 6-tert-butyl phenol) phosphonate and the derivatives thereof is (2-5: 1), and the structural formula of N, N' -di (phenyl) glutaramide in the embodiment is as follows:
in other embodiments, the diamide compounds may also be selected from those of the formula: r1-NH-C(O)-R-C(O)-NH-R1The bisamide-based substances of (1).
The preparation method of the modified graphene/polybutylene composite master batch material comprises the following steps:
(1) preparing a modified graphene dispersion liquid:
adding a surface treatment agent into the mixed solvent, uniformly stirring, adding graphene powder, stirring at a high speed, and performing ultrasonic dispersion to obtain a modified graphene dispersion solution; wherein the mixed solvent is a mixed solvent of one or more of isopropanol, acetone, methanol and ethanol and water.
(2) Preparation of polybutene resin solution:
the solvent used by the polybutene resin solution is one or more of dimethylbenzene, methylbenzene and benzene, ultrasonic dispersion is carried out, the power is 100-500W, the time is 2-3 h, the final polybutene solution is obtained, and then continuous stirring is carried out, and the temperature is controlled below 38 ℃.
(3) Preparation of modified graphene/polybutylene composite master batch material
Adding an antioxidant, a nucleating agent and a dispersing agent into the polybutene resin solution, mixing, and performing ultrasonic dispersion to obtain a blend; and adding the modified graphene dispersion liquid, and precipitating to obtain the modified graphene/polybutylene composite master batch material. The polybutylene resin is a pipe grade polybutylene resin, and can be natural color granules, colored granules or powder, the molecular weight range of the polybutylene resin is 40-60 ten thousand, and the melt mass flow rate is 0.5-0.6 g/min. At a suitable rate of flow of the solution,
the surface treatment agent, the mixed solvent, the amount ratio (mass ratio) of the surface treatment agent to the graphene, and the relevant process parameters are shown in table 2.
TABLE 2
Of these, the composition and the preparation method of the material 5 and the material 1 are substantially the same, except that the solution flow rate of the polybutene resin in the material 5 is 0.3 g/min. The optional range of the dosage ratio of the surface treating agent to the mixed solvent to the graphene is (0.1-1): (100-10000): 10 in the above embodiment, preferably (0.5 to 1): (500-1000): 10.
examples 2 to 4, comparative examples 1 to 3
The embodiment provides an application of the 6 modified graphene/polybutylene composite masterbatch materials described in embodiment 1 in polybutylene tubing.
The modified graphene/polybutylene composite master batch materials described in examples 2-4 and comparative examples 1-3 and the pipe grade polybutylene resin are uniformly stirred and then added into a plastic pipe extruder to prepare the polybutylene composite pipe. The specific compositions of examples 2-4 and comparative examples 1-3 are shown in Table 3:
TABLE 3 polybutylene composite pipe compositions
| Modified graphene/polybutylene composite master batch material | Pipe grade polybutylene resin | |
| Example 2 | 1 to 5 portions of master batch material | 100 parts by weight |
| Example 3 | 2 to 1 weight portion of master batch material | 100 parts by weight |
| Example 4 | Master batch material 3-100 weight portions | 100 parts by weight |
| Comparative example 1 | 4 to 5 portions of master batch material | 100 parts by weight |
| Comparative example 2 | 5-5 parts of master batch material | 100 parts by weight |
The properties of the polybutene composite pipes described in preparation examples 2 to 4 and comparative examples 1 to 3 were measured according to the following criteria, and the results are shown in table 2.
The properties of the polybutene composite pipes of examples 4-6 and comparative example 1 were tested according to the GB/T1843-2008, GB/T1040.1-2006, GB/T3399-1982 and GB/T19466.6-2009 standards, and the results are shown in Table 4.
Table 4 performance test results of polybutene composite pipes of examples 4 to 6 and comparative example 1
As can be seen from the above table, in embodiments 2 to 4 of the present invention, the modified graphene/polybutylene composite masterbatch material is prepared by adding the modified graphene, the polybutylene resin and the nucleating agent, and the compatibility between the graphene and the polybutylene resin in the modified graphene/polybutylene composite masterbatch material is good and the dispersion is uniform due to the reasonable matching between the components and the reasonable selection of the solvent in the preparation process; the modified graphene/polybutylene composite master batch material is prepared by mixing graphene and a small amount of polybutylene resin, and then the composite master batch material is mixed with the polybutylene resin which is the main component of the pipe, so that the compatibility of the graphene and the polybutylene resin is further increased, the mixing is more uniform, and the finally prepared polybutylene composite pipe has good mechanical property and heat conductivity.
