CN102002181A - High-toughness and high-strength polyethylene composite material and preparation method thereof - Google Patents
High-toughness and high-strength polyethylene composite material and preparation method thereof Download PDFInfo
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- CN102002181A CN102002181A CN201010602235XA CN201010602235A CN102002181A CN 102002181 A CN102002181 A CN 102002181A CN 201010602235X A CN201010602235X A CN 201010602235XA CN 201010602235 A CN201010602235 A CN 201010602235A CN 102002181 A CN102002181 A CN 102002181A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polyethylene composite material and a preparation method thereof, in particular to a high-toughness and high-strength polyethylene composite material and a preparation method thereof. The high-toughness and high-strength polyethylene composite material comprises the following components in percentage by weight: 60-85 percent of polyethylene, 5-30 percent of phenolic resin, 0.4-3 percent of curing agent, 3-15 percent of compatilizer, 5-10 percent of toughener, 0.1-1 percent of antioxidant and 0.3-0.8 percent of lubricating agent. The phenolic resin is thermoplastic linear phenolic resin. The preparation method comprises the following steps of: (1) weighing up the polyethylene, the phenolic resin, the curing agent, the compatilizer, the toughener, the antioxidant and the lubricating agent according to the proportion, adding the mixture in a high-speed stirrer and stirring for 5 minutes; and (2) adding the prepared material in a double-screw extruder and extruding and peletting, wherein the material stays in the double-screw extruder for 2-3 minutes, the temperature of the screw is 150-200DEG C and the rotating speed of the screw is 300-400turns/minute. The invention has the characteristics of high strength, high heat resistance and high toughness and can replace the traditional engineering plastics.
Description
Technical field
The invention belongs to macromolecular material and forming process field thereof, relate to a kind of composite polyethylene material and preparation method thereof, a kind of specifically high-toughness high-strength composite polyethylene material and preparation method thereof.
Background technology
Polyethylene is by the resulting polymkeric substance of ethene direct polymerization, is chemical constitution and molecular structure is the simplest, turnout is maximum plastics variety.Because polyethylene has good resistance to low temperature (minimum use temperature can reach-70～-100 ℃), chemical stability is good, the erosion of the most of soda acids of ability (not anti-acid) with oxidizing property, be insoluble to common solvent under the normal temperature, water-absorbent is little, electrical insulation capability is good, and its output and consumption occupy first of the various synthetic resins, and its average growth rate per annum is up to 3%-5%.Polyethylene is exclusively used in the high-frequency insulation material at first, existing is used for also that the various films of extrusion moulding, hollow blow molding become various containers, the various section bars of extrusion molding and monofilament, are injection molded into various industrial goods and articles for daily use, extrusion moulding electric wire foreskin etc.The apparent consumption of calendar year 2001 China's polyethylene is 7189 kt, wherein the consumption of polyethylene resin dedicated (refering in particular to 8 kinds of products such as canopy film, high-strength thin-film, tubing, hollow container, composited aluminum and plastic decking, electric wire, coating material, EVA resin) is about 2600 kt, accounts for 36.2% of its aggregate consumption.
But because shortcoming such as the mechanical strength of PE is low, shrinking percentage is big has greatly limited it as structural material applications.Adopt fiber reinforcement can improve the mechanical property of PE material effectively, therefore in recent decades fiber reinforcement PE as the material of multi-usage, high-performance and economy, have a wide range of applications in fields such as automobile, communications and transportation and ocean industries, but the strongthener that uses mostly is staple fibre, and higher occasion can not meet the demands; Though and glassmat enhancing PE has the good mechanical performance, its method for processing forming has limited its Application Areas.Simultaneously, a problem of existence is, strongthener add the loss material inherent impact property to a great extent of joining, for this reason, in to the material enhancing modified, must improve the material impact performance simultaneously, could satisfy a lot of application scenarios.Yet the polyolefinic many methods of existing enhancing toughening modifying all exist decides shortcoming, as add the rubber elastomer particle in hard plastic, can increase substantially shock strength, but its tensile strength descends to some extent; Add fiber and can increase substantially tensile strength, but shock strength, particularly elongation at break usually descend to some extent; Adopt the compound enhancing of original position of liquid crystalline polymers polymer material section etc., the stretching of material and shock strength are all made moderate progress, but elongation at break still descends to some extent.
