[go: up one dir, main page]

WO2024205529A1 - Élastomères thermoplastiques autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production - Google Patents

Élastomères thermoplastiques autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production Download PDF

Info

Publication number
WO2024205529A1
WO2024205529A1 PCT/TR2023/051625 TR2023051625W WO2024205529A1 WO 2024205529 A1 WO2024205529 A1 WO 2024205529A1 TR 2023051625 W TR2023051625 W TR 2023051625W WO 2024205529 A1 WO2024205529 A1 WO 2024205529A1
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
mixing
maleic anhydride
poly
triazole
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.)
Pending
Application number
PCT/TR2023/051625
Other languages
English (en)
Inventor
Ali DURMUS
Mine Begum ALANALP
Serkan Naci KOC
Nurcan SIVRI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Istanbul Universitesi Cerrahpasa Rektorlugu
Original Assignee
Istanbul Universitesi Cerrahpasa Rektorlugu
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from TR2023/003360 external-priority patent/TR2023003360A1/xx
Application filed by Istanbul Universitesi Cerrahpasa Rektorlugu filed Critical Istanbul Universitesi Cerrahpasa Rektorlugu
Publication of WO2024205529A1 publication Critical patent/WO2024205529A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the invention is related to styrene block copolymer-based self-healing thermoplastic elastomers (TPE) and the production method thereof.
  • TPE thermoplastic elastomers
  • the self-healing TPEs that are the subject of the invention can be processed with industrial shaping processes and are recyclable and reprocessable.
  • the self-healing styrene block copolymer-based TPEs, which are the subject of the invention can be manufactured without the need for the use of any catalysts and solvents by minimising the damage to the environment and health of living organisms and eliminating the need for extra separation and/or purification processes.
  • Thermoplastic elastomers are soft and flexible plastics that can be processed in processing machines used in the plastic and rubber industry and do not require vulcanisation like rubbers.
  • Thermoplastic elastomers are frequently preferred in applications requiring soft, flexible and long-term using of plastics due to their low density, wide hardness range, low permanent deformation properties, high resistance to ultraviolet (UV) rays and ozone, applicability/usability in a wide temperature range, being recyclable and colouring.
  • UV ultraviolet
  • TPEs also exhibit temperature resistance, mechanical strength, recyclability and reprocessability properties like thermoplastic materials.
  • Self-healing feature can provide long-term durability in the structure by eliminating destructive damages such as micro, meso or macro cracks and tearing and punctures that occur on the material during its service life with autonomous (without any external stimulus) or non-autonomous (with the help of an external stimulus) repairing mechanisms. In this way, the service life of the materials can be extended, and significant application advantages can be obtained both technically and economically.
  • thermosetting systems the self-healing mechanism is generally achieved by microparticles embedded into the material and containing reaction-initiating chemicals. When damage occurs, micro particles are broken in the failuring domain then the reactive component in the particles is dispersed, and healing occurs by a chemical reaction in the damaged area. This healing provides a one-time repairing for each failuring domain for the material.
  • the self-healing feature of thermoplastics is achieved by re-fusing of material in molten form (hot welding), but this is not defined as self- healing since it does not provide a healing by maintaining the shape of plastic in solid form.
  • the self-healing mechanism is based on constructing chemical interactions between reactive groups on the polymer molecule. Therefore, there are a limited number of rubber and elastomer raw materials which are suitable for self-healing processes. These raw materials are generally halogen-containing and/or halogenated rubbers, and the reactivation of the polymer requires special organic reactions such as Diels-Alder reaction, disulphide metathesis, click reactions. In the state of the art, a blend that provides dynamic interactions can be produced by introducing additives and chemicals containing functional groups into the formulation during the preparation of the elastomer mixture, without the need for special polymeric raw materials and organic syntheses.
