CN110951149A - Preparation method of polyolefin-based composite material - Google Patents

Preparation method of polyolefin-based composite material Download PDF

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Publication number
CN110951149A
CN110951149A CN201911133557.1A CN201911133557A CN110951149A CN 110951149 A CN110951149 A CN 110951149A CN 201911133557 A CN201911133557 A CN 201911133557A CN 110951149 A CN110951149 A CN 110951149A
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liquid
polyolefin
composite material
based composite
preparing
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Inventor
张新庄
张书勤
闫鹏
窦倩
董昭
张铎
裴婷
刘志玲
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Shaanxi Yanchang Petroleum Group Co Ltd
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Shaanxi Yanchang Petroleum Group Co Ltd
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Abstract

The invention discloses a preparation method of a polyolefin-based composite material, which comprises the following steps: dissolving polyolefin in an excessive solvent at the temperature of 120-260 ℃ under the stirring state, adding a modifying material, stirring and mixing, transferring to a separator to separate solid and liquid, putting the separated solid into melting equipment, adding an additive, melting and preforming at the temperature of 110-260 ℃, and then processing and molding; wherein the solvent is at least one of liquid silane coupling agent, liquid titanate coupling agent, liquid aluminate coupling agent, liquid phthalate ester, liquid terephthalate ester, liquid trimellitate ester, liquid citric acid ester, salicylic acid, white oil, p-phenylenediamine, fatty acid and maleic anhydride. The composite material prepared by the method has more stable performance, and the volume resistivity, the thermal deformation temperature and the elongation at break are improved.

Description

Preparation method of polyolefin-based composite material
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a preparation method of a polyolefin-based composite material.
Background
Polyolefins are a generic name for a class of high molecular substances formed by single polymerization or copolymerization of one or more unsaturated olefin monomers as basic units, wherein Polyethylene (PE) and polypropylene (PP) are mainly used as representatives, and the polyolefins also include substances such as poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid (ester) copolymer, ethylene-octene copolymer, cyclic olefin copolymer, and the like. The production of polyolefin is closely related to the industries of petrochemical industry, coal chemical industry, fine chemical industry and the like, the application field of the polyolefin is very wide, and rich terminal products are provided for clothes, food, lives and rows of human beings. Polyolefin belongs to thermoplastic polymers, has good thermal forming performance, generally has excellent electrical insulation, chemical stability and biological safety, but has generally poor thermal stability, aging resistance, mechanical property, weather resistance and the like, so that the application of the polyolefin in specific fields is limited. Therefore, the high-end and functional deep processing of the existing common polyolefin capacity is urgently needed to widen the application market and improve the product yield.
At present, researchers mainly introduce some functional substances and fillers into a polyolefin matrix in a physical addition or chemical compounding mode to improve the comprehensive performance and the practicability of the polyolefin matrix in the aspects of electric conduction, mechanics, thermal stability, ageing resistance and the like, wherein additives/modified substances take carbon isomers as the main direction and comprise conventional graphite, carbon black, activated carbon and the like and modified substances thereof, and novel carbon materials (graphene, carbon nano tubes, carbon fibers and the like) and modified substances thereof. The unique properties of the additive/modifier can exactly compensate the inherent defects of the polyolefin and improve or strengthen the functionality of the polyolefin, for example, the higher elastic modulus can improve the mechanical properties (flexural modulus, impact strength, tensile strength, flexural strength, elongation at break and the like) of the polyolefin; the larger specific surface area can reduce the permeability of polyolefin to organic vapor and enhance the sealing property of the material; the excellent electrical property can eliminate the static accumulation of the polyolefin in the forming and application process, or can be made into conductive products and electrode materials for special purposes; the good light transmission and the obvious interface effect can delay the processes of oxidation, degradation, aging and the like of the polyolefin material in the use environment.
