CN1298777C - Thermal oxidative degradation-promoting mother particle used for plastics and its preparation method - Google Patents
Thermal oxidative degradation-promoting mother particle used for plastics and its preparation method Download PDFInfo
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- CN1298777C CN1298777C CNB031004954A CN03100495A CN1298777C CN 1298777 C CN1298777 C CN 1298777C CN B031004954 A CNB031004954 A CN B031004954A CN 03100495 A CN03100495 A CN 03100495A CN 1298777 C CN1298777 C CN 1298777C
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- 229920003023 plastic Polymers 0.000 title claims abstract description 64
- 239000004033 plastic Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 title claims description 9
- 230000001590 oxidative effect Effects 0.000 title 1
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 63
- 239000000945 filler Substances 0.000 claims abstract description 29
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- 238000005453 pelletization Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001398 aluminium Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
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- 229940074391 gallic acid Drugs 0.000 claims description 2
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- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001684 low density polyethylene Polymers 0.000 claims 1
- 239000004702 low-density polyethylene Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 abstract 2
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 230000036314 physical performance Effects 0.000 abstract 1
- 239000013502 plastic waste Substances 0.000 abstract 1
- 239000002361 compost Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 229920000704 biodegradable plastic Polymers 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000003413 degradative effect Effects 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 206010067482 No adverse event Diseases 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002362 mulch Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses a thermal oxidation and degradation promotion master batch for plastic and a preparation method thereof. The thermal oxidation and degradation promotion master batch is composed of the following components of the percentages by weight: 25 to 60% of modifying filler, 30 to 50% of polyolefine resin, 1 to 15% of thermal oxidation and degradation promotion agent and 1 to 10% of evocating agent. The modifying filler is composed of components of the parts by weight: 100 parts of filler, 1 to 2 parts of resin acceptor and 1 to 3 parts of lubricant. The preparation method comprises a mixing procedure and an extrusion and pelletization procedure. The thermal oxidation and degradation promotion master batch of the present invention has good compatibility with plastic, and can be added to the plastic to be processed into various products. The thermal oxidation and degradation promotion master batch is suitable for film inflation, injection molding, mould pressing and other molding techniques. The master batch is added when various plastic products are prepared, the use performance and the physical performance of the products can not be influenced, and the degradation of the plastic products can be accelerated after usage periods without causing plastic waste pollution to environments. The thermal oxidation and degradation promotion master batch for plastic of the present invention has the advantages of no toxicity, no abnormal smell, no corrosion and no harm to human bodies.
Description
Technical field
The present invention relates to short degradable master batch of a kind of thermooxidizing and preparation method thereof, especially be added on the short degradable master batch of thermooxidizing in common plastics, photodegradable plastics and the biodegradable plastic, can quicken native part of burying of plastics and the non-degradation rate that buries the soil part.
Background technology
At present, plastics have been widely used in the every field of national economy and people's daily life.But plastic material is owing to be subjected to itself and extraneous role and influence (as heat, light, electricity, machinery, chemical mediator, mould etc.), will wear out gradually and loses use properties, after these plastics are dropped environment has been caused severe contamination.At present, a lot of to the treatment process of waste plastic goods both at home and abroad, as landfill method and burning method, though can dispose some rubbish by these methods, but can waste land resources like this, be not suitable for the high country of the density of population, produce a large amount of carbonic acid gas and other waste gas because of burning simultaneously, encouraged Greenhouse effect and polluted air.Succeeding in developing of degradative plastics solved the problem of environmental pollution with waste land resources effectively.Degradative plastics can be divided into photodegradable plastics and biodegradable plastic by its mechanism of degradation.Owing to added photosensitizers in the photodegradable plastics, the film that is exposed under the sunlight is easy to degraded, lacks ultraviolet irradiation and bury the soil part, is difficult to degraded, still can cause soil pollution; Biodegradable materials such as starch have been added in the biodegradable plastic, though burying the soil part can degrade, but its degradative phase is subjected to that the influence of metallic salt content, temperature, humidity, microbe population and kind in the soil is bigger, and degradative phase is longer, can not satisfy user's requirement.
