CN100457816C - Prepn of composite polyethylene/glass material - Google Patents
Prepn of composite polyethylene/glass material Download PDFInfo
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- CN100457816C CN100457816C CNB2006100296932A CN200610029693A CN100457816C CN 100457816 C CN100457816 C CN 100457816C CN B2006100296932 A CNB2006100296932 A CN B2006100296932A CN 200610029693 A CN200610029693 A CN 200610029693A CN 100457816 C CN100457816 C CN 100457816C
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Abstract
The present invention is preparation process of composite polyethylene/glass material. The composite polyethylene/glass material is prepared through mixing polyethylene, polar polymer, high molecular reaction compatilizer and antioxidant in a high speed stirrer; mixing the mixture with glass fiber reactively at certain temperature and rotation speed, extruding and pelletizing in a double screw extruder. The composite polyethylene/glass material greatly improved interface compatibility between polymer and glass fiber, high strength, high toughness, high heat resistance and expanded application range.
Description
Technical field
The present invention relates to a kind of preparation method of polyethylene/glass fiber compound material, adopt twin screw extruder that polyethylene, polar polymer, high molecular weight reactive compatilizer, oxidation inhibitor and glass fibre are carried out reactive blending, obtain having high performance matrix material.The invention belongs to technical field of polymer processing.
Background technology
Polyethylene because have that water-tolerant, softness, low-temperature impact are good, resistance to chemical attack, cheap, be easy to excellent performance such as forming process, and used as general-purpose plastics, its demand is big, wide application.But its rigidity deficiency, poor heat resistance has limited it and has used widely.In order to improve the shortcoming of its rigidity deficiency and poor heat resistance, people consider as engineering plastics glass fibre modification, but because polyethylene is a non-polar polymer, the interface compatibility of it and glass fibre is poor, and the material property of simple adding glass fibre is not only improved, also descend to some extent, want to make glass fibre to play and strengthen poly effect, must solve glass fibre and poly interface problem.
In order to solve the problem of polyethylene and glass fibre interface compatibility difference, people have carried out some researchs, carry out the dynamic injection forming short glass fiber as people such as yellow kindheartedness and righteousness and strengthened high density polyethylene(HDPE) Mechanical Properties work (engineering plastics application, 2006,34 (1), 26), they have added polyethylene and polyethylene vinyl acetate ester mixture grafted maleic anhydride as compatilizer, mainly be on working method, promptly to adopt the Electromagnetic Dynamic injection moulding machine to improve the interface problem of polyethylene and short glass fiber, though the interface problem of polyethylene and glass fibre is had to a certain degree improvement, but it is still not ideal enough, so the gained performance is also bad, tensile strength is up to 36MPa, and shock strength also is no more than 3.6KJ/m
2, slightly improve than the tensile strength of pure high density polyethylene(HDPE), and shock strength also having apparent in view reduction, performance is far from reaching the effect of picture fiberglass reinforced engineering plastics.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of polyethylene/glass fiber compound material is provided, technology is simple, and the matrix material that obtains has high strength, high tenacity and good heat endurance, and then can enlarge the range of application of material.
For realizing such purpose, the present invention proposes to add the polar polymer that excellent compatibility is arranged with glass fibre in polyethylene/glass fiber compound material, adds the interface compatibility that the high molecular weight reactive compatilizer improves polyethylene and polar polymer or glass fibre simultaneously.The present invention is in common twin screw extruder, be added in the mixture of the polyethylene, polar polymer, high molecular weight reactive compatilizer and the oxidation inhibitor that mix on the homogenizer, under certain temperature and rotating speed, carry out reactively blending with glass fibre, extruding pelletization, the polyethylene for preparing/glass fibre high performance composite are compared with pure polyethylene, and toughness, intensity and thermotolerance all are significantly improved.
Method of the present invention is specially: by weight, feed composition is: polyethylene 40-85 part, polar polymer 1-15 part, high molecular weight reactive compatilizer 1-20 part, oxidation inhibitor 0.1-5 part, 10-40 part glass fibre.At first with polyethylene; polar polymer; the high molecular weight reactive compatilizer; oxidation inhibitor mixes on homogenizer; the rotating speed of homogenizer is 3000-10000 rev/min; then mixture being put into common twin screw extruder with glass fibre extrudes and makes pellet; extruder temperature is 80-280 ℃; rotating speed is 90-600 rev/min; the residence time of material in screw rod is 1-10 minute; after the material cooling of extruding; through the dicing machine pelletizing; obtain pellet; in vacuum drying oven 60-120 ℃ dry 10-35 hour, obtain polyethylene/glass fibre high performance composite.
