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KR-102962159-B1 - Poly(arylene sulfide) polymer and corresponding polymer composition and articles

KR102962159B1KR 102962159 B1KR102962159 B1KR 102962159B1KR-102962159-B1

Abstract

Poly(arylene sulfide) ("PAS") polymers (PASP) comprising repeating units formed from selected dihalofluorene monomers are described herein. Surprisingly, at relatively low dihalofluorene monomer concentrations, the PAS polymer (PASP) exhibited a significantly increased glass transition temperature ("T g" ) and impact performance compared to similar PAS homopolymers and PAS polymers (PASP) comprising repeating units formed from 4,4′-dibromobiphenyl ("DBBP"). At the same time, the PAS polymer (PASP) also maintains a high elastic modulus. Furthermore, the PAS polymer (PASP) does not contain repeating units formed from polyhalogenated biphenyls (e.g., DBBP and polychlorinated biphenyls) and, accordingly, is not subject to current restricted government regulations. Due at least in part to the excellent thermal properties (T g , T c , and T m ) and impact properties of the PAS polymer (PASP), the PAS polymer (PASP) and PAS polymer compositions can be preferably introduced into a wide variety of articles, including but not limited to automotive articles, electrical and electronic articles, aerospace articles, and oil and gas articles.

Inventors

  • 닐슨 매튜
  • 제올 스테빤

Assignees

  • 사이언스코 스페셜티 폴리머즈 유에스에이, 엘엘씨

Dates

Publication Date
20260507
Application Date
20201012
Priority Date
20191104

Claims (16)

  1. Poly(arylene sulfide)("PAS") polymer (PASP) comprising repeating units R PAS1 and R PAS2 , respectively represented by the following chemical formulas: [Chemical Formula 1] [-Ar 1 -S-] [Chemical Formula 2] [-Ar 2 -S-] (In the above formula, - -Ar 1 - is selected from the group of chemical formulas consisting of: [Chemical Formula 3] , [Chemical Formula 4] , and [Chemical Formula 5] ; - -Ar 2 - is represented by the following chemical formula: [Chemical Formula 6] , - R and R' are each independently selected from the group consisting of C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, C7 - C24 aralkyl groups, C6 - C24 arylene groups, and C6 - C18 aryloxy groups; - T is selected from the group consisting of bonds, -CO-, -SO2- , -O-, -C( CH3 ) 2- , phenylene, and -CH2- ; - i is an integer from 0 to 4 selected independently in each case; - j and k are integers from 0 to 3 selected independently in each case; - R1 is selected from the group consisting of hydrogen, fluorine, C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, and C6 - C24 aryl groups; - R2 is selected from the group consisting of fluorine, C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, and C6 - C24 aryl groups).
  2. In claim 1, the PAS polymer (PASP) is represented by the following chemical formula -Ar 1- : [Chemical Formula 7] .
  3. In claim 1, the PAS polymer (PASP) is represented by the following chemical formula -Ar 2 -: [Chemical Formula 8] .
  4. A PAS polymer (PASP) according to claim 1, wherein R1 and R2 are fluorine.
  5. PAS polymer (PASP), wherein R1 and R2 are independently selected C1 - C12 alkyl groups.
  6. A PAS polymer (PASP) according to claim 1, wherein -Ar 2 - is a diradical of a dihalofluorene monomer selected from the group consisting of 2,7-dibromo-9,9-dimethyl-9 H -fluorene; 2,7-dibromo-9,9-dipropyl-9 H -fluorene; 2,7-dibromo-9,9-dihexyl-9 H -fluorene; 2,7-dibromo- 9,9 -dioctyl-9 H -fluorene; 2,7-dibromo-9,9-didodecyl-9 H -fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9 H-fluorene; 2,7-dibromo-9,9-diphenyl-9 H -fluorene; and 2,7-dibromo-9,9-difluoro-9 H-fluorene.
  7. A PAS polymer (PASP) according to claim 1, wherein the ratio of the number of repeating units (R PAS2 ) to the total number of repeating units (R PAS1 ) and repeating units (R PAS2 ) is 0.5 mol% to 15 mol%.
  8. A PAS polymer (PASP) according to claim 1, wherein the ratio of the number of repeating units (R PAS2 ) to the total number of repeating units (R PAS1 ) and repeating units (R PAS2 ) is 0.5 mol% to 8 mol%.
  9. A PAS polymer (PASP) according to claim 1, comprising a T g of at least 95°C.
  10. A PAS polymer (PASP) according to claim 1, comprising a T m of at least 200°C.
  11. A PAS polymer (PASP) according to claim 1, comprising an impact strength of at least 30 J/g when determined according to ASTM D256.
  12. A polymer composition (PC) comprising a PAS polymer (PASP) and a toughening agent according to any one of claims 1 to 11.
  13. A polymer composition (PC) comprising a PAS polymer (PASP) and glass fibers according to any one of claims 1 to 11.
  14. A PAS polymer (PASP) of any one of claims 1 to 11, A polymer composition (PC) comprising the above PAS polymer (PASP) and a toughening agent, or Polymer composition (PC) comprising the above PAS polymer (PASP) and glass fiber Automotive components including
  15. A method for manufacturing a PAS polymer (PASP) according to any one of claims 1 to 11, The method comprises the step of reacting a dihaloaromatic compound having the chemical formula X1 - Ar1 - X2 ; a dihalofluorene monomer having the chemical formula X3 - Ar2 - X4 ; and a sulfur compound in a reaction mixture state, In the above formula - X 1 to X 4 are independently selected halogens, and - A method in which a sulfur compound is selected from the group consisting of thiosulfates, thiourea, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organic sulfides, alkali metal sulfides and disulfides, and hydrogen sulfide.
  16. A PAS polymer (PASP) of any one of claims 1 to 11, A polymer composition (PC) comprising the above PAS polymer (PASP) and a toughening agent, or Polymer composition (PC) comprising the above PAS polymer (PASP) and glass fiber As a component for oil and gas comprising, The above oil and gas components are selected from the group consisting of a compressor ring, a poppet, a backup seal ring, an electrical connector, a labyrinth seal, a motor end plate, a bearing, a bushing, a suck rod guide, and down hole tubing.