Though also added degradation accelerating agent (oxidized petroleum waves, vegetables oil, iron stearate) or photodegradation promotor (stearate, oleate etc.) in Chinese patent 97125221.1 and 96122161.5, the short degradation agents of the chemistry that uses all has various darker colors, and remote effect the color and the outward appearance thereof of plastics.
Summary of the invention
Technical problem to be solved by this invention provides the short degradable master batch of a kind of thermooxidizing, and color is that white is extremely faint yellow, can not influence the color and the outward appearance of plastics, all can promote plastic degradation in visible light and invisible light system.It can effectively solve the problem that the photodegradable plastics underground part is not degraded, and can solve the problem that the biodegradable plastic over-ground part is difficult for degraded again, also can reach the effect of degraded to common plastics.The preparation method of the short degradable master batch of thermooxidizing who is used for plastics is simple, can finish in the universalization construction equipment, and the raw materials for production cost is low, and addition is few, can not increase production cost to plastics.
In order to address the above problem, the technical solution used in the present invention is: a kind of short degradable master batch of thermooxidizing that is used for plastics, (weight %) composed of the following components: modified filler 25～60%, polyolefin resin 30～50%, thermooxidizing degradation accelerating agent 1～15%, initiator 1～10%, the consisting of of described modified filler (parts by weight): 100 parts of fillers, 1～2 part of coupling agent, 1～3 part of lubricant.
Described filler is one or more mixtures in inorganic carbonate, grouan, talcum powder, magnesium hydroxide, aluminium hydroxide, diatomite, mica, the natural synthesizing organo-silicon, and packing material size is less than 0.1mm.
When described filler was used for the blown film goods, packing material size was less than 0.013mm.
Described polyolefin resin is a kind of in high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), the polyvinyl chloride (PVC).
Described coupling agent is a kind of in silicane, titanate ester or the aluminium esters of gallic acid.
In the carboxylate salts of described thermooxidizing degradation accelerating agent employing iron, zinc, tin, manganese, cobalt, cerium, nickel, copper, gallium, lithium, molybdenum, potassium, tungsten, vanadium, zirconium one or more.
Described initiator adopts a kind of in unsaturated olefin or the unsaturated ester.
Described initiator is a kind of in the multipolymer (SBS), polyhutadiene, oxidic polyethylene, polyisoprene of polystyrene-divinyl.
Described lubricant adopts a kind of in stearic amide, polyethylene wax, stearic acid, the stearyl alcohol.
A kind of preparation method who is used for the short degradable master batch of thermooxidizing of plastics is characterized in that may further comprise the steps:
(1) filler is put into high-speed mixer, carry out high-speed stirring, when temperature rises to 80～120 ℃, add coupling agent and carry out coupling processing, stirred 15～30 minutes, add lubricant again after the modification and stir, stir, obtain modified filler;
(2) modified filler is put into cold mixer, after temperature is lower than 80 ℃, add polyolefin resin, thermooxidizing degradation accelerating agent, initiator, mechanical stirring 10～20 minutes mixes;
(3) with the extruding pelletization in twin screw extruder of the mixture in the above-mentioned operation; the barrel temperature scope of screw rod is 100～200 ℃; head temperature is 100～180 ℃; characteristic according to polyolefin resin; select air-cooled pelletizing or water-cooled pelletizing for use, obtaining color is that white is to the particle faint yellow, that outward appearance is regular.
It is applied widely that degradable master batch is urged in the thermooxidizing that is used for plastics provided by the invention, be easy to be processed into various degraded goods, the degraded controllability is good, mechanical property is superior, can require to add masterbatch according to the reality degraded, make corresponding product, and the short degradable master batch of thermooxidizing of the present invention has nontoxic, free from extraneous odour, non-corrosiveness, harmless characteristic, can not cause new pollution.Preparation process of the present invention is simple, adopts the universalization construction equipment, and cost is low.