Polyethylene of the present invention is new LDPE (film grade), linear low density polyethylene or high density polyethylene(HDPE), or the mixture of being made up of them.
Polar polymer of the present invention is that a class and glass fibre have better agglutinating polymkeric substance, be polymeric amide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, Synolac or urea-formaldehyde resin, or the mixture of forming by them.
High molecular weight reactive compatilizer of the present invention is that a class had not only had excellent compatibility but also with glass fibre or polar polymer agglutinating one class material in better interface arranged with polyethylene, be polythene-ethenol multipolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), maleic anhydride grafted ethene-vinyl acetate copolymer (EVA-g-MAH), maleic anhydride grafted polyethylene multipolymer (PE-g-MAH), polyethylene acrylic acid grafts (PE-g-AA), glycidyl methacrylate graft polyethylene and ethylene copolymers (PE-g-GMA), the silane grafted polyethylene multipolymer, maleic anhydride graft styrene-butadiene-styrene multipolymer (SBS-g-MAH), maleic anhydride graft acrylonitrile-butadiene-styrene copolymer (ABS-g-MAH), ethylene-acrylic acid copolymer (EAA) or ethylene-acrylate copolymer (EMA), or their mixture.
Oxidation inhibitor of the present invention can be Tyox B (anti-oxidant DLTP), triphenyl phosphite, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine (oxidation inhibitor 1098), 2,6-di-tert-butyl-4-methy phenol (antioxidant 264), 4,4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl) 2,2-propane (dihydroxyphenyl propane), get wherein two kinds of components or the mixture of two or more components.
Glass fibre of the present invention is long glass fibres or short glass fiber.
The inventive method is simple, and prepared polyethylene/glass fiber compound material has high strength, high tenacity and good heat endurance, compares performance with pure polyethylene and obviously improves, and has enlarged poly use range, and important Practical significance is arranged.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Testing method among the embodiment: tensile strength is pressed GB1040, and notched Izod impact strength is pressed GB1843, and heat-drawn wire is tested by GB1633.
Embodiment 1
Feed composition is by weight: 40 parts of high density polyethylene(HDPE)s, 15 parts of polyethylene terephthalates, 20 parts of ethylene-acrylic acid copolymers, antioxidant 1010 are that 2 parts, oxidation inhibitor 168 are 20 parts of 3 parts, long glass fibres.
Earlier with high density polyethylene(HDPE); polyethylene terephthalate; ethylene-acrylic acid copolymer; antioxidant 1010; oxidation inhibitor 168 mixes on homogenizer; the rotating speed of homogenizer is 5000 rev/mins; then mixture being put into twin screw extruder with long glass fibres extrudes and makes pellet; extruder temperature is 80/160/180/240/240/240 ℃; rotating speed is 120 rev/mins; the residence time of material in screw rod is 5 minutes; after the material cooling of extruding; through the dicing machine pelletizing; obtain pellet; 80 ℃ of dryings are 35 hours in vacuum drying oven, obtain high density polyethylene(HDPE)/glass fibre high performance composite.
Pure high density polyethylene(HDPE) and above-mentioned gained matrix material are carried out performance test, and the result who obtains is: the high density polyethylene(HDPE) tensile strength is 30MPa, and shock strength is 7.6KJ/m
2, heat-drawn wire is 82 ℃; High density polyethylene(HDPE)/glass fibre high performance composite tensile strength is 49MPa, and shock strength is 8.6KJ/m
2, heat-drawn wire is 123 ℃.
Embodiment 2
Feed composition is by weight: 60 parts of high density polyethylene(HDPE)s, polyamide 6 part, 3 parts of maleic anhydride grafted polyethylene multipolymers, oxidation inhibitor 1098 are 0.5 part; Antioxidant 264 is 30 parts of 0.5 parts, long glass fibres.
