TW561180B - Compositions containing a polyarylene ether and a dispersible reactive solvent and articles prepared therefrom - Google Patents

Abstract

A blend of a polyarylene ether and a dispersible reactive solvent such as a thermoplastic polyurethane or a cyclopentadiene can be processed at temperatures below the oxidative degradation temperature of the polyarylene ether, yet form an article upon cooling that substantially retains the properties of the polyarylene ether.

Description

5. Description of the invention (1) The present invention relates to a composition comprising a polyarylene bond and a dispersible reactive solvent. Polyarylene (PAE) series—a thermoplastic resin with excellent mechanical and electrical properties, thermal resistance, flame retardancy, low moisture absorption, and dimensional stability. These resins are widely used in automotive interiors, especially in dashboards and electrical and electronic applications. A PAE is difficult to handle (for example, by injection molding) because of its high melt viscosity relative to its oxidative degradation temperature and its processing temperature. As a result, PAE-like blends with compatible polymers, such as polystyrene (WO 97/21771 and U.S. Patent No. 4,8,04,712); polyamines (U.S. Patent No. 3,379,792) Polyolefins (U.S. Patent No. 3,351,851), rubber modified styrene resins (U.S. Patent Nos. 3,383,435 and 3,959,211 and Ger · Offen · No. 2,047,613); and mixtures of polystyrene and polycarbonate (U.S. Patent Nos. 3,933,941 and 4,446,278). Unfortunately, improvements in processing are generally obtained by paying for flexural modulus, flexural strength, and heat distortion temperature. Epoxy resins have also been studied as reactive solvents for PAE (see Venderbosch, R.W., "Processing difficult polymers with reactive solvents", Ph.D. thesis, Eindhoven (1995); Vanderbosch et al. , Poly. "Vol. 35", p. 4349 (1994); \ ^ 11 (161 * 130081, et al., Polymers, Vol. 36, p. 1167 (1995a); and Vanderbosch et al., Polymerization Materials, Book 36, Page 2903 (1995b). In this example, PAE is first dissolved in epoxy resin to form a better homogeneous solution. Objects are then formed from this solution, and the solution solidifies at elevated temperatures , Forming a phase separation, which can produce a continuous PAE phase with epoxide interspersed between them. The final physical paper size applies the Chinese national standard (_) A4 specification (21〇 > < 297 public director) 561180 A7 B7 5 2. Description of the invention (The nature of the 2 pieces is mainly determined by PAE; however, it is not practical to use epoxy resin as a PAE reaction solvent in a continuous melting method (for example, injection molding), because epoxy resin requires a curing agent to cure. The curing agent will accumulate in the main mold barrel over time, and Machine clogging. In addition, curing and subsequent phase separation must occur at least 150 ° C, which is not practical in the mold environment. Based on the lack of the industry, the expectant is to find a solution that can be used for some PAE The reaction solvent for processing problems in the reaction solvent, which does not adversely affect the physical properties of the PAE. The present invention focuses on the needs of the industry, on the one hand, by providing a molten t-subunit bond and a reaction solvent (which is Thermoplastic polyurethane or cyclopentadiene) composition, wherein the polyarylene ether is represented by the following chemical formula-(Ar-0) n- wherein Ar is a substituted or unsubstituted aromatic core , And n is an integer of at least 10, but when the reaction solvent is a thermoplastic polyamino f acid S having less than 50 tiTg, the polyarylene fluorene and the reaction solvent include at least 60% by weight of the composition. In a second aspect, the present invention is a dispersion containing a) a dispersible reaction solvent, which is a thermoplastic polyurethane or cyclopentane; and a dispersion of a polyarylene ether represented by the following chemical formula: (Ar-0) n. Among them, the domain is replaced or not replaced Aromatic nucleus, heart 〆 an integer of at least 'the reaction solvent but having less of the private ⑽1 when the thermoplastic polyurethane vinegar' poly (arylene ether) and the reaction solvent containing the composition of matter at least 60 10

