Classifications

• • 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
  • C08G75/14—Polysulfides
• • 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
• • 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

Definitions

• the present disclosure provides a composition which is radiation curable to a polythioether polymer, comprising: a) at least one dithiol monomer; b) at least one diene monomer; c) at least one polyyne monomer comprising at least two ethyne groups; and d) at least one photoinitiator.
• the composition may additionally comprise e) at least one epoxy resin.
• the present disclosure provides a composition which is radiation curable to a polythioether polymer, comprising: a) at least one dithiol monomer; b) at least one diene monomer; c) at least one diyne monomer; and d) at least one photoinitiator.
• the composition may additionally comprise e) at least one epoxy resin.
• the present disclosure provides a composition which is radiation curable to a polythioether polymer, comprising: f) at least one thiol terminated polythioether polymer; g) at least one diyne monomer; and h) at least one photoinitiator.
• the thiol terminated polythioether polymer comprises pendent hydroxide groups.
• compositions described herein may additionally comprise a filler, in some embodiments a nanoparticle filler.
• the composition may additionally comprise calcium carbonate.
• the composition may additionally comprise nanoparticle calcium carbonate.
• compositions described herein visibly change color upon cure.
• the compositions described herein are curable by an actinic light source.
• the compositions described herein are curable by a blue light source.
• the compositions described herein are curable by a UV light source.
• the present disclosure provides a sealant comprising any of the compositions described herein.
• the sealant is transparent. In some embodiments, the sealant is translucent.
• the present disclosure provides a polythioether polymer obtained by radiation cure of any the radiation curable compositions described herein.
• the polythioether polymer has a Tg less than -55°C.
• the polythioether polymer exhibits high jet fuel resistence characterized by a volume swell of less than 30% and a weight gain of less than 20% when measured according to Society of Automotive Engineers (SAE) International Standard AS5127/1.
• the present disclosure provides a seal comprising any of the
• the seal is transparent. In some embodiments, the seal is translucent.
• the present disclosure provides radiation curable polythioether polymers including alkyne linkages which may be particularly useful as sealant materials due to characterics such as low Tg and high resistance to solvemts such as jet fuel.
• the present disclosure relates to mercaptan based polythioether sealants containing radical photoinitiators.
• the present disclosure relates to sealants that may be cured on demand in a one-step process in seconds by UV/LED radiation sources.
• the sealants include fillers.
• the sealants exclude fillers.
• the sealant formulation contains a mercaptan based monomer (such as a dithiol) or oligomer (such as a linear polythioether or polysulfide), a diene or divinylether, a diyne, and a radical photoinitiator (such as Irgacure 819).
• the sealant formulation includes an epoxy resin.
• the sealant formulation includes calcium carbonate or nanoparticle calcium carbonate.
• the sealant according to the present disclosure can simultaneously provide a long application life and cured on demand.
• the sealant according to the present disclosure exhibit favorable solvent and fuel resistance properties.
• the sealant according to the present disclosure exhibit favorable thermal resistance properties.
• the user applies the sealant according to the present disclosure as a single-component liquid formulation to the structure requiring sealing. In some embodiments, the user applies the sealant according to the present disclosure as a multi-component liquid formulation to the structure requiring sealing. In some embodiments, the sealant remains liquid and usable until the user applies an external source of electromagnetic (EM) radiation. Any suitable source of EM radiation can be used, most typically selected from actinic, blue and/or UV radiation. Upon application of the external EM radiation the liquid sealant then cures or crosslinks. In some embodiments, the sealant cures or crosslinks to an at least partially elastomeric solid in less than one minute.
• EM electromagnetic
• This disclosure is useful in sealants, and in particular for the aerospace industry.
• DMDO l,8-Dimercapto-3,6-dioxaoctane, obtained from Arkena, Inc., King of Prussia,
• DVE-2 Diethyleneglycol divinyl ether, obtained from BASF Corp., Florham Park, New Jersey.
• DVE-3 Triethyleneglycol divinylether, obtained under the trade designation "RAPI-
• HDY 1.6- heptadiyne, obtained from GFS Chemicals, Inc., Powell, Ohio.
• Phenylbis(2,4,6-trimethylbenzoyl)phosphine Oxide obtained under the trade designation "IRGACURE 819" from BASF Corp., Florham Park, New Jersey.
• NCC Nanoparticle (70 - 100 nm) calcium carbonate, obtained under the trade
• ODY 1.7- octadiyne, obtained from ChemSampCo, Inc., Trenton, New Jersey.
