CN105254990A - Ultraviolet-light-ageing-resistant high-intensity polyethylene IBC inner container material and preparation method - Google Patents
Ultraviolet-light-ageing-resistant high-intensity polyethylene IBC inner container material and preparation method Download PDFInfo
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- CN105254990A CN105254990A CN201510695379.7A CN201510695379A CN105254990A CN 105254990 A CN105254990 A CN 105254990A CN 201510695379 A CN201510695379 A CN 201510695379A CN 105254990 A CN105254990 A CN 105254990A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
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- C08K5/13—Phenols; Phenolates
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- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
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- C08K5/49—Phosphorus-containing compounds
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
The invention discloses an ultraviolet-light-ageing-resistant high-intensity polyethylene IBC inner container material and a preparation method. The ultraviolet-light-ageing-resistant high-intensity polyethylene IBC inner container material is mainly prepared from, by mass, 100 parts of ethylene hexylene copolymer polyethylene resin, 0.05-0.1 part of antioxidant, 0.05-0.1 part of antioxidant aid and 0.15-0.20 part of composite light stabilizer. The invention further discloses a preparation method of the material. An IBC bucket inner container manufactured through the material is good in formability, excellent in environmental stress cracking resistance and light stability, and all mechanical properties are stable.
Description
Technical field
The present invention relates to a kind of construct blow-molded, be specifically related to a kind of ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material.Meanwhile, the invention still further relates to the preparation method of this material.
Background technology
IBC(IntermediateBulkContainer) refer to for loading and transporting liquid, compound bulk container with rigidity plastics inner jar, it is primarily of the part such as high-density polyethylene plastics inner bag, Plastic protective corner annex, high precision ball valve, steel basetray and guardrail steelframe composition, be a kind of can the packing container of filling II, III class hazardous substance liquid.Whole world IBC container has formed the series product of 1000 ~ 2000L, becomes at the indispensable product of packaging field.Along with IBC range of application is more and more extensive, demand increases fast with the speed of annual growth more than more than 10%.After China joined WTO, rapidly, the paces of the alternative steel vessels such as IBC collection barrelling, in rapid quickening, greatly have stimulated the development of Large Hollow Container industry in export trade development.IBC bucket inner bag is research and development application along with polymer and supra polymer resin material and a kind of packaging vessel grown up in chemical liquid packaging industry, it be with molecular-weight average about 250,000 high density polyethylene(HDPE) (HDPE), blow through large-scale extrusion-blown modling blow moulding machine, can be used for the packaging of all kinds of liquid (gluing) the state dangerous property Chemicals such as acids, bases, lipid.Because it has excellent erosion resistance, high intensity, the number of turnover being several times as much as steel drum and easy recyclability, to transport by sea extremely both at home and abroad the attention on boundary, again because can completely meets the requirement of hazard product packaging vessel in " International Maritime hazardous substance transportation of cargo rule ", applied more and more widely in hazardous product transport.The barrelling of IBC collection has the advantages such as light weight, high-strength, corrosion resistant wholesomeness is good, and add that the protection of external metallization framework uses more safe and reliable, can repeatedly use, the advantage embodied when filling, accumulating and transport can reduce costs significantly.Compared with drum, IBC bucket can save the storage area of 35%.Current IBC container has been widely used in the liquid packaging of the industries such as oil, medicine, building, chemical industry, food, and the main products of storage, turnover, packed and transported has lubricating oil, solvent, glycerine, medical, alcohol and foodstuff additive etc.
High-density polyethylene material is synthesizing, is storing, is processing, is making product so that between the usage period, all there will be signs of degradation.Degraded makes outward appearance and the performance degradation of high-density polyethylene material.This kind of signs of degradation is called (aging).The consequence of high-density polyethylene material degraded is the change of material appearance, variable color, efflorescence and check surface, tarnish and lower transparency, the molecular weight of material changes, melting index changes and loses mechanical property, lose shock strength, lose tensile strength and elongation, embrittlement finally causes goods to use.One of inducement that high-density polyethylene material is aging, be that the chromophoric group of high-density polyethylene material under irradiation by sunlight can generate free radical after absorption UV-light, the UV-light namely in sunlight can cause the photo-oxidative degradation of high-density polyethylene material.At present, domestic enterprise does not also form scale in IBC bucket PP Pipe Compound, and the ageing resistance difference of prepared product and other various cause for quality existed, cannot meet manufacturer production demand.So the domestic PP Pipe Compound for the manufacture of IBC bucket is mainly based on import material, be difficult to like this meet the need of market.And IBC bucket is an important component part of wrapping material, say that the height of a national packaging industry level is not only the mark of all wrapped product external images in a sense, and be the comprehensive embodiment of this National Industrial Development Technology level.
