WO2018014746A1 - Composition de polymère de sulfone et composition de moulage thermoplastique constituée par celle-ci et utilisation correspondante - Google Patents

Composition de polymère de sulfone et composition de moulage thermoplastique constituée par celle-ci et utilisation correspondante Download PDF

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Publication number
WO2018014746A1
WO2018014746A1 PCT/CN2017/092328 CN2017092328W WO2018014746A1 WO 2018014746 A1 WO2018014746 A1 WO 2018014746A1 CN 2017092328 W CN2017092328 W CN 2017092328W WO 2018014746 A1 WO2018014746 A1 WO 2018014746A1
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WIPO (PCT)
Prior art keywords
sulfone polymer
polymer composition
total weight
sulfone
dimethylquinoline
Prior art date
Application number
PCT/CN2017/092328
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English (en)
Chinese (zh)
Inventor
高红军
代惊奇
吴浩滨
曾祥斌
曹民
姜苏俊
龙杰明
Original Assignee
金发科技股份有限公司
珠海万通化工有限公司
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Publication of WO2018014746A1 publication Critical patent/WO2018014746A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a sulfone polymer composition and a thermoplastic molding composition composed thereof and an application thereof.
  • Sulfone polymer is a special high temperature resistant transparent thermoplastic engineering plastic with outstanding thermal properties, excellent chemical resistance, excellent high temperature creep resistance, excellent dimensional stability, extremely low smoke and toxic gas emissions, and superior heat resistance. Water and superheated steam, good electrical properties, mainly including polysulfone PSU, polyethersulfone PES and polyphenylene sulfone PPSU.
  • polysulfone PSU polyethersulfone PES
  • polyphenylene sulfone PPSU polyphenylene sulfone
  • the patent US2002010307 realizes the preparation of the lighter PPSU by controlling the particle size of the salt forming agent sodium carbonate
  • the patent CN101479321 uses d/D.
  • US2003011501 prepares a light colored PSU by adding an antioxidant of phosphorous acid.
  • CN 104530431 discloses the addition of 3,4'-dihalobenzophenone.
  • the present inventors have unexpectedly discovered that a trace component having a specific structure has a significant influence on the color of a sulfone polymer resin, and the present invention controls a trace component having a specific structure in a sulfone polymer, and controls the weight content thereof to be less than or equal to At 1000 ppm, the resulting sulfone polymer composition has a yellowness index of less than 5, which can significantly improve the color of the sulfone polymer composition.
  • a sulfone polymer composition comprising:
  • V a sulfonic acid or a sulfate lactone
  • the total weight content of the trace component is less than or equal to 1000 ppm based on the total weight of the sulfone polymer composition.
  • the total weight content of the trace components is determined by headspace-gas chromatography-mass spectrometry, and is determined by headspace-gas chromatography-mass spectrometry: using the US CDS8000 dynamic headspace sample concentrator headspace equipment, A trap filled with Tenax-GC organic adsorption packing was placed, 0.3 g of the sulfone polymer composition to be tested was placed in a headspace injection chamber, and kept at 300 ° C for 1 h, and the collected gas phase was used with Agilent's 7890B-5977A MSD type.
  • GC-MS monitoring equipment was tested; chromatographic conditions: capillary column was HP-5MS (30m ⁇ 250 ⁇ m, 0.25m); temperature program was raised to 390 ° C at 15 ° C / min, inlet temperature was 390 ° C, carrier gas was He gas, flow rate is 0.8mL / min, split ratio is 50:1; mass spectrometry conditions are EI source, ionization voltage of 70eV, ion source temperature 250 °C, scanning range: 30-600m / z; total weight content of trace components Calculated by the external standard method.
  • the total weight content of the minor component is 800 ppm or less, more preferably 500 ppm or less, based on the total weight of the sulfone polymer composition, and the total weight content of the minor component is not 0.
  • the sulfolene is 2-sulfolene or 3-sulfolene;
  • the hydroxy-substituted, aliphatic branched-chain sulfolane or thiophene sulfone is 2-hydroxysulfolane, 3-hydroxysulfolane, 2- C / butyl / pentane / hexyl sulfolane, 3-propion / butyl / pentane / hexyl sulfolane or benzo sulfolane;
  • the dimethyl substituted quinoline is 2,3-dimethylquinoline, 2, 4 - dimethylquinoline, 2,5-dimethylquinoline, 2,6-dimethylquinoline, 2,7-dimethylquinoline or 2,8-dimethylquinoline;
  • the methyl substituted quinoline species is 2,4,8-trimethyl-1,2,3,4-tetrahydroquinoline or 2,2,4-trimethyl-1,2-dihydroquinoline.
  • the sulfonic acid or sulfate lactone is 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,6-hexane sulfonic acid Ester, propylene dilactone, butyrolactone sulfate, or glutaractone sulfate.
  • the sulfone polymer composition has a yellowness index of less than 5 as measured on a 2 mm thick injection molded panel according to ASTM D1925.
  • the aromatic sulfone polymer is polyphenylene sulfone PPSU, polyether sulfone PES or polysulfone PSU.
  • Sulfone polymers generally include polysulfone PSU, polyethersulfone PES and polyphenylenesulfone PPSU, all of which are amorphous transparent amber high temperature resistant polymers.
  • PSU is prepared by reacting 4,4'-dichlorodiphenyl sulfone (DCDPS) with a unit of bisphenol A (BPA) by making 4,4'-dichlorodiphenyl sulfone (DCDPS) with 4 , 4'-dihydroxydiphenyl sulfone (bisphenol S) unit reaction
  • PPSU is made by 4,4'-dichlorodiphenyl sulfone (DCDPS) and 4,4'-bisphenol (BP) unit reaction made.
  • the general solvent is mainly sulfolane or N-methylpyrrolidone.
  • the present inventors have found through research that a trace component having a specific structure has a significant influence on the color of the sulfone polymer resin, and the source of the minor component can be directly added to a specific structural trace component in the synthesis of the sulfone polymer.
  • the sulfone polymer composition contains at least one trace component selected from the group consisting of:
  • sulfolene including:
  • sulfolane or thiophene sulfone containing a hydroxy-substituted, aliphatic branched-chain substituent including:
  • dimethyl substituted quinoline including:
  • Trimethyl substituted quinoline species including:
  • V sulfonic acid or sulphate, including:
  • the unexpected discovery of the present invention is that in the sulfone polymer, by adding a trace component having a specific structure, and controlling the total weight content of the trace component to 1000 ppm or less, and the total weight content of the trace component is not 0, the obtained
  • the sulfone polymer composition has a yellowness index of less than 5 and the sulfone polymer composition has a significantly improved color level.
  • the present invention also provides a thermoplastic molding composition comprising the above sulfone polymer composition.
  • the molding compositions of the invention may contain fillers, especially fibers, particularly preferably glass fibers.
  • fillers especially fibers, particularly preferably glass fibers.
  • Any glass fiber known to those skilled in the art and suitable for use in thermoplastic molding compositions can be present in the thermoplastic molding composition.
  • the molding compositions of the invention may contain auxiliaries as further components, in particular processing aids, pigments, stabilizers, flame retardants, or mixtures of different additives.
  • auxiliaries as further components, in particular processing aids, pigments, stabilizers, flame retardants, or mixtures of different additives.
  • processing aids pigments, stabilizers, flame retardants, or mixtures of different additives.
  • Other examples of conventionally added materials are antioxidants, heat stabilizers, UV stabilizers, lubricants and mold release agents, and pigments.
  • Antioxidants and heat stabilizers may use hindered phenols, hydroquinones, substituted forms of the groups, secondary aromatic amines, or phosphite or phosphonite compounds, optionally with phosphorus-containing acids. Used in combination, or a salt thereof, or a mixture of the compounds.
  • UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones, and lubricants and mold release agents may be stearyl alcohol, alkyl stearates, stearic fats. Amides, as well as esters of pentaerythritol with long chain fatty acids, may also be used with dialkyl ketones such as distearyl.
  • the pigment may be a white pigment such as zinc oxide, zinc sulfide, white lead, zinc antimony white, antimony white and titanium dioxide.
  • Black pigments such as iron oxide black, spinel black, manganese black, cobalt black, and black, carbon black, and the like can also be used in accordance with the present invention.
  • thermoplastic molding compositions of the present invention can be prepared by methods known per se, such as extrusion.
  • the molding compositions of the invention can be prepared, for example, by mixing the starting components in a conventional mixing apparatus, such as a screw-based extruder, preferably a twin-screw extruder.
  • the above sulfone polymer composition of the present invention can be widely used in the fields of aerospace, medical and health, food safety, household appliances, electronic appliances or energy and chemical engineering.
  • the invention has the following beneficial effects:
  • the unexpected discovery of the present invention is that in the sulfone polymer, by adding a trace component having a specific structure, and controlling the total weight content of the trace component to 1000 ppm or less, and the total weight content of the trace component is not 0, the obtained sulfone is obtained.
  • the polymer composition has a yellowness index of less than 5 and has a significantly improved color level.
  • the raw materials used in this example were all commercially available.
  • the xylene is further distilled and discharged, and the temperature is gradually increased to 230 ° C to start the polymerization reaction. At this time, the viscosity is detected to increase, and the temperature is constant.
  • Yellowness index The yellowness index (YI) was measured by injection molding on a 2 mm thick test panel according to ASTM D1925.
  • the total weight content of the trace components was determined by headspace gas chromatography and mass spectrometry: using the US CDS8000 dynamic headspace sample concentrator headspace equipment with a trap filled with Tenax-GC organic adsorption packing, 0.3g
  • the sulfone polymer composition to be tested was placed in a headspace sample chamber at 300 ° C for 1 h, and the collected gas phase was tested with Agilent's Model 7890B-5977A MSD GC-MS monitoring device; chromatographic conditions: capillary column for HP -5MS (30m ⁇ 250 ⁇ m, 0.25m); the temperature program is raised to 390 ° C at 15 ° C / min, the inlet temperature is 390 ° C, the carrier gas is He gas, the flow rate is 0.8 mL / min, the split ratio is 50:1
  • Mass spectrometry conditions were EI source, ionization voltage of 70 eV, ion source temperature 250 ° C, scanning range: 30-600 m/z; total weight
  • the obtained sulfone polymer composition has a yellowness index of less than 5, and has a significantly improved color level
  • the total weight content of the trace components in the comparative example is more than 1000 ppm
  • the obtained sulfone polymer composition has a yellowness index of more than 5, and the color The level is significantly worse than the embodiment.

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

Abstract

L'invention concerne une composition de polymère de sulfone et une composition de moulage thermoplastique constituée par celle-ci et une utilisation correspondante. La composition de polymère de sulfone comprend : (A) un polymère de sulfone aromatique et (B) au moins un microconstituant choisi parmi les structures suivantes : I : les sulfolènes, II: les sulfolanes ou les thiophènesulfones contenant un substituant hydroxy ou un substituant à chaîne ramifiée aliphatique, III : les quinoléines substituées par diméthyle, IV : les substances à base de quinoléine substituées par triméthyle et V : les substances à base d'acide sulfonique ou de lactone d'acide sulfurique, dans laquelle, sur la base du poids total de la composition de polymère de sulfone, la teneur en poids total des microconstituants est inférieure ou égale à 1000 ppm et la teneur en poids total des microconstituants n'est pas égale à 0. Les microconstituants présentant une structure spécifique sont ajoutés au polymère de sulfone, la teneur en poids total des microconstituants est régulée, l'indice de jaunissement de la composition de polymère de sulfone obtenue est inférieur à 5 et le niveau de couleur est remarquablement amélioré.
PCT/CN2017/092328 2016-07-21 2017-07-10 Composition de polymère de sulfone et composition de moulage thermoplastique constituée par celle-ci et utilisation correspondante WO2018014746A1 (fr)

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CN201610578005.1A CN106189235B (zh) 2016-07-21 2016-07-21 一种砜聚合物组合物及由其组成的热塑性模塑组合物与应用
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10767004B1 (en) 2020-01-13 2020-09-08 Dairen Chemical Corporation Tricyclodecane dimethanol composition and uses thereof

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CN106189235B (zh) * 2016-07-21 2017-10-24 金发科技股份有限公司 一种砜聚合物组合物及由其组成的热塑性模塑组合物与应用
WO2018064521A1 (fr) * 2016-09-30 2018-04-05 Vanderbilt Chemicals, Llc Inhibiteur de grillage à faibles émissions pour mousse de polyuréthane
CN109796762B (zh) * 2019-01-21 2021-07-27 江西金海新能源科技有限公司 一种砜聚合物组合物及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10767004B1 (en) 2020-01-13 2020-09-08 Dairen Chemical Corporation Tricyclodecane dimethanol composition and uses thereof

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CN106189235A (zh) 2016-12-07

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