Description

Poly(arylene sulfide) polymer and corresponding polymer composition and articles Cross-reference regarding related applications This application claims priority to U.S. Provisional Application No. 62/915150 filed on October 15, 2019 and European Patent Application No. 19206822.9 filed on November 4, 2019, the full contents of each of these applications are incorporated herein by reference for all purposes. Technology field The present invention relates to a poly(arylene sulfide) ("PAS") polymer having excellent thermal and mechanical properties. The present invention also relates to a PAS polymer composition, a PAS polymer and a method for preparing a PAS composition, and an article incorporating a PAS polymer and a PAS polymer composition. Poly(arylene sulfide) ("PAS") polymers generally have high chemical resistance and desirable mechanical properties, but also have a relatively low Tg (typically 85°C to 98°C) (which limits their use in some applications (e.g., thermoplastic composites)) and low toughness (impact strength). Methods known to increase the Tg and toughness of PAS polymers involve forming polymer compositions that include additives (e.g., tougheners) and introduce a tough comonomer, such as 4,4′-dibromobiphenyl ("DBBP"), into the PAS polymer. Regarding polymer compositions, while the toughener increases the toughness of the PAS polymer, it also dramatically reduces the elastic modulus (e.g., typically to less than 2.5 GPa). Regarding DBBP, relatively high concentrations are required to obtain a Tg higher than 100°C, but in such cases, the melting temperature is also very high (over 360°C), which makes processing very difficult. Furthermore, DBBP is a polybrominated biphenyl ("PBB"), which belongs to the class of strictly regulated compounds (polyhalogenated biphenyls). For example, DBBP is regulated by the U.S. Environmental Protection Agency under the Toxic Substances Control Act ("TSCA"). Therefore, the use of DBBP monomers is almost impossible under current regulatory policies. In one embodiment, the present invention relates to a poly(arylene sulfide) ("PAS") polymer (PASP) comprising repeating units R PAS1 and R PAS2 , each represented by the following chemical formulas: [Chemical Formula 1] [-Ar 1 -S-] [Chemical Formula 2] [-Ar 2 -S-] (In the above formula, - -Ar 1 - is selected from the group of chemical formulas consisting of: [Chemical Formula 3] , [Chemical Formula 4] , and [Chemical Formula 5] ; - -Ar 2 - is represented by the following chemical formula: [Chemical Formula 6] , - R and R' are each independently selected from the group consisting of C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, C7 - C24 aralkyl groups, C6 - C24 arylene groups, and C6 - C18 aryloxy groups; - T is selected from the group consisting of bonds, -CO-, -SO2- , -O-, -C( CH3 ) 2 , phenyl, and -CH2- ; - i is an integer from 0 to 4 selected independently in each case; - j and k are integers from 0 to 3 selected independently in each case; - R1 is selected from the group consisting of hydrogen, fluorine, C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, and C6 - C24 aryl groups; - R2 is selected from the group consisting of fluorine, C1 - C12 alkyl groups, C7 - C24 alkylaryl groups, and C6 - C24 aryl groups). In some embodiments, -Ar 2 - is a diradical of a dihalofluorene monomer selected from the group consisting of 2,7-dibromo-9,9-dimethyl-9 H - fluorene; 2,7-dibromo-9,9-dipropyl-9 H -fluorene; 2,7-dibromo-9,9-dihexyl-9 H -fluorene; 2,7-dibromo-9,9-dioctyl-9 H -fluorene; 2,7-dibromo-9,9-didodecyl-9 H -fluorene; 2,7-dibromo-9,9-di-(2-ethylhexyl)-9 H -fluorene; 2,7-dibromo-9,9-diphenyl-9 H -fluorene; and 2,7-dibromo-9,9-difluoro-9 H-fluorene. In some embodiments, the PAS polymer (PASP) has a T g of at least 95°C. Additionally or alternatively, in some embodiments, the PAS polymer (PASP) has a T m of at least 200°C. In another additional or alternative embodiment, the PAS polymer (PASP) has an impact strength of at least 30 J/g when determined according to ASTM D256. In another aspect, the present invention relates to a polymer composition (PC) comprising a PAS polymer (PASP) and a toughening agent, glass fiber, or both. In a further aspect, the present invention relates to an automotive component, an oil and gas component, or an aerospace component comprising a PAS polymer (PASP) or a polymer composition (PC). In another additional aspect, the present invention relates to a method for preparing a PAS polymer (PASP), the method comprising the step of reacting a dihaloaromatic compound having the formula X1 - Ar1 - X2 ; a dihalofluorene monomer having the formula X3 - Ar2 - X4 ; and a sulfur compound in a reaction mixture state, wherein X1 to X4 are independently selected halogens, and the sulfur compound is selected from the group consisting of thiosulfates, thiourea, thioamides, elemental sulfur, thiocarbamates, metal disulfides and oxysulfides, thiocarbonates, organic mercaptans, organic mercaptides, organi