Summary of the invention
Technical problem to be solved by this invention is: at the shortcoming of above prior art existence, a kind of high-toughness high-strength composite polyethylene material and preparation method thereof is proposed, has high strength, high heat-resisting, the characteristics of high tenacity, alternative existing engineering plastics are widely used in fields such as automobile, electrical equipment.
The technical scheme that the present invention solves above technical problem is:
A kind of high-toughness high-strength composite polyethylene material, composed of the following components by weight percentage:
Polyethylene 60-85%, resol 5-30%, solidifying agent 0.4-3%, compatilizer 3-15%, toughner 5-10%, oxidation inhibitor 0.1-1%, lubricant 0.3-0.8%; Resol is thermoplastic novolac phenolic resin.
The use of thermoplastic novolac phenolic resin can be guaranteed in extrusion, and the abundant fusion and the uniform mixing of resin form inierpeneirating network structure with polyethylene simultaneously.
The high-toughness high-strength preparation method of polyethylene composite material, carry out according to the following steps:
⑴ prepare burden: polyethylene, resol, solidifying agent, compatilizer, toughner, oxidation inhibitor, lubricant are weighed to be placed in proportion mixes 5-10 minute in the homogenizer;
⑵ extrude: the material that will prepare joins extruding pelletization in the twin screw extruder, and the residence time of material in screw extrusion press is 2-3 minute, and extruder temperature is 150-200 ℃, and screw speed is 300-400 rev/min.
The technical scheme that the present invention further limits is:
Aforesaid high-toughness high-strength composite polyethylene material, polyethylene melting index are 2-20g/10min.
Aforesaid high-toughness high-strength composite polyethylene material, polyethylene is the mixture of linear low density polyethylene or high density polyethylene(HDPE) or linear low density polyethylene and high density polyethylene(HDPE), and the proportioning of the mixture of linear low density polyethylene and high density polyethylene(HDPE) is 3:7-7:3.
Aforesaid high-toughness high-strength composite polyethylene material, oxidation inhibitor are the composite antioxidant that phosphite ester kind antioxidant and Hinered phenols antioxidant are formed, and wherein phosphite ester kind antioxidant and Hinered phenols antioxidant are formed by weight 1:0.3-1:0.7.
Aforesaid high-toughness high-strength composite polyethylene material, solidifying agent are a kind of in hexamethylenetetramine, hexamethoxy methyl cyanuramide, Paraformaldehyde 96, many methylols cyanamid dimerization or the many methylol dicyandiamides.
Aforesaid high-toughness high-strength composite polyethylene material, compatilizer are toxilic acid stem grafting branch polyethylene, and its percentage of grafting is 0.5%-1%.
Aforesaid high-toughness high-strength composite polyethylene material, toughner are a kind of in octene-ethylene copolymer (POE), ethylene-propylene rubber(EPR) (EPR), the terpolymer EP rubber (EPDM), and the melting index of described toughner is 0.1-20 g/10min.
Aforesaid high-toughness high-strength composite polyethylene material, lubricant are hydro carbons lubricant or aliphatic amide series lubricant agent.
Advantage of the present invention is: resol has characteristics such as mechanical strength height, electrical insulation capability are good, fine heat-resisting performance, difficult combustion, and very big modification leeway is arranged, and is widely used in preparing glass reinforced plastic, moulding compound, coating, tackiness agent etc.To polyethylene alloyization, can improve the polyethylene over-all properties with resol, and have advantage cheaply.
The present invention adds novolac resin and solidifying agent in polyethylene melting mixing process, carry out melting and solidification, obtains a kind of polyethylene/phenolic resin composite with half interpenetrating network structure, high strength, high tenacity.Because the intensity of polyethylene own is relatively poor, thermotolerance is not high, and the resol after solidifying, because special crosslinking structure, have higher intensity and superior resistance toheat, in polyethylene, add resol and solidifying agent, under the effect of the polycthylene grafted maleic anhydride of compatilizer, both have half interpenetrating network structure at formation, and the matrix material with certain consistency, simultaneously, the adding of toughner has improved the impact property of material, make this matrix material combine the advantage of performance in many ways, have high strength, high heat-resisting, the characteristics of high tenacity, alternative existing engineering plastics are widely used in automobile, fields such as electrical equipment.
