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KR-102963767-B1 - Poly(arylene ether) composition

KR102963767B1KR 102963767 B1KR102963767 B1KR 102963767B1KR-102963767-B1

Abstract

A composition comprising a (poly)isocyanate compound and a capped poly(arylene ether) copolymer, wherein the capped poly(arylene ether) copolymer is derived from the reaction of a capping agent and an uncapped poly(arylene ether) copolymer comprising phenolic terminal groups, the uncapped poly(arylene ether) copolymer is an oxidative copolymerization product of monomers comprising monovalent phenol, trivalent phenol, or a combination thereof, and optionally a hydroxyaromatic terminal siloxane, and the capped poly(arylene ether) copolymer comprises terminal groups comprising aliphatic alcohols.

Inventors

  • 바나크, 티모시 에드워드
  • 타킨-타스, 에일렘

Assignees

  • 에스에이치피피 글로벌 테크놀러지스 비.브이.

Dates

Publication Date
20260512
Application Date
20200731
Priority Date
20190731

Claims (15)

  1. A composition comprising a (poly)isocyanate compound and a capped poly(arylene ether) copolymer, The above-mentioned capped poly(arylene ether) copolymer is derived by reacting an uncapped poly(arylene ether) copolymer containing a capping agent and phenol terminal groups, and The above-mentioned uncapped poly(arylene ether) copolymer is an oxidative copolymerization product of monomers comprising monovalent phenol, divalent phenol, or a combination thereof, and optionally hydroxyaromatic terminated siloxane, and The above-mentioned capped poly(arylene ether) copolymer comprises terminal groups including aliphatic alcohols, and The above-mentioned capped poly(arylene ether) copolymer is of the following chemical formula (1). Q(JD) y (1) Here Q is derived from monovalent phenol or divalent phenol, and optionally from hydroxyaromatic terminal siloxane; If the above Q is derived from a divalent phenol, the divalent phenol is as follows: chemical formula (3). (3) Here In each case of R1 , R2 , R3 , and R4 , the hydrogen, halogen, and hydrocarbyl groups are independently C1 - C12 hydrocarbyl, C1 -C12 hydrocarbylthio, C1 - C12 hydrocarbyloxy, or C2 - C12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and oxygen atoms, and z is 0 or 1, and; Y is a divalent linker of the following chemical formula , Here, each case of R a , R b , R c , R d , and R e is independently hydrogen, C 1 –C 12 hydrocarbyl, or C 1 –C 6 hydrocarbylene, and optionally R a and R b or R c and R d together are C 4 –C 12 cycloalkylene groups, and J has the structure of the following chemical formula (2). (2) Here Q 1a is a C 1 -C 12 primary or secondary alkyl; Q 1b is a halogen, where the hydrocarbyl group is not a tertiary hydrocarbyl but C 1 -C 12 hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and oxygen atoms; Each case of Q 2 is independently a C 1-C 12 hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and oxygen atoms, where hydrogen, halogen , and hydrocarbyl groups are not tertiary hydrocarbyls; e is 1 to 200, and D is a terminal group containing an aliphatic alcohol; and A composition in which y is 1 or 2.
  2. In paragraph 1, The above monomer is a composition comprising a divalent phenol.
  3. In paragraph 1, The above monovalent phenol is as follows: chemical formula (4) (4) Here, Q1a , Q1b , and Q2 are compositions as defined in claim 1.
  4. In paragraph 1, The above hydroxyaromatic terminal siloxane is of the following chemical formula (5). (5) Here Each R6 is independently hydrogen or a C1-14 monovalent organic group; Each R7 is a C1-6 hydrocarbylene group; Each R8 is the same or different and is a halogen, cyano, nitro, C1-8 alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, C6-10 aryl, C6-10 aryloxy, C7-12 aralkyl, C7-12 arylalkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy ; Each n is independently an integer from 0 to 4; A composition in which E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20.
  5. In paragraph 1, The above-mentioned capped poly(arylene ether) copolymer is of the following chemical formula (6) or (7). (6) (7) Here Each case of Q 1a is a C 1 -C 12 primary or secondary alkyl; In each case of Q 1b , the halogen and hydrocarbyl group are not tertiary hydrocarbyl but C 1 -C 12 hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and oxygen atoms; Each case of Q2 is independently a C1 -C12 hydrocarbyl, C1- C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2 - C12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and oxygen atoms, where the hydrogen , halogen, and hydrocarbyl groups are not tertiary hydrocarbyls but are unsubstituted or substituted ; In each case of R1 , R2 , R3 , and R4 , the hydrogen, halogen, and hydrocarbyl groups are independently C1 -C12 hydrocarbyl, C1- C12 hydrocarbylthio, C1 - C12 hydrocarbyloxy, if Y is not a silicon-containing group , or C2-C12 halohydrocarbyloxy , where at least two carbon atoms separate the halogen and oxygen atoms; Each case of R 5 is independently Q 1a or (C 1 -C 6 -hydrocarbyl)(C 1 -C 6 -hydrocarbyl)aminomethylene ((C 1 -C 6- hydrocarbyl)(C 1 -C 6 -hydrocarbyl)aminomethylene) group; x' and y' are independently 0 to 50, or 0 to 30, wherein the sum of x' and y' is at least 2; e is 1 to 200; z is 0 or 1 and; Each D is independently a substituted or unsubstituted C2 - C30 hydroxyhydrocarbyl, a substituted or unsubstituted C3 - C30 hydroxyhydrocarbylcarbonyl, a substituted or unsubstituted C4 - C30 hydroxy -terminated poly( C2 - C4 alkylene ether), or C5 - C30 hydroxy -terminated poly( C2 - C4 alkylene ether)carbonyl, wherein the hydroxyl group is directly connected to an aliphatic carbon atom; Y is the following chemical formula , or as a connector Here Each of R a , R b , R c , R d , and R e is independently hydrogen, C 1- C 12 hydrocarbyl, or C 1 -C 6 hydrocarbylene, and optionally R a and R b or R c and R d together are C 4 -C 8 alkylene groups, and Each case of R6 is independently hydrogen, C1-14 hydrocarbyl, C1-14 halohydrocarbyl , or C1-14 heterohydrocarbyl , and each R7 is a C1-6 hydrocarbylene group, and A composition in which E is 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, 10 to 60, or 5 to 20.
  6. In paragraph 5, The above-mentioned capped poly(arylene ether) copolymer is of the following chemical formula (7a). (7a) A composition in which each case of D is independently C2 - C20 hydroxyhydrocarbyl or C4 - C20 hydroxy-terminated poly(ethylene ether).
  7. In paragraph 1, The above-mentioned capped poly(arylene ether) copolymer has a number average molecular weight of 200 to 2,500 grams per mole and a weight average molecular weight of 600 to 6,000 grams per mole, and A composition in which the number average molecular weight and weight average molecular weight are determined by gel permeation chromatography.
  8. In paragraph 1, The above-mentioned capped poly(arylene ether) copolymer is a composition having 1.5 to 5 hydroxyl groups per average mole.
  9. In paragraph 1, A composition in which the above-mentioned capped poly(arylene ether) copolymer has an intrinsic viscosity of 0.04 to 0.15 deciliters per gram when measured in chloroform at 25°C.
  10. In paragraph 1, The above (poly)isocyanate compounds are 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate, and cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis(4-isocyanatocyclohexyl)methane, 2,4'-dicyclohexyl-methane diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis-(isocyanatomethyl)-cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, alpha,alpha,alpha,alpha',alpha'-tetramethyl-1,3-xylylene diisocyanate, alpha,alpha,alpha',alpha'-tetramethyl-1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4-hexahydrotoluene Diisocyanate (2,4-hexahydrotoluene diisocyanate), 2,6-hexahydrotoluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-diisocyanatonaphthalene, average more than 2 per molecule A composition comprising an oligomeric diphenylmethane diisocyanate having four or fewer isocyanate groups, or a combination thereof.
  11. In paragraph 1, The above composition further comprises one or more polyols; or a foaming agent; or a catalyst.
  12. A method for manufacturing a capped poly(arylene ether) copolymer according to any one of claims 1 to 11, The above method comprises the step of reacting an uncapped poly(arylene ether) copolymer containing phenolic terminal groups and a capping agent under conditions providing a reaction mixture containing a capped poly(arylene ether) copolymer.
  13. In Paragraph 12, The above capping agent comprises one or more of the compounds of the following chemical formulas (10) to (13): (10) (11) (12) (13) Here R9 to R12 , R20 , and R21 are each independently hydrogen, C1 - C12 primary alkyl, C2-12 alkenyl, C7 - C12 arylalkyl, C2 -C12 alkoxyalkyl, C7 -C12 aryloxyalkyl , or C1 - C12 hydroxyalkyl; Each case of R13 , R14 , R22 , and R23 is independently hydrogen, C1 - C12 primary alkyl, C7 -C12 arylalkyl, C2 - C12 alkoxyalkyl, C7 - C12 aryloxyalkyl, or C1-C12 hydroxyalkyl ; R 15 to R 18 Each case is independently hydrogen or methyl; R 19 is hydrogen or a C 1 -C 18 primary alkyl; X is a halogen; a is 0 or 1 and; b is 0 to 10; c is 0 to 3; g is 1 or 2, method.
  14. A product manufactured from a composition according to any one of claims 1 to 11.
  15. delete