However, both polyolefin and additive/modifier are non-polar or non-polar materials, and if non-polar treatment is performed (polar group is introduced), the adhesion and compatibility of the polyolefin and the additive/modifier are generally poor, and uniform and functional combination is difficult to realize by directly mixing the polyolefin and the additive/modifier. At present, the preparation method of the polyolefin-based composite material mainly comprises the following steps: a solution blending method, a melt blending method, an in-situ polymerization method, an in-situ reduction method, a solvent volatilization method, a solid phase shearing and grinding method and the like, wherein the solution blending method and the melt blending method are two preparation methods of polyolefin-based composite materials which are related to the maximum in open literature. However, these methods have some drawbacks and disadvantages: 1) the solution blending method needs a large amount of organic solvents, such as o-dichlorobenzene, xylene and trichlorotoluene, is poor in environmental friendliness and difficult to realize large-scale production, and although part of the solvents can be recovered by separation, the residual solvents are not the components of the final composite material, so that the increased purification treatment is time-consuming and energy-consuming, and the cost is increased, and therefore, the method is more suitable for laboratory pilot study; 2) the additive/modifier and the filler are added into the polyolefin in a molten state to realize hot-state mixing, but the polyolefin in the molten state is not highly uniform and has a large molecular spacing solvent, so that the solid additive/modifier and the filler are difficult to uniformly disperse, and therefore, the homogenization degree of a final product is low, and a relatively dense region of the material exists in the composite material, so that the comprehensive performance of the composite material is seriously influenced; 3) in-situ polymerization, which needs to pre-modify polyolefin monomers (introduce functional groups), and then realizes polymerization of modified monomers into modified polyolefin products under a catalyst, wherein the process conditions are strict, the conversion rate is low, the products contain catalyst impurities, and single product functions need to introduce additives for secondary compounding; 4) the method mainly aims at the graphene modified polyolefin composite material, uses polar graphene oxide and polyolefin to pre-compound, and then reduces the graphene oxide in the composite material into graphene by using a reducing agent so as to realize in-situ reduction. However, the comprehensive properties of graphene and reduced graphene oxide are different, the pre-compounding of polar graphene oxide and non-polar polyolefin is difficult to realize uniform dispersion, and the later reduction does not help to improve the dispersion; 5) the solvent volatilization method is similar to the solution blending method, needs to use a large amount of organic solvent, but the solvent is mainly separated from the compound in a form of enhanced volatilization, has high energy consumption and time consumption, and still needs further purification treatment in the later stage of volatilization; 6) the solid phase shearing and grinding method includes the steps of firstly, smashing polyolefin and additives/modifiers in a physical shearing mode, adding fillers, and then, realizing mixing of all components by means of grinding, wherein different substances have no combination effect, only simple physical dispersion is realized, and no synergistic enhancement effect is realized, so that the prepared composite material is poor in uniformity and unstable in overall performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the polyolefin-based composite material, which selects the liquid additive as the solvent of the polyolefin, avoids subsequent purification treatment, and utilizes the polarity or compatibility of the solvent to ensure that the modified substance is dispersed more uniformly in the system, and the prepared composite material has more stable performance.
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving polyolefin in an excessive solvent at the temperature of 120-260 ℃ under the stirring state, adding a modifying material, stirring and mixing, transferring to a separator to separate solid and liquid, putting the separated solid into melting equipment, adding an additive, melting and preforming at the temperature of 110-260 ℃, and then processing and molding;
wherein the solvent is at least one of liquid silane coupling agent, liquid titanate coupling agent, liquid aluminate coupling agent, liquid phthalate ester, liquid terephthalate ester, liquid trimellitate ester, liquid citric acid ester, salicylic acid, white oil, p-phenylenediamine, fatty acid and maleic anhydride; when the solvent is a plurality of components, the proportion of the components is any proportion;
the modified material is at least one of graphene, carbon nano tubes, carbon fibers, graphite, activated carbon and carbon black; or at least one of a graphene chemical modifier, a carbon nanotube chemical modifier, a carbon fiber chemical modifier, a graphite chemical modifier, an active carbon chemical modifier and a carbon black chemical modifier; when the modified material is a plurality of components, the proportion of the components is any proportion;
the additive is at least one of calcium carbonate, an antioxidant, diethyl toluene diamine, paraffin, polyethylene wax, polypropylene wax, talcum powder, ammonium polyphosphate and pentaerythritol; when the additive is a plurality of components, the ratio of the components is any ratio.