The present invention adopts polyethylene and resol in-situ solidifying, blend, promptly in mixing, resol generation crosslinking curing, polyethylene interts in resol network gap simultaneously, form inierpeneirating network structure, improved poly rigidity, thermotolerance, intensity, surface hardness greatly, can satisfy of the requirement of different field such as automobile material.Because what adopt is in-situ solidifying, material has distinctive half interpenetrating network structure, detains mutually between the different components and stings, and can improve the adhesiveproperties between polyethylene and the resol, gives full play to the advantage on both performances.
Embodiment
Embodiment one
A kind of high-toughness high-strength composite polyethylene material, (seeing Table 1) composed of the following components by weight percentage:
The high-toughness high-strength preparation method of polyethylene composite material, carry out according to the following steps:
⑴ prepare burden: polyethylene, resol, solidifying agent, compatilizer, toughner, oxidation inhibitor, lubricant are weighed to be placed in proportion mixes 5 minutes in the homogenizer;
⑵ extrude: the material that will prepare joins extruding pelletization in the twin screw extruder, and the residence time of material in screw extrusion press is 2 minutes, and extruder temperature is 150 ℃, and screw speed is 300 rev/mins.
Embodiment two
A kind of high-toughness high-strength composite polyethylene material, (seeing Table 2) composed of the following components by weight percentage:
The high-toughness high-strength preparation method of polyethylene composite material, carry out according to the following steps:
⑴ prepare burden: polyethylene, resol, solidifying agent, compatilizer, toughner, oxidation inhibitor, lubricant are weighed to be placed in proportion mixes 7 minutes in the homogenizer;
⑵ extrude: the material that will prepare joins extruding pelletization in the twin screw extruder, and the residence time of material in screw extrusion press is 3 minutes, and extruder temperature is 180 ℃, and screw speed is 350 rev/mins.
Embodiment three
A kind of high-toughness high-strength composite polyethylene material, (seeing Table 3) composed of the following components by weight percentage:
The high-toughness high-strength preparation method of polyethylene composite material, carry out according to the following steps:
⑴ prepare burden: polyethylene, resol, solidifying agent, compatilizer, toughner, oxidation inhibitor, lubricant are weighed to be placed in proportion mixes 10 minutes in the homogenizer;
⑵ extrude: the material that will prepare joins extruding pelletization in the twin screw extruder, and the residence time of material in screw extrusion press is 3 minutes, and extruder temperature is 200 ℃, and screw speed is 400 rev/mins.
Material among embodiment one, two and three is carried out performance test, and the result is as follows: see Table 4
Claims (9)
1. high-toughness high-strength composite polyethylene material is characterized in that: composed of the following components by weight percentage:
Polyethylene 60-85%
Resol 5-30%
Solidifying agent 0.4-3%
Compatilizer 3-15%
Toughner 5-10%
Oxidation inhibitor 0.1-1%
Lubricant 0.3-0.8%;
Described resol is thermoplastic novolac phenolic resin.
2. high-toughness high-strength composite polyethylene material as claimed in claim 1 is characterized in that: described polyethylene melting index is 2-20g/10min.
3. high-toughness high-strength composite polyethylene material as claimed in claim 2, it is characterized in that: described polyethylene is the composition of linear low density polyethylene or high density polyethylene(HDPE) or linear low density polyethylene and high density polyethylene(HDPE), and the proportioning of the composition of described linear low density polyethylene and high density polyethylene(HDPE) is 3:7-7:3.
4. high-toughness high-strength composite polyethylene material as claimed in claim 1, it is characterized in that: described oxidation inhibitor is the composite antioxidant that phosphite ester kind antioxidant and Hinered phenols antioxidant are formed, and wherein phosphite ester kind antioxidant and Hinered phenols antioxidant are formed by weight 1:0.3 ~ 1:0.7.
5. high-toughness high-strength composite polyethylene material as claimed in claim 1 is characterized in that: described solidifying agent is a kind of in hexamethylenetetramine, hexamethoxy methyl cyanuramide, Paraformaldehyde 96, many methylols cyanamid dimerization or the many methylol dicyandiamides.
6. high-toughness high-strength composite polyethylene material as claimed in claim 1 is characterized in that: described compatilizer is tasteless maleic anhydride grafted polyethylene, and its percentage of grafting is 0.5%-1%.