Embodiment
Below in conjunction with specific embodiment short degradable master batch of thermooxidizing that is used for plastics of the present invention and preparation method thereof is described in further detail:
Embodiment 1:
To put into high-speed mixer less than the lime carbonate 200kg of 0.013mm (1000 order) and carry out high-speed stirring, when temperature is 100 ℃, add titanate coupling agent 3kg, mixed 25 minutes, and added lubricant polyethylene wax 4kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
40kg puts into cold mixer modified calcium carbonate, when being cooled to 60～80 ℃, add new LDPE (film grade) (LDPE) 50kg, thermooxidizing degradation accelerating agent nickel stearate 5kg, initiator oxidic polyethylene 5kg thorough mixing, after mixing, use the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
110 115 120 125 130 130 125 125
Embodiment 2:
To put into high-speed mixer less than the talcum powder 200kg of 0.013mm (1000 order) and carry out high-speed stirring, when temperature is 110 ℃, add silane coupling agent 3kg, mixed 20 minutes, and added lubricant stearic acid 5kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
50kg puts into cold mixer modified calcium carbonate, when being cooled to 60～80 ℃, after adding linear low density polyethylene (LLDPE) 30kg, cobalt stearate 5kg, cerium stearate 8kg, initiator polyhutadiene 7kg mix, uses the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
150 155 160 170 170 170 165 160
Embodiment 3:
To put into high-speed mixer less than the lime carbonate 200kg of 0.013mm (1000 order) and carry out high-speed stirring, when temperature is 120 ℃, add silane coupling agent 3kg, mixed 20 minutes, and added lubricant stearic acid 4kg again, high-speed stirring 10 minutes, dispose, be the modified calcium carbonate filler.
30kg puts into cold mixer modified calcium carbonate, when being cooled to 60～80 ℃, adds the multipolymer 5kg of polypropylene (PP) 50kg, cobalt stearate 15kg, initiator polystyrene-divinyl, after mixing, uses the twin screw extruder extruding pelletization.Adopt the water-cooled pelletizing, make the short degradable master batch of the regular intact thermooxidizing that is used for plastics of particle shape.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
140 145 150 155 160 160 156 150
Embodiment 4:
To put into high-speed mixer less than the talcum powder of 0.1mm (150 order) and each 100kg of diatomite and carry out high-speed stirring, when temperature is 100 ℃, add titanate coupling agent 3kg, mixed 25 minutes, and adding stearic amide 4kg, high-speed stirring 10 minutes, dispose, be the modification mixed fillers.
Above-mentioned modification mixed fillers 200kg is put into the cold mixing machine, when being cooled to 60～80 ℃, after adding new LDPE (film grade) (LDPE) 120kg, cerium stearate 5kg, nickel stearate 5kg, polyisoprene 20kg mix, use the twin screw extruder extruding pelletization.Adopt air-cooled pelletizing, make the short degradable master batch of the rational intact thermooxidizing that is used for plastics.Processing temperature can by following temperature (℃) set:
Eight districts, seven districts, six districts, five districts, four districts, three districts, two districts, one district
110 115 120 125 130 130 125 125
Above example explanation, adopt different ratios and different types of raw material all can carry out normal granulation with mixed processes and extruding pelletization operation, the short degradable master batch particle shape made from twin screw extruder of the thermooxidizing that is used for plastics is regular intact, and color is that white is to light yellow.Degradable master batch is urged in these different types of thermooxidizings, can be when complete processing moulding such as blown film, extrusion molding, injection moulding, mold pressing and other raw material mechanical stirring mix the back and use, convenient and safe, and do not need processing temperature is adjusted.Can select the consumption of the short degradable master batch of suitable thermooxidizing according to different degradation times.
Above-mentioned filler is inorganic carbonate, grouan, talcum powder, magnesium hydroxide, aluminium hydroxide, diatomite, mica, natural synthesizing organo-silicon etc., can use one or more mixtures as filler.Employed packing material size is less than 0.1mm.If be used for the blown film goods, the particle diameter of used filler should be littler, and for example the particle diameter of lime carbonate is less than 0.013mm, otherwise, can produce flake or hole on the film article, cause the rerum natura of film to descend so that defective.