  • a catalyst is needed for grafting of reactive groups to the polymer chain.
  • Catalysts used for grafting reactive groups onto plastics are organic peroxides such as dicumyl peroxide (DCP), benzoyl peroxide, lauryl peroxide (LP). These catalysts decompose at the reaction temperature to form active oxygen radicals and lead to grafting another organic group onto the polymer molecule via free radical mechanism.
  • Organic peroxides are explosive and harmful compounds.
  • Catalysts used in the production of functional elastomers are organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, and peroxides as chemical effects and UV, microwave, light, sound waves and other physical stimuli as physical effects. Additionally, the use of catalysts in any reaction means process costs due to both raw materials and separation/purification operations. Primarily considering the environmental and health of living organisms, and then the process cost, completely eliminating the use of catalysts in the production of self- healing TPE materials provides a significant technical advantage.
  • the mentioned separation and purification processes may include one or more of the unit operations such as precipitation, filtration, dissolving, extraction, concentration, neutralisation, washing and drying. These processes are techniques that are especially applied in the production of self- healing TPEs in solution medium.
  • polymer functionalisation processes carried out by reactive melt blending the organic compounds remaining unreacted and the catalysts used might be needed to seperate. Because it is known that each component in the product composition has significant effects on the physical properties and application areas of end products. The application of such secondary separation processes in industrial polymer processing operations means both technical difficulty and very high production costs.
  • TPEs in the state of the art are not recyclable and reprocessable, TPEs in the state of the art are not suitable for elastomer shaping processes, and extra separation and/or purification processes are used when producing self-repairing TPE materials, it has become necessary to introduce self-repairing, recyclable and reprocessable thermoplastic elastomers (TPE) that are suitable for elastomer shaping processes and the production method of these elastomers, in which all these problems are eliminated.
  • TPE thermoplastic elastomers
  • styrene block copolymer-based self-healing thermoplastic elastomers TPE
  • the self-healing TPEs that are the subject of the invention can be processed with industrial shaping processes and are recyclable and reprocessable.
  • the production of self-healing styrene block copolymer-based TPEs, which are the subject of the invention can be manufactured without the need of catalysts using by minimising the damage to the environment and health of living organisms and eliminating the need for extra separation and/or purification processes.
  • the reactive blending method in melt state is used.
  • An aim of the invention is to provide a self-healing thermoplastic elastomer that is suitable for industrial polymer processing operations.
  • rubbers and elastomers with different properties and compositions are first mixed, compounded and kneaded to components are distributed among each other, and then a shaping process such as extrusion, injection moulding, compression moulding, casting, coating, calendaring and granulating, which is suitable to form the final product shape.
  • Forming processes are the operations in which the vulcanisation reactions also occur in rubbers, and only kneading and shaping are applied for TPEs.
  • the production of TPE, which is the subject of the invention is carried out only by kneading and shaping processes among these mentioned methods.
  • a self-healing TPE that is suitable for shaping processes is achieved by using the reactive melt blending method in the production method of the TPE that is the subject of the invention.
  • Another aim of the invention is to produce self-healing TPE without a need of catalyst using.
  • the functional group grafting reaction to the styrene-based block copolymer is carried out without the use of any catalyst (e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.).