7. high-toughness high-strength composite polyethylene material as claimed in claim 1 is characterized in that: described toughner is a kind of in octene-ethylene copolymer, ethylene-propylene rubber(EPR), the terpolymer EP rubber, and the melting index of described toughner is 0.1-20 g/10min.
8. high-toughness high-strength composite polyethylene material as claimed in claim 1 is characterized in that: described lubricant is hydro carbons lubricant or aliphatic amide series lubricant agent.
9. the described high-toughness high-strength preparation method of polyethylene composite material of arbitrary claim among the claim 1-8 is characterized in that: carry out according to the following steps:
⑴ prepare burden: polyethylene, resol, solidifying agent, compatilizer, toughner, oxidation inhibitor, lubricant are weighed to be placed in proportion mixes 5-10 minute in the homogenizer;
⑵ extrude: the material that will prepare joins extruding pelletization in the twin screw extruder, and the residence time of material in screw extrusion press is 2-3 minute, and extruder temperature is 150-200 ℃, and screw speed is 300-400 rev/min.
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Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942764A (en) * | 2012-11-20 | 2013-02-27 | 开滦能源化工股份有限公司 | High-content fiber-reinforced polyoxymethylene composite material and preparation method thereof |
| CN103524838A (en) * | 2013-09-25 | 2014-01-22 | 吴江市天源塑胶有限公司 | Tube stock prepared from recycled plastics |
| CN103897239A (en) * | 2012-12-28 | 2014-07-02 | 江苏金波新材料科技有限公司 | Reclaimed high-density polyethylene modified material and preparation method thereof |
| CN104829922A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Silane-crosslinked polyethylene insulation composite material for vehicles and preparation method thereof |
| CN104829924A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Silane-crosslinked polyethylene insulation composite material used in ships and preparation method thereof |
| CN104829921A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Rice husk modified silane-crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104829923A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | High-weatherability silane-crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104829920A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Antibacterial insect-proof silane-crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104844902A (en) * | 2015-04-28 | 2015-08-19 | 蚌埠市正园电子科技有限公司 | High-strength anti-scraping silane crosslinked polyethylene insulation composite and preparation method thereof |
| CN104844903A (en) * | 2015-04-28 | 2015-08-19 | 蚌埠市正园电子科技有限公司 | Organosilane crosslinked polyethylene insulating composite material for mine and preparation method thereof |
| CN104861265A (en) * | 2015-04-28 | 2015-08-26 | 蚌埠市正园电子科技有限公司 | Peanut shell powder modified silane crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104877213A (en) * | 2015-04-28 | 2015-09-02 | 蚌埠市正园电子科技有限公司 | High-stability silane crosslinked polyethylene insulating composite material and preparation method thereof |
| CN104987567A (en) * | 2015-06-25 | 2015-10-21 | 合肥蓝科新材料有限公司 | Oil-resistance and high-temperature-resistance silane cross-linked polyethylene insulating composite material and preparation method thereof |
| CN104987571A (en) * | 2015-06-25 | 2015-10-21 | 合肥蓝科新材料有限公司 | Cold-resistant silane cross-linked polyethylene insulating composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942764A (en) * | 2012-11-20 | 2013-02-27 | 开滦能源化工股份有限公司 | High-content fiber-reinforced polyoxymethylene composite material and preparation method thereof |
| CN103897239A (en) * | 2012-12-28 | 2014-07-02 | 江苏金波新材料科技有限公司 | Reclaimed high-density polyethylene modified material and preparation method thereof |
| CN103524838A (en) * | 2013-09-25 | 2014-01-22 | 吴江市天源塑胶有限公司 | Tube stock prepared from recycled plastics |
| CN104829923A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | High-weatherability silane-crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104829924A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Silane-crosslinked polyethylene insulation composite material used in ships and preparation method thereof |
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| CN104829922A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Silane-crosslinked polyethylene insulation composite material for vehicles and preparation method thereof |
| CN104829920A (en) * | 2015-04-28 | 2015-08-12 | 蚌埠市正园电子科技有限公司 | Antibacterial insect-proof silane-crosslinked polyethylene insulation composite material and preparation method thereof |
| CN104844902A (en) * | 2015-04-28 | 2015-08-19 | 蚌埠市正园电子科技有限公司 | High-strength anti-scraping silane crosslinked polyethylene insulation composite and preparation method thereof |
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Application publication date: 20110406 |