The surface of these fillers must be handled through modification, prevent to absorb moisture content, increases consistency and dispersiveness with polyolefin resin, otherwise can produce hole or reduce the physical and mechanical properties of plastics when blown film.Therefore, these fillers, for example lime carbonate after organic acid or ester coupling agent treatment, has improved its processing characteristics and water resistance.
The short degradable master batch of thermooxidizing that is used for plastics can discharge free radical at low temperatures lentamente, causes the fracture of polyolefine c h bond, the oxidising process of acceleration molecular chain; And at high temperature have certain stability, can under polyolefinic processing temperature, not decompose fast.The short degradable master batch of thermooxidizing that is used for plastics of the present invention can be directly as a kind of interpolation composition that uses at plastics forming.It and plastics have good consistency, moulding process such as be fit to blowing, injection moulding, mold pressing, extrude, and the material performance of goods had no adverse effects.Utilize the short degradable master batch of the thermooxidizing that is used for plastics of the present invention can be formed in plastic material and the goods that chemical degradation takes place behind the certain hour; As being used with photodegradable plastics and biodegradable plastic, can also improve the degradation rate of photodegradable plastics and biodegradable plastic, form the small shreds of environmental sound.Under heating or ultraviolet light conditions, can quicken to add the chemical degradation reaction that the present invention urgees the plastics of degradable master batch; Equally, under unglazed photograph or composting conditions, also can promote the degraded of plastics.Should short degradable master batch nontoxic, free from extraneous odour, non-corrosiveness, harmless not only can be used for ordinary packing, but also can be used for food product pack.
Can produce the characteristics of 55～70 ℃ of corruption temperature-rise periods during at garbage compost, the short degradable master batch of thermooxidizing that is used for plastics of the present invention, make the plastics that add this masterbatch can be under compost environment, accelerated degradation efficiently solves the degradation problem of plastics under compost environment.
Below the result of use that is used for the short degradable master batch of thermooxidizing of plastics of the present invention is described further, that uses in the prescription all is weight percentage:
The prescription of blown film experiment is as shown in table 1,
Table 1
| Sequence number | Prescription | Ratio |
| 1# | BM1150∶HDPE∶LLDPE | 50∶25∶25 |
| 2# | BM1150: HDPE: LLDPE: short degradable master batch | 50∶23∶23∶4 |
| 3# | BM1150: HDPE: LLDPE: short degradable master batch | 50∶21∶21∶8 |
| 4# | DM2150∶LDPE∶LLDPE | 30∶35∶35 |
| 5# | DM215: LDPE: LLDPE: short degradable master batch | 30∶33∶33∶4 |
| 6# | DM2150: LDPE: LLDPE: short degradable master batch | 30∶31∶31∶8 |
BM1150, DM2150 are respectively packing film masterbatch and mulching film master batch, it is the amyloid biodegradable master batch that Danhai Co., Ltd., Tianjin produces, be suitable for blowing biodegradable mulch film and packing film, the masterbatch that the short degradable master batch of thermooxidizing is embodiment 1 preparation.Above the mechanical performance index of blowing degradable package film and mulch film see Table 2, table 3, table 4
Table 2
| 1# | 2# | 3# | 4# | 5# | 6# | |
| Short degradable master batch consumption % | 4 | 8 | 4 | 8 | ||
| Thickness mm | 0.018～0.020 | 0.019～0.020 | 0.019～0.020 | 0.008～0.010 | 0.008～0.010 | 0.008～0.010 |
