CN104744795A - Preparation method of high-hexene grafted high-density polyethylene geomembrane blow molding material - Google Patents
Preparation method of high-hexene grafted high-density polyethylene geomembrane blow molding material Download PDFInfo
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- 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
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Abstract
The invention discloses a preparation method of a high-hexene grafted high-density polyethylene geomembrane blow molding material. The method comprises the following steps: (1) when a diluting agent is always under a circulation state, placing monomer ethylene and 1-hexene in a reaction vessel; adding an antistatic agent and an catalyst subjected to an activation treatment; adjusting the reaction temperature in the reaction vessel to 92-98 DEG C until the melt flow rate of a reaction product is 10.0-13.0g/10min and the density of the reaction product is 0.937-0.939kg/m<3>, thereby obtaining ethylene-hexene polyethylene copolymer base resin with weight average molecular weight of 200,000 to 300,000, 1-hexene content of not less than 1.20% and crystallinity of 46.5-49.5%; (2) uniformly mixing 99.5-99.8 parts of the ethylene-hexene polyethylene copolymer base resin and 0.20-0.50 part of an antioxidant; and adding the mixture to a mixer for extrusion granulation, so as to obtain the geomembrane blow molding material. According to the method, a high-activity novel chromium catalyst is adopted, the equipment limitation of a loop slurry process is overcome, and high-hexene grafted high-density polyethylene is produced. With the method, reaction scale is effectively ameliorated, a reactor wall attachment phenomenon is reduced, production is smooth, and the productivity of the special material is high.
Description
Technical field
The present invention relates to geomembrane construct blow-molded, be specifically related to a kind of high hexene grafted high density polyethylene geomembrane construct blow-molded.
Background technology
High-density polyethylene geomembrane is the saturating material of a kind of Novel seepage, has very high antiseepage coefficient, separately as barrier material, also can combine with non-woven fabrics and make the use of composition type permeation-proof permeable membrane.High-density polyethylene geomembrane has good thermotolerance, winter hardiness, and resistance to deterioration, is not subject to the restriction of area surroundings temperature during use, can long-time exposed use and keep original performance, imbeds laying, longer service life as adopted.
Compared with advanced country in the world, geo-membrane material is started late in the application of China.At present, high-density polyethylene geomembrane material conventional on market, substantially based on import material, can not meet the market requirement far away.Due to the reason of raw material production enterprises' production capacity and price, domestic HDPE geomembrane manufacturing enterprise is difficult to buy satisfactory domestic raw materials, except the competent enterprise of part buys except import geomembrane PP Pipe Compound produces as main raw material(s), major part manufacturing enterprise then simply mix with linear low density polyethylene with the domestic non-dedicated trade mark after produce, thus geomembrane unstable product quality and be difficult to arrival standard-required.Therefore, produce the medium high density polyethylene geomembrane PP Pipe Compound met the demands to accord with the demands of the market.
Loop Slurry Process temperature controls can precisely to ± 0.1 DEG C, compared to the temperature fluctuation of 2 ~ 3 DEG C of gas phase process method, the technology stability of Loop Slurry Process is higher, and the HDPE product that thus Loop Slurry method is produced has the innate advantage of good uniformity, good stability.High-density polyethylene geomembrane often requires to have excellent resisting environmental stress and cracking ability, and in order to improve resisting environmental stress and cracking ability, need aborning to introduce more long-chain branch, that just must more effectively access 1-hexene co-monomer.But adopting Loop Slurry explained hereafter high density polyethylene(HDPE), because reaction system is slurry system, easily causing reaction system to be clamminess when introducing the 1-hexene monomers of high density, easily occur reaction dirtization phenomenon.Reaction dirtization phenomenon refers to that reaction system viscosity is too high, and easily sticky wall, makes reactor actual temperature uprise, obviously depart from and higher than set(ting)value, simultaneously because reaction heat cannot dispel the heat, cause the phenomenon that jacket water (J.W.) temperature drop is low, with occurring that Lao Lunsi pump horsepower is uprushed, there is fluctuation in reaction.And after there is reaction dirtization, easily cruelly poly-during production, produce and be difficult to control.Therefore the geomembrane PP Pipe Compound of Loop Slurry explained hereafter is adopted to be very difficult to break through 0.939g/cm
3lower density limit.Easily there is a large amount of Transition Materials products during production, from the transformation efficiency reducing PP Pipe Compound, reduce output.