  • any catalyst e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.
  • a TPE production method in which the damage to the environment and human health is minimised.
  • the functional group grafting reaction to the styrene-based block copolymer is carried out without the use of any catalyst (e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.), eliminating the chemical effects that pose a threat to the environment and health of living organisms.
  • any catalyst e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.
  • Another aim of the invention is to provide a production method in which the cost of self- healing TPE production is minimised.
  • the functional group grafting reaction to the styrene-based block copolymer is carried out without the use of any catalyst (e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.). Therefore, a lower-cost self-healing TPE production is achieved, compared to the state of the art, since the catalyst cost is eliminated in the production method of the invention.
  • any catalyst e.g. organo-metallic esterification catalysts, strong acid or base catalysts, nano-sized heterogeneous catalysts with high surface area, specific bioagents, enzymes, peroxides, external stimuli such as UV, microwave, light or sound waves, etc.
  • Another aim of the invention is to produce a TPE that eliminates the extra separation and/or purification processes in the production of self-healing TPE.
  • the production of TPE, which eliminates the extra separation and/or purification processes in the production of self-healing TPE is made by adding proper amount of reactive components equivalently according to the amount of functional groups.
  • self-healing TPE materials are also ensured to be recyclable and reprocessable.
  • Self-healing TPE materials which are recyclable and reprocessable, are provided by the fact that cross-linking reactions do not occur in the production method of the invention. Since the functional compounds used in reactive melt blending in the invention do not contain more than two reactive groups that make covalent bonds in the same molecule, no cross-linking reaction occurs between polymer chains. However, the reactive additives and functional groups used in this invention are compounds that create dynamic bonding.
  • FIG. 1 FTIR spectra of TPEs produced by reactive blending, (a) SEBS-PMAO blend, (b) functional SEBS-PMAO blend compounded with triazole, (c) functional SEBS-PMAO blend compounded with zinc nitrate tetrahydrate (Zn(NO3)2.4H2O).
  • Figure 4 Change in the intensity of imide bond formed by maleic anhydride/triazole equivalent; where A) MAh:Triazole of 1 :1 and B) MAh:Triazole of 2:1 .
  • Figure 5 Optical microscope (Nikon Eclipse E200) images of the damaged crossection of TPE obtained using 45 g poly(styrene-b-ethylene-r-butylene-b-styrene) (SEBS), 45 g paraffinic oil with a viscosity of 8.3 cSt at 40°C, 10 g poly(maleic anhydride-alt-1 -octadecene) (PMAO), 2.4 g 3-amino-1 ,2,4 triazole and 3.6 g Zn(NO3)2.4H2O, before damage and healed for 6 hours and 24 hours.
  • SEBS poly(styrene-b-ethylene-r-butylene-b-styrene)
  • PMAO poly(maleic anhydride-alt-1 -octadecene)
  • PMAO poly(maleic anhydride-alt-1 -octadecene)
  • Zn(NO3)2.4H2O 3.6 g Zn(NO
  • the invention is related to styrene block copolymer-based self-healing thermoplastic elastomers (TPE) and the production method thereof.
  • TPE thermoplastic elastomers
  • the self-healing TPEs that are the subject of the invention can be manufactured with industrial shaping processes and are recyclable and reprocessable.
  • the production of self-repairing styrene block copolymer-based TPEs, which are the subject of the invention, is achieved without the need of catalyst using, minimising the damage to the environment and health of living organisms and eliminating the need for extra separation and/or purification processes.
  • the self-healing TPE production that is the subject of the invention is implemented by functionalising styrene block copolymer-based TPEs that do not contain functional groups in four-stage by reactive blending method in the melt state and creating dynamic chemical bonds that are sensitive to external effects.
