CN104629156A - Geomembrane blow-molding material and preparation method thereof - Google Patents
Geomembrane blow-molding material and preparation method thereof Download PDFInfo
- Publication number
- CN104629156A CN104629156A CN201510026010.7A CN201510026010A CN104629156A CN 104629156 A CN104629156 A CN 104629156A CN 201510026010 A CN201510026010 A CN 201510026010A CN 104629156 A CN104629156 A CN 104629156A
- Authority
- CN
- China
- Prior art keywords
- geomembrane
- molded
- construct blow
- hexene
- blow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a geomembrane blow-molding material and a preparation method thereof. The geomembrane blow-molding material has a melt flow rate of 13.0-14.0g/10min, a density of 0.939-0.941kg/m<3>, a degree of crystallinity of 50-50.8% and a weight average molecular weight of 200,000-300,000 and comprises 99.5-99.9 parts of ethylene-hexene copolymer polyethylene resin and 0.05-0.50 part of an antioxidant. The geomembrane blow-molding material has the characteristics of high content of hexene, wide molecular weight distribution, high antioxidant property and the like. A product has the advantages of prominent environmental stress cracking resistance and creep resistance, excellent oxidation resistance and good chemical resistance and is applicable to processing and molding of various geomembranes, especially a rough mask. By the preparation method disclosed by the invention, limitations of the device in a loop slurry process are overcome, a medium-density product is produced by introducing a large number of hexane and both the process and the supply are stable.
Description
Technical field
The present invention relates to construct blow-molded, be specifically related to a kind of geomembrane construct blow-molded.The invention also discloses the preparation method of this geomembrane construct blow-molded.
Background technology
Geomembrane be a kind of for civil engineering work, the film material that there is pole low-permeability, play waterproof, seepage control effect.As far back as nineteen thirties, the U.S. brings into use geomembrane.And first geomembrane was used for concrete dam antiseepage by China in 1966, after entering the eighties, geomembrane use at home just obtains develop rapidly.
The main process for processing mode of geomembrane has two kinds: blowing cylinder embrane method peace squeezes casting method.At present, occupy an leading position with blowing in market.Product type, geomembrane product have light facial mask and exasperate film point, light facial mask is generally used in plane and lays, and exasperate film can increase frictional coefficient, antiskid function, is more applicable for abrupt slope and vertical seepage control, improves engineering stability.Need to use specific equipment owing to producing exasperate film, require higher to raw-material machine-shaping property, most domestic manufacturer only produces light facial mask, but requirement must use the exasperate film of significant proportion in engineering construction.
The main raw producing geomembrane has high density polyethylene, linear polyethylene LLDPE, polyvinylchloride, ethylene vinyl acetate EVA.Due to PE have that good barrier performance, weldability, punctured resistance are high, nontoxicity, wear-resistant, resistance to low temperature, resistance to chemical attack and resisting environmental stress and cracking excellence over-all properties, become current most popular geotechnological raw material.
The resin grade that Vehicles Collected from Market can meet HDPE geomembrane performance requriements is also few, it is resin dedicated that domestic and international each petro-chemical corporation all develops some medium high density polyethylene geomembranes, as TR400G, the FB 2310 of Borealis, the MF3713 etc. of Iranian husky Suo Shihua that Philips Corporate of Singapore produces.But, these products are not only expensive, and be difficult to ensure that supply is stable, and performance is very different, antioxidant property is general, and the processing characteristics when producing high-grade geomembrane (especially exasperate film), the stability of finished film performance are difficult to ensure.Also just because of this, user needs to use multiple trade mark non-dedicated resin and resin dedicated blending to use, and could meet processing request and finished film performance requriements, but this brings the production cost of larger production difficulty and Geng Gao for geomembrane manufacturer.Therefore, for adapting to market situation day by day with keen competition and meeting user demand, break the situation relying on imported product, Development and Production geomembrane PP Pipe Compound has great importance.
But the density of geomembrane construct blow-molded is 0.937g/cm
3~ 0.941g/cm
3, density is lower, and belong to the production lower limit of high density polyethylene(HDPE) production equipment, the production difficulty of this series products is higher, is all a challenge for high density polyethylene(HDPE) production equipment both domestic and external.
Summary of the invention
First object of the present invention is to provide a kind of geomembrane construct blow-molded, this geomembrane construct blow-molded ahexene content is high, molecular weight distribution is wide, antioxidant property is high, there is outstanding environmental stress cracking resistance (NCTL), excellent antioxidant property, good chemical resistance, is applicable to the machine-shaping of all kinds of geomembrane especially exasperate film.
