WO2019066516A1 - 배관용 수지 조성물의 장기 내구성 예측 방법 및 배관용 수지에 사용되는 올레핀계 고분자 - Google Patents

배관용 수지 조성물의 장기 내구성 예측 방법 및 배관용 수지에 사용되는 올레핀계 고분자 Download PDF

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WO2019066516A1
WO2019066516A1 PCT/KR2018/011478 KR2018011478W WO2019066516A1 WO 2019066516 A1 WO2019066516 A1 WO 2019066516A1 KR 2018011478 W KR2018011478 W KR 2018011478W WO 2019066516 A1 WO2019066516 A1 WO 2019066516A1
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Prior art keywords
molecular weight
content
term durability
olefin
resin
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Ceased
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PCT/KR2018/011478
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English (en)
French (fr)
Korean (ko)
Inventor
박성현
이현섭
박종상
김중수
유영석
홍대식
이명한
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020170127803A external-priority patent/KR102184390B1/ko
Priority claimed from KR1020180014323A external-priority patent/KR102486846B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18860648.7A priority Critical patent/EP3674334B1/en
Priority to CN201880057741.XA priority patent/CN111133013B/zh
Priority to US16/647,751 priority patent/US11697699B2/en
Priority to JP2020513310A priority patent/JP6942245B2/ja
Publication of WO2019066516A1 publication Critical patent/WO2019066516A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N3/56—Investigating resistance to wear or abrasion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather
    • G01N33/442—Resins; Plastics
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • 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
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
    • G01N2203/0058—Kind of property studied
    • G01N2203/0069—Fatigue, creep, strain-stress relations or elastic constants
    • G01N2203/0071—Creep
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather

Definitions

  • the present application relates to a method for predicting long-term durability of a resin for piping or a composition comprising the resin.
  • the present application also relates to an olefin-based polymer contained in a composition that can be used for forming a resin for piping.
  • ISO 9080 and ISO 16770 methods for evaluating long-term durability of well-known piping pipes.
  • ISO 9080 is a method for estimating the pressure expected to cause cracks over 50 years by extrapolating and measuring the crack occurrence time over one year according to the temperature and pressure of water passing through the pipe.
  • Products with long-term durability recognized by ISO 9080 have an environmental stress crack resistance (ESCR) of 4.0 MPa stress and a full notch creep test (FNCT) according to ISO 16770 at 80 ° C. This is about 2,000 hours or more.
  • ESCR environmental stress crack resistance
  • FNCT full notch creep test
  • the product has durability to such an extent that the sample breaks after more than 2000 hours have elapsed.
  • the product has durability to such an extent that the sample breaks after more than 2000 hours have elapsed.
  • it takes a time of at least three months to one year to perform the above two methods. Therefore, there is a need for a method that can predict the long-term durability in order to shorten the product development time by selecting samples to be measured for long-term durability among various samples in the product development stage.
  • One object of the present invention is to provide a method for predicting the long term durability of a resin composition for piping in a short time.
  • Another object of the present application is to provide a method for comparatively evaluating long term durability for a plurality of resin compositions for piping.
  • Another object of the present invention is to provide a polymer which can be used for manufacturing a pipe for a heating pipe excellent in long-term durability.
  • Another object of the present invention is to provide a resin composition for a heating pipe excellent in environmental stress cracking resistance.
  • the present application relates to a method for predicting or evaluating the long-term durability of a resin composition for piping.
  • the sample to be predicted or evaluated may be a resin or a resin composition containing other components.
  • the resin (composition) for piping may mean a resin (composition) used in a pipe forming a moving path of a fluid or the like, and may mainly mean a resin (composition) for a heating pipe .
  • the long-term durability prediction method of the present application uses a tie molecule, an entanglement molecular weight (M e ) and a mass-average molecular weight (M w ) as factors for predicting long-term durability.
  • Tie molecule which is one of the factors used in predicting long-term durability, means a polymer connecting the crystals of the amorphous polymer resin.