  • the production method of styrene block copolymer-based self-healing thermoplastic elastomers (TPE) comprises the process steps of; i. Swelling the block copolymer by mixing styrene block copolymer and plasticizer and waiting, ii. Preparing an elastomer blend by loading the mixture of plasticizer and styrene block copolymer with maleic anhydride or maleic acid copolymer into the melt blending device, mixing and kneading, iii.
  • Carrying out a reaction between maleic anhydride or maleic acid groups and the amine compound by adding a cyclic amine compound into the elastomer blend, mixing and kneading, and iv. Forming complex and/or chelate bonds between the functional groups of maleic anhydride or maleic acid and the amine compound and the metal by adding metal salt to the elastomer blend functionalised with maleic anhydride or maleic acid groups and amine compound, mixing and kneading.
  • the production method of styrene block copolymer-based self-healing thermoplastic elastomers (TPE) comprises the processing steps of; i. Swelling the block copolymer by mixing styrene block copolymer and plasticizer and waiting, ii. Preparing an elastomer blend by loading the mixture of plasticizer and styrene block copolymer with maleic anhydride or maleic acid copolymer into the melt blending device, mixing and kneading at 130-200°C and for 5-15 minutes, iii.
  • the melt blending device used in the method of the invention can be single screw, twin screw, multi-screw (planetary type), tandem extruders, banbury, kneader, internal mixer or compaunder and the mixing speed is 50-200 rpm. These devices are used in mixture preparation and kneading steps.
  • Styrene block copolymers mentioned in the process steps (i) and (ii) in the method that is subject of the invention are;
  • SEEPS poly(styrene-b-ethylene-b-ethylene-r-propylene-b-styrene)
  • SEEPS-OH poly(styrene-b-ethylene-b-ethylene-r-propylene-b-styrene)
  • the styrene ratios of these styrene block copolymers can vary between 10-70% by weight, and they can possess different molecular weights.
  • plasticizers mentioned in the process steps (i) and (ii) in the method that is the subject of the invention are;
  • the mentioned plasticizers can be in liquid or solid form and possess different viscosity and density values.
  • SMA styrene-maleic anhydride copolymers
  • the maleic anhydride and maleic acid ratios of said maleic anhydride and maleic acid copolymers are 0.2-70% by weight and they can possess different molecular weights.
  • the formulation is created by calculating the amount of functional groups according to the maleic anhydride or acid ratio or the acid number of the copolymers.
  • the metal salts mentioned in process step (iv) of the method that is the subject of the invention are all inorganic or organic salts of Fe 2+ , (Fe 3+ ), (Zn 2+ ), (Co 2+ ), (Ni 2+ ) or (Cu 2+ ) metals.
  • the production method of styrene block copolymer-based self-healing thermoplastic elastomers comprises the process steps of; i. Swelling the block copolymer by mixing 45 g of poly(styrene-b-ethylene-r- butylene-b-styrene) (SEBS) and 45 g of paraffinic oil with a viscosity of 8.3 cSt at 40°C as a plasticizer and waiting for 2 hours, ii.
  • Forming complex and/or chelate bonds between 3-amino-1 ,2,4 triazole and PMAO functional groups and metal by adding 3.6 g of zinc nitrate tetrahydrate (Zn(NO3)2.4H2O) as a metal salt to the elastomer blend functionalised with 3-amino-1 ,2,4 triazole and PMAO and mixing and kneading in a melt blending device for 10 minutes at 165°C at a mixing speed of 75 rpm.
  • Zn(NO3)2.4H2O zinc nitrate tetrahydrate
  • the production method of styrene block copolymer-based self-healing thermoplastic elastomers comprises the process steps of; i. Swelling the block copolymer by mixing 41 g of poly(styrene-b-ethylene-r- butylene-b-styrene) (SEBS) and 41 g of paraffinic oil with a viscosity of 8.3 cSt at 40°C as a plasticizer and waiting for 2 hours, ii.
  • Forming complex and/or chelate bonds between 3-amino-1 ,2,4 triazole and SMA functional groups and metal by adding 3.6 g of zinc nitrate tetrahydrate (Zn(NO3)2.4H2O) as a metal salt to the elastomer blend functionalised with 3-amino-1 ,2,4 triazole and PMAO and mixing and kneading in a melt blending device for 10 minutes at 165°C at a mixing speed of 75 rpm.
  • Zn(NO3)2.4H2O zinc nitrate tetrahydrate
  • the production method of styrene block copolymer-based self-repairing thermoplastic elastomers (TPE) comprises the process steps of; i. Swelling the block copolymer by mixing 20 g of poly(styrene-b-ethylene-r- butylene-b-styrene) (SEBS) and 20 g of paraffinic oil with a viscosity of 8.3 cSt at 40°C as a plasticizer and waiting for 2 hours, ii.