Earlier with high density polyethylene(HDPE); polymeric amide; the maleic anhydride grafted polyethylene multipolymer; oxidation inhibitor 1098; antioxidant 264 mixes on homogenizer; the rotating speed of homogenizer is 6000 rev/mins; then mixture being put into twin screw extruder with long glass fibres extrudes and makes pellet; extruder temperature is 150/200/240/280/280/280 ℃; rotating speed is 600 rev/mins; the residence time of material in screw rod is 1 minute; after the material cooling of extruding; through the dicing machine pelletizing; obtain pellet; 120 ℃ of dryings are 10 hours in vacuum drying oven, obtain high density polyethylene(HDPE)/glass fibre high performance composite.
Pure high density polyethylene(HDPE) and above-mentioned gained matrix material are carried out performance test, and the result who obtains is: the high density polyethylene(HDPE) tensile strength is 30MPa, and shock strength is 7.6KJ/m
2, heat-drawn wire is 82 ℃; High density polyethylene(HDPE)/glass fibre high performance composite tensile strength is 60MPa, and shock strength is 13KJ/m
2, heat-drawn wire is 131 ℃.
Embodiment 3
Feed composition is by weight: 1 part of 85 parts of high density polyethylene(HDPE), 1 part of urea-formaldehyde resin, glycidyl methacrylate graft polyethylene and ethylene copolymers (GMA-g-PE), 2,1 part of 6-di-tert-butyl-4-methy phenol (antioxidant 264), 4,4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl) 2,2 parts in 2-propane (dihydroxyphenyl propane), 10 parts of short glass fibers.
Earlier with high density polyethylene(HDPE); urea-formaldehyde resin; glycidyl methacrylate graft polyethylene and ethylene copolymers (GMA-g-PE); 2; 6-di-tert-butyl-4-methy phenol (antioxidant 264); 4; 4 '-(β; β '-dihydroxyl dipropyl oxygen phenyl) 2; 2-propane (dihydroxyphenyl propane) mixes on homogenizer; the rotating speed of homogenizer is 8000 rev/mins; then mixture being put into twin screw extruder with short glass fiber extrudes and makes pellet; extruder temperature is 80/120/160/180/180/180 ℃; rotating speed is 180 rev/mins; the residence time of material in screw rod is 3 minutes; after the material cooling of extruding,, obtain pellet through the dicing machine pelletizing; 60 ℃ of dryings are 20 hours in vacuum drying oven, obtain high density polyethylene(HDPE)/glass fibre high performance composite.
Pure high density polyethylene(HDPE) and above-mentioned gained matrix material are carried out performance test, and the result who obtains is: the high density polyethylene(HDPE) tensile strength is 30MPa, and shock strength is 7.6KJ/m
2, heat-drawn wire is 82 ℃; High density polyethylene(HDPE)/glass fibre high performance composite tensile strength is 42MPa, and shock strength is 8.3KJ/m
2, heat-drawn wire is 93 ℃.
Embodiment 4
Feed composition is by weight: 50 parts of new LDPE (film grade)s, 5 parts of polycarbonate, 8 parts of urea-formaldehyde resins, 5 parts of maleic anhydride graft styrene-butadiene-styrene multipolymers,, N, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine (oxidation inhibitor 1098) is 0.8 part; Tyox B (anti-oxidant DLTP) is 30 parts of 1.2 parts, long glass fibres
Earlier with new LDPE (film grade); polycarbonate; urea-formaldehyde resin; maleic anhydride graft styrene-butadiene-styrene multipolymer; oxidation inhibitor 1098; anti-oxidant DLTP mixes on homogenizer; the rotating speed of homogenizer is 3000 rev/mins; then mixture being put into twin screw extruder with long glass fibres extrudes and makes pellet; extruder temperature is 150/220/270/270/270/270 ℃; rotating speed is 240 rev/mins; the residence time of material in screw rod is 2 minutes; after the material cooling of extruding; through the dicing machine pelletizing; obtain pellet; 60 ℃ of dryings are 20 hours in vacuum drying oven, obtain new LDPE (film grade)/glass fibre high performance composite.
Pure new LDPE (film grade) and above-mentioned gained matrix material are carried out performance test, and the result who obtains is: the new LDPE (film grade) tensile strength is 21MPa, and shock strength is 6.8KJ/m
2, heat-drawn wire is 50 ℃; New LDPE (film grade)/glass fibre high performance composite tensile strength is 42MPa, and shock strength is 9.8KJ/m
2, heat-drawn wire is 87 ℃.