(Please read the precautions on the back before filling this page)., '^ 丨: Line 丨 561180 A7 ---_____ B7 ____ 5. Description of the invention (3) Weight%. In another aspect, the present invention is a composition comprising a molten polyarylene ether and a thermoplastic polyurethane, which has a Tg of not less than 50 ° C, wherein the polyarylene ether is as follows The chemical formula table shows:-(Ar-0) n- which makes' Ar a substituted or unsubstituted aromatic nucleus, and η is an integer of at least 10. TPU is not polymerizable at high temperatures, causing a significant reduction in melt viscosity ′ and repolymerizable at low temperatures. Similarly, cyclopentadiene engages the trans-Diels-Alder reaction at high temperatures, and in the presence of cooling and a suitable catalyst, the molecular weight is constructed to re-form polycyclopentadiene. Therefore, TPU and cyclopentadiene can be favorably cured without adding heat. Furthermore, PAE / TPU or PAE / cyclopentanthyl fused blends are homogeneous, while cooling objects are phase separated. This feature enables the melt to be processed at a temperature below the degradation temperature of the PAE, but retains the properties of unblended pAE. In one aspect, the present invention is a melt comprising PAE and TPU or cyclopentadiene, preferably TPU. PAE is represented by the following chemical formula:-(Ar-0) n- wherein Aι * is a substituted or unsubstituted aromatic core, and η is an integer of at least 10. The aromatic core may be, for example, phenylene, alkylated phenylene, chlorophenylene, bromophenyl, and naphthyl. Aι · Preferably 2,6-Difluorenyl-1,4-phenylene, 2-methyl-6-ethyl · 1,4-phenylene, 2,6-diethyl-1,4 -Phenylene, and 2,3,6-trifluorenyl-1,4-phenylene; Ar is more preferably 2,6-diamidyl-1,4-phenylene. The preferred PAE is a poly (2,6-dimethyl-1,4-phenylene) ether, and according to this paper size, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied (please read the note on the back first) (Fill in this page again)