  • SEBS poly(styrene-b-ethylene-r- butylene-b-styrene)
  • paraffinic oil with a viscosity of 8.3 cSt at 40°C as a plasticizer
  • an elastomer blend by loading the mixture of SEBS and plasticizer paraffinic oil into the melt blending device together with 60 g of maleic anhydride graft poly(styrene-b-ethylene-r-butylene-b-styrene) (SEBS-g-MA) with a maleic anhydride ratio of 1.0% by weight and an acid number of 10 mg CHgONa/g and mixing and kneading in a melt blending device at 165°C at a mixing speed of 75 rpm for 10 minutes, iii.
  • SEBS-g-MA maleic anhydride graft poly(styrene-b-ethylene-r-butylene-b-styrene)
  • Forming complex and/or chelate bonds between 3-amino-1 ,2,4 triazole and SEBS-g-MA functional groups and metal by adding 0.8 g of zinc nitrate tetrahydrate (Zn(NO3)2.4H2O) as a metal salt to the elastomer blend functionalised with 3-amino-1 ,2,4 triazole and SEBS-g-MA and mixing and kneading in a melt blending device for 10 minutes at 165°C at a mixing speed of 75 rpm.
  • Zn(NO3)2.4H2O zinc nitrate tetrahydrate
  • test specimens were prepared by moulding the functional elastomer blends produced by the melt blending method in a hot pres at 160°C, under 5 tons for 5 minutes.
  • the prepared test specimens were kept under room conditions for 24 hours and then cutting-joining operations were carried out.
  • the parts with cut surfaces attached to each other were kept at a temperature between 60-120°C for 2-48 hours to form dynamic bonds that enable functional elastomers to heal themselves.
  • the self-healing performances of functional elastomer blends were quantified by mechanical tests such as weight bearing and tensile test.
  • Figure 1 shows the FTIR spectra, (a) SEBS-PMAO blend, (b) functional SEBS-PMAO blend compounded with triazole, (c) functional SEBS-PMAO blend compounded with zinc nitrate tetrahydrate (NO3)2.4H2O), of TPEs produced by reactive blending.
  • Figure 2 shows the change in FTIR spectra of TPEs produced by reactive blending depending on the blending time.
  • Figure 3 shows the change in the ratio of intensity of the 1725 cm -1 peak, which indicates the formation of the imide bond, to the intensity of the characteristic peak of the -CH2 groups, which remains unchanged in the copolymer structure, over time, depending on the mixing time. It was determined that the intensity of the imide peak did not change depending on the mixing time and the functionalisation reaction occurred within 10 minutes of mixing.
  • Figure 4 shows the change in the intensity of the imide bond formed by the reaction between equivalent maleic anhydride and triazole. It was determined that the intensity of imide bond increased with the increasing amount of cyclic amine.
  • Figure 6 shows the tensile test results performed with a crosshead speed of 20 mm/minute for TPEs produced with the method in which 20 g poly(styrene-b-ethylene- r-butylene-b-styrene) (SEBS), 20 g paraffinic oil with a viscosity of 8.3 cSt at 40°C as plasticizer, 60 g maleic anhydride grafted poly(styrene-b-ethylene-r-butylene-b- styrene) (SEBS-g-MA), 0.5 g 3-amino-1 ,2,4 triazole and 0.8 g Zn(NO3)2.4H2O are used.
  • SEBS poly(styrene-b-ethylene- r-butylene-b-styrene)
  • SEBS-g-MA poly(styrene-b-ethylene-r-butylene-b-styrene)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des élastomères thermoplastiques (TPE) autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production. Les TPE autocicatrisants qui font l'objet de l'invention peuvent être fabriqués à l'aide de procédés industriels de mise en forme et sont recyclables et peuvent être retraités. La production de TPE autocicatrisants à base de copolymère séquencé de styrène, qui font l'objet de l'invention, est obtenue sans nécessiter l'utilisation de catalyseur tout en réduisant au minimum des dommages causés à l'environnement et à la santé d'organismes vivants et en éliminant le besoin de procédés de séparation et/ou de purification supplémentaires.
PCT/TR2023/051625 2023-03-28 2023-12-21 Élastomères thermoplastiques autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production Pending WO2024205529A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2023/003360 TR2023003360A1 (tr) 2023-03-28 Stiren blok kopolimer esaslı kendini onaran termoplastik elastomerler ve bu elastomerlerin üretim yöntemi.
TR2023003360 2023-03-28