The antioxidant is an antioxidant in the prior art.
Preferably, the polyolefin is at least one of homo-polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-octene copolymer, and cyclic olefin copolymer; when the polyolefin is a multi-component, the ratio between the components is arbitrary.
The ethylene-propylene copolymer, the ethylene-vinyl acetate copolymer, the ethylene-octene copolymer and the cycloolefin copolymer are all copolymers in the prior art.
Preferably, the mass ratio of the polyolefin to the modified material to the additive is (60-90): (5-30): (0-5).
Preferably, the stirring device used for stirring is any one of a paddle stirring device, a magnetic stirring device and a vibration stirring device.
Preferably, the separator is any one of an evaporation recovery device, a vacuum filtration device and a mechanical filter pressing device.
Preferably, the melting equipment is at least one of an internal mixer, an extruder, an open mill, a hot press and an injection molding machine.
Preferably, the processing and shaping is at least one of extrusion, hot pressing, injection molding, blow molding and cutting.
The excess solvent ensures that the polyolefin is dissolved in the solvent.
The invention has the advantages that:
according to the invention, the liquid additive is selected as the solvent of the polyolefin, so that the subsequent purification treatment is avoided, and the polarity or compatibility of the solvent is utilized, so that the modified substance is dispersed in the system more uniformly, the performance of the prepared composite material is more stable, and the volume resistivity, the thermal deformation temperature and the elongation at break are improved.
Detailed Description
Example 1
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of ethylene-vinyl acetate copolymer in 25 parts by weight of liquid silane coupling agent KH-550 at 120 ℃ by using a paddle stirrer, then adding 0.15 part by weight of carbon nano tubes, stirring and mixing, transferring to a vacuum filtering device to separate solid and liquid, putting the separated solid into an internal mixer, adding 0.06 part by weight of additive paraffin/calcium carbonate mixture, melting and preforming at 110 ℃, and then carrying out hot pressing; wherein the mass ratio of the paraffin to the calcium carbonate in the paraffin/calcium carbonate mixture is 2: 1.
Example 2
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of low-density polyethylene in 30 parts by weight of liquid titanate coupling agent NDZ-201 at 120 ℃ by using a magnetic stirrer, then adding 0.2 part by weight of graphene, stirring and mixing, transferring to an evaporation recovery device to separate solid and liquid, putting the separated solid into an extruder, adding 0.05 part by weight of additive polyethylene wax, melting and preforming at 130 ℃, and then carrying out injection molding.
Example 3
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of homopolymerized polypropylene in 35 parts by weight of liquid dioctyl phthalate by using a vibrating stirrer at 160 ℃, then adding 0.06 part by weight of graphite into the solution, stirring and mixing the solution, transferring the solution into a mechanical filter pressing device to separate solid and liquid, putting the separated solid into an open mill, adding 0.05 part by weight of a mixture of additive polyethylene wax/ammonium polyphosphate into the open mill, melting and preforming the mixture at 150 ℃, and then carrying out hot pressing and cutting; wherein the mass ratio of the polyethylene wax to the ammonium polyphosphate in the polyethylene wax/ammonium polyphosphate mixture is 4: 1.
Example 4
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of homopolymerized polypropylene in 40 parts by weight of liquid isopropyl terephthalate by a magnetic stirrer at 180 ℃, adding 0.056 part by weight of carbon black, stirring and mixing, transferring to an evaporation recovery device to separate solid and liquid, putting the separated solid into an internal mixer, adding 0.03 part by weight of additive polypropylene wax/antioxidant mixture, melting and preforming at 170 ℃, and then blowing; wherein the antioxidant is phosphite ester, and the mass ratio of the polypropylene wax to the antioxidant in the polypropylene wax/antioxidant mixture is 3: 1.