Summary of the invention
The object of the present invention is to provide a kind of ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material, this material is for good processability during industrial production IBC bucket inner bag, the IBC bucket inner bag plasticity manufactured is good, environmental stress crack resistance and light stability excellence, every stable mechanical property.
The present invention is achieved through the following technical solutions: a kind of ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material, and the component primarily of following mass parts is prepared from:
Ethene hervene copolymer polyvinyl resin 100 parts
Oxidation inhibitor 0.05-0.1 part
Aid anti-oxidants 0.05-0.1 part
Composite light stabilizer 0.15 ~ 0.20 part.
The melt flow rate (MFR) of ethene hervene copolymer polyvinyl resin of the present invention is 5.60 ~ 7.0g/10min(190 DEG C/21.6Kg counterweight), density is 0.943 ~ 0.947kg/m
3, weight-average molecular weight 25 ~ 290,000, molecular weight distribution 13 ~ 18, hexene-1 content 0.3 ~ 0.6%, be prepared from by monocycle pipe slurry process, the temperature of reaction in reaction vessel is 92.0 ± 2.0 DEG C, and hexene-1/ ethylene feed is than being 17-22%.Thinner of the present invention is preferably Trimethylmethane.The consumption of thinner is 26 ~ 31t/h.The consumption of described hexene-1 is about the 2-4.5 of catalyst levels doubly.
The thinner used in monocycle pipe slurry process preparation of the present invention is preferably Trimethylmethane, and the catalyzer of use is chromium-based catalysts, is preferably the 963T of W. R. Grace & Co.
Oxidation inhibitor of the present invention and aid anti-oxidants, by suitable proportioning, produce synergy, improve the long-acting thermal oxidative aging of material.Wherein, oxidation inhibitor adopts phenolic antioxidant, and aid anti-oxidants adopts phosphite ester kind antioxidant, adopts the antioxidant systems of the mixing of phenolic antioxidant and phosphite ester kind antioxidant to can be the long-acting thermal oxidative aging providing material enough.Phenolic antioxidant of the present invention is preferably four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester (1010); Described phosphite ester kind antioxidant is preferably two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (168).
Adding photostabilizer in material can available protecting material light stability in use, material color is not easily turned to be yellow and aging.In the present invention, described photostabilizer is preferably UV3529, namely gather [1,6-hexanediamine, N, N '-bis-
(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
Second object of the present invention is the preparation side providing above-mentioned ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material.
The preparation method of ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material of the present invention; get ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and photostabilizer in proportion; after mixing, add mixing roll extruding pelletization and obtain particulate state high density polyethylene(HDPE) IBC liner material.
the present invention compared with prior art has the following advantages:
1. the present invention selects ethene hervene copolymer polyvinyl resin to have higher hexene-1 monomer content, hexene-1 monomer content is 0.3 ~ 0.6%, rational molecular weight, density and molecular weight distribution, meet the requirement of processing characteristics required by IBC inner bag construct blow-molded and every physical and mechanical property, and rebound resilience and good moldability.Adding antioxidant and photostabilizer, to make the IBC bucket inner bag plasticity of IBC inner bag construct blow-molded product manufacturing good, has outstanding resistance of oxidation (corrosion-resistant) environmental stress crack resistance energy and light stability.Realize domestic IBC bucket PP Pipe Compound and form scale production, not only products obtained therefrom quality is good, and stable processing technique, can stable supplying, meets manufacturer production demand.
2. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC bucket liner material provided by the invention is after the ultraviolet light and aging test of 1000 hours, and stretching strength retentivity still can keep 77%.The detection such as UV xenon lamp aging, FNCT, oxidative degradation rate of the relevant surveying society of the domestic and international well-known producer such as Shang Shuchi container company limited and Kingsoft, Zhenjiang packaging invented by the IBC bucket manufactured for raw material with this product by global IBC, and have passed food sanitation, FDA, 94/62/EC, EU, SVHC(REACH regulation of country), the certification such as the food packaging polyvinyl resin hygienic standard of RoHS, PAHs, GB9691-88.Industrial application shows, the IBC bucket inner bag environmental stress crack resistance energy of manufacture and light stability excellence, fill up the blank of domestic IBC bucket liner material.
3. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC bucket liner material provided by the invention has good comprehensive mechanical property, and relative its load-bearing of butene-1 copolymerized product is high, can manufacture thinner IBC bucket inner bag.
