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WO2008065732A1 - Procédé de production d'un mélange à base d'isocyanate modifié contenant une liaison allophanate et une liaison isocyanurate - Google Patents

Procédé de production d'un mélange à base d'isocyanate modifié contenant une liaison allophanate et une liaison isocyanurate Download PDF

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Publication number
WO2008065732A1
WO2008065732A1 PCT/JP2007/000864 JP2007000864W WO2008065732A1 WO 2008065732 A1 WO2008065732 A1 WO 2008065732A1 JP 2007000864 W JP2007000864 W JP 2007000864W WO 2008065732 A1 WO2008065732 A1 WO 2008065732A1
Authority
WO
WIPO (PCT)
Prior art keywords
bond
organic polyisocyanate
allophanate
modified isocyanate
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/000864
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English (en)
Japanese (ja)
Inventor
Ryusuke Kishimoto
Hiroyuki Orito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Polyurethane Industry Co Ltd
Original Assignee
Nippon Polyurethane Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Polyurethane Industry Co Ltd filed Critical Nippon Polyurethane Industry Co Ltd
Priority to JP2008546866A priority Critical patent/JPWO2008065732A1/ja
Publication of WO2008065732A1 publication Critical patent/WO2008065732A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Definitions

  • the present invention relates to a method for producing a mixture of an allophanate bond and an isocyanurate bond-containing modified isocyanate having excellent solvent solubility (hereinafter referred to as tolerance) in a nonpolar organic solvent or a low odor solvent.
  • Paint ⁇ In the field of painting and adhesives, 1,6-hexamethylene diisocyanate (hereinafter referred to as HDI), isophorone diisocyanate, and other aliphatic dissociates, alicyclic dissociates
  • HDI 1,6-hexamethylene diisocyanate
  • isophorone diisocyanate and other aliphatic dissociates
  • alicyclic dissociates Non-yellowing polyisocyanate derived from cocoon has excellent weather resistance, but polyisocyanate type containing isocyanurate bond has high chemical and thermal stability, especially weather resistance. Because of its excellent heat resistance and durability, it is widely used according to its application, and further application development is expected in the future.
  • This type containing an isocyanurate bond has better tolerance than the burette type and the urethane type, and is soluble in nonpolar aromatic hydrocarbon solvents such as toluene and xylene, but usually such as toluene and xylene.
  • the solvent currently has practical limitations in terms of solvent selectivity, such as being unable to reapply until the base is cured in the coating process, because it has a strong solubility that affects plastics. .
  • Patent Document 1 and Patent Document 2 and the method of Patent Document 3 are obtained by modifying a diisocyanate with alcohol to obtain a polyisocyanate containing an isocyanate bond.
  • Methods have been proposed for improving tolerance to non-polar organic solvents by using a mixture of ⁇ and a polysocyanate containing an allophanate bond.
  • non-polar organic solvents are preferred because they cause pungent odors from the viewpoint of malodor prevention.
  • low-odor solvents such as paraffinic hydrocarbons, but there are currently no hardeners with good solubility.
  • Patent Document 4 proposes a method for producing a low-viscosity allophanate bond and a isocyanurate bond-containing modified isocyanate compound with further improved tolerance to various solvents, curability, drying property, and weather resistance.
  • the modified isocyanate compounds containing allophanate bonds and isocyanurate bonds obtained by the method disclosed in Patent Document 4 are still sufficiently satisfactory in tolerance to nonpolar solvents such as mineral spirits and low odor solvents. It's hard to say.
  • Patent Document 1 Japanese Patent Publication No. 6 2-5 1 9 6 8
  • Patent Document 2 Japanese Patent Application Laid-Open No. Sho 62-2-2 1 5 6 6 2
  • Patent Document 3 Japanese Patent Laid-Open No. 4-3 0 6 2 18
  • Patent Document 4 Japanese Patent Laid-Open No. 2 0 0 2 _ 6 0 4 5 9
  • the object of the present invention is to ensure excellent curability, drying property, and weather resistance, and in particular, low viscosity allophanate bond and isocyanurate bond-containing modification excellent in tolerance to nonpolar organic solvents and low odor solvents. It is to provide a process for the preparation of a isocyanate mixture.
  • the present invention relates to a monoalcohol and an excess amount of an organic polyisocyanate in the presence of an allophanatization catalyst in a proportion of 1.8 to 2.0 with respect to the hydroxyl group of the monoalcohol.
  • an allophanatization catalyst After reacting at 70 to 150 ° C. within the range that consumes a double molar amount of isocyanate group, it is converted to allophanate, and the content of unreacted organic polyisocyanate is 1.0% by mass.
  • the viscosity at 25 ° C is 2, OOO m P a ⁇ characterized in that it is then removed in the presence of an isocyanuration catalyst and then isothermally converted at 40 to 90 ° C. s
  • the following is a process for producing a modified isocyanate mixture containing allophanate bonds and isocyanurate bonds.
  • the organic polyisocyanate is an aliphatic diisocyanate.
  • the present invention provides a monoalcohol and an excess amount of an organic polyisocyanate, when reacting in the presence of an aromatication catalyst to make an allophanate.