Publications (1)

Publication Number Publication Date
WO2024205529A1 true WO2024205529A1 (fr) 2024-10-03

Family

ID=92907261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2023/051625 Pending WO2024205529A1 (fr) 2023-03-28 2023-12-21 Élastomères thermoplastiques autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production

Country Status (1)

Country Link
WO (1) WO2024205529A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016132127A2 (fr) * 2015-02-18 2016-08-25 Gnosys Global Limited Câble auto-réparant
EP3351595A1 (fr) * 2015-09-17 2018-07-25 JXTG Nippon Oil & Energy Corporation Composition d'élastomère thermoplastique et son procédé de production
CN108342048A (zh) * 2018-03-21 2018-07-31 广东电网有限责任公司电力科学研究院 一种具有自修复功能的电缆护套材料、制备方法及电缆护套
CN110684364A (zh) * 2019-11-09 2020-01-14 南通林格橡塑制品有限公司 一种自愈合热塑性弹性体材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016132127A2 (fr) * 2015-02-18 2016-08-25 Gnosys Global Limited Câble auto-réparant
EP3351595A1 (fr) * 2015-09-17 2018-07-25 JXTG Nippon Oil & Energy Corporation Composition d'élastomère thermoplastique et son procédé de production
CN108342048A (zh) * 2018-03-21 2018-07-31 广东电网有限责任公司电力科学研究院 一种具有自修复功能的电缆护套材料、制备方法及电缆护套
CN110684364A (zh) * 2019-11-09 2020-01-14 南通林格橡塑制品有限公司 一种自愈合热塑性弹性体材料

Similar Documents

Publication Publication Date Title
DE3688466T3 (de) End-modifiziertes blockkopolymer und dieses kopolymer enthaltende zusammensetzung.
DE69020039T2 (de) Azlakton-Pfropfcopolymere.
CN1077898C (zh) 官能化聚烯烃的母料及其制备方法
CN1100087C (zh) 一种增韧聚烯烃用填充母粒的制备方法
WO2019206288A1 (fr) Résine de polypropylène greffée avec un monomère polaire, son procédé de préparation et son application
JPH02132126A (ja) ブロック共重合体
DE69615159T2 (de) Verfahren zur herstellung von epoxidiertem organischem polymer, thermoplastische harzzusammensetzung, primerzusammensetzung, nicht-vulkanisierte kautschukzusammensetzung, kautschukformmassen und verfahren zu deren herstellung
KR102188700B1 (ko) 기능화된 열가소성 엘라스토머의 제조방법
CN110041624A (zh) 一种tpv材料及其制备方法和应用方法
CN1117808C (zh) 一种交联聚丙烯树脂材料及其用途
JPS6317297B2 (fr)
WO2024205529A1 (fr) Élastomères thermoplastiques autocicatrisants à base de copolymère séquencé de styrène et leur procédé de production
Murillo et al. Study of the impact resistance of physically and dynamically vulcanized mixtures of PP/EPDM
CN111892794A (zh) 一种pbat-滑石粉全生物降解共混物及其制备方法
Jo et al. An efficient chain transfer reaction of the trithiocarbonate unit as a tool to prepare a functional polyolefin: a post-polymerization modification of ethylene–propylene–diene terpolymer for improved oil resistance
DE69406474T2 (de) Propylenpolymer Zusammensetzung
JPH0730187B2 (ja) ポリオレフイン系樹脂用コーテイング樹脂組成物
CN1279113C (zh) 一种热塑性弹性体及其制备方法
CN116655855A (zh) 一种具有形状记忆性能的热塑性弹性体及其制备方法
EP0487678B1 (fr) Elastomeres thermoplastiques et procede de fabrication
US6063867A (en) Stable polymer blends from a two-step crosslinking process
CN101684189B (zh) 一种可喷涂、增韧聚丙烯组合物及其制备方法
WO2005056612A1 (fr) Produit caoutchouteux ou substance caoutchouteuse le contenant
Wan et al. Reactive melt modification of polypropylene with a crosslinkable polyester
CN102964823A (zh) 一种超韧绿色尼龙11纳米复合材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23931107

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE