CN1147529C - Formula and production process of filling modified reinformed PE/PP/PS composite material - Google Patents
Formula and production process of filling modified reinformed PE/PP/PS composite materialInfo
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- CN1147529C CN1147529C CNB001266004A CN00126600A CN1147529C CN 1147529 C CN1147529 C CN 1147529C CN B001266004 A CNB001266004 A CN B001266004A CN 00126600 A CN00126600 A CN 00126600A CN 1147529 C CN1147529 C CN 1147529C
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- mica
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Abstract
The present invention discloses a formula and a production process of a filling modification reinforced PE/PP/PS composite material. The filling modification reinforced PE/PP/PS composite material is prepared by that mica, asbest and calcium carbonate are used as filling materials, and polyethylene, polypropylene and polystyrene are used as basal body resin; firstly, the three filling materials are modified; secondly, the modified filling materials, the basal body resin, a compatilizer, a toughening agent, a dispersing agent, a lubricating agent and a stabilizing agent are blended in a building block type equidirectional double-screw extruder. The present invention can be used for solving the problems of the recovery, the regeneration and the use of two main waste and old plastic sources PO and PS in addition, to have the composite performance beneficial conditions of the PO(PE and PP) and the PS, i.e. high hardness, high rigidity and moderate toughness. The filling modification reinforced PE/PP/PS composite material can be widely used for replacing engineering plastics, such as ABS, etc. and used as thermoplastic molding raw materials of profiled bars, such as vehicles, materials of casing bodies of electric appliances and industrial components, etc.
Description
Technical field
The present invention relates to a kind of prescription and production technique thereof of many components filled modified thermoplastic matrix material.
Background technology
Up to now, filling-modified enhancing thermoplastic composite great majority are the resin of one or both and single kind of fibrous, sheet, spherical three kinds of geometrical shape fillers or multiple consistency resin matrix to be carried out blending form.And it is the filler of three kinds of geometrical shapies is shared and do not see as yet with the filling-modified enhancing plasticity-matrix material that two kinds of incompatible resin matrixes carry out blend.
The adding of filler may bring desirable variation to the original mechanical property of matrix resin, also undesirable influence can occur simultaneously.Filling-modified enhancing thermoplastic composite uses as structured material, just must satisfy the requirement to certain intensity and certain two aspects of toughness.Generally speaking, the physics of filling-modified enhancing thermoplastic composite and mechanical property, inflexible targets such as hardness, Young's modulus, tensile strength and flexural strength can increase with the increase of the adding umber of filler, and with the aspect ratio of the geometrical shape of filler be directly proportional be fibrous raising maximum, secondly be sheet, less be spherical.And shock strength, elongation at break, toughness indexs such as solution flow index can descend with the increase of the umber of the adding of filler, especially single geometrical shape and single resin or multiple consistency resin high fill under the enhanced situation the most serious.
Summary of the invention
The objective of the invention is shortcoming and defect part, a kind of prescription and production technique thereof of filling-modified enhancing PE/PP/PS matrix material is provided at above-mentioned filling-modified enhancing thermoplastic composite.
Purpose of the present invention mainly shows following four aspects:
(1) on packing geometric shape coupling, adopts the filler height of fibrous, sheet, spherical three kinds of geometrical shapies to pile up the novel filling of coupling and strengthen mode, can realize that the height of filler is filled.
(2) on filler modified, adopt the fluorochemical on the present invention peculiar fibrous magnesium silicate surface and sheet mica surface to handle the new modified treatment process of its specific surface of increase, but the mechanical engagement effect of reinforcement filler and resin.
(3) (on the inconsistent problem of polyethylene (PE), polypropylene (PP) and PS resin (polystyrene), adopt the styrene/ethylene-butylene/styrene block copolymer (SEBS) and chlorinatedpolyethylene (CPE) synergistic effect that have appearance agent and toughner concurrently to solve at polyolefine (PO) resinoid.