• PTE A liquid polythioether polymer prepared as follows. Into a 5 liter round bottom flask equipped with an air driven stirrer, thermometer, and a condenser, was added 167.1 grams (0.51 mol) E-8220 and 1641 grams (9.0 mol) DMDO. After several minutes of stirring the mixture exothermed to 45°C. After another 30 minutes, the temperature of the flask was increased 75°C and a mixture of 1428.1 grams (7.1 mol) DVE-3, 50.7 grams (0.2 mol) TAC and 13.1 grams (0.07 mol) VAZO-67 was added drop wise. The reaction proceeded substantially to completion affording 3,300 grams of polythioether polymer.
• TAC Triallylcyanurate, obtained from Sartomer, Inc., Exton, Pennsylvania.
• VAZO-67 2,2'-azobis(2-methylbutyronitrile, obtained under the trade designation "VAZO- 67" from E.I. du Dupont de Nemours and Company, Wilmington, Delaware.
• a curable polythioether composition was prepared as follows. A 40 ml. amber glass vial was charged with 7.000 grams DMDO, 5.212 grams DVE-2, 0.125 grams 1-819 and 0.251 grams HDY at 21°C. The vial was then sealed and placed on a laboratory roller mill for 10 minutes until the I- 819 had dissolved. Example 2.
• a curable polythioether composition was prepared as generally described in Example 1 , wherein after the resin and initiator were dissolved, 1.888 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute.
• a curable polythioether composition was prepared as generally described in Example 1 , wherein the HDY was substituted with 0.289 grams ODY. Example 4.
• a curable polythioether composition was prepared as generally described in Example 3, wherein after the resin and initiator were dissolved, 1.894 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute.
• Example 5 A curable polythioether composition was prepared as generally described in Example 3, wherein after the resin and initiator were dissolved, 1.894 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute. Example 5.
• a 40 ml. amber glass vial was charged with 10.000 grams PTE, 0.102 grams 1-819 and 0.172 grams HDY at 21°C. The vial was then sealed and placed on a laboratory roller mill for 12 hours until the 1-819 had dissolved.
• Example 6 A 40 ml. amber glass vial was charged with 10.000 grams PTE, 0.102 grams 1-819 and 0.172 grams HDY at 21°C. The vial was then sealed and placed on a laboratory roller mill for 12 hours until the 1-819 had dissolved.
• a curable polythioether composition was prepared as generally described in Example 5, wherein after the resin and initiator were dissolved, 1.545 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute.
• Example 7
• a curable polythioether composition was prepared as generally described in Example 5, wherein the HDY was substituted with 0.198 grams ODY.
• a curable polythioether composition was prepared as generally described in Example 7, wherein after the resin and initiator were dissolved, 1.545 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute.
• Example 9 A curable polythioether composition was prepared as generally described in Example 7, wherein after the resin and initiator were dissolved, 1.545 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute.
• a curable polythioether composition was prepared as generally described in Example 3, wherein the amount of 1-819 was increased to 0.250 grams.
• Example 10 A curable polythioether composition was prepared as generally described in Example 3, wherein the amount of 1-819 was increased to 0.250 grams. Example 10.
• a curable polythioether composition was prepared as generally described in Example 9, wherein after the resin and initiator were dissolved, 1.913 grams NCC was homogeneously dispersed in the composition by means of a high speed mixer for 1 minute. Samples were poured into a nominally 2 cm by 2 cm silicone rubber mold of various heights, at 21°C and cured by exposure, according to the times listed in Table 1, to one of the following actinic light sources:
• Shore A Hardness Measured using a model "1600” hardness gauge, obtained from Rex Gauge Company, Inc., Buffalo Grove, Illinois.
• T g Measured using a model "DSC Q2000" differential scanning calorimeter, obtained from TA Instruments, New Castle, Delaware.
• Jet Fuel Resistance Measured according to Society of Automotive Engineers (SAE) International Standard AS5127/1, wherein samples were immersed in Jet Reference Fluid Type 1 (JRF1) for 7 days at 60°C, after which % swell and % weight gain of the sample were determined.
• JRFl composition is defined by SAE Standard AMS2629.
• Color Change Measured before and after curing using a model "MINISCAN XE PLUS D/8S" colorimeter, in mode D65/10*, obtained from Hunter Associates Laboratory, Inc., Reston, Virginia.
• Results listed in Table 1 represent the average values of triplicate samples measured for thickness and Shore A hardness, and the average values for duplicate measurements of T g .

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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)
• Sealing Material Composition (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2014
  • 2014-03-05 PT PT147129183T patent/PT2970589T/pt unknown
  • 2014-03-05 US US14/775,018 patent/US20160032059A1/en not_active Abandoned
  • 2014-03-05 KR KR1020157026902A patent/KR20150127635A/ko not_active Ceased
  • 2014-03-05 JP JP2016500637A patent/JP6463723B2/ja not_active Expired - Fee Related
  • 2014-03-05 CN CN201480013692.1A patent/CN105073837B/zh not_active Expired - Fee Related
  • 2014-03-05 EP EP14712918.3A patent/EP2970589B1/en not_active Not-in-force
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  • 2014-03-05 WO PCT/US2014/020587 patent/WO2014164103A1/en not_active Ceased
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