CN101914240A - Regenerated wire drawing modified material of waste polypropylene woven bags and preparation method thereof - Google Patents
Regenerated wire drawing modified material of waste polypropylene woven bags and preparation method thereof Download PDFInfo
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Abstract
The invention provides a regenerated wire drawing modified material of waste polypropylene woven bags, comprising the following components in percentage by weight: 1-35 percent of polyolefin fresh material, 25-95 percent of waste polypropylene material, 1-55 percent of enhanced modifier, 1-30 percent of toughening modifier, 0.01-5 percent of activator, 0.1-3 percent of antioxidant, 0.01-6 percent of lubricant and 0.01-6 percent of dispersing agent. The invention also provides a preparation method of the regenerated wire drawing modified material of the waste polypropylene woven bags. In the preparation method, based on the arecovery treatment on the waste polypropylene woven bags, the new wire drawing modified material of woven bags are produced by adding proper amount of other raw materials and auxiliary materials and can be directly used for producing polyolefine flat fibers with stable performance. The performance of a new polypropylene woven tape produced from the prepared material and a small quantity of fresh material is equivalent to a woven bag wholly produced by carrying out granulation and wire drawing on the fresh material. The new polypropylene woven tape can completely satisfy the use performance requirements, dramatically lower the product production cost and provide a proper way for waste recycling utilization and environmental pollution reduction.
Description
Technical field
The invention belongs to the chemical industry environmental protection technical field, relate to polyolefins braiding material enhancing modified technology, be specifically related to a kind of regenerated wire drawing modified material of waste polypropylene woven bags and preparation method thereof.
Background technology
Nearly 3,000,000 tons of the waste woven bag in China every year is with the same white pollution that is called as of agricultural film of very difficult natural degradation.And waste woven bag regenerated wire drawing material factory is for the recycling of waste woven bag at present, and basic is to adopt simple the cleaning, shreds again, melt extrudes granulation through the spiral heating forcing machine under band regimen condition, there is no to carry out any modification processing.This method one the has been loss original auxiliary agent of part in the waste polypropylene woven bags, because the type of heating of band water can make the further aging and charing of plastics, the reclaimed materials that adds in the woven bag is through repeatedly processing in addition, reasons such as the oxidation of aging, the physical environment of in use tensile deformation of woven bag, uviolizing, acidizing corrosion cause the braided material molecular weight to diminish, snappiness, physical strength, resistance to impact shock reduce greatly, melting index rises, and draw ratio also reduces greatly.The 2nd, handle and reclaim the also corresponding production cost that increased of waste and old material.Therefore the production of present domestic woven bag all is based on virgin material, and the waste and old braiding reworked material that dopes a small amount of no modification does not more accomplish fully rationally to utilize the waste woven bag resource to reduce cost.A small amount of patent and bibliographical information about the waste polypropylene woven bags recycling also arranged at present, and the waste polypropylene woven bags material of mentioning as patent application " the waste woven bag reclaimed materials is made moulded polypropylene (PP) tubing " (number of patent application 200510018315.X) lining that utilizes carries out the pressing mold tubing; Teng Jingchen is about " waste woven bag is produced the applied research of polypropylene regeneration masterbatch " article, be based on 300 purpose lime carbonate and strengthen the regenerated wire drawing material research report that material is the basis, what introduced is basic regenerated wire drawing material based on strengthen material with 300 purpose lime carbonate, (particle diameter≤(25～30um), practical significance is little 50um) to surpass flat filament thickness for its particle diameter.Though recycling waste woven bag, these technical information have certain reference, do not utilize waste polypropylene woven bags material regeneration and granulation but be not based on, carry out wire drawing again and make the technology that new woven bag material is applied, therefore for recycling the waste woven bag regenerated wire drawing modified material, all little with the action value of the consumption that saves material, minimizing environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of regenerated wire drawing modified material of waste polypropylene woven bags and preparation method thereof, by recycling to waste polypropylene woven bags, add an amount of other raw material and subsidiary material, it is material modified to generate new loraided bag wiredrawing, has solved existing problem to existing in the waste polypropylene woven bags recycling technology.