Example 5
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 weight part of ethylene-propylene copolymer in 45 weight parts of liquid aluminate coupling agent XY-AL81 by a paddle stirrer at 200 ℃, then adding 0.3 weight part of activated carbon, stirring and mixing, transferring to a mechanical filter pressing device to separate solid and liquid, putting the separated solid into a hot press, melting and preforming at 190 ℃, and then cutting.
Example 6
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of cycloolefin copolymer in 50 parts by weight of liquid mixture of p-phenylenediamine/triethyl citrate by using a vibrating stirrer at 220 ℃, then adding 0.2 part by weight of carbon fiber into the mixture, stirring and mixing the mixture, transferring the mixture into a vacuum filtering device to separate solid and liquid, sequentially putting the separated solid into an internal mixer and an extruder, adding 0.07 part by weight of mixture of additive calcium carbonate/pentaerythritol into the internal mixer, performing melt preforming at 210 ℃, and performing blow molding to obtain the polypropylene composite material; wherein the mass ratio of the p-phenylenediamine to the triethyl citrate in the liquid mixture of the p-phenylenediamine and the triethyl citrate is 1: 1; the mass ratio of calcium carbonate to pentaerythritol in the calcium carbonate/pentaerythritol mixture was 3: 4.
Example 7
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of poly (4-methyl-1-pentene) in 20 parts by weight of liquid titanate coupling agent NDZ-101 at 250 ℃ by using a magnetic stirrer, then adding 0.36 part by weight of graphene/carbon nanotube mixture into the solution, stirring and mixing the solution, transferring the mixture into a mechanical filter pressing device to separate solid and liquid, putting the separated solid into an injection molding machine, adding 0.04 part by weight of additive talcum powder into the injection molding machine, melting and preforming the mixture at 260 ℃, and then extruding the mixture; wherein the mass ratio of graphene to carbon nanotubes in the graphene/carbon nanotube mixture is 2: 1.
Example 8
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of poly-1-butene in 30 parts by weight of trioctyl trimellitate/white oil liquid mixture at 150 ℃ by using a paddle stirrer, adding 0.12 part by weight of graphene/carbon nanotube mixture into the mixture, stirring and mixing, transferring the mixture into an evaporation recovery device to separate solid and liquid, sequentially putting the separated solid into an open mill and an extruder, adding 0.06 part by weight of additive antioxidant/paraffin/ammonium polyphosphate mixture into the open mill, performing melt preforming at 140 ℃, and extruding; wherein the mass ratio of trioctyl trimellitate to white oil in the trioctyl trimellitate/white oil liquid mixture is 1: 3; the mass ratio of graphene to carbon nanotubes in the graphene/carbon nanotube mixture is 1: 1; the mass ratio of the antioxidant hindered phenol 1010 to the paraffin to the ammonium polyphosphate in the mixture of the antioxidant hindered phenol 1010/the paraffin/the ammonium polyphosphate is 1:2: 2.
Example 9
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of a mixture of low-density polyethylene/ethylene-octene copolymer in 40 parts by weight of a salicylic acid/octanoic acid/maleic anhydride liquid mixture at 140 ℃ by using a magnetic stirrer, adding 0.5 part by weight of a graphene/carbon fiber/graphite mixture, stirring and mixing, transferring to a vacuum filtering device to separate solid and liquid, putting the separated solid into an internal mixer, adding 0.08 part by weight of a mixture of additive polyethylene wax/polypropylene wax/calcium carbonate, performing melt preforming at 130 ℃, and then extruding, blow molding and cutting; wherein the mass ratio of the low-density polyethylene to the ethylene-octene copolymer in the mixture of the low-density polyethylene and the ethylene-octene copolymer is 1: 1; the mass ratio of the salicylic acid to the octanoic acid to the maleic anhydride in the salicylic acid/octanoic acid/maleic anhydride liquid mixture is 1:1: 1; the mass ratio of graphene to carbon fiber to graphite in the mixture of graphene/carbon fiber/graphite is 3:1: 1; the mass ratio of the polyethylene wax to the polypropylene wax to the calcium carbonate in the mixture of the polyethylene wax/the polypropylene wax/the calcium carbonate is 4:4: 1.