561180 A7 ~ ------- 57 V. Description of the invention (4) 2,6-monomethylphenol and 2,3,6-trimethylphenol and poly (2,6_dimethyl- benzene) The copolymer obtained by the polymerization reaction of a (based) ether is more preferred. As used herein, the term "dispersible reaction solvent" refers to a substance that forms a solution with PAE at high temperature and forms a homogeneous dispersion with pAE when cooled. This solution is preferably a homogeneous solution and is dispersible The reaction solvent is preferably a dispersed phase. Examples of such dispersible reaction solvents include thermoplastic polyurethane (TPU) and cyclopentadiene, and TPU is preferred. TPU contains self-polyisocyanate and polyfunctional chain extension A structural unit formed by the reaction of an agent and a selective high-molecular-weight polyol. The polyisocyanate used to form the TPU is preferably a diisocyanate, which may be aromatic, aliphatic, or cycloaliphatic. Representatives of these preferred diisocyanates Exemplary examples can be found in U.S. Patent Nos. 4,385,133; 4,522,975 and 5,167,899. Preferred diisocyanates include 4,4, -diisocyanate diphenylmethane, p-phenylene diisocyanate, 1 , 3-bis (isocyanatofluorenyl) cyclohexane, 丨, 'diisocyanocyclohexane, hexamethylidene diisocyanate, 1,5-naphthyl diisocyanate, 3,3, _dimethyl 4,4 -dibenzyl diisocyanate, 4,4'-diiso Acid-based cyclohexyl fluorene and 2,4-toluene diisocyanate, or a mixture thereof. More preferred are 4,4, · diisocyanatocyclohexylmethane and 4,4, -diisocyanate diphenyl. Melamine. As used herein, the term "multifunctional chain extender" refers to a low molecular weight polyol 'preferably a glycol having a molecular weight of not more than 200. A preferred bond extender includes ethylene diethylene glycol. Alcohol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl diethylene glycol Alcohols, 1,4 · cyclohexanediethanol and 1.4-bishydroxyethylhydroquinone and mixtures thereof. Particularly preferred bifunctional chain extenders include 1,6-hexanediol and 1,4-butanediol. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 561180 A7 _ B7__ V. Description of the invention (5) ㈣ ~ '~ A mixture of alcohol and diethylene glycol, 1,4-butanediol and three Ethylene glycol and 丨 4-butanediol and tetraethylene glycol. TPU can also include units derived from the reaction of aromatic diols, preferably at a sufficient concentration to reduce rigidity. TPU can be melt processed. Temperature. These TPUs are disclosed in U.S. Patent No. 5,574,092. Examples of suitable square group monohydric alcohols include m-phenylene, catechol, hydrogen g-quinone, dibasic naphthalene, dihydroxy anthranilene, bis ( Hydroxyaryl) nu, dihydroxyphenanthrene, dihydroxydiphenyl, and bis (hydroxyphenyl) propane. Preferred aromatic secondary systems include hydroquinone, 4,4, dihydroxybisbenzene, 9,9, _bis (' Hydroxyphenyl) fluorene and bisphenol-A. When aromatic diols are used, the amount of aromatic diols is preferably not more than the amount that causes the tensile elongation of the TPU at break to be less than 5%, which It is determined by ASTM D-638. Preferably, the concentration of the aromatic diol is not less than 0 m (more preferably, not less than 0.5, most preferably not less than 丨) mole%, and more preferably not more than 20 (more preferably, no More than 10, the best is not more than 5) mole%, which is based on the total mole number of the glycol used to prepare the TPU. As used herein, the term high molecular weight polyol refers to a polyol, preferably a glycol having a molecular weight of less than about 500,000 amu, more preferably not less than about 600 amu, more preferably The line is not less than about 1,000 amu, and preferably is not more than about 6,000 noodles, more preferably is not more than about 3 coffee, and the best is not more than about 2 coffee. Examples of selective high molecular weight difluorenes include polyscale glycols such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol; and polyester glycols such as polycaprolactone glycol, and Can be linear, branched or cyclic diols or ether-containing diols from aliphatic diesters or bis (acid chlorides) and C2_CS ^ This paper size applies to China National Standard (CNS) A4 (210X297 mm) ( (Please read the precautions on the back before filling this page) •,? 1:: line 丨 561180 A7 B7 V. Compound prepared by the condensation reaction of the description of the invention (6), or its blend. More preferred high molecular weight polyglycol glycols include polycaprolactone glycol, poly (ethylene adipate) and poly (butylene adipate) glycol. TPU favors are prepared in the presence of a suitable catalyst, such as those disclosed in U.S. Patent No. 5,068,306, line 5 from line 46 to line 0, line 5. Preferred catalysts include stannous octoate and stannous oleate. Dibutyltin dioctanoate and dibutyltin dilaurate. The amount of the catalyst used is sufficient to increase the reactivity of the isocyanate group and the oxo group without adversely affecting the properties of the final product, and a preferred range is from about 0.02 to about 2.0% by weight based on the total weight of the reactants. The ratio of the isocyanate to 〇Η of the reactant is preferably no less than 0.95: 1, more preferably no less than 0.975: 1, most preferably no less than 0.985: 1, and more preferably no more than 1.05 : 1, more preferably no more than L025: 1, most preferably no more than 1015: 1. TPU can be appropriately prepared by, for example, batch or continuous methods known in the industry. A preferred continuous mixing method is reactive extrusion, such as the twin-screw extrusion method disclosed in U.S. Patent No. 3,642,964. The TPU suitable for use as a PAE reaction solvent may be a rigid τρυ or a soft TPU. The rigid TPU has a glass transition temperature of not less than 50 ° C, and its further feature is that it has a hard segment (ie, a structural unit formed from the polymerization reaction of a polyisocyanate and a difunctional chain extender), which is preferably Based on the weight of the TPU is not less than about 75% by weight, more preferably not less than about 90% by weight, and up to about 100% by weight. Available types of rigid TPU include isoplasttm polyurethane engineering thermoplastic resin (The Dow Chemical paper size applies Chinese National Standard (⑽) A4 specification (21〇 > < 297mm) (Please read the back first (Notes for filling in this page)