Embodiment 5
Feed composition is by weight: 75 parts of linear low density polyethylenes, 3 parts of polybutylene terephthalates, 6 parts of polythene-ethenol multipolymers; 5 parts of polyethylene acrylic acid graftss, four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) are that 0.4 part, Tyox B (anti-oxidant DLTP) are 10 parts of 0.6 parts, long glass fibres.
Earlier with linear low density polyethylene; polybutylene terephthalate; the polythene-ethenol multipolymer; the polyethylene acrylic acid grafts; four [β-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010); Tyox B (anti-oxidant DLTP) mixes on homogenizer; the rotating speed of homogenizer is 10000 rev/mins; then mixture being put into twin screw extruder with long glass fibres extrudes and makes pellet; extruder temperature is 180/220/250/250/250/250 ℃; rotating speed is 90 rev/mins; the residence time of material in screw rod is 10 minutes; after the material cooling of extruding; through the dicing machine pelletizing; obtain pellet; 80 ℃ of dryings are 24 hours in vacuum drying oven, obtain linear low density polyethylene/glass fibre high performance composite.
Pure linear low density polyethylene and above-mentioned gained matrix material are carried out performance test, and the result who obtains is: the linear low density polyethylene tensile strength is 26MPa, and shock strength is 8.1KJ/m
2, heat-drawn wire is 70 ℃; New LDPE (film grade)/glass fibre high performance composite tensile strength is 37MPa, and shock strength is 10.1KJ/m
2, heat-drawn wire is 85 ℃.
From the result of embodiment as can be seen, what the present invention obtained polyethylene/glass fiber compound material has a good comprehensive performance, toughness obviously is better than the poly performance of identical base-material with intensity etc., and thermotolerance also is significantly improved, prepared the polyethylene/glass fiber compound material of excellent performance, wide application and industrial prospect have been arranged.
Claims (4)
1, a kind of preparation method of polyethylene/glass fiber compound material is characterized in that: feed composition is by weight: polyethylene 40-85 part, polar polymer 1-15 part, high molecular weight reactive compatilizer 1-20 part, oxidation inhibitor 0.1-5 part, 10-40 part glass fibre; At first with polyethylene, polar polymer, the high molecular weight reactive compatilizer, oxidation inhibitor mixes on homogenizer, the rotating speed of homogenizer is 3000-10000 rev/min, then mixture being put into twin screw extruder with glass fibre extrudes and makes pellet, extruder temperature is 80-280 ℃, rotating speed is 90-600 rev/min, the residence time of material in screw rod is 1-10 minute, after the material cooling of extruding, through the dicing machine pelletizing, obtain pellet, in vacuum drying oven 60-120 ℃ dry 10-35 hour, obtain polyethylene/glass fibre high performance composite; Wherein, described polar polymer is polymeric amide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, Synolac or urea-formaldehyde resin, or the mixture of being made up of them; Described high molecular weight reactive compatilizer is polythene-ethenol multipolymer, ethylene-vinyl acetate copolymer, maleic anhydride grafted ethene-vinyl acetate copolymer, maleic anhydride grafted polyethylene multipolymer, polyethylene acrylic acid grafts, glycidyl methacrylate graft polyethylene and ethylene copolymers, silane grafted polyethylene multipolymer, maleic anhydride graft styrene-butadiene-styrene multipolymer, maleic anhydride graft acrylonitrile-butadiene-styrene copolymer, ethylene-acrylic acid copolymer or ethylene-acrylate copolymer, or their mixture.
2, according to the preparation method of the polyethylene/glass fiber compound material of claim 1, it is characterized in that described polyethylene is new LDPE (film grade), linear low density polyethylene or high density polyethylene(HDPE), or the mixture of forming by them.
3, preparation method according to the polyethylene/glass fiber compound material of claim 1, it is characterized in that described oxidation inhibitor is Tyox B, triphenyl phosphite, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 2, the 6-di-tert-butyl-4-methy phenol, 4,4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl) 2,2-propane is got the wherein mixture of two or more component.
4, according to the preparation method of the polyethylene/glass fiber compound material of claim 1, it is characterized in that described glass fibre is long glass fibres or short glass fiber.
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| CNB2006100296932A CN100457816C (en) | 2006-08-03 | 2006-08-03 | Prepn of composite polyethylene/glass material |
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| CNB2006100296932A CN100457816C (en) | 2006-08-03 | 2006-08-03 | Prepn of composite polyethylene/glass material |
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| CN100457816C true CN100457816C (en) | 2009-02-04 |
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