| Tensile strength MPa indulges/horizontal stroke | 31.2/18.6 | 30.5/19.1 | 30.1/18.3 | 20.0/15.3 | 21.1/14.5 | 19.2/14.2 |
| Elongation at break % indulges/horizontal stroke | 270/350 | 290/360 | 280/340 | 410/630 | 420/620 | 410/600 |
| Grammes per square metre (g/m 2) | 19.4 | 19.9 | 20.3 | 7.3 | 7.5 | 7.5 |
Table 3
| Project | 400 hours degraded situations of simulation compost temperature experiment | |||||||||||
| Tensile strength MPa | Elongation at break % | |||||||||||
| Former film | After the degraded | Retention rate % | Former film | After the degraded | Retention rate % | |||||||
| Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | |
| 1# | 31.2 | 18.6 | 31.4 | 18.5 | 100 | 100 | 270 | 350 | 275 | 345 | 100 | 100 |
| 2# | 30.5 | 19.1 | 9.2 | 6.9 | 30 | 36 | 290 | 360 | 100 | 110 | 35 | 30 |
| 3# | 30.1 | 18.3 | 3.6 | 1.8 | 11 | 9.8 | 280 | 340 | 10 | 0 | 3.6 | 0 |
| 4# | 20.0 | 15.3 | 20.2 | 15.2 | 100 | 100 | 410 | 630 | 400 | 630 | 100 | 100 |
| 5# | 21.1 | 14.5 | 5.3 | 3.2 | 25 | 22 | 420 | 620 | 115 | 120 | 28 | 19. 4 |
| 6# | 19.2 | 14.2 | 0.9 | 0.8 | 4.7 | 5.6 | 410 | 600 | 0 | 0 | 0 | 0 |
The variation of the viscosity-average molecular weight of table 4 simulation compost temperature experiment after 400 hours
| 1# | 2# | 3# | 4# | 5# | 6# | |
| The initial molecule amount | 157000 | 173000 | 166000 | 94300 | 86500 | 87600 |
| Degraded back molecular weight | 159000 | 71280 | 38350 | 93500 | 29950 | 12090 |
| Retention rate % | 100 | 41.2 | 23.1 | 100 | 34.6 | 13.8 |
Table 5 experiment biological growth rank
| 1# | 2# | 3# | 4# | 5# | 6# | |
| Fungi | Level Four | Level Four | Level Four | Level Four | Level Four | Level Four |
| Bacterium | Level Four | Level Four | Level Four | Level Four | Level Four | Level Four |
| Rate of weight loss % | 18.5 | 19.7 | 18.6 | 10.5 | 10.2 | 11.1 |
The prescription of blown film experiment is as shown in table 6, and short degradable master batch is the masterbatch of embodiment 2 preparations.
Table 6
| Sequence number | Prescription | Ratio |
| 7# | HDPE∶LLDPE | 80∶20 |
| 8# | HDPE: LLDPE: short degradable master batch | 76∶20∶4 |
| 9# | HDPE: LLDPE: short degradable master batch | 72∶20∶8 |
| 10# | LLDPE∶LDPE | 80∶20 |
| 11# | LLDPE: LDPE: short degradable master batch | 76∶20∶4 |
| 12# | LLDPE: LDPE: short degradable master batch | 72∶20∶8 |
The original rerum natura of 7～12# is a table 7, and the experimental physics performance sees Table 8,9.
Table 7
| 7# | 8# | 9# | 10# | 11# | 12# | |
| Short degradable master batch consumption % | 4 | 8 | 4 | 8 | ||
| Thickness mm | 0.012～0.019 | 0.011～0.017 | 0.012～0.018 | 0.018～0.022 | 0.019～0.022 | 0.019～0.022 |
| Tensile strength MPa indulges/horizontal stroke | 46.3/38.8 | 49.4/41.8 | 48.0/34.9 | 27.3/28.2 | 24.6/23.8 | 23.6/23.3 |
| Elongation at break % indulges/horizontal stroke | 295/435 | 290/380 | 275/395 | 630/690 | 600/730 | 580/675 |
| Grammes per square metre (g/m 2) | 12.67 | 12.18 | 12.26 | 17.14 | 16.87 | 16.79 |
Table 8
| Project | 400 hours degraded situations of simulation compost temperature experiment | |||||||||||
| Tensile strength MPa | Elongation at break % | |||||||||||
| Former film | After the degraded | Retention rate % | Former film | After the degraded | Retention rate % | |||||||
| Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | |
| 7# | 46.3 | 38.8 | 46.1 | 38.6 | 100 | 100 | 295 | 435 | 290 | 433 | 100 | 100 |
| 8# | 49.4 | 41.8 | 22.2 | 13.6 | 44.9 | 32.5 | 290 | 380 | 100 | 130 | 34.5 | 34 |
| 9# | 48.0 | 34.9 | 10.2 | 3.8 | 21.3 | 10.9 | 275 | 395 | 35 | 30 | 12.7 | 7.6 |
| 10# | 27.3 | 28.2 | 28.1 | 28.6 | 100 | 100 | 630 | 690 | 620 | 680 | 100 | 100 |
| 11# | 24.6 | 23.8 | 1.1 | 1.4 | 4.5 | 6 | 600 | 730 | 12 | 23 | 2 | 3.2 |
| 12# | 23.6 | 23.3 | 0 | 0 | 0 | 0 | 580 | 675 | 0 | 0 | 0 | 0 |