(4) on strengthening, toughness of material adopts toughner terpolymer EP rubber (EPDM) and have compatilizer concurrently and the styrene/ethylene of toughner-butylene/styrene block copolymer chlorinatedpolyethylene (CPE) effect realizes.
To achieve these goals, technical solution of the present invention is:
At first mica, asbestos, three kinds of fillers of lime carbonate are carried out modification and handle, it specifically changes method and is respectively:
(1) micaceous modification
Grinding made the mica powder granularity reach 400-1250 order (radius-thickness ratio 60-120) in 1-5 hour to mica in high speed dry mixing mill by following mica modified formula, formed modified micaceous powder by the mechanics of machinery modification.
The mica modified formula:
Mica powder (100-300 order) 90-98%
Potassium hydrogen fluoride 0.5-5%
The cured 0.5-3.5% of brown coal
Aluminate coupling agent 0.5-1.5%
(2) modification of asbestos
By chrysotile staple fibre 30-50%, contain the prescription of the mixed aqueous solution 50-70% of 0.1-1.0%HCL+0.01-0.5%HF, in stirring immersion machine, stir and soak pre-treatment 30-60min through the extremely neutrality of after washing of dewatering, the sulfonyl azide silane coupling agent that adds the 0.5-1.5% that accounts for asbestos weight then, add water to and the same volume of above-mentioned formula solution, stir immersion and forming modified asbestos through dehydrating after 24-48 hour.
(3) modification of lime carbonate
In high speed dry mixing mill, grind modification 5-30min by following calcium carbonate modified prescription, form modified calcium carbonate by mechanical-chemical modification.
Calcium carbonate modified prescription
Precipitated chalk 95-99%
Montanic acid cerium 0.5-3.5%
Aluminic acid lipoprotein coupling agent 0.5-1.5%
Mica, asbestos, three kinds of filler and polyethylene (PE), polypropylene (PP), three kinds of matrix resins of polystyrene (PS) and compatilizer, toughner, dispersion agent, lubricant, stablizers through modification of lime carbonate are carried out the blend pelletizing and form in the cord wood parallel dual-screw extruding machine by following prescription then.
The prescription of filling-modified enhancing PE/PP/PS matrix material:
Modified micaceous powder (400-1250 order, radius-thickness ratio 60-120) 15-25%
Modified asbestos 5-10%
Modified calcium carbonate 10-20%
Polyethylene (PE) 15-25%
Polypropylene (PP) 10-20%
Polystyrene (PS) 10-15%
Have styrene/ethylene-butylene/styrene block copolymer (SEBS) 1-5% of compatilizer and toughner concurrently
Have chlorinatedpolyethylene (CPE) 5-10% of compatilizer and toughner concurrently
Toughner terpolymer EP rubber (EPDM) 5-10%
Dispersion agent 0.5-1.6%
Lubricant 0.5-1.8%
Stablizer 0.1-0.5%
A kind of filling-modified enhancing PE/PP/PS matrix material, mica also can be magnesium mica or rubellan or biotite or sericite; Asbestos also can be glass fibre or processing silicate mineral fiber; Lime carbonate also can be talcum powder or wollastonite; Polyethylene, polypropylene, polystyrene also can be respectively various waste or used plastics source polyethylene, polypropylene, polystyrene.
The filling-modified enhancing PE/PP/PS matrix material that the present invention produced, except that the composite performance advantage with polyolefine (PO) (polyethylene (PE), polypropylene (PP)) and polystyrene (PS) is high rigidity, high rigidity and the moderate toughness, its another importance is that it can be used for solving the waste or used plastics source PO of two maximums and the reclaiming of PS utilizes problem, extensively model is used for substituting engineering plastics such as ABS, as the thermoplastic shaping raw material of profiled materials such as vehicle housing, casing for electric appliances, industrial part.Advantages such as its forming process product has the hardness height, rigidity is strong, toughness is moderate, production cost is low, fire-retardant and ageing-resistant.