Accompanying drawing explanation
Fig. 1 is the contrast bar graph of aberration after the ultraviolet light and aging of the material of embodiment 7-9 and comparative example 3-4.
Fig. 2 is the contrast bar graph of the ultraviolet light and aging back draft intensity of the material of embodiment 7-9 and comparative example 3-4.
Fig. 3 is the contrast bar graph of the ultraviolet light and aging back draft strength retention of the material of embodiment 7-9 and comparative example 3-4.
Fig. 4 is the contrast bar graph of modulus in flexure after the ultraviolet light and aging of the material of embodiment 7-9 and comparative example 3-4.
Fig. 5 is the contrast bar graph of modulus in flexure conservation rate after the ultraviolet light and aging of the material of embodiment 7-9 and comparative example 3-4.
Embodiment
The ethene of the employing in the present invention and hexene-1 are preferably the ethene of following specification:
Ethene: purity>=99.20%C
2h
2≤ 5 × 10
-6cO≤1 × 10
-6
O
2≤2×10
-6H
2O≤1×10
-6COS≤0.02×10
-6。
Hexene-1: purity>=98.5%H
2o≤20 × 10
-6cO≤5 × 1O
-6
Positive non-alhpa olefin≤1% of structure of monoolefine >=98.5% isomery alhpa olefin≤1%
Positive structure alhpa olefin>=96% superoxide≤1 × 10
-6sulphur≤1 × 10
-6.
The thinner Trimethylmethane that the present invention adopts is preferably the Trimethylmethane of following specification:
Trimethylmethane: purity>=95.0% acetylene≤2 × 10
-6total sulfur≤1 × 10
-6
Total olefin≤100 × 10
-6water≤20 × 10
-6o
2≤ 5 × 10
-6.
Extrusion machine is the extrusion machine of a CoperionZSK-350 type, and extrusion machine has 7 sections of cylindrical shells; Time mixing, regulate mixing roll the 5th section of barrel temperature to be 240 DEG C, the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 255 ~ 260 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C, and regulates the temperature of particle water coolant to be 65 ~ 72 DEG C, and particle cooling water flow is 600 ~ 650m
3/ h.
The activation treatment of catalyzer of the present invention is undertaken by being contacted in the ebullated bed by fuel gas combustion heating with heated drying air by catalyzer, and catalyzer, by opening pot bottom valve, relies on gravity to fall into activator; Come from the burning gas of the burner hearth heat of activation furnace and the fluidization air heat-activated stove of heat and catalyzer, combustion gases upwards fluidized gas, by after grid distributor, fully contact with catalyzer and make catalyst activation.
embodiment 1
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 37.5t/h, hexene-1/ ethylene ratio 17.6kg/t, catalyzer 963T feeding quantity 193kg/h, thus to obtain melt flow rate be 5.95g/10min, density is 0.9448kg/m
3, weight-average molecular weight 28.0 ten thousand, molecular weight distribution 16.4, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.34%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
embodiment 2
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 36.3t/h, hexene-1/ ethylene ratio 18.4kg/t, catalyzer 963T feeding quantity 185kg/h, thus to obtain melt flow rate be 5.84g/10min, density is 0.9452kg/m
3, weight-average molecular weight 28.6 ten thousand, molecular weight distribution 17.7, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.41%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 245 DEG C, and the 6th section of barrel temperature is 254 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 262 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
embodiment 3
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 38.1t/h, hexene-1/ ethylene ratio 18.8kg/t, catalyzer 963T feeding quantity 204kg/h, thus to obtain melt flow rate be 6.10g/10min, density is 0.9455kg/m
3, weight-average molecular weight 27.2 ten thousand, molecular weight distribution 15.3, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.42%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 247 DEG C, and the 6th section of barrel temperature is 256 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 264 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
embodiment 4
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 37.8t/h, hexene-1/ ethylene ratio 20.6kg/t, catalyzer 963T feeding quantity 193kg/h, thus to obtain melt flow rate be 6.10g/10min, density is 0.946kg/m
3, weight-average molecular weight 26.9 ten thousand, molecular weight distribution 13.5, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.49%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 243 DEG C, and the 6th section of barrel temperature is 255 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 265 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
embodiment 5
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 36.9t/h, hexene-1/ ethylene ratio 21.1kg/t, catalyzer 963T feeding quantity 196kg/h, thus to obtain melt flow rate be 6.28g/10min, density is 0.9465kg/m
3, weight-average molecular weight 25.2 ten thousand, molecular weight distribution 16.6, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.53%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 249 DEG C, and the 6th section of barrel temperature is 254 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 265 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
embodiment 6
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 38.1t/h, hexene-1/ ethylene ratio 21.8kg/t, catalyzer 963T feeding quantity 202kg/h, thus to obtain melt flow rate be 5.82g/10min, density is 0.9469kg/m
3, weight-average molecular weight 28.4 ten thousand, molecular weight distribution 14.7, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.55%.