Second object of the present invention is to provide the preparation method of above-mentioned geomembrane construct blow-molded, the method overcomes the device limitation of Loop Slurry technique, can introduce a large amount of hexene in production, and technique is simple, and cost is low.
First object of the present invention is achieved by the following technical solution: a kind of geomembrane construct blow-molded, and its melt flow rate (MFR) is 13.0 ~ 14.0g/10min, and density is 0.939 ~ 0.941kg/m
3, degree of crystallinity is 50 ~ 50.8%, and weight-average molecular weight is 200,000 ~ 300,000, and its raw material primarily of following weight part is made:
Ethene hervene copolymer polyvinyl resin 99.5 ~ 99.9 parts
0.10 ~ 0.50 part, oxidation inhibitor,
Wherein, the weight-average molecular weight of described ethene hervene copolymer polyvinyl resin is 200,000 ~ 300,000, and melt flow rate (MFR) is 13.0 ~ 14.0g/10min, and density is 0.939 ~ 0.941kg/m
3prepare by the following method: under thinner is in recurrent state all the time, monomer ethylene and 1-hexene are placed in reaction vessel, and the catalyzer added after static inhibitor and activation, be react under the condition of 90 ~ 94 DEG C in temperature of reaction, until the melt flow rate (MFR) of reaction product is 13.0 ~ 14.0g/10min and density is 0.939 ~ 0.941kg/m
3time, i.e. obtained ethene hervene copolymer polyvinyl resin.Ethene hervene copolymer polyvinyl resin prepared by the present invention has suitable density, good rigid-tough balance and excellent environmental stress cracking resistance.
The amount ratio of ethene of the present invention and 1-hexene is 1000 ﹕ 40 ~ 80; The consumption of 1-hexene is 4 ~ 6 times of catalyst levels, is 40 ~ 80 times of thinner.Described static inhibitor is ASA.
Because the 1-hexene add-on of this product is more much higher than other products, during production, reactor viscosity is higher, easily causes temperature of reactor too high, causes sticky wall, increases the power of Lao Lunsi pump running simultaneously, produces reaction dirtization phenomenon.For reducing the operating load of Lao Lunsi pump, need static inhibitor add-on in increasing system, the ratio between static inhibitor and thinner brings up to 2 ~ 3 ﹕ 100 by 1 ﹕ 100 producing other universal HDPE product.
Thinner of the present invention is preferably Trimethylmethane.
Catalyzer of the present invention is chromium-based catalysts, the 988A type chromium-based catalysts that the Grace company of the U.S. for import produces.
Oxidation inhibitor described in the present invention, for improving the processing stability of material and long-acting thermal oxidative aging, preferably adopts phenolic antioxidant.Due to geomembrane goods be mainly used in garbage loading embeading, water conservancy paving is buried in purposes, goods need to add carbon black, not high to resin chromaticity requirements, adopt separately phenolic antioxidant just to can be the processing stability and thermo-oxidative ageing that provide material enough.As one embodiment of the present of invention, described phenolic antioxidant is preferably four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The present invention's second object is achieved by the following technical solution: the preparation method of above-mentioned geomembrane construct blow-molded, comprises the following steps:
(1) under thinner is in recurrent state all the time, monomer ethylene and 1-hexene are placed in reaction vessel, and the catalyzer added after static inhibitor and activation, be react under the condition of 90 ~ 94 DEG C in temperature of reaction, until the melt flow rate (MFR) of reaction product is 13.0 ~ 14.0g/10min and density is 0.939 ~ 0.941kg/m
3time, obtain ethene hervene copolymer polyvinyl resin;
(2) by metering ratio, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add extruding pelletization in mixing roll, particle cools in water coolant, obtains geomembrane construct blow-molded.
In described step (2), the temperature of water coolant is 50 ~ 70 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
Because 1-hexene add-on in step (1) is more much higher than other products, during production, reactor viscosity is higher, produces reaction dirtization phenomenon, easily increases the power of Lao Lunsi pump running.For reducing the operating load of Lao Lunsi pump, the viscosity of reaction system need be reduced, controls from following three aspects in production process, solve the production difficulty of this product:
(1) regulate, improve the add-on of thinner in reaction process according to response situation, reduce solids content.The amount ratio of described ethene and 1-hexene is 1000 ﹕ 40 ~ 80 particularly; The consumption of 1-hexene is 4 ~ 6 times of catalyst levels, is 40 ~ 80 times of thinner.Described static inhibitor is ASA.