  • amorphous polymers crystals of Lamellar structure are formed by chain folding below the crystallization temperature.
  • the portion does not form crystals and remains amorphous.
  • a lamellar can be formed in a portion where no? -Olefin or LCB structure exists, one polymer chain can form a crystal-amorphous-crystal structure.
  • the amorphous portion serves to connect the crystal to the crystal, which is called a tiemolecule.
  • the content of tiemolecule is used as a factor of predicting long-term durability.
  • the content of tiemolecule means the percentage of the polymer forming the tiemolecule, that is, the% by weight based on the weight of the total polymer included in the resin composition.
  • the content of Tie molecule can be determined as described below.
  • the entangled molecular weight As the molecular weight of the polymer is high, the longer the length of the polymer chain, the greater the probability that a tangled point will be formed, so that the entangled molecular weight will decrease.
  • the entangled molecular weight is used as one of the factors of long-term durability prediction. The entangled molecular weight can be measured as described below.
  • the ultra high molecular weight means a case where the mass average molecular weight (Mw) is at least 1,000,000, and the content of the ultrahigh molecular weight component is the percentage of the polymer having a mass average molecular weight of at least 1,000,000 based on the weight of the entire polymer contained in the resin composition, That is,% by weight.
  • Mw mass average molecular weight
  • the content of the ultrahigh molecular weight component is used as a factor of predicting long term durability.
  • the content of the ultrahigh molecular weight component can be measured as described below.
  • the long-term durability of the resin composition can be predicted or evaluated in a short time even if a small amount of a sample is used.
  • the method according to the present application can predict or evaluate the long-term durability of the resin composition as a sample by using the following equation.
  • X, Y, and Z are a value relating to molecular characteristics that can be measured in a resin composition as a sample. Specifically, X is the content (wt%) of the tie molecule, Y is the entanglement molecular weight (g / mol), Z is the content (wt%) of the component having a mass average molecular weight (Mw) . At this time, X, Y, and Z are used as non-dimensional constants excluding the unit.
  • the inventors of the present application found that the predicted values for the long term durability calculated according to the above equations are very similar to the environmental stress crack resistance evaluation results measured by the full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ⁇ Respectively. Therefore, if the predicted value of the long-term durability of the resin composition as the sample is calculated according to the present application, the long-term durability of the resin composition for piping can be predicted within a short period of time by simple calculation without performing the durability evaluation over a long period of time such as ISO 9080 or ISO 16770 Can be evaluated.
  • FNCT full notch creep test
  • the calculation of the predicted value of long-term durability can be made for a plurality of samples. In this case, it can be judged that the long-term durability of the sample having the largest calculated value is the most excellent.
  • a sample to be evaluated or evaluated for long-term durability that is, a resin composition
  • a resin composition comprises a homopolymer formed from one kind of monomer component and / or a copolymer formed from a plurality of different monomer components .
  • the resin composition may also comprise at least one homopolymer or copolymer.
  • the resin composition as a sample may include a polyolefin.
  • the kind of the polyolefin is not particularly limited.
  • the polyolefin may be a polymer formed from ethylene, butylene, propylene, and / or alpha-olefin-based monomers.
  • the kind of the? -olefin-based monomer is not particularly limited. Butene, 1-hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene, 1-eicosene and the like can be used, but there is no particular limitation thereto.
  • the present application relates to an olefin-based polymer.
  • the polymer may be used in a pipe forming a moving path of a fluid or the like, and mainly used for forming a heating pipe. Since the polymer satisfies predetermined conditions and / or constructions described below, it has excellent long-term durability which can be confirmed, for example, through evaluation of environmental stress cracking resistance.
  • the design factors of the olefin-based polymer may include the content of tie molecule, the entanglement molecular weight (M e ) and the content of the ultrahigh molecular component.
  • Tie molecule which is one of the design factors of a polymer, means a polymer connecting the crystals of the amorphous polymer resin.