The raw material (weight part) of IBC liner material:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, and composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of IBC liner material:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene IBC liner material.Mixing roll the 5th section of barrel temperature is 246 DEG C, and the 6th section of barrel temperature is 253 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 267 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
comparative example 1
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 37.2t/h, hexene-1/ ethylene ratio 16.3kg/t, catalyzer 963T feeding quantity 198kg/h, thus to obtain melt flow rate be 6.04g/10min, density is 0.9427kg/m
3, weight-average molecular weight 27.3 ten thousand, molecular weight distribution 15.2, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.29%.
The raw material (weight part) of large hollow construct blow-molded:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of large hollow construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain the large hollow construct blow-molded of particulate polyethylene product.Mixing roll the 5th section of barrel temperature is 247 DEG C, and the 6th section of barrel temperature is 255 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 267 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h
comparative example 2
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in ethene, hexene respectively injection ring pipe reactor, strict control ethene hexene feed ratio, and add the catalyzer activated in advance, control the temperature of reaction 92.0 ± 2.0 DEG C in reactor, ethylene feed amount 38.7t/h, hexene-1/ ethylene ratio 15.5kg/t, catalyzer feeding quantity 204kg/h, thus to obtain melt flow rate be 6.25g/10min, density is 0.9423kg/m
3, weight-average molecular weight 26.8 ten thousand, molecular weight distribution 14.2, hexene monomers content is the ethene hervene copolymer polyvinyl resin of 0.26%.
The raw material (weight part) of large hollow construct blow-molded:
Ethene hervene copolymer polyvinyl resin 100
Oxidation inhibitor 0.09
Aid anti-oxidants 0.07
Photostabilizer 0.18
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Aid anti-oxidants is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Composite light stabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
The preparation method of large hollow construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin, oxidation inhibitor, aid anti-oxidants and composite light stabilizer are mixed, add mixing roll and extrude particle in water coolant, obtain the large hollow construct blow-molded of particulate polyethylene product.Mixing roll the 5th section of barrel temperature is 245 DEG C, and the 6th section of barrel temperature is 256 DEG C, and the 7th section of barrel temperature is 260 ~ 270 DEG C; The thermal oil temperature of heating mixing roll is 268 DEG C, and the temperature of water coolant is 50 ~ 65 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
Can find out from above result, embodiment 1-6 is compared with comparative example 1-2, and hexene-1/ ethylene ratio is within the scope of 17.5-22kg/t, and material has excellent low temperature impact strength and FNCT performance, reaches the requirement of high density polyethylene(HDPE) IBC liner material.
embodiment 7
Get the ethene hervene copolymer polyvinyl resin powder that 100 parts of embodiments 3 are obtained; add 0.15 part of photostabilizer UV3529,0.09 part of primary antioxidant 1010 and 0.07 part of auxiliary antioxidant 168; after super mixer high speed mixing 2min; extruding pelletization in dual-screw pelletizer, obtains anti-light aging high density polyethylene(HDPE) IBC liner material.
Primary antioxidant is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester (1010); Auxiliary antioxidant is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (168).
embodiment 8
As different from Example 7:
Get the ethene hervene copolymer polyvinyl resin powder that 100 parts of embodiments 3 are obtained; add 0.18 part of photostabilizer UV3529,0.09 part of primary antioxidant 1010 and 0.07 part of auxiliary antioxidant 168; after super mixer high speed mixing 2min; extruding pelletization in dual-screw pelletizer, obtains anti-light aging high density polyethylene(HDPE) IBC liner material.
embodiment 9
As different from Example 7:
Get the ethene hervene copolymer polyvinyl resin powder that 100 parts of embodiments 3 are obtained; add 0.20 part of photostabilizer UV3529,0.09 part of primary antioxidant 1010 and 0.07 part of auxiliary antioxidant 168; after super mixer high speed mixing 2min; extruding pelletization in dual-screw pelletizer, obtains anti-light aging high density polyethylene(HDPE) IBC liner material.
comparative example 3
Get the ethene hervene copolymer polyvinyl resin powder that 100 parts of embodiments 3 are obtained; add photostabilizer 9440.18%; primary antioxidant 10100.09%; auxiliary antioxidant 1680.07%; after super mixer high speed mixing 2min; extruding pelletization in dual-screw pelletizer, obtains anti-light aging high density polyethylene(HDPE) IBC liner material.
comparative example 4
Get the ethene hervene copolymer polyvinyl resin powder that 100 parts of embodiments 3 are obtained; add photostabilizer 20200.18%; primary antioxidant 10100.09%; auxiliary antioxidant 1680.07%; after super mixer high speed mixing 2min; extruding pelletization in dual-screw pelletizer, obtains anti-light aging high density polyethylene(HDPE) IBC liner material.
The test of 7-9 and comparative example 3-4 is set forth beneficial effect of the present invention by the following examples.Testing standard:
Ultraviolet light and aging standard: QUVB313
Yield of radiation: 0.67W/m2310nm
Loop cycle: 8hUV60 degree, 4h condensation 50 degree
DeltaE standards of chromatic aberration: ASTMD2244
Tensile strength standard: ISO527
Modulus in flexure standard: ISO178
Can find out from Fig. 1-5 and table 3-7, embodiment 7-9 is compared with comparative example 3-4, adding UV3529 UV light stabilizing agent, after ultraviolet light and aging, show aberration little, tensile strength and modulus in flexure conservation rate high, there is excellent anti-light aging effect, reach the requirement of high density poly propylene IBC liner material.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention instead of restriction, any change therefore in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (5)
1. an ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material, is characterized in that, the component primarily of following mass parts is prepared from:
Ethene hervene copolymer polyvinyl resin 100 parts
Oxidation inhibitor 0.05-0.1 part
Aid anti-oxidants 0.05-0.1 part
Composite light stabilizer 0.15 ~ 0.20 part.
2. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material according to claim 1, it is characterized in that, the melt flow rate (MFR) of described ethene hervene copolymer polyvinyl resin is 5.60 ~ 7.0g/10min, and density is 0.943 ~ 0.947kg/m
3, weight-average molecular weight 25 ~ 29, molecular weight distribution 13 ~ 18, hexene-1 content 0.3 ~ 0.6%, is prepared from by monocycle pipe slurry process, and the temperature of reaction in reaction vessel is 92.0 ± 2.0 DEG C, and hexene-1/ ethylene feed is than being 17-22%.
3. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material according to claim 1, it is characterized in that, described oxidation inhibitor is phenolic antioxidant, and described aid anti-oxidants is phosphite ester kind antioxidant.
4. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material according to claim 3, it is characterized in that, described phenolic antioxidant is preferably four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphite ester kind antioxidant is preferably two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
5. ageing resistance by ultraviolet light high density polyethylene(HDPE) IBC liner material according to claim 1, is characterized in that, described photostabilizer is poly-[1,6-hexanediamine, N, N '-bis-(2,2,6,6-tetramethyl--4-pyridyl)-morpholine-2,4,6-tri-chloro-1,3,5-triazines].
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745552A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Rigidity-toughness balanced blow molding material for medium-sized hollow container |
| CN113652022A (en) * | 2020-05-12 | 2021-11-16 | 威高集团有限公司 | Infusion pipeline material, preparation method and application thereof |
| CN114426722A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Material for preparing photovoltaic floating pontoon on water and preparation method and application thereof |
| CN114621377A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | High-density polyethylene resin |
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| CN102942733A (en) * | 2012-10-24 | 2013-02-27 | 中国石油化工股份有限公司 | Large hollow container blow molding material and preparation method thereof |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
| CN104744796A (en) * | 2015-01-19 | 2015-07-01 | 中国石油化工股份有限公司 | High-hexene grafted high-density polyethylene geomembrane blow-molding material |
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| CN102942733A (en) * | 2012-10-24 | 2013-02-27 | 中国石油化工股份有限公司 | Large hollow container blow molding material and preparation method thereof |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
| CN104744796A (en) * | 2015-01-19 | 2015-07-01 | 中国石油化工股份有限公司 | High-hexene grafted high-density polyethylene geomembrane blow-molding material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745552A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Rigidity-toughness balanced blow molding material for medium-sized hollow container |
| CN113652022A (en) * | 2020-05-12 | 2021-11-16 | 威高集团有限公司 | Infusion pipeline material, preparation method and application thereof |
| CN114426722A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Material for preparing photovoltaic floating pontoon on water and preparation method and application thereof |
| CN114621377A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | High-density polyethylene resin |
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