A kind of regenerated wire drawing modified material of waste polypropylene woven bags provided by the present invention, by mass percentage, it consists of: polyolefine virgin material 1%～35%, waste and old polypropylene material 25%～95%, reinforced modifier 1%-55%, plasticized modifier 1%～30%, activator 0.01%～5%, oxidation inhibitor 0.1%～3%, lubricant 0.01%～6%, dispersion agent 0.01%～6%;
Wherein: described reinforced modifier is above mica powder or glass fibre of 800 orders, carbon fiber, fibrous magnesium silicate, talcum powder;
Described plasticized modifier is: thermoplastic elastomer, terpolymer EP rubber (EDPM), propylene and ethene semi-crystalline co-polymers (VISTAMAXX), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid formicester multipolymer (EMA), ethylene-acrylic acid fourth resin copolymer (EBA), Resins, epoxy, maleic anhydride graft second third elastomerics, the maleic anhydride graft vinyl acetate copolymer, maleic anhydride graft propylene-octene copolymer, maleic anhydride grafted ethene-vinylformic acid formicester multipolymer, maleic anhydride grafted ethene-Butyl acrylate multipolymer;
Described activator is: silane coupling agent, titanate coupling agent, aluminic acid lipoprotein coupling agent, maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is Polyphenols oxidation inhibitor phosphite kind antioxidant;
Described lubricant, dispersion agent are: Poly Propylene Wax, paraffin, stearic acid, calcium stearate.
Regenerated wire drawing modified material of waste polypropylene woven bags of the present invention, its feature also be,
Waste silk rim charge when described waste and old polypropylene material is waste polyolefine woven bag plastic waste material and production polyolefine wire drawing material, general melting index is in 1～11 scope.
Described reinforced modifier is sheet or acicular mica powder, glass fibre, carbon fiber, fibrous magnesium silicate, talcous one or more blended inorganic materials.
The present invention also provides the preparation method of this regenerated wire drawing modified material of waste polypropylene woven bags, and this method is carried out according to the following steps:
Step 1, the waste polypropylene woven bags material with 25%～95% are cleaned, shred, dry stand-by;
Step 2, the plasticized modifier with 0.1%～30%, 0.01%～5% activator, 0.01%～6% lubricant, 0.01%～6% dispersion agent, the homogenizer that input can heat up stir mediate after the activation treatment stand-by;
Step 3, stand-by material that step 1 and step 2 are handled well and 1%～55% activated inorganic powder reinforced modifier, 0.1%～3% oxidation inhibitor and 10%～35% polyolefine virgin material drop into stirrer and stir;
Step 4, the mixing back material that will stir drop into the heating of screw rod drawing wire machine, carry out wire drawing when temperature is heated to 180～220 ℃, produce woven bag finished product material.
Regenerated wire drawing modified material of waste polypropylene woven bags provided by the present invention, by recycling to waste polypropylene woven bags, add an amount of other raw material and subsidiary material again, it is material modified to generate new loraided bag wiredrawing, this material can be directly used in produces the polyolefins flat filament, reduced reclaimed materials each analog assistant of the easy loss of this link of granulation and reduce the performance probability once more again, reduced the generation of the dispersion associativity unfavorable condition of virgin material and old material and each analog assistant, the 3rd, reduced reclaimed materials granulation production cost per ton 300 yuan.Also improve simultaneously every performance index that waste woven bag is unfavorable for that wire drawing is reproduced, with recycle, minimizing white pollution, reduction oil loss and the enterprise's production cost purpose that reaches waste woven bag.
Material property of the present invention is stable, new polypropylene woven bag with the material produce of the present invention preparation, only need a spot of virgin material, and performance is suitable with the woven bag that all adopts virgin material granulation wire drawing to produce, can reach the requirement of product use properties fully, and significantly reduce the products production cost, provide the suitable approach that utilizes for refuse again.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
A kind of regenerated wire drawing modified material of waste polypropylene woven bags, by mass percentage, it consists of: polyolefine virgin material 1%～35%, waste and old polypropylene material 25%～95%, reinforced modifier 1%-55%, plasticized modifier 1%～30%, activator 0.01%～5%, oxidation inhibitor 0.1%～3%, lubricant 0.01%～6%, dispersion agent 0.01%～6%;
Wherein: described reinforced modifier is above mica powder or glass fibre of 800 orders, carbon fiber, fibrous magnesium silicate talcum powder;
Described plasticized modifier is: thermoplastic elastomer, terpolymer EP rubber (EDPM), propylene and ethene semi-crystalline co-polymers (VISTAMAXX), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid formicester multipolymer (EMA), ethylene-acrylic acid fourth resin copolymer (EBA), Resins, epoxy, maleic anhydride graft second third elastomerics, the maleic anhydride graft vinyl acetate copolymer, maleic anhydride graft propylene-octene copolymer, maleic anhydride grafted ethene-vinylformic acid formicester multipolymer, maleic anhydride grafted ethene-Butyl acrylate multipolymer;
Described activator is: silane coupling agent, titanate coupling agent, aluminic acid lipoprotein coupling agent, maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is Polyphenols oxidation inhibitor phosphite kind antioxidant;
Described lubricant, dispersion agent are: Poly Propylene Wax, paraffin, stearic acid, calcium stearate.
Waste silk rim charge when waste and old polypropylene material of the present invention is waste polyolefine woven bag plastic waste material and production polyolefine wire drawing material, general melting index is in 1～11 scope.
The sheet of reinforced modifier of the present invention or needle inorganic powder are meant the above mica powder of 800 orders, glass fibre, carbon fiber, fibrous magnesium silicate etc., and the consumption number is 1%-55% part.Usually reclaim in the polypropylene woven Bag Material and substantially all do plastic filler with calcium carbonate masterbatch, this calcium carbonate masterbatch is many with 400 orders (particle diameter≤38um) Paris white manufacturing.By GB or common flat filament thickness is 25～30um, and 400 order lime carbonate maximum particle diameters are 38um, greater than the thickness of flat filament, calcium carbonate particles is random bulk, can not be seized on both sides by the arms orientation between macromole, big to the mutual resistance of motion of macromole, it is outstanding to produce crystal defect, shrinking percentage is big, elongation is low, and drawing-off is not in place, and molecular orientation can cause tensile strength low inadequately, calcium carbonate particles is easily overflowed, and regenerated wire drawing also easily produces the flat filament broken end.In sum, therefore for addressing these problems, the present invention adopts the inorganic materials of reinforced modifier, and the sheet of this reinforced modifier or needle inorganic powder are meant that the above mica powder of 800 orders, glass fibre, carbon fiber, fibrous magnesium silicate etc. strengthen, and the consumption number is 1%-55% part.Control polyacrylic shrinking percentage key in the polyacrylic crystallization of control, the adding of inorganic powder increases viscosity of material, and creep properties descends.Because this class inorganic powder to the nucleogenesis mechanism of polyester, plays the effect that changes the polypropylene structure, prevents the formation of the big spherocrystal of polypropylene with this.Sheet or the shrinkage-void of needle inorganic powder own, thus the integral material molding shrinkage reduced; Because the sheet structure powder, surface area ratio lime carbonate is big, also has the orientation effect with the drawing-off direction, and potential energy drops to minimum, is stable therefore, does not have particle and overflows.The flat filament tensile strength can be brought up to 30～35MPa; Bright in color, well-pressed, pliable and tough, the hand feel and drape of flat filament; Anti-splitting; It is good to compile cloth technology; Thermotolerance first mate improves; It is strong to refuse ultraviolet function; Acid resistance is strong; Ageing resistance is strong.
Because waste polypropylene woven bags reclaimed materials molecular weight diminishes, snappiness is low, resistance to impact shock reduces greatly, and draw ratio is far below virgin material, so must add suitable plasticized modifier during regeneration and granulation.To toughness reinforcing various in style of polypropylene modification, its toughening mechanism difference, some also is not suitable on the polypropylene wiredrawing product toughness reinforcing, the plasticized modifier that the present invention adopts is: thermoplastic elastomer, terpolymer EP rubber (EDPM), propylene and ethene semi-crystalline co-polymers (VISTAMAXX), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid formicester multipolymer (EMA), ethylene-acrylic acid fourth resin copolymer (EBA), Resins, epoxy, maleic anhydride graft second third elastomerics, the maleic anhydride graft vinyl acetate copolymer, maleic anhydride graft propylene-octene copolymer, maleic anhydride grafted ethene-vinylformic acid formicester multipolymer, one or more of maleic anhydride grafted ethene-Butyl acrylate multipolymer mix, and add according to the demand difference to the woven bag performance.
The preparation method of regenerated wire drawing modified material of waste polypropylene woven bags of the present invention, this method is carried out according to the following steps:
Step 1, the waste polypropylene woven bags material with 25%～95% are cleaned, shred, dry stand-by;
Step 2, the plasticized modifier with 0.1%～30%, 0.01%～5% activator, 0.01%～6% lubricant, 0.01%～6% dispersion agent, the homogenizer that input can heat up stir mediate after the activation treatment stand-by;
Step 3, stand-by material that step 1 and step 2 are handled well and 1%～55% activated inorganic powder reinforced modifier, 0.1%～3% oxidation inhibitor and 1%～35% polyolefine virgin material drop into stirrer and stir;
Step 4, the mixing back material that will stir drop into the heating of screw rod drawing wire machine, carry out wire drawing when temperature is heated to 180～220 ℃, produce woven bag finished product material.