  • crystals of Lamellar structure are formed by chain folding below the crystallization temperature.
  • a polymer structure capable of forming a defect in the crystal structure for example, an? -Olefin or an LCB (long chain branch) exists, the portion does not form crystals and remains amorphous.
  • a lamellar structure can be formed in a portion where no ⁇ -olefin or LCB structure is present, so that one polymer chain can form a crystal-amorphous-crystal structure.
  • the amorphous portion serves to connect the crystal to the crystal, which is called a tiemolecule.
  • the content of tiemolecule is used as a factor of designing a polymer used for the above-mentioned use.
  • the content of the tiemolecule refers to the percentage of the (polymer) component forming the tiemolecule based on the weight 100 of the whole polymer, that is, the% by weight.
  • the content of Tie molecule can be determined as described below.
  • the entanglement molecular weight (M e ), which is another factor used in the present application, is one in which a single polymer chain is tangled with the surrounding polymer or itself to form a tangent point that functions as a physical crosslink Quot; means the average molecular weight between such entanglement points.
  • M e The entanglement molecular weight
  • the entangled molecular weight can be measured as described below.
  • the ultra high molecular weight means a case where the mass average molecular weight (Mw) is 1 million or more, and the content of the ultrahigh molecular weight component is the percentage of the (mass) molecular weight component having a weight average molecular weight of 100,000 or more %.
  • Mw mass average molecular weight
  • the content of the ultrahigh molecular weight component is the percentage of the (mass) molecular weight component having a weight average molecular weight of 100,000 or more %.
  • the higher the content of the ultrahigh molecular weight component the larger the number of polymer chains having a longer chain length of the polymer chain. Therefore, the entanglement of polymer chains and the content of tiemolecule are also increased.
  • the present application uses the content of ultra-high molecular weight components as a factor in the design of polymers used for such applications.
  • the content of the ultrahigh molecular weight component can be measured as described below.
  • the inventors of the present application have confirmed that when the olefin-based polymer is designed to satisfy a predetermined relationship with respect to the above factors, it is possible to provide a heating tube resin excellent in long-term durability.
  • the olefin-based polymer of the present application may be an olefin-based polymer satisfying at least two or more of the following conditions [A] to [C].
  • the content of tie molecule is more than 10 wt%
  • the polymer may further satisfy the condition that the content of the tie molecule is not more than 30 wt%, not more than 25 wt%, or not more than 20 wt% with respect to the above condition [A].
  • an increase in the content may be taken into account in consideration of the content of the tiemolecule as described above.
  • the density of the polymer should be lowered or the content of the higher molecular weight component should be increased.
  • the endurance performance of the final pipe product is deteriorated.
  • the polymer may have an entangled molecular weight (Me) of 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, or 5000 g / mol. < / RTI >
  • Me entangled molecular weight
  • a decrease in the molecular weight can be considered in consideration of the content of the entangled molecular weight as described above. However, if the entangling molecular weight is too low, the content of the high molecular weight component becomes high, and thus the workability is lowered.
  • the polymer may further include a condition that the content of the component having a mass average molecular weight (Mw) of not less than 1,000,000 is not more than 20 wt%, not more than 15 wt%, or not more than 10 wt% Can be satisfied. If the content of the ultrahigh molecular weight component exceeds the above range, the workability may be deteriorated.
  • Mw mass average molecular weight
  • the polymer may satisfy all of the conditions [A] to [C]. When all three of the above conditions are satisfied, excellent durability can be ensured.
  • the kind of the monomer for forming the olefin-based polymer is not particularly limited.
  • the olefin-based polymer may be formed from a monomer mixture comprising ethylene, butylene, propylene, or? -Olefin-based monomer. That is, the polymer of the present application may be one produced by polymerizing one or more monomers of the above monomers.
  • the kind of the? -Olefin-based monomer is not particularly limited.
  • Butene, 1-hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene, 1-eicosene and the like can be used, but there is no particular limitation thereto.