The variation of the viscosity-average molecular weight of table 9 simulation compost temperature experiment after 400 hours
| 7# | 8# | 9# | 10# | 11# | 12# | |
| The initial molecule amount | 213000 | 180000 | 207000 | 129400 | 113700 | 115600 |
| Degraded back molecular weight | 214000 | 81540 | 54850 | 129000 | 28080 | 17570 |
| Retention rate % | 100 | 45.3 | 26.5 | 100 | 24.7 | 15.2 |
The molding experiment:
After using the short degradable master batch of plastic hot oxidation of embodiment 3 and polypropylene (PP) to stir, mixing on two roller mixing rolls evenly discharging refining in the rolling press goes out calendared sheet, and the temperature that calendared sheet uses is 170～180 ℃.Calendared sheet can be molded into the plastics of the different shape of actual needs, makes non-returnable containers such as mess-tin with the short degradation property of chemistry, medicine box, bowl, pastry case.
Prescription sees Table 10, and performance sees Table 11.
Table 10
| Sequence number | Prescription | Ratio |
| 13# | PP | 100 |
| 14# | PP: short degradable master batch | 96∶4 |
| 15# | PP: short degradable master batch | 92∶8 |
The variation of the viscosity-average molecular weight of table 11 simulation compost temperature experiment after 400 hours
| 13# | 14# | 15# | |
| The initial molecule amount | 136000 | 134000 | 128000 |
| Degraded back molecular weight | 135000 | 43410 | 18810 |
| Retention rate % | 100 | 32.4 | 14.7 |
Through experimental results demonstrate, the short degradable master batch of plastic hot oxidation has certain stability under hot conditions, can not decompose fast under the polyolefine processing temperature, but can discharge free radical lentamente under the compost temperature condition, bring out the fracture of polyolefine c h bond, quicken the degradation rate of plastics.
The short degradable master batch of plastic hot oxidation can directly use as a kind of additive in plastics forming.Its use range is very extensive, moulding process such as be fit to blowing, injection moulding, mold pressing, extrude, and physical properties of articles is had no adverse effects.After adding this masterbatch, degradative plastics products such as the short membrane product of degrading of chemistry, bag product, sheet material products, injecting products take place after can being formed in certain hour, can also promote simultaneously the degradation speed of photodegradation and biodegradable plastic, accelerate degradation rate, form the small shreds of environmental sound.So that the short degradable master batch of thermooxidizing of the present invention has more is nontoxic, free from extraneous odour, non-corrosiveness, harmless characteristic, can not cause new pollution.
Claims (7)
1, the short degradable master batch of a kind of thermooxidizing that is used for plastics is composed of the following components, and wherein the amount of each component is in weight %:
Modified filler 25～60%
Polyolefin resin 30～50%
Thermooxidizing degradation accelerating agent 1～15%
Initiator 1～10%
Consisting of of described modified filler, the amount of each component are in parts by weight:
100 parts of fillers
1～2 part of coupling agent
1～3 part of lubricant
Described filler is one or more mixtures in inorganic carbonate, grouan, talcum powder, magnesium hydroxide, aluminium hydroxide, diatomite, mica, the natural synthesizing organo-silicon, and packing material size is less than 0.1mm;
Described polyolefin resin is a kind of in high density polyethylene, low density polyethylene, linear low density polyethylene LLDPE, polypropylene PP, the polyvinylchloride;
In the carboxylate salts of described thermooxidizing degradation accelerating agent employing iron, zinc, tin, manganese, cobalt, cerium, nickel, copper, gallium, lithium, molybdenum, potassium, tungsten, vanadium, zirconium one or more.