  • This is a process for producing a mixture of modified allophanate bonds and isocyanurate bond-containing modified isocyanates, wherein a mixture of an organic polyisocyanate and a urethane group-containing isocyanate compound is synthesized by reacting with an isocyanate.
  • the modified isocyanate mixture produced according to the present invention is obtained by urethanizing a part of an organic polyisocyanate with monoalcohol and then allocating (all urethane groups) to an organic polyisocyanate (monomer). ) Is removed to synthesize a modified polyisocyanate containing substantially only an allophanate group, which is further isocyanurated, so it has low viscosity and good compatibility with solvents and polyhydric hydroxy compounds. In particular, it can be used as a curing agent (for polyurethane coating compositions and adhesive compositions) that has both tolerance to non-polar organic solvents and / or low odor solvents and curability, drying properties, and weather resistance.
  • Examples of the organic polyisocyanate used for the synthesis of the modified isocyanate mixture in the present invention include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane.
  • Tandiisocyanate 2, 4_Toluene diisocyanate, 2,6_Toluene diisocyanate, 4, 4 '— Diphenylterdiisocyanate, 2_Nitrodiphenyl-1,4'—Diisocyanate 2, 2 '-Diphenylpropane 4,4'-Diisocyanate, 3, 3 '-Dimethyldiphenyl methane 4,4'-Diisocyanate, 4, 4 '-Diphenylpropanedisorbate, 1, 2_Fue Diylene diisocyanate, 1,3_Phenylene diisocyanate, 1,4_Phenylene diisocyanate, 1,4-Naphtha diisocyanate, 1,5_Naphtha Diisocyanate, 3, 3'-dimethyoxydiphenyl-1,4'-aromatic diisocyanate such as diisocyanate, HD I, 1,4-tetram
  • organic polyisocyanates can be used alone or in admixture of two or more.
  • organic polyisocyanates when considering weather resistance and the like, aliphatic diisocyanates are preferable, and HDI is more preferable.
  • the monoalcohol is used to further increase tolerance to nonpolar organic solvents and low odor solvents.
  • a monoalcohol having 1 to 20 carbon atoms is preferred.
  • the isocyanate content of the modified isocyanate mixture decreases, and for example, in the case of stearic alcohol, it tends to solidify at a low temperature.
  • monoalcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, n-pentanol, iso-pentanol, n_hexanol, n-heptanol, n-octanol, 2_ethylhexanol, ethyldimethyl-1-hexanol, methyl_1-nonanol, dimethyl_1-octanol, tetramethyl_1-hexanol, 3_ethyl-4 , 5, 6_trimethyloctanol, 4, 5, 6, 7-tetramethylnonanol, 4, 5, 8-trimethyldephenol, 4, 7, 8_trimethyltridecanol, tridecano 1, tetradecanol, 2_hexyldodecanol, 2-octyldodecanol,
  • the amount of monoalcohol used is preferably such that the urethanation rate in the reaction with the organic polyisocyanate is 2 to 20 mol% based on the total isocyanate groups. If the amount of monoalcohol used is less than 2 mol%, the yield is poor and inefficient. If the urethanization ratio exceeds 20 mol%, the NCO content of the resulting modified isocyanate decreases, and the hardness, dryness and weather resistance of the coating composition or adhesive composition are improved. Cannot be achieved.
  • the urethanization reaction can be suitably carried out in the range of 20 to 120 ° C.
  • the halophanation reaction is carried out using a known halophanation catalyst.
  • Preferred examples of the halophanation catalyst include a metal salt of a carboxylic acid or a mixed catalyst of this with a phosphite, and more preferably a metal salt of strong sulfonic acid.
  • the carboxylic acid that is a raw material of the metal salt of the carboxylic acid include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 2-ethylhexanoic acid.
  • a mixture of the above carboxylic acids such as oleic acid, linoleic acid, linolenic acid, unsaturated fatty acid such as soybean oil fatty acid, tall oil fatty acid, etc. arabic acid carboxylic acid such as diphenylacetic acid, benzoic acid, tolyl Aromatic carboxylic acids such as acids can be mentioned.
  • Examples of the metal in the metal salt of carboxylic acid include alkaline earth metals such as magnesium, calcium, and barium, transition metals such as manganese, iron, cobalt, nickel, copper, zinc, and zirconium, and boron groups such as aluminum, Examples include carbon group metals such as tin and lead.
  • These metal salts of rubonic acid can be used alone or in admixture of two or more.
  • zirconium salts one or more selected from the group consisting of zirconium salts, tin salts, zinc salts and lead salts of saturated aliphatic carboxylic acids are preferred.
  • Phosphites used as cocatalysts include phosphite diesters and phosphite triesters.
  • phosphorous acid triesters include triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite.
  • Tristearyl phosphite Tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t_butylphenyl) phosphite, diphenyldecyl phosphite, diphenyl (tridecyl) Examples include monophosphites such as phosphites.
  • dialkyl bisphenol A diphosphite having 1 to 20 carbon atoms 4, 4 '— Butylidene monobis (3_methyl _ 6 _ t _ butylphenyl ditridecyl) phosphite, etc.
  • Polyphosphites such as derivatized diphosphites, hydrogenated bisphenol A phosphite polymers (molecular weight 2400-300), tris (2,3-dichloroprop) and phosphites are also listed. I can get lost.
  • phosphite diester examples include dilauryl hydrogen phosphate, diphenyl hydrogen phosphate, and the like.
  • phosphites can be used alone or in admixture of two or more.
  • the amount of the carboxylic acid metal salt itself may be less than when used alone.
  • the amount of the metal salt of the carboxylic acid varies depending on the type, but is usually preferably from