  • the monomer mixture may comprise two or more monomers selected from ethylene, butylene, propylene, and alpha -olefin-based monomers.
  • the two or more monomers contained in the monomer mixture may be different from each other, and the kinds of the? -Olefin-based monomers are the same as those listed above.
  • the olefin-based polymer may include ethylene as a main component.
  • the main component monomer in relation to the component of the polymer may mean that the content of the main component monomer exceeds 50 wt% based on the total monomer content 100 used for polymer formation.
  • the upper limit of the main component monomer content is not particularly limited, but may be, for example, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, or 70 wt% or less.
  • the monomer mixture may contain at least one monomer selected from among butylene, propylene, and? -Olefin-based monomers as copolymerizable monomers besides ethylene as a main component.
  • the copolymerizable monomer may be used in the monomer mixture in an amount other than the content of ethylene as the main monomer.
  • 1-butene (1-C4) may be used as a copolymerizable monomer for forming the olefin-based polymer.
  • a monomer having a short length for example, 1-butene may be used due to the characteristics of the polymerization equipment and the influences of raw material supply and the like.
  • the long-term durability may be lowered compared with a product produced using a relatively long copolymerized monomer such as 1-hexene (1-C6) or 1-octene (1-C8).
  • the content of 1-butene to be used is not particularly limited, but it can be used in a range of about 7.0 to 10.1 / 1,000C as a result of FT-IR analysis.
  • the polymer satisfying the above conditions and configuration may have an environmental stress cracking resistance (ESCR) of at least 1500 hours measured by a full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ⁇ . More preferably, the polymer may have an environmental stress cracking resistance (ESCR) of 2000 hours to 8000 hours measured by a full notch creep test (FNCT) according to the same conditions and methods.
  • ESCR environmental stress cracking resistance
  • a method of predicting the long-term durability of a resin for a pipe in a short time can be provided by using a small amount of a sample. Further, since the long-term durability of the resin for piping can be evaluated within a short period of time, a polymer structure having excellent long-term durability can be usefully designed, and a sample worthy of actual long-term durability can be selected in a short time It is possible to increase the efficiency of the product development stage and shorten the development time. Further, according to the present application, an olefin-based polymer structure having excellent long-term durability can be usefully designed, and a pipe for piping excellent in long-term durability can be provided.
  • FIG. 1 is a graph showing the correlation between an actual FNCT value of the resin used in the production example and a predicted FNCT value calculated for each resin of the present application corresponding to the production example.
  • n is the number of macromolecules having a molecular weight M, and can be obtained from (dw / dlogMw) / M in the GPC curve data in which the x-axis is logMw and the y-axis is dw / dlogMw.
  • the above-mentioned P can be calculated from the following equations (1) to (3) as the probability of the polymer having a molecular weight of M forming tiemolecule, and dM is the interval between the x-axis (molecular weight M) data of the GPC curve.
  • r is the end-to-end distance of a random coil
  • b 2 is 3 / 2r 2
  • l c is the crystal thickness
  • l a is the amorphous thickness, which is obtained from the following equation (3).
  • T o m is 415 K
  • ⁇ e is 60.9 ⁇ 10 -3 J / m 2
  • ⁇ h m is 2.88 ⁇ 10 3 J / m 3 .
  • ⁇ c is a density of crystalline of 1,000 kg / m 3
  • ⁇ a is a density of amorphous phase of 852 kg / m 3
  • ⁇ c is a mass fraction crystallinity (weight fraction crystallinity).
  • each of X, Y and Z is a content (wt%) of tiemolecule in the resin composition as a sample, (G / mol), and the content (wt%) of the component having a mass average molecular weight (Mw) of 1,000,000 or more.
  • Mw mass average molecular weight
  • a resin to be a long term durability measurement object was prepared as follows. Then, the time was measured according to the FNCT (Full Notch Creep Test). The results are shown in Table 1.