2, the short degradable master batch of thermooxidizing that is used for plastics according to claim 1, when it is characterized in that described filler is used for the blown film goods, packing material size is less than 0.013mm.
3, the short degradable master batch of the thermooxidizing that is used for plastics according to claim 1 is characterized in that described coupling agent is a kind of in silicane, titanate ester or the aluminium esters of gallic acid.
4, the short degradable master batch of the thermooxidizing that is used for plastics according to claim 1 is characterized in that described initiator adopts a kind of in unsaturated olefin or the unsaturated ester.
5, the short degradable master batch of the thermooxidizing that is used for plastics according to claim 4 is characterized in that described initiator is a kind of among the multipolymer SBS, polyhutadiene, oxidic polyethylene, polyisoprene of polystyrene-divinyl.
6, the short degradable master batch of the thermooxidizing that is used for plastics according to claim 1 is characterized in that described lubricant adopts a kind of in stearic amide, polyethylene wax, stearic acid, the stearyl alcohol.
7, a kind of preparation method who is used for the short degradable master batch of thermooxidizing of plastics as claimed in claim 1 is characterized in that may further comprise the steps:
(1) filler is put into high-speed mixer, carry out high-speed stirring, when temperature rises to 80～120 ℃, add coupling agent and carry out coupling processing, stirred 15～30 minutes, add lubricant again after the modification and stir, stir, obtain modified filler;
(2) modified filler is put into cold mixer, after temperature is lower than 80 ℃, add polyolefin resin, thermooxidizing degradation accelerating agent, initiator, mechanical stirring 10～20 minutes mixes;
(3) with the extruding pelletization in twin screw extruder of the mixture in the above-mentioned operation; the barrel temperature scope of screw rod is 100～200 ℃; head temperature is 100～180 ℃; characteristic according to polyolefin resin; select air-cooled pelletizing or water-cooled pelletizing for use, obtaining color is that white is to the particle faint yellow, that outward appearance is regular.
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| CN100432132C (en) * | 2005-06-03 | 2008-11-12 | 上海林达塑胶化工有限公司 | Transparent film mother material and its preparation process |
| AU2007337126B2 (en) | 2006-12-20 | 2010-09-23 | Saint-Gobain Ceramics & Plastics, Inc. | Composite materials having improved thermal performance |
| CN102295793A (en) * | 2011-07-07 | 2011-12-28 | 宋旭 | A highly filled oxidatively degradable polymer packaging material and its preparation method |
| CN102660068A (en) * | 2012-04-15 | 2012-09-12 | 云南省农业科学院甘蔗研究所 | Controllable sugarcane photo-thermal degradable mulch film |
| CN103421234A (en) * | 2012-05-25 | 2013-12-04 | 李健德 | Thermal oxidative degradation polypropylene sheet |
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| CN106750775A (en) * | 2016-12-02 | 2017-05-31 | 苏州天兼新材料科技有限公司 | A kind of biodegradable additive and the food packaging plastic products being prepared from using the additive |
| CN109486011A (en) * | 2018-11-26 | 2019-03-19 | 铜陵熙成塑料制品有限公司 | A kind of ageing-resistant polyolefine material of packaging bag |
| CN111019218A (en) * | 2019-12-23 | 2020-04-17 | 田勇 | Preparation method of easily-degradable and easily-incineratable composite material |
| CN111269466A (en) * | 2020-04-02 | 2020-06-12 | 李守本 | Plastic master batch, preparation method and plastic |
| CN114276600B (en) * | 2021-12-23 | 2022-09-30 | 南通宝加利新材料有限公司 | Preparation method of degradable PE film |
| CN115302904B (en) * | 2022-07-25 | 2023-10-03 | 厦门理工学院 | Degradable heat shrinkable film and preparation method thereof |
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