• 、 可 I: line 丨 9 561180 A7 _ _B7__ V. Description of Invention (7) Trademark of the company). The soft TPU has a Tg of less than 50 ° C, preferably less than 25 ° C. It is further characterized by having a hard segment of not more than 75% by weight based on the weight of the TPU. A preferred example of a soft TPU is PELLETHANEtm thermoplastic polyurethane (trademark of The Dow Chemical Company). One unusual feature of PAE / TPU blends is that the mixture is homogeneous when melted, but becomes heterogeneous when the melt cools. The homogeneity of the melt allows the blend to be processed at a temperature below the oxidative degradation temperature of the PAE: When the melt is cooled, the TPU phase separates, and the TPU forms a dispersion in the continuous phase of the PAE. In this way, the physical properties of the final object (Eg, heat distortion temperature, flexural modulus, and flexural strength) are more like unblended PAE. The weight-to-weight ratio of PAE to TPU in the melt blend (and the final article) is generally greater than 1: 1. It is also possible to include other thermoplastic polymers in PAE / TPU blends, such as polyethylene (PS), syndiotactic PS or polyvinylcyclohexane. PAE / TPU blends are particularly useful in injection molding applications where the high thermal properties of PAE need to be maintained. The following examples are only for illustration and not for limiting the scope of the present invention. Example 1-6 Various blends of poly (2,6-dimethyl-1,4-phenylene ether) (PPO 803, available from General Electric Plastics, Bergen op Zoom, the Netherlands) with rigid TPU (ISOPLASTtm 2530 Polyurethane Engineering Thermoplastic 'Resin, Trade Name of The Dow Chemical Company) or Soft TPU (PELLETHANEtm 2102-75A Thermoplastic Polyurethane Purpose, Trade Name of P Hungarian Chemical Company) and Selective Polystyrene N5000 resin (by Shell 10 (please read the precautions on the back before filling in this page): the line applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 561180 A7 ___B7_ V. Description of the invention (8) , Weight average molecular weight is 35,000; Mw / Mn is 2.37). Samples of PPO resin and polystyrene were prepared in a single screw extruder at 245 ° C in a 50/50 weight to weight ratio and at 250 ° C in a 75/25 weight to weight ratio. These samples were pelletized and blended with rigid TPU or soft TPU, and then mixed in an Arburg 270M single screw injection molding machine in different temperature modes, pressures, and molding temperatures (as shown in Table I). Samples of PPO resin and TPU were prepared in an injection molding machine. The PPO / soft TPU blend was mixed at 245 ° C before the double-roller mixer, which was due to the difficulty in crushing the soft TPU. Table I-Molding conditions for preparing placque (please read the notes on the back before filling this page) Sample (w / w) Temperature mode (C) Pressure (bar) Molding temperature (° 〇70PPE / 30 Rigid TPU 235 / 240/245/250/250 1860 60 70 (50PPE-50PS) 30 Rigid TPU 230/240/250/260/260 1700 30 70 (50PPE-50PS) 30 Soft TPU 230/240/250/260/260 1700 30 70 (75PPE-25PS) 30 Soft TPU 270/280/290/295/300 1860 30 70 (75PPE-25PS) 30 Soft TPU 240/250/260/265/270 1550 30. Order 丨: Line 丨 T of various samples g using thermal mechanical thermal analysis. Two T g were observed in each case. The samples were polished to 丨 -claws and 3 · 111111 thickness, and to 13-mm and 25-mm thickness, and used 2 ° C / The heating rate of minutes is analyzed in the tensile mode. Table II illustrates the Tg, flexural modulus, and flexural strength of various samples. 11 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 561180 A7 B7 V. Description of the invention (9) Table 2-Physical properties of PPE TPU blend samples (w / w) Tg (° C) Flexural modulus (MPa) Flexural strength (MPa) 70PPE / 30 Rigid TPU 110,230 4.6 26 70 (50PPE -50PS) 30 Rigid TPU 110,164 3.3 32 70 (50PPE-50PS) 30 Soft TPU -40,164 2.0 16 70 (75PPE-25PS) 30 Soft TPU 110,190 3.1 35 70 (75PPE-25PS) 30 Soft TPU -40,191 2.8 21 (Please first (Read the notes on the back and fill out this page)