Embodiment
Embodiment:
Filling-modified enhancing PE/PP/PS matrix material
At first carry out the modification of mica, asbestos, three kinds of fillers of lime carbonate and handle, its concrete modification processing method is respectively:
(1) micaceous modification
Grinding made the mica powder granularity reach 400-1250 order (radius-thickness ratio 60-120) in 1-5 hour to mica in high speed dry mixing mill by following mica modified formula, formed modified micaceous powder by the mechanics of machinery modification.
The mica modified formula:
White mica powder (200 order) 95%
Potassium hydrogen fluoride 1%
Cured (saponification value 50%) 3% of brown coal
Aluminate coupling agent (DL-411-A) 1%
(2) modification of asbestos
Stir in stirring immersion machine by chrysotile staple fibre (0.5-1.0mm) 50%, the prescription that contains the mixed aqueous solution 50% of 0.5%HCL+0.1%HF and to soak pre-treatment 60min, extremely neutral through the dehydration after washing, add the 1.5% sulfonyl azide silane coupling agent that accounts for asbestos weight then, add water to the same volume of above-mentioned formula solution, stir and soak after 24 hours, form modified asbestos through dehydrating again.
(3) modification of lime carbonate
In high speed dry mixing mill, grind modification 15min by following calcium carbonate modified prescription, form modified calcium carbonate by mechanical-chemical modification.
Calcium carbonate modified prescription:
Precipitated chalk (0.05-2.5 μ m) 95%
Montanic acid cerium (containing cerium 4.5) 4%
Aluminic acid lipoprotein coupling agent (DL-411-A) 1%
Then by the blend prescription of following filling-modified enhancing PE/PP/PS matrix material in the cord wood parallel dual-screw extruding machine with three kinds on mica, asbestos, lime carbonate through the filler of modification and polyethylene, polypropylene, three kinds of basic resin of polystyrene, and compatilizer, toughner, dispersion agent, lubricant, stablizer carry out the blend pelletizing and form new filling-modified enhancing PE/PP/PS matrix material.
The blending technology parameter is: preheating mixing zone temperature 120-130 ℃, and 170-180 ℃ of synthetic district temperature, crystallization breeding blanket temperature 175-180 ℃; Blend time 2-5min, extrusion pressure 5-10MPa.
The blend prescription of filling-modified enhancing PE/PP/PS matrix material:
Modified micaceous powder (600 orders, radius-thickness ratio 60-120) 25%
Modified asbestos (0.5-1.0mm) 10%
Modified calcium carbonate (0.05-2.5 μ m) 20%
Polyethylene (HDPE) 15%
Polypropylene (IPP) 10%
Polystyrene (GPPS) 10%
Have styrene/ethylene-butylene/styrene block copolymer (SEBS, KG1650) 2% of compatilizer and toughner concurrently
Have the chlorinatedpolyethylene (CPE, chloride 35%) 4% of compatilizer and toughner concurrently
Toughner terpolymer EP rubber (EPDM-5015,1-15um) 2%
Dispersion agent (the montanic acid cerium contains cerium 4-6%) 0.8%
Lubricant (montanic acid glycol ester, saponification value 100-160%) 1.0%
Stablizer 0.2%
Claims (5)
1, a kind of filling-modified enhancing PE/PP/PS matrix material, it is characterized in that with mica, asbestos and lime carbonate be filler, respectively these three kinds of fillers being carried out modification handles, use the cord wood parallel dual-screw extruding machine will be then, and compatilizer, toughner, dispersion agent, lubricant, stablizer blend form through three kinds of fillers of mica, asbestos, lime carbonate and polyethylene (PE), polypropylene (PP) and three kinds of matrix resins of polystyrene (PS) of modification; The prescription of each component (by weight percentage following) is: modified micaceous powder 15-25%, modified asbestos 5-10%, modified calcium carbonate 10-20%, polyethylene (PE) 15-25%, polypropylene (PP) 10-20%, polystyrene (PS) 10-15%, have styrene/ethylene-butylene/styrene block copolymer (SEBS) 1-5% of compatilizer and toughner concurrently, have chlorinatedpolyethylene (CPE) 5-10% of compatilizer and toughner concurrently, toughner terpolymer EP rubber (EPDM) 5-10%, dispersion agent 0.5-1.6%, lubricant 0.5-1.8%, stablizer 0.1-0.5%.
2, according to the described a kind of filling-modified enhancing PE/PP/PS matrix material of claim 1, it is characterized in that mica also can be magnesium mica or rubellan or biotite or sericite; Asbestos also can be glass fibre or processing silicate mineral fiber; Lime carbonate also can be talcum powder or wollastonite; Polyethylene, polypropylene, polystyrene also can be respectively various waste or used plastics source polyethylene, polypropylene, polystyrene.
3, according to the described a kind of filling-modified enhancing PE/PP/PS matrix material of claim 1, it is characterized in that its polyethylene and polypropylene and polystyrene compatible be that synergistic effect by styrene/ethylene-butylene/styrene block copolymer that has compatilizer and toughner concurrently (SEBS) and chlorinatedpolyethylene (CPE) realizes.
4,, it is characterized in that its toughness strengthens and be by toughner terpolymer EP rubber (EPDM) and have compatilizer concurrently and the synergistic effect of styrene/ethylene-butylene/styrene block copolymer of toughner (SEBS) and chlorinatedpolyethylene (CPE) realizes according to the described a kind of filling-modified enhancing PE/PP/PS matrix material of claim 1.
5, a kind of production technique of filling-modified enhancing PE/PP/PS matrix material, it is characterized in that with mica, asbestos and lime carbonate be filler, respectively these three kinds of fillers being carried out modification handles, use the cord wood parallel dual-screw extruding machine will be then, and compatilizer, toughner, dispersion agent, lubricant, stablizer blend form through three kinds of fillers of mica, asbestos, lime carbonate and polyethylene (PE), polypropylene (PP) and three kinds of matrix resins of polystyrene (PS) of modification; Wherein the modification of mica, asbestos, three kinds of fillers of lime carbonate is handled and is respectively:
(1) the micaceous modification is handled by following mica modified formula and was ground 1-5 hour in high speed dry mixing mill, makes the mica powder granularity reach the 400-1250 order by mechanical-chemical modification, and radius-thickness ratio 60-120 forms modified micaceous powder;
Mica modified formula: 100-300 purpose mica powder 90-98%, potassium hydrogen fluoride, 0.5-5%, the cured 0.5-3.5% of brown coal, aluminate coupling agent 0.5-1.5%;
(2) modification of asbestos is handled by asbestos 30-50%, is contained the prescription of the mixed aqueous solution 50-70% of 0.1-1.0%HCL and 0.01-0.5%HF, in stirring immersion machine, stir and soak pre-treatment 30-60min, extremely neutral through the dehydration after washing, the silane coupling agent that adds the 0.5-1.5% that accounts for asbestos weight then, add water to and the same volume of the above-mentioned prescription aqueous solution, stir and soak after 24-48 hour, form modified asbestos through dehydrating again;
(3) modification of lime carbonate is handled by following calcium carbonate modified prescription and grind modification 5-30min in high speed dry mixing mill, forms modified calcium carbonate by mechanical-chemical modification;
Calcium carbonate modified prescription: precipitated chalk 95-99%, montanic acid cerium 0.5-3.5%, aluminate coupling agent 0.5-1.5%.
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CNB001266004A CN1147529C (en) | 2000-10-01 | 2000-10-01 | Formula and production process of filling modified reinformed PE/PP/PS composite material |
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CN101290818B (en) * | 2008-06-24 | 2010-06-16 | 四川川东电缆有限责任公司 | Combination of chlorinated polythylene insulating material and insulated cable |
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