Summary of the invention
The object of this invention is to provide a kind of preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded.The method adopts high reactivity novel chromium system catalyzer, overcome the device limitation of Loop Slurry technique, break through the 1-hexene add-on of the production upper limit before this, produce the high density polyethylene(HDPE) obtaining high hexene grafting, effective improvement reaction dirtization, reduce reactor wall sticking phenomenon, produce steadily, PP Pipe Compound productivity is high.
The object of the invention is to realize by following technical solution: the preparation method of high hexene grafted high density polyethylene 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 add the catalyzer of static inhibitor and activated process, regulate the temperature of reaction in reaction vessel to be 92 ~ 98 DEG C, the melt flow rate (MFR) to reaction product is 10.0 ~ 13.0g/10min and density is 0.937 ~ 0.939kg/m
3time, obtaining weight-average molecular weight is 200,000 ~ 300,000,1-ahexene content>=1.20%, the ethene hervene copolymer polyethylene base resin of degree of crystallinity 46.5% ~ 49.5%;
(2) after ethene hervene copolymer polyvinyl resin 99.5 ~ 99.8 parts and 0.20 ~ 0.50 part, oxidation inhibitor mix, add extruding pelletization in mixing roll, particle cools in water coolant, obtains geomembrane construct blow-molded.
As mentioned before, improve hexene amount can cause and the increasing of reaction system viscosity, easily there is the phenomenon of device reaction device dirtization, easily cruelly poly-when causing producing, occur that reactor actual temperature uprises, depart from the phenomenon of reaction set temperature, production is difficult to control, and easily there is a large amount of Transition Materials products when producing, from the transformation efficiency reducing PP Pipe Compound, make the special construct blow-molded material of the geomembrane of Loop Slurry explained hereafter be difficult to break through 0.939g/cm
3lower density limit.Meanwhile, because reaction stability is difficult to control, reaction fluctuation is larger, constantly need observe manufacturing parameter, adjust in time, once fluctuation acquires a certain degree, product actual measurement index exceeds product product control scope, then must production switch to Transition Materials feed bin, as the outbound of the transition trade mark.When producing owing to frequently switching the trade mark, easily occur a large amount of Transition Materials products, thus the productivity that result in geomembrane PP Pipe Compound is very low.In order to solve the problem, contriver proposes different solutions in all its bearings, and final decision solves production problem from raising catalyst activity., after having attempted current existing multiple catalysts, although satisfactory geomembrane construct blow-molded also can be obtained, but need aborning to reduce reaction load, output is not high, and production control is very loaded down with trivial details, the expection object of contriver can not be reached.Then jointly study targetedly with Nachuan Chemical Co., Ltd., Shanghai, finally developed the high activated catalyst that can solve above-mentioned production problem by Nachuan Chemical Co., Ltd., Shanghai.This catalyzer is novel chromium system catalyst n TR-975, can effectively overcome because adding of 1-hexene causes catalyst deactivation and reaction dirtization phenomenon.Because catalyst activity is higher, when producing ethene hervene copolymer polyvinyl resin, can efficiently initiation reaction; Simultaneously, because catalyzer is high to comonomer responsiveness, effectively can access the 1-hexene monomers of more high-content within the reaction times, thus improve the 1-hexene monomers content in high density polyethylene(HDPE) product, overcome reaction system viscosity to increase, avoid device reaction device dirtization phenomenon.Because catalyst activity is high, and reaction system viscosity also has controllability, therefore the inlet amount of vinyl monomer can be strengthened, improve and produce load, and Transition Materials output obviously reduces aborning, the transformation efficiency of production increases substantially, and the amount effectively accessing the 1-hexene in polyethylene in reaction is high, high-density polyethylene resin 1-ahexene content compared with existing like product of the high hexene grafting obtained is higher, has better rigid-tough balance and excellent environmental stress cracking resistance.There is not reactor dirtization phenomenon in process of production, produce more steady, safer.
1-ahexene content of the present invention is 1.20 ~ 1.40%.
The amount ratio of ethene of the present invention and 1-hexene is 1000 ﹕ 30 ~ 60; The consumption of 1-hexene is 6 ~ 12 times of catalyst levels, is 30 ~ 60 times of thinner.Described static inhibitor is ASA, and the ratio between static inhibitor and thinner is 1 ~ 1.5 ﹕ 100.
Thinner of the present invention is preferably Trimethylmethane.
Oxidation inhibitor described in the present invention, for improving the processing stability of material and long-acting thermal oxidative aging, preferably adopts phenolic antioxidant.For improving the stability of stability and the quality product of producing, phenolic antioxidant of the present invention is preferably four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
In step of the present invention (2), the temperature of water coolant is 50 ~ 70 DEG C, and cooling water flow is 600 ~ 700m
3/ h.
the present invention compared with prior art has the following advantages:
(2) in the preparation method of geomembrane construct blow-molded provided by the invention, by adopting NTR-975 type chromium-based catalysts, good to the responsiveness of 1-hexene co-monomer, effective raising 1-hexene grafting amount, therefore effective control 1-hexene co-monomer add-on, avoid causing reaction system to be clamminess, effectively can improve reaction dirtization, reduce reactor wall sticking phenomenon.In addition, highly active catalyzer overcomes the device limitation of Loop Slurry technique, the percentage of grafting of effective increase 1-hexene monomers, form more how long side chain, produce the high density polyethylene(HDPE) of high hexene grafting, bring better environmental stress crack resistance (NCTL) to material.Because catalyst activity improves, production stability improves, and thus can improve the inlet amount of ethene during production, and production can be carried out under high loads.Considerably reduce in production the number of times switching the transition trade mark when producing geomembrane PP Pipe Compound, Transition Materials output significantly reduces, and transformation efficiency increases substantially, and cost is low simultaneously, and supply is stable, improves economic benefit.
(2) the geomembrane construct blow-molded molecular weight obtained by method provided by the invention is high, and molecular weight distribution is reasonable, and high antioxygenic property, meets the processing characteristics required by geomembrane blowing and every physical and mechanical property.Because ahexene content is high, have more how long side chain, compared with existing like product, lower density, has more excellent environmental stress cracking resistance.
(3) catalyst activity of the present invention's employing is high, and production process is very steady, and under higher load (ethylene feed amount), reaction stably can produce the high density polyethylene(HDPE) of high hexene grafting.
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 Nachuan Chemical Co., Ltd., Shanghai to produce NTR-975 type chromium-based catalysts.
Adopt this catalyzer, when Loop Slurry Process is produced, to 1-hexene co-monomer, there is good responsiveness, effectively can improve 1-hexene grafting amount, produce high hexene grafted high density polyethylene geomembrane PP Pipe Compound, thus the risk of reaction dirtization is significantly reduced, reactor is avoided to occur the phenomenons such as sticky wall, because solving the problems referred to above, reaction is produced steadily, not easily occur that reaction fluctuation causes reactor actual temperature to depart from set(ting)value annular-pipe reactor jacket water (J.W.) temperature reduction simultaneously, Lao Lunsi pump horsepower such as to be uprushed at the unusual phenomenon, reduce the probability that Transition Materials produces, obvious minimizing Transition Materials output, simultaneously, highly active catalyzer can cause under higher production load produces reaction, thus the transformation efficiency that PP Pipe Compound is produced significantly improves.
Ethene: purity>=99.20%
c
2h
2≤ 5 × 10
-6cO≤1 × 10
-6
O
2≤2×10
-6H
2O ≤1×10
-6 COS≤0.02×10
-6。
1-hexene: 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.
Trimethylmethane: purity>=95.0% acetylene≤2 × 10
-6total sulfur≤1 × 10
-6
Total olefin≤100 × 10
-6water≤20 × 10
-6o
2≤ 5 × 10
-6.
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 NTR-975 type chromium-based catalysts reacts, temperature of reaction 92.8 DEG C, ethylene feed amount 38t/h, 1-hexene add-on 1440 kg/h, catalyzer feeding quantity 149kg/h, Trimethylmethane feeding quantity 38.0kg/h, static inhibitor 0.39kg/h, the melt flow rate of reacting to reaction product is 11.9g/10min and density is 0.937 ~ 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 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 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 650m
3/ h.
embodiment 2
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 NTR-975 type chromium-based catalysts reacts, temperature of reaction 93.7 DEG C, ethylene feed amount 38t/h, 1-hexene add-on 1897 kg/h, catalyzer feeding quantity 169kg/h, Trimethylmethane feeding quantity 38.6kg/h, static inhibitor 0.56kg/h, the melt flow rate of reacting to reaction product is 12.3g/10min and density is 0.938kg/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 99.70 parts
0.30 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 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 difference injection ring pipe reactor, and add static inhibitor ASA and activated NTR-975 type chromium-based catalysts reacts, temperature of reaction 95.2 DEG C, ethylene feed amount 36t/h, 1-hexene add-on 2059 kg/h, catalyzer feeding quantity 198kg/h, Trimethylmethane feeding quantity 36kg/h, static inhibitor 0.36kg/h, the melt flow rate of reacting to reaction product is 12.6g/10min and density is 0.937kg/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 68 DEG C, and particle cooling water flow is 650m
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 NTR-975 type chromium-based catalysts reacts, temperature of reaction 96.7 DEG C, ethylene feed amount 37t/h, 1-hexene add-on 1668 kg/h, catalyzer feeding quantity 242kg/h, Trimethylmethane feeding quantity 37.8kg/h, static inhibitor 0.38kg/h, the melt flow rate of reacting to reaction product is 12.2g/10min and 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 99.52 parts
0.48 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 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 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 NTR-975 type chromium-based catalysts reacts, temperature of reaction 97.3 DEG C, ethylene feed amount 35t/h, 1-hexene add-on 1788 kg/h, catalyzer feeding quantity 189kg/h, Trimethylmethane feeding quantity 35.9kg/h, static inhibitor 0.36kg/h, the melt flow rate of reacting to reaction product is 12.5g/10min and density is 0.938kg/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 99.50 parts
0.50 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 60 DEG C, and particle cooling water flow is 650m
3/ h.
embodiment 6
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 NTR-975 type chromium-based catalysts reacts, temperature of reaction 95.8 DEG C, ethylene feed amount 36t/h, 1-hexene add-on 2013 kg/h, catalyzer feeding quantity 210kg/h, Trimethylmethane feeding quantity 38kg/h, static inhibitor 0.38kg/h, the melt flow rate of reacting to reaction product is 12.2g/10min and density is 0.938kg/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 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 700m
3/ h.
comparative example 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 Grace company 988A type chromium-based catalysts reacts, temperature of reaction 91.0 DEG C, ethylene feed amount 24t/h, 1-hexene add-on 1883 kg/h, catalyzer feeding quantity 385kg/h, Trimethylmethane feeding quantity 24kg/h, static inhibitor 0.54kg/h, the melt flow rate of reacting to reaction product is 13.4g/10min and 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 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 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.
comparative example 2
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 Grace company 988A type chromium-based catalysts reacts, temperature of reaction 93.7 DEG C, ethylene feed amount 28t/h, 1-hexene add-on 1561kg/h, catalyzer feeding quantity 325kg/h, Trimethylmethane feeding quantity 28kg/h, static inhibitor 0.62kg/h, the melt flow rate of reacting to reaction product is 13.4g/10min and density is 0.941kg/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 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 68 DEG C, and particle cooling water flow is 650m
3/ h.
comparative example 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 difference injection ring pipe reactor, and add static inhibitor ASA and activated Grace company 988A type chromium-based catalysts reacts, temperature of reaction 93.7 DEG C, ethylene feed amount 34t/h, 1-hexene add-on 1211kg/h, catalyzer feeding quantity 301kg/h, Trimethylmethane feeding quantity 34kg/h, static inhibitor 0.68kg/h, the melt flow rate of reacting to reaction product is 13.5g/10min and density is 0.943kg/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 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 68 DEG C, and particle cooling water flow is 650m
3/ h.
Get the embodiment of the present invention 1 ~ 6 to contrast with comparative example 1 ~ 3, the controling parameters in production reaction process is as shown in table 1.
From table 1 result, because in comparative example 1 and 2, catalyst activity is low, have to reduce in reaction process and produce load, the stability that guarantee is produced, because 1-hexene and ethylene feed are than remaining on relatively high ratio, the dirtization that reacts is very easy in reaction process, reaction fluctuation is larger, constantly need observe manufacturing parameter, adjust in time, steadily do not cause frequently switching the transition trade mark owing to producing, catalytic conversion initiation ethene and 1-hexene oligomerization are that the productivity of qualified PP Pipe Compound is lower.Compare ratio 1 and comparative example 2, comparative example 3 improves ethylene feed amount, under the prerequisite of producing load raising, in order to ensure the stability of producing, the risk of reaction dirtization must be reduced, reduce the charge ratio of 1-hexene and ethene, reduce the impact added reaction system viscosity because of 1-hexene, the continuity of producing could be kept.And the catalyst activity adopted in the embodiment of the present invention 1 ~ 6 is more than 2 times of comparative example 1 and 2, because production stability is higher, production status is more steady, the reaction dirtization phenomenon that effective improvement causes because of the increase of 1-hexene monomers add-on, the ratio of the 1-hexene and ethylene feed amount that add reactor is significantly improved, produce steadily, productivity significantly improves.Time needed for contrast continuous seepage 500 tons of PP Pipe Compound, the embodiment of the present invention 1 ~ 6 just can obtain the qualified geomembrane construct blow-molded (namely melting means density reaches the PP Pipe Compound of target zone) of 500 tons in 20 hours, and the time needed for comparative example 1 ~ 3 is respectively 105.7 hours, 77.2 hours and 73.4 hours.
As shown in table 2, compared with comparative example 1, the melting index of geomembrane construct blow-molded of the present invention under high-shear (190 DEG C, 21.6kg counterweight) is lower slightly, shows that the molecular-weight average of material is larger.
As can be seen from result of Table 3, with comparative example 1 and import geotechnique coating materials 1-hexene co-monomer comparision contents, the 1-hexene monomers content of the embodiment of the present invention 1 ~ 6 significantly improves, show that in the present invention, 1-hexene can more effectively access in fluoropolymer resin, thus obtain the high-density polyethylene geomembrane construct blow-molded of the 1-ahexene content higher than the geomembrane PP Pipe Compound trade mark on market.Associative list 1 again, although the ahexene content of comparative example 1 is 1.05%, comparative example 2 is lower slightly, be 0.96%, substantially the level of import geomembrane PP Pipe Compound can be reached, but due to the increase of 1-hexene inlet amount when producing related products, reaction dirtization, fluctuation obviously, has to ethylene feed amount to be down to 24 ~ 25t/h; And comparative example 3 is produced under higher ethylene feed amount, under higher ethylene feed amount, in order to produce steadily, only have and 1-hexene inlet amount is reduced, reduce system viscosity, it is steady that guarantee is produced, thus 1-ahexene content only 0.68% in comparative example 3 gained resin.Contrast known thus, the present invention can keep the high-density polyethylene geomembrane PP Pipe Compound producing high hexene grafting under stable higher production load.
As shown in the result of table 4, compared with the former geomembrane production technology in Maoming and import PP Pipe Compound, geomembrane construct blow-molded fusing point of the present invention and ctystallizing point lower slightly, degree of crystallinity obviously declines.
The result display of table 5, due to the raising of 1-ahexene content, density of the present invention reduces, and over-all properties is better than existing geomembrane construct blow-molded, and tensile property promotes to some extent.
NCTL is the key index of geomembrane, because current geomembrane is mainly used as the purposes of 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.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, and the NCTL of comparative example 1 reaches 1500 hours, the NCTL of comparative example 3 is 1000 hours, geomembrane construct blow-molded provided by the invention is because 1-ahexene content is than the height of comparative example 1 ~ 3, and NCTL test result was up to more than 3000 hours.
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 preparation method for high hexene grafted high density polyethylene geomembrane construct blow-molded, is characterized in that, comprise the following steps:
(1) under thinner is in recurrent state all the time, monomer ethylene and 1-hexene are placed in reaction vessel, and add the catalyzer of static inhibitor and activated process, regulate the temperature of reaction in reaction vessel to be 92 ~ 98 DEG C, the melt flow rate (MFR) to reaction product is 10.0 ~ 13.0g/10min and density is 0.937 ~ 0.939kg/m
3time, obtaining weight-average molecular weight is 200,000 ~ 300,000,1-ahexene content>=1.20%, the ethene hervene copolymer polyethylene base resin of degree of crystallinity 46.5% ~ 49.5%;
(2) after ethene hervene copolymer polyvinyl resin 99.5 ~ 99.8 parts and 0.20 ~ 0.50 part, oxidation inhibitor mix, add extruding pelletization in mixing roll, particle cools in water coolant, obtains geomembrane construct blow-molded.
2. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 1, it is characterized in that, this catalyzer described is chromium-based catalysts
nTR-975.
3. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 1 or 2, it is characterized in that, described 1-ahexene content is 1.20 ~ 1.40%.
4. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 1 or 2 or 3, it is characterized in that, the ratio of the inlet amount of described ethene and 1-hexene is 1000 ﹕ 30 ~ 60.
5. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 4, it is characterized in that, the consumption of described 1-hexene is 6 ~ 12 times of catalyst levels, is 30 ~ 60 times of thinner.
6. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 4, it is characterized in that, the ratio between described static inhibitor and thinner is 1 ~ 1.5 ﹕ 100.
7. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 4, it is characterized in that, described thinner is Trimethylmethane.
8. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 4, it is characterized in that, described oxidation inhibitor is phenolic antioxidant.
9. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 8, it is characterized in that, described phenolic antioxidant is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester.
10. the preparation method of high hexene grafted high density polyethylene geomembrane construct blow-molded according to claim 1, it 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.
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| CN105254991A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Preparation method of high-density polyethylene IBC inner container blow molding material |
| CN109575408A (en) * | 2017-09-28 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of geomembrane polyethylene composition |
| CN113652022A (en) * | 2020-05-12 | 2021-11-16 | 威高集团有限公司 | Infusion pipeline material, preparation method and application thereof |
| CN114456474A (en) * | 2021-11-24 | 2022-05-10 | 中国石油化工股份有限公司 | Thin-wall multilayer hollow blow molding material and preparation method thereof |
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254991A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Preparation method of high-density polyethylene IBC inner container blow molding material |
| CN109575408A (en) * | 2017-09-28 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of geomembrane polyethylene composition |
| CN113652022A (en) * | 2020-05-12 | 2021-11-16 | 威高集团有限公司 | Infusion pipeline material, preparation method and application thereof |
| CN114456474A (en) * | 2021-11-24 | 2022-05-10 | 中国石油化工股份有限公司 | Thin-wall multilayer hollow blow molding material and preparation method thereof |
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