This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) 12 Shen 4 said collapse ............... ............ ______ Case No. ^ ju ^ priced category (the above columns are filled out by this bureau)

C4 561180 Shellfish Consumer Cooperation, Duyin t • No. 88103297 of the Ministry of Economic Affairs ^ Patent specification. It is said that the Chinese composition containing polyarylene ether and a dispersible reaction solvent and articles prepared therefrom COMPOSITIONS CONTAINING A POLYARYLENE ETHER AND A DISPERSIBLE REACTIVE SOLVENT AND ARTICLES PREPARED THF.RRFROM 56 St. Hidwick Street (2) 9011 Beautiful Forest Road, Spartanburg, South Carolina, USA Name (Name) ... -—_ 1 American Business · Dow Global Technology Co., Ltd. Nationality US III. Applicant's Residence (Office) Midland City, Post-Western United States • Washington Title 丨 No. 79 Representative of Building No. D · Warik's i-size paper applies Zhongguanjia standard (CNS> A4g72 丨 〇 > < 297)

Claims (1)

561180 ABCD Notice I, Patent Application Scope < No. 088103297 Patent Reexamination Application, Patent Scope Amendment, Revised Date: February 1992 1. A composition containing polyarylene ether and a dispersible reaction A melt of a solvent, the reaction solvent contains a thermoplastic polyaminophosphonate having a Tg of not less than 50 ° C, wherein the polyarylene ether is represented by the following chemical formula:-(Ar-0) n. Where 'Ar • A substituted or unsubstituted aromatic core, and η is an integer of at least 10. ~ * ι ff; Jr 2 · As for the composition of the scope of application for patent, it is homogeneous when molten, and becomes a dispersible reaction solvent in the polyarylene ether when the molten is cooled. Dispersion. 3. The composition as described in any one of items 1 or 2 of the patent scope, wherein Ar is 2,6-difluorenyl-1,4 · phenylene, 2-fluorenyl-6-ethyl-1 , 4-phenylene, 2,6-diethyl-fluorenyl, 4-benzyl, or 2,3,6-trimethyl-fluorenyl, 4-benzyl or a mixture thereof. 4. The composition according to any one of claims 丨 or 2 in the scope of application for a patent, wherein the polyarylene ether is a poly (2,6-diamidino-1,4-phenylene) ether or by 2 A copolymer obtained by the polymerization of 2,6-dimethylphenol and 2,3,6-trimethylphenol. 5. The composition according to any one of the claims 1 or 2, wherein the reaction solvent further comprises a thermoplastic polyurethane having a Tg of less than 50 t :. 6. The composition of any one of claims 1 or 2 of the scope of patent application, which further comprises an additional thermoplastic copolymer or an impact modifier or both. 7. The composition according to item 6 of the patent application scope, which comprises polystyrene or polyethylene-butadiene-grafted rubber. 13 561180 A8 B8 C8 D8 Patent application scope 8. If the composition of any one of item 1 or 2 of the patent application scope, wherein the% is not less than 5 (the thermoplastic polyurethane of TC contains autohydroquinone, 4 Aromatic diol-shaped red structure monomers of 4,4, -dihydroxybisbenzyl, 9,9_bis (4_hydroxybenzyl), or bisphenol octa or mixtures thereof, and composed of the aromatic difluorene The concentration of the structural unit formed by the alcohol is determined based on the total mole number of the diol prepared from the thermoplastic polyurethane by using beta β, which is not less than 1 mole% and not much. 10 mol%. This paper size applies to China National Standard (CNS) A4 (210 × 297 mm) gutter ⑩ 14