(2) the static inhibitor add-on in increasing system, the ratio in the present invention between static inhibitor and thinner brings up to 2 ~ 3 ﹕ 100 by 1 ﹕ 100 producing other general HDPE product.
(3) when perceiving the situations such as Lao Lunsi pump horsepower is increased significantly in continuous flow procedure, reduce in time and produce load, until Lao Lunsi pump horsepower recovers normal.
The present invention compared with prior art has the following advantages:
(1) ahexene content of geomembrane construct blow-molded provided by the invention is high, molecular weight distribution is wide, antioxidant property is high, processing characteristics and every physical and mechanical property meet the requirement of geomembrane blowing, there is excellent long-acting antioxidant property and environmental stress cracking resistance, filled up the blank of domestic Loop Slurry explained hereafter geomembrane PP Pipe Compound.
(2) in the present invention, because reaction system viscosity is high, therefore in reaction process, improve the add-on of thinner to reduce solids content, strengthen the adding proportion of static inhibitor and thinner simultaneously, prevent powder from gluing wall at reactor, and when situations such as Lao Lunsi pump horsepower are increased significantly, load is produced in timely reduction, overcome 1-ahexene content in reaction system too high to reaction system cause reaction viscosity too high, react unmanageable impact, thus break through existing Loop Slurry production equipment process limitation, thus obtain the geomembrane construct blow-molded of appropriate density.
Accompanying drawing explanation
Fig. 1 is the crystallization curve correlation curve figure of geo-membrane material of the present invention and import geotechnique coating materials;
Wherein, TR400M is geo-membrane material of the present invention.
Embodiment
The catalyst activation treatment of following examples adopts ordinary method, be specially: catalyzer is by opening pot bottom valve, gravity is relied on to fall into activator, come from the hot burning gas of the burner hearth of activation furnace and fluidized hot air heating activation furnace and catalyzer, fluidizing agent upwards by after grid distributor, fully contacts with catalyzer and makes catalyst activation.
Mixing roll adopts the extrusion machine of Coperion ZSK-350 type, and extrusion machine has 7 sections of cylindrical shells.
Catalyzer is chromium-based catalysts, adopts the 988A type chromium-based catalysts that Grace company of the U.S. produces.
Because in the preparation of ethene hervene copolymer ethenoid resin, 1-hexene add-on is more much higher than other products, during production, reactor viscosity is higher, easily increases the power of Lao Lunsi pump running, produces reaction dirtization phenomenon.For reducing the operating load of Lao Lunsi pump, the viscosity of reaction system need be reduced, controls from following three aspects in production process, solve the production difficulty of this product:
(1) regulate, improve the add-on of thinner in reaction process according to response situation, reduce solids content.The amount ratio of described ethene and 1-hexene is 1000 ﹕ 40 ~ 80 particularly; The consumption of 1-hexene is 4 ~ 6 times of catalyst levels, is 40 ~ 80 times of thinner.Described static inhibitor is ASA.
(2) the static inhibitor add-on in increasing system, the ratio in the present invention between static inhibitor and thinner brings up to 2 ~ 3 ﹕ 100 by 1 ﹕ 100 producing other general HDPE product.
(3), when perceiving the situations such as Lao Lunsi pump horsepower is increased significantly in continuous flow procedure, reduce at once and produce load.
Embodiment 1
The preparation of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene difference injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 25t/h, 1-hexene inlet amount is 1308kg/h, Trimethylmethane feeding quantity 26.9kg/h, catalyzer feeding quantity 309kg/h, static inhibitor ASA feeding quantity is 0.54kg/h, temperature of reaction 93.5 DEG C, until the melt flow rate of reaction product is 13.2g/10min, density is 0.939kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.65 parts
0.35 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By said ratio, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate state geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 260 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C.The temperature of water coolant is 68 DEG C, and particle cooling water flow is 650m
3/ h.
Embodiment 2
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene difference injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 28t/h, 1-hexene inlet amount is 1960kg/h, Trimethylmethane feeding quantity 28.3kg/h, catalyzer feeding quantity 365kg/h, static inhibitor ASA feeding quantity is 0.57kg/h, temperature of reaction 93.7 DEG C, until the melt flow rate of reaction product is 13.2g/10min, density is 0.940kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.90 parts
0.10 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene product geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 265 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C, and the temperature of water coolant is 65 DEG C, and particle cooling water flow is 680m
3/ h.