Embodiment
Example one,
Step 1 is got the waste polypropylene woven bags material that accounts for gross weight 50% and is cleaned, shreds, dries stand-by;
Step 2,20% plasticized modifier 1000 order mica powders, get the plasticized modifier ethylene-vinyl acetate copolymer (EVA) that accounts for gross weight 5%, 0.6% activator metatitanic acid fat coupling agent, 0.4% lubricant dispersion agent Poly Propylene Wax, drop into the homogenizer that is warming up to 180 ℃ stir mediate after the activation treatment stand-by;
Step 3, the stand-by material that step 1 and step 2 are handled well drops into stirrer with the polyolefine virgin material of the phosphite kind antioxidant that accounts for gross weight 4% and 20% and stirs;
Step 4, the mixing back material that will stir drop into the heating of screw rod drawing wire machine, carry out wire drawing when temperature is heated to 220 ℃, promptly produce woven bag finished product material.
Example two
Step 1 is got the waste polypropylene woven bags material that accounts for gross weight 57% and is cleaned, shreds, dries stand-by;
Step 2, get the propylene-based elastomeric (VISTAMAXX) that accounts for gross weight 5% and two kinds of plasticized modifiers of maleic anhydride inoculated polypropylene of 1%, 0.5% activator metatitanic acid fat coupling agent, 0.5% lubricant dispersion agent Poly Propylene Wax, drop into the homogenizer that is warming up to 180 ℃ stir mediate after the activation treatment stand-by;
Step 3 drops into stirrer with the polyolefine virgin material of step 1 and step 2 stand-by material of handling well and the plasticized modifier 1500 order mica powders that account for gross weight 15%, 1% phosphite kind antioxidant and 20% and stirs;
Step 4, the mixing back material that will stir drop into the heating of screw rod drawing wire machine, carry out wire drawing when temperature is heated to 200 ℃, promptly produce woven bag finished product material.
The material property that the embodiment of the invention is produced is stable, and the woven bag material with whole employing virgin material granulation wire drawings productions is suitable after testing, can reach the requirement of product use properties fully,
Enforcement of the present invention and interest field, all equivalences of making according to the described content of the present patent application scope of patent protection change and modify, and all should be included in the present patent application claim.
Claims (4)
1. regenerated wire drawing modified material of waste polypropylene woven bags, by mass percentage, it consists of: polyolefine virgin material 1%～35%, waste and old polypropylene material 25%～95%, reinforced modifier 1%-55%, plasticized modifier 1%～30%, activator 0.01%～5%, oxidation inhibitor 0.1%～3%, lubricant 0.01%～6%, dispersion agent 0.01%～6%;
Wherein: described reinforced modifier is above mica powder or glass fibre of 800 orders, carbon fiber, fibrous magnesium silicate, talcum powder;
Described plasticized modifier is: thermoplastic elastomer, terpolymer EP rubber (EDPM), propylene and ethene semi-crystalline co-polymers (VISTAMAXX), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid formicester multipolymer (EMA), ethylene-acrylic acid fourth resin copolymer (EBA), Resins, epoxy, maleic anhydride graft second third elastomerics, the maleic anhydride graft vinyl acetate copolymer, maleic anhydride graft propylene-octene copolymer, maleic anhydride grafted ethene-vinylformic acid formicester multipolymer, maleic anhydride grafted ethene-Butyl acrylate multipolymer;
Described activator is: silane coupling agent, titanate coupling agent, aluminic acid lipoprotein coupling agent, maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is Polyphenols oxidation inhibitor phosphite kind antioxidant;
Described lubricant, dispersion agent are: Poly Propylene Wax, paraffin, stearic acid, calcium stearate.
2. regenerated wire drawing modified material of waste polypropylene woven bags according to claim 1, it is characterized in that, waste silk rim charge when described waste and old polypropylene material is waste polyolefine woven bag plastic waste material and production polyolefine wire drawing material, general melting index is in 1～11 scope.
3. regenerated wire drawing modified material of waste polypropylene woven bags according to claim 1, it is characterized in that, described reinforced modifier is sheet or acicular mica powder, glass fibre, carbon fiber, fibrous magnesium silicate, talcous one or more blended inorganic materials.
4. the preparation method of a regenerated wire drawing modified material of waste polypropylene woven bags, this method is carried out according to the following steps:
Step 1, the waste polypropylene woven bags material with 25%～95% are cleaned, shred, dry stand-by;
Step 2, the plasticized modifier with 0.1%～30%, 0.01%～5% activator, 0.01%～6% lubricant, 0.01%～6% dispersion agent, the homogenizer that input can heat up stir mediate after the activation treatment stand-by;
Step 3, stand-by material that step 1 and step 2 are handled well and 5%～55% activated inorganic powder reinforced modifier, 0.1%～3% oxidation inhibitor and 1%～35% polyolefine virgin material drop into stirrer and stir;
Step 4, the mixing back material that will stir drop into the heating of screw rod drawing wire machine, carry out wire drawing when temperature is heated to 180～220 ℃, produce woven bag finished product material.
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Application publication date: 20101215 |