Description

Poly(arylene ether) composition Cross-reference of related applications This application claims the priority and benefit of European patent application no. 19189450.0 filed with the European Patent Office on July 31, 2019, the entire contents of which are incorporated herein by reference. Poly(arylene ether) copolymers are a class of thermoplastic resins known for their excellent water resistance, dimensional stability, and inherent flame retardancy, as well as their superior dielectric properties over a wide frequency and temperature range. Properties such as ductility, stiffness, chemical resistance, and heat resistance allow thermosetting poly(arylene ether) copolymers to be reacted with various crosslinking agents to meet the requirements of various end applications, such as fluid engineering components, electrical enclosures, automotive parts, and insulation for wires and cables. In particular, poly(arylene ether) copolymers have been used in thermosetting compositions for electronic applications, providing improved toughness and dielectric properties among other advantages. Phenols, such as uncapped poly(phenylene ether) (PPE), are used as blocking agents for polyurethanes, particularly for coating and adhesive applications. PPE blocking agents can minimize moisture sensitivity in the system, thereby reducing free isocyanates in polyurethane systems and extending storage stability. The phenolic terminal groups of PPE blocking agents form reversible bonds with isocyanates, where deblocking occurs at high temperatures. However, the reversible nature of these bonds limits the use of phenolic PPE in final polyurethane products due to a lack of thermal stability. It would be advantageous to use capped PPE copolymers in final polyurethane products to impart improved properties, including low moisture absorption, an increased glass transition temperature ( Tg ), improved tear strength, chemical resistance, and flame retardancy. Polyurethanes are generally prepared by reacting a polyol with a (poly)isocyanate in the presence of a catalyst. For stability during preparation, the (poly)isocyanate may be blocked by a blocking agent, wherein at least one isocyanate group reacts with the protective agent or blocking agent to form a derivative (also referred to as "blocked poly(isocyanate)"), and this derivative can be dissociated upon heating to remove the protective agent or blocking agent (also referred to as de-blocking) and release a reactive isocyanate group. The reactive isocyanate group can subsequently react with the polyol to achieve the polymerization of the polyurethane. However, due to the nature of the blocking chemical, both heating and a longer reaction time may be required to proceed. In sheet applications, polyurethane coatings can be applied to flat or gently curved end parts manufactured by injection molding or thermoforming via flow or dip coating, performed under conditions that minimize deblocking before curing, and subsequently cured by heat or irradiation. In the case of thermoplastic polyurethanes, the thermopolymer can be shaped and then post-coated and cured to produce a final product for a given application. These techniques have the disadvantage of being time-intensive because the blocking chemical reactions of (poly)isocyanates are inherently slow. For processes such as dip coating, there is additional time required to apply the coating to the substrate before curing even begins. Phenolic compounds, such as uncapped poly(phenylene ether) (PPE) copolymers, can be used as blocking agents in polyurethanes to reduce free isocyanate groups and provide extended storage stability. Additionally, uncapped PPE copolymers can react with isocyanate groups under specific conditions to allow the uncapped PPE copolymer to be incorporated into the structure of the final polyurethane product. The phenolic terminal groups of uncapped PPE copolymers can form reversible bonds with the isocyanate groups of (poly)isocyanates, which makes uncapped PPE copolymers useful as blocking agents. However, the reversible nature of these bonds can also limit the use of uncapped PPE copolymers in polyurethane compositions because they react with isocyanate groups as polyols during polymer formation, and also limit the thermal stability of the bond formed between the phenolic hydroxyl group and the isocyanate group, so the thermal stability of the final polyurethane product is similarly limited, especially at high temperatures. In overcoming the limitations of uncapped PPE copolymers in this type of polyurethane composition, the inventors have discovered that a capped poly(arylene ether) copolymer containing an aliphatic hydroxyl terminal cap (also called a terminal group) can be used instead of an uncapped PPE copolymer. The aliphatic alcohol group of the capped poly(arylene ether) copolymer reacts favorably to form a thermally strong bond with the isocyanate group of the (poly)isocyanate, and the resulting polyurethan