Embodiment 3
The preparation of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene respectively injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 24t/h, 1-hexene inlet amount is 1883kg/h, Trimethylmethane feeding quantity 24kg/h, catalyzer feeding quantity 385kg/h, static inhibitor ASA feeding quantity is 0.54kg/h, temperature of reaction 91 DEG C, until the melt flow rate of reaction product is 13.3g/10min, density is 0.940kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.80 parts
0.20 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene product geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 265 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C.The temperature of water coolant is 60 DEG C, and particle cooling water flow is 600m
3/ h.
Embodiment 4
The preparation of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene difference injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 29t/h, 1-hexene inlet amount is 1538kg/h, Trimethylmethane feeding quantity 29kg/h, catalyzer feeding quantity 384.5kg/h, static inhibitor ASA feeding quantity is 0.58kg/h, temperature of reaction 92.8 DEG C, until the melt flow rate of reaction product is 13.0g/10min, density is 0.939kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.55 parts
0.45 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene product geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 270 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C.The temperature of water coolant is 55 DEG C, and particle cooling water flow is 600m
3/ h.
Embodiment 5
The preparation of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene difference injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 28t/h, 1-hexene inlet amount is 1561kg/h, Trimethylmethane feeding quantity 31kg/h, catalyzer feeding quantity 325kg/h, static inhibitor ASA feeding quantity is 0.62kg/h, temperature of reaction 93.7 DEG C, until the melt flow rate of reaction product is 13.4g/10min, density is 0.940kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.75 parts
0.25 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By said ratio, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene product geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 270 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C.The temperature of water coolant is 68 DEG C, and particle cooling water flow is 650m
3/ h.
Embodiment 6
The preparation method of ethene hervene copolymer ethenoid resin:
Thinner Trimethylmethane is in recurrent state all the time, by in monomer ethylene and 1-hexene difference injection ring pipe reactor, and add static inhibitor ASA and activated 988A type chromium-based catalysts reacts, wherein, ethylene feed amount 25t/h, 1-hexene inlet amount is 1809kg/h, Trimethylmethane feeding quantity 23.5kg/h, catalyzer feeding quantity 450kg/h, static inhibitor ASA feeding quantity is 0.48kg/h, temperature of reaction 90.8 DEG C, until the melt flow rate of reaction product is 13.3g/10min, density is 0.940kg/m
3time, stopped reaction, obtains ethene hervene copolymer polyvinyl resin.
The raw material (weight part) of geomembrane construct blow-molded:
Ethene hervene copolymer polyvinyl resin 99.51 parts
0.49 part, oxidation inhibitor
Wherein oxidation inhibitor is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method of geomembrane construct blow-molded:
By above-mentioned consumption, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add mixing roll and extrude particle in water coolant, obtain particulate polyethylene product geomembrane construct blow-molded.Wherein, when mixing roll is mixing, regulate mixing roll second segment barrel temperature to be 225 DEG C, the 3rd section of barrel temperature is 230 DEG C, and the 4th section of barrel temperature is 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, and the 7th section of barrel temperature is 265 DEG C; The thermal oil temperature of heating mixing roll is 260 DEG C.The temperature of water coolant is 70 DEG C, and particle cooling water flow is 700m
3/ h.
The geomembrane construct blow-molded and the new luxuriant and rich with fragrance TR400G and Iranian MF3713 that get the embodiment of the present invention 1 ~ 6 carry out Performance comparision, and result is see table 1 ~ 6.
Table 1 melt flow rate
Table 2 melting, crystallization parameters
As shown in the result of table 2 and Fig. 1, compared with import material, the melting index of geomembrane construct blow-molded of the present invention under high-shear (190 DEG C, 21.6kg counterweight) is higher, is more conducive to extrude machine-shaping.Meanwhile, geotechnological construct blow-molded crystallization onset temperature of the present invention, crystallization summit temperature are substantially suitable with import material.But the temperature range of crystallization is narrower than TR400G, the temperature that crystallization terminates is also lower, and peak crystallization area is also less, and degree of crystallinity is also lower.
Table 3 apparent property
In apparent property (see table 3), geomembrane construct blow-molded of the present invention is all better than import material in the tensile property such as tensile yield strength, angle tear strength test event, this and geomembrane construct blow-molded of the present invention have lower degree of crystallinity, and toughness is higher is identical.
Oxidation induction period at 200 DEG C, table 4
The oxidation induction period of geomembrane construct blow-molded of the present invention at 200 DEG C is obviously better than import material, its oxidation induction period time is up to 1 ~ 2 times of import material, wherein, embodiment 6 is higher than 2 times of import geomembrane PP Pipe Compound oxidization time, and visible geomembrane construct blow-molded of the present invention has better oxidation-resistance.