Example 10
A method for preparing a polyolefin-based composite material comprises the following steps: dissolving 1 part by weight of a mixture of high-density polyethylene/medium-density polyethylene/poly-1-butene in 50 parts by weight of a mixture of a liquid silane coupling agent KH-560/tributyl citrate/salicylic acid by using a magnetic stirrer at 160 ℃, adding 0.4 part by weight of a mixture of carbon fiber/activated carbon/graphene, stirring and mixing, transferring to a mechanical pressure filtration device to separate solid and liquid, putting the separated solid into an extruder, adding 0.08 part by weight of a mixture of an additive antioxidant/polyethylene wax/talcum powder, melting and performing at 150 ℃, and then performing injection molding, blow molding, hot pressing and cutting to obtain the composite material; wherein the mass ratio of the high-density polyethylene to the medium-density polyethylene to the poly-1-butene is 2:2: 1; the mass ratio of the liquid silane coupling agent KH-560 to the tributyl citrate to the salicylic acid in the mixture of the liquid silane coupling agent KH-560/the tributyl citrate/the salicylic acid is 5:3: 2; the mass ratio of carbon fibers to activated carbon to graphene in the carbon fiber/activated carbon/graphene mixture is 2:1: 2; the antioxidant is hindered phenol 1076, and the mass ratio of the antioxidant to the polyethylene wax to the talcum powder in the mixture of the antioxidant/the polyethylene wax/the talcum powder is 1:4: 1.
Performance detection
The decrease in volume resistivity, increase in heat distortion temperature and increase in elongation at break of each example relative to each comparative example are shown in Table 1, referring to comparative examples 1 to 10, in which only polyolefin is contained in each example.
TABLE 1 Properties of polyolefin-based composites
Figure DEST_PATH_IMAGE002
。

Claims (7)

1. A method for preparing a polyolefin-based composite material, which is characterized by comprising the following steps: the preparation method comprises the following steps: dissolving polyolefin in an excessive solvent at the temperature of 120-260 ℃ under the stirring state, adding a modifying material, stirring and mixing, transferring to a separator to separate solid and liquid, putting the separated solid into melting equipment, adding an additive, melting and preforming at the temperature of 110-260 ℃, and then processing and molding;
wherein the solvent is at least one of liquid silane coupling agent, liquid titanate coupling agent, liquid aluminate coupling agent, liquid phthalate ester, liquid terephthalate ester, liquid trimellitate ester, liquid citric acid ester, salicylic acid, white oil, p-phenylenediamine, fatty acid and maleic anhydride;
the modified material is at least one of graphene, carbon nano tubes, carbon fibers, graphite, activated carbon and carbon black;
the additive is at least one of calcium carbonate, an antioxidant, diethyl toluene diamine, paraffin, polyethylene wax, polypropylene wax, talcum powder, ammonium polyphosphate and pentaerythritol.
2. The method for preparing a polyolefin-based composite material according to claim 1, wherein: the polyolefin is at least one of homopolymerized polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-octene copolymer and cycloolefin copolymer.
3. The method for preparing a polyolefin-based composite material according to claim 1 or 2, wherein: the mass ratio of the polyolefin to the modified material to the additive is (60-90): (5-30): (0-5).
4. The method for preparing a polyolefin-based composite material according to claim 1 or 2, wherein: the stirring device used during stirring is any one of a paddle type stirring device, a magnetic type stirring device and a vibration type stirring device.
5. The method for preparing a polyolefin-based composite material according to claim 1 or 2, wherein: the separator is any one of an evaporation recovery device, a vacuum filtering device and a mechanical filter pressing device.
6. The method for preparing a polyolefin-based composite material according to claim 1 or 2, wherein: the melting equipment is at least one of an internal mixer, an extruder, an open mill, a hot press and an injection molding machine.
7. The method for preparing a polyolefin-based composite material according to claim 1 or 2, wherein: the processing and forming is at least one of extrusion, hot pressing, injection molding, blow molding and cutting.
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