  • Production Example 1 Hexane slurry
  • a resin was polymerized using a metallocene catalyst while supplying ethylene, hydrogen, and 1-butene at a predetermined feed rate.
  • the prepared resin had a density measured according to ASTM D 1505 of 0.9396 g / cm < 3 > , And an MI (melt index) measured at 190 ⁇ and 2.16 kg / 10 min according to ASTM D 1238 was 0.26.
  • Production Example 2 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9392 g / cm < 3 > And MI was 0.34.
  • Production Example 3 A resin was prepared in the same manner as in Production Example 1 except that the feed rate of the raw material was controlled differently.
  • the density of the resin produced was 0.9358 g / cm < 3 > And MI was 0.75.
  • Production Example 4 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the produced resin was 0.9359 g / cm < 3 > And MI was 0.47.
  • Production Example 5 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9363 g / cm < 3 > , And MI was 0.27.
  • Production Example 6 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9396 g / cm < 3 > And MI was 0.32.
  • Production Example 7 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9365 g / cm < 3 > And MI was 0.60.
  • Production Example 8 A resin was prepared in the same manner as in Production Example 3, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9367 g / cm < 3 > And MI was 0.47.
  • Production Example 9 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9369 g / cm < 3 > And MI was 0.38.
  • Production Example 10 A resin was prepared in the same manner as in Production Example 1, except that the feed rate of the raw materials was controlled differently.
  • the density of the prepared resin was 0.9364 g / cm < 3 > And MI was 0.48.
  • PREPARATION EXAMPLE 11 Density of 0.9362 g / cm < 3 > , And a resin was prepared in the same manner as in Production Example 1, except that the MI measured under the same conditions was 0.43.
  • Preparation 12 a density of 0.9363 g / cm 3 , And a resin was prepared in the same manner as in Production Example 1, except that the MI measured at the same conditions was 0.26.
  • Production Example 13 Density of 0.9362 g / cm < 3 > , And a resin was prepared in the same manner as in Production Example 1, except that the MI measured under the same conditions was 0.44.
  • Preparation 14 a density of 0.9357 g / cm 3 , And a resin was prepared in the same manner as in Production Example 1, except that the MI measured under the same conditions was 0.25.
  • Preparation Example 15 a density of 0.9363 g / cm 3 , And a resin was prepared in the same manner as in Preparation Example 1, except that the MI measured under the same conditions was 0.39.
  • the content of tiemolecule, the amount of entangled molecular weight, and the content of ultrahigh molecular weight component were measured in the same manner as in Example 1 except that each of the resins of Examples 2 to 15 was produced in accordance with Production Examples 2 to 15 in this order , And durability related prediction values were calculated.
  • n is the number of macromolecules having a molecular weight M, and can be obtained from (dw / dlogMw) / M in the GPC curve data in which the x-axis is logMw and the y-axis is dw / dlogMw.
  • the above-mentioned P can be calculated from the following equations (1) to (3) as the probability of the polymer having a molecular weight of M forming tiemolecule, and dM is the interval between the x-axis (molecular weight M) data of the GPC curve.
  • r is the end-to-end distance of a random coil
  • b 2 is 3 / 2r 2
  • l c is the crystal thickness
  • l a is the amorphous thickness, which is obtained from the following equation (3).
  • T o m is 415 K
  • ⁇ e is 60.9 ⁇ 10 -3 J / m 2
  • ⁇ h m is 2.88 ⁇ 10 3 J / m 3 .
  • ⁇ c is a density of crystalline of 1,000 kg / m 3
  • ⁇ a is a density of amorphous phase of 852 kg / m 3
  • ⁇ c is a mass fraction crystallinity (weight fraction crystallinity).
  • Production Example 1 hexane slurry A resin was polymerized while supplying ethylene, hydrogen, and 1-butene at a predetermined feeding rate using a metallocene catalyst capable of producing a bimodal molecular weight distribution in a CSTR process.
  • the prepared resin had a density measured according to ASTM D 1505 of 0.9365 g / cm < 3 > , And an MI (melt index) measured at 190 ⁇ and 2.16 kg / 10 min according to ASTM D 1238 was 0.02.
  • Production Example 2 A resin was prepared in the same manner as in Production Example 1, except that a metallocene catalyst of a different kind from that of Production Example 1 was used.
  • the density of the prepared resin was 0.9396 g / cm < 3 > And MI was 0.26.
  • Production Example 3 A resin was prepared in the same manner as in Production Example 2 except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9392 g / cm < 3 > And MI was 0.34.
  • Production Example 4 A resin was prepared in the same manner as in Production Example 2, except that the feed rate of the raw material was controlled differently.
  • the density of the resin produced was 0.9358 g / cm < 3 > And MI was 0.75.
  • Production Example 5 A resin was prepared in the same manner as in Production Example 2, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9363 g / cm < 3 > , And MI was 0.27.
  • Production Example 6 A resin was prepared in the same manner as in Production Example 2 except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9396 g / cm < 3 > And MI was 0.32.
  • Production Example 7 A resin was prepared in the same manner as in Production Example 2 except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9365 g / cm < 3 > And MI was 0.60.
  • Production Example 8 A resin was prepared in the same manner as in Production Example 2, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9367 g / cm < 3 > And MI was 0.47.
  • Production Example 9 A resin was prepared in the same manner as in Production Example 2, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9369 g / cm < 3 > And MI was 0.38.
  • Production Example 10 A resin was prepared in the same manner as in Production Example 2, except that the feed rate of the raw material was controlled differently.
  • the density of the prepared resin was 0.9364 g / cm < 3 > And MI was 0.48.
  • PREPARATION EXAMPLE 11 Density of 0.9362 g / cm < 3 > , And a resin was prepared in the same manner as in Production Example 2, except that the MI measured under the same conditions was 0.43.
  • Preparation 12 a density of 0.9363 g / cm 3 , And a resin was prepared in the same manner as in Production Example 2, except that the measured MI was 0.26 under the same conditions.
  • Production Example 13 Density of 0.9362 g / cm < 3 > , And a resin was prepared in the same manner as in Production Example 2, except that the MI measured under the same conditions was 0.44.
  • Preparation 14 a density of 0.9363 g / cm 3 , And a resin was prepared in the same manner as in Production Example 2, except that the MI measured under the same conditions was 0.39.

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PCT/KR2018/011478 2017-09-29 2018-09-28 배관용 수지 조성물의 장기 내구성 예측 방법 및 배관용 수지에 사용되는 올레핀계 고분자 Ceased WO2019066516A1 (ko)

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EP18860648.7A EP3674334B1 (en) 2017-09-29 2018-09-28 Method for predicting long-term durability of pipe resin composition and olefin-based polymer used for pipe resin
CN201880057741.XA CN111133013B (zh) 2017-09-29 2018-09-28 预测管道用树脂组合物的长期耐久性的方法以及用于管道用树脂的烯烃聚合物
US16/647,751 US11697699B2 (en) 2017-09-29 2018-09-28 Method for predicting long-term durability of resin composition for piping and olefinic polymer used for resin for piping
JP2020513310A JP6942245B2 (ja) 2017-09-29 2018-09-28 配管用樹脂組成物の長期耐久性予測方法及び配管用樹脂に用いられるオレフィン系高分子

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KR102431339B1 (ko) * 2018-12-10 2022-08-10 주식회사 엘지화학 폴리에틸렌 및 이의 염소화 폴리에틸렌
KR20230013466A (ko) * 2021-07-19 2023-01-26 코오롱인더스트리 주식회사 개선된 내구성을 갖는 폴리에스테르 필름 및 그 내구성 평가 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827211A (ja) * 1994-07-19 1996-01-30 Tonen Corp 耐環境応力亀裂性ポリエチレン
WO1999011684A1 (en) * 1997-08-29 1999-03-11 Chisso Corporation Polypropylene/propylene-ethylene copolymer composition and process for the preparation thereof
EP0892979B1 (en) * 1996-04-10 2003-05-21 The Dow Chemical Company Ethylene polymer composition for cable applications
US20130011716A1 (en) * 2010-03-24 2013-01-10 Teijin Limited Polyolefin microporous membrane and method of producing the same, separator for non-aqueous secondary battery and non-aqueous secondary battery
KR20170127803A (ko) 2016-05-12 2017-11-22 (주)애드라이트 지하철 승강장 안전문 비상개방장치
KR20180014323A (ko) 2016-07-29 2018-02-08 엘지디스플레이 주식회사 타이밍 제어부, 이를 이용한 표시장치 및 이의 구동방법

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8701219A (nl) * 1987-05-22 1988-12-16 Stamicarbon Werkwijze voor het bereiden van een ultra-verstrekbaar polymeer materiaal, ultra-verstrekbaar polymeermateriaal, alsmede werkwijze voor het vervaardigen van voorwerpen.
JP2004169037A (ja) * 1997-11-28 2004-06-17 Idemitsu Petrochem Co Ltd ポリエチレン系重合体の製造方法
JPH11230962A (ja) 1998-02-10 1999-08-27 Osaka Gas Co Ltd ポリエチレン樹脂製管の耐久性についての迅速な評価方法、及び、管用ポリエチレン樹脂の迅速な良否判定方法
JP3867236B2 (ja) 1998-05-26 2007-01-10 大阪瓦斯株式会社 ポリエチレン樹脂製管の耐久性についての迅速な評価方法、及び、管用ポリエチレン樹脂の迅速な良否判定方法
CN101423573B (zh) 2007-10-31 2011-05-18 中国石油化工股份有限公司 管材用聚乙烯树脂和制备方法及其组合物
KR101705340B1 (ko) * 2014-06-03 2017-02-09 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
KR102097132B1 (ko) * 2016-11-24 2020-04-03 주식회사 엘지화학 폴리에틸렌 수지의 물성 평가 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827211A (ja) * 1994-07-19 1996-01-30 Tonen Corp 耐環境応力亀裂性ポリエチレン
EP0892979B1 (en) * 1996-04-10 2003-05-21 The Dow Chemical Company Ethylene polymer composition for cable applications
WO1999011684A1 (en) * 1997-08-29 1999-03-11 Chisso Corporation Polypropylene/propylene-ethylene copolymer composition and process for the preparation thereof
US20130011716A1 (en) * 2010-03-24 2013-01-10 Teijin Limited Polyolefin microporous membrane and method of producing the same, separator for non-aqueous secondary battery and non-aqueous secondary battery
KR20170127803A (ko) 2016-05-12 2017-11-22 (주)애드라이트 지하철 승강장 안전문 비상개방장치
KR20180014323A (ko) 2016-07-29 2018-02-08 엘지디스플레이 주식회사 타이밍 제어부, 이를 이용한 표시장치 및 이의 구동방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CAZENAVE, J. ET AL.: "Short-term Mechanical and Structural Approaches for the Evaluation of Polyethylene Stress Crack Resistance", POLYMER, vol. 47, 2006, pages 3904 - 3914, XP028061030, DOI: doi:10.1016/j.polymer.2006.03.094 *
SARDASHTI, A.: "Methodologies for Obtaining Reliable Indicators for the Environmental Stress Cracking Resistance of Polyethylene", A THESIS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY, 2014, pages 1 - 214, XP055586856 *
See also references of EP3674334A4

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EP3674334B1 (en) 2025-07-23
CN111133013B (zh) 2023-05-12
EP3674334A4 (en) 2021-01-06
US11697699B2 (en) 2023-07-11
JP2020532736A (ja) 2020-11-12
EP3674334A1 (en) 2020-07-01
JP6942245B2 (ja) 2021-09-29
CN111133013A (zh) 2020-05-08
US20200223964A1 (en) 2020-07-16

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