Table 5 NCTL data
NCTL in table 5 is the key index of geomembrane, because current geomembrane is mainly used in waterproof, seepage control, garbage loading embeading.Need landfill in underground at least 50 years, therefore its environmental stress cracking resistance is the test index of most important its useful life longevity of measurement.Adopt traditional ESCR index cannot weigh out the quality of material, single-point otch dead load tensile stress cracking (NCTL) becomes the most important index evaluating geo-membrane material resisting environmental stress and cracking ability.At present, geomembrane industry does not formulate the NCTL standard of resin aspect, mainly firmly to build the testing method of portion CJ/T234-2006 and standard to weigh geomembrane environmental stress crack resistance, firmly the portion of building be required of the NCTL test result of finished film must higher than 300 hours, as can be seen from the results of table 5, the actual effect of the geomembrane construct blow-molded of the embodiment of the present invention 1 ~ 6 is far above industry standard.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character, the above embodiment of the present invention all can only be thought explanation of the present invention instead of restriction, every above embodiment is done according to substantial technological of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (10)
1. a geomembrane construct blow-molded, is characterized in that, its melt flow rate (MFR) is 13.0 ~ 14.0g/10min, and density is 0.939 ~ 0.941kg/m
3, degree of crystallinity is 50 ~ 50.8%, and weight-average molecular weight is 200,000 ~ 300,000, and its raw material primarily of following weight part is made:
Ethene hervene copolymer polyvinyl resin 99.5 ~ 99.9 parts
0.10 ~ 0.50 part, oxidation inhibitor,
Wherein, described ethene hervene copolymer polyvinyl resin prepares by the following method: under thinner is in recurrent state all the time, feed ethylene and 1-hexene are placed in reaction vessel, and the catalyzer added after static inhibitor and activation, be react under the condition of 90 ~ 94 DEG C in temperature of reaction, until the melt flow rate (MFR) of reaction product is 13.0 ~ 14.0g/10min and density is 0.939 ~ 0.941kg/m
3time, i.e. obtained ethene hervene copolymer polyvinyl resin.
2. geomembrane construct blow-molded according to claim 1, it is characterized in that, the mass ratio of described ethene and 1-hexene is 1000 ﹕ 40 ~ 80; The consumption of described 1-hexene is 4 ~ 6 times of catalyst levels, is 40 ~ 80 times of thinner.
3. geomembrane construct blow-molded according to claim 1, it is characterized in that, the ratio between described static inhibitor and thinner is 2 ~ 3 ﹕ 100.
4. geomembrane construct blow-molded according to claim 1, it is characterized in that, described thinner is Trimethylmethane; Described catalyzer is 988A type chromium-based catalysts; Described oxidation inhibitor is phenolic antioxidant.
5. geomembrane construct blow-molded according to claim 1, it is characterized in that, described phenolic antioxidant is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
6. the preparation method of the geomembrane construct blow-molded described in any one of Claims 1 to 5, is characterized in that, comprise the following steps:
(1) under thinner is in recurrent state all the time, feed ethylene and 1-hexene are placed in reaction vessel, and the catalyzer added after static inhibitor and activation, be react under the condition of 90 ~ 94 DEG C in temperature of reaction, until the melt flow rate (MFR) of reaction product is 13.0 ~ 14.0g/10min and density is 0.939 ~ 0.941kg/m
3time, obtain ethene hervene copolymer polyvinyl resin;
(2) by metering ratio, after ethene hervene copolymer polyvinyl resin and oxidation inhibitor mixing, add extruding pelletization in mixing roll, particle cools in water coolant, obtains geomembrane construct blow-molded.
7. the preparation method of geomembrane construct blow-molded according to claim 6, it is characterized in that, in described step (1), in described step (1), in continuous flow procedure, perceive Lao Lunsi pump horsepower when being increased significantly situation, need to reduce in time to produce load.
8. the preparation method of the geomembrane construct blow-molded described in claim 6 or 7, is characterized in that, in described step (1), the ratio between described static inhibitor and thinner is 2 ~ 3 ﹕ 100.
9. the preparation method of geomembrane construct blow-molded according to claim 8, is characterized in that, the mass ratio of described ethene and 1-hexene is 1000 ﹕ 40 ~ 80; The consumption of described 1-hexene is 4 ~ 6 times of catalyst levels, is 40 ~ 80 times of thinner.