In comparative example 1, the modified graphene/polybutene composite master batch material does not contain a nucleating agent, lacks pi-pi conjugation formed between the nucleating agent and the modified graphene, and has low interfacial bonding force, thus resulting in low crystallinity and poor mechanical properties of polybutene. In comparative example 2, since the selection of the solution flow rate of polybutene resin is no longer within a reasonable range, the dispersion uniformity of graphene in polybutene resin is slightly poor, and the distribution is discontinuous, resulting in poor heat conductivity.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the modified graphene/polybutylene composite master batch material is characterized by comprising the following steps of:
the preparation process of the modified graphene/polybutylene composite master batch comprises the following steps:
adding the antioxidant, the nucleating agent and the dispersing agent into a polybutene resin solution, mixing, and performing ultrasonic dispersion to obtain a blend; adding the modified graphene dispersion liquid, and precipitating to obtain a modified graphene/polybutylene composite master batch material;
the modified graphene dispersion liquid is prepared by dispersing a surface treatment agent and graphene in a mixed solvent, stirring at a high speed and then ultrasonically dispersing, wherein the nucleating agent is one of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol, 2-dimethylidene bis (4, 6-di-tert-butylphenol) phosphonate and one of diamide compounds;
the mixed solvent is a mixed solvent of one or more of isopropanol, acetone, methanol and ethanol and water;
the solvent of the polybutene resin solution is one or more of xylene, toluene and benzene.
2. The preparation method of the modified graphene/polybutene composite masterbatch material according to claim 1, wherein the polybutene resin has a molecular weight of 40-60 ten thousand and a melt mass flow rate of 0.5-0.6 g/min.
3. The preparation method of the modified graphene/polybutylene composite masterbatch material according to claim 1, wherein the mass ratio of the modified graphene to the polybutylene resin is (0.1-20): 100.
4. the preparation method of the modified graphene/polybutene composite masterbatch material according to claim 1, wherein the dispersant is selected from the group consisting of: paraffin wax, polyethylene glycol and fatty acid.
5. The preparation method of the modified graphene/polybutylene composite masterbatch material according to claim 1, wherein the surface treatment agent is one or two of a silane coupling agent, a titanate coupling agent, octadecylamine and isocyanate.
6. The preparation method of the modified graphene/polybutylene composite masterbatch material according to claim 5, wherein the mass ratio of the silane-based coupling agent to the graphene is (9-12): 100, respectively; or
The mass ratio of the titanate coupling agent to the graphene is (0.1-0.3): 100; or
The mass ratio of the total amount of the octadecylamine and the isocyanate to the graphene is (0.8-1.2): 100.
7. The preparation method of the modified graphene/polybutylene composite masterbatch material according to claim 1, wherein the antioxidant is 1010 and/or 168.
8. The preparation method of the modified graphene/polybutene composite masterbatch material according to claim 7, wherein the ratio of the antioxidant 168 to the antioxidant 1010 is 2: (0.8 to 1).
9. The preparation method of the modified graphene/polybutene composite masterbatch material according to any one of claims 1 to 8, wherein the ultrasonic dispersion power is 100-500W, and the time is 2-3 h.
10. A polybutene pipe characterized by that, the raw material of the polybutene pipe comprises the modified graphene/polybutene composite masterbatch material prepared by the method of any one of claims 1 to 9 and pipe grade polybutene resin.
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| CN111205568A (en) * | 2020-02-28 | 2020-05-29 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Oxygen-blocking polybutylene tubing containing uniformly-dispersed graphene and preparation method thereof |
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| CN103627094A (en) * | 2013-10-31 | 2014-03-12 | 青岛科技大学 | Graphene/isotactic polybutylene-1 composite material and preparation method thereof |
| CN105504552A (en) * | 2016-02-03 | 2016-04-20 | 山东东方宏业化工有限公司 | Polybutylene material for pipes and preparation method of polybutylene material |
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| CN105504552A (en) * | 2016-02-03 | 2016-04-20 | 山东东方宏业化工有限公司 | Polybutylene material for pipes and preparation method of polybutylene material |
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