10. the preparation method of geomembrane construct blow-molded according to claim 6, is characterized in that, in described step (2), the temperature of water coolant is 50 ~ 70 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026010.7A CN104629156B (en) | 2015-01-19 | 2015-01-19 | A kind of geomembrane construct blow-molded and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026010.7A CN104629156B (en) | 2015-01-19 | 2015-01-19 | A kind of geomembrane construct blow-molded and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104629156A true CN104629156A (en) | 2015-05-20 |
| CN104629156B CN104629156B (en) | 2017-10-10 |
Family
ID=53208423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510026010.7A Active CN104629156B (en) | 2015-01-19 | 2015-01-19 | A kind of geomembrane construct blow-molded and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104629156B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264598A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Preparation method of medium-density polyethylene resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5736237A (en) * | 1996-11-25 | 1998-04-07 | Union Carbide Chemicals & Plastics Technology Corporation | Geomembranes |
| US20060217490A1 (en) * | 2005-03-22 | 2006-09-28 | Lee Chun D | Polyethylene compositions having improved printability |
| CN101423573A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Polyethylene resin for tubular material and preparation method and composition thereof |
| CN101787157A (en) * | 2009-01-23 | 2010-07-28 | 赢创奥克森诺有限责任公司 | Comprise and use 3-to replace C 4-10The PE film SS of the interpolymer of-alkene and single site catalysts |
-
2015
- 2015-01-19 CN CN201510026010.7A patent/CN104629156B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5736237A (en) * | 1996-11-25 | 1998-04-07 | Union Carbide Chemicals & Plastics Technology Corporation | Geomembranes |
| US20060217490A1 (en) * | 2005-03-22 | 2006-09-28 | Lee Chun D | Polyethylene compositions having improved printability |
| CN101423573A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Polyethylene resin for tubular material and preparation method and composition thereof |
| CN101787157A (en) * | 2009-01-23 | 2010-07-28 | 赢创奥克森诺有限责任公司 | Comprise and use 3-to replace C 4-10The PE film SS of the interpolymer of-alkene and single site catalysts |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264598A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Preparation method of medium-density polyethylene resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104629156B (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104744796B (en) | A kind of hexene grafted high density polyethylene geomembrane construct blow-molded high | |
| CN102863712B (en) | High shock resistant PVC tubular product and preparation method thereof | |
| CN102382344B (en) | Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof | |
| CN102002191B (en) | PPR/EVOH/POE (Pentatricopeptide Repeats/Ethylene-Vinyl Alcohol/Polyolefin Elastomer) blending high-impact barrier pipe and manufacturing method thereof | |
| CN105754179A (en) | Flame retardant HDPE cable material and preparation method thereof | |
| CN109503926A (en) | A kind of preparation method of composite barrier material | |
| CN104744795B (en) | The preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded | |
| CN105733023B (en) | Composite assistant for high-density polyethylene pressure-resistant pipe, preparation method thereof and resin raw material containing composite assistant | |
| CN106700193A (en) | Polyethylene composition | |
| CN104629156A (en) | Geomembrane blow-molding material and preparation method thereof | |
| CN101746547B (en) | Modified asphalt packaging film bag and preparation method thereof | |
| CN103374117A (en) | Preparation method of heat-resistant degradable resin | |
| CN103881248A (en) | Chlorinated polyethylene rubber composition | |
| CN104788780A (en) | Polyethylene tearing film and preparation method thereof | |
| CN105254990B (en) | A kind of ageing resistance by ultraviolet light high density polyethylene (HDPE) IBC liner materials and preparation method | |
| CN104072907B (en) | A kind of PVC profile for wear-resisting indoor floor and production method thereof | |
| CN104311980B (en) | A kind of high-stiffness polyethylene blown film material and preparation method thereof | |
| CN102952220A (en) | Preparation method of polyvinyl chloride spherical resin | |
| CN108264680B (en) | Medium-density polyethylene resin and application thereof in waterproof barrier geomembrane | |
| CN102216662A (en) | Cross-linked polyethylene pipe | |
| CN105585764B (en) | A kind of special construct blow-molded of automobile plastic fuel tank and preparation method thereof | |
| CN101402765A (en) | Method for producing polythene/polystyrene alloy with capacity increasing of reaction in-situ | |
| CN100427386C (en) | Medium grade insoluble sulphur preparing process and producing apparatus | |
| CN109575408A (en) | A kind of geomembrane polyethylene composition | |
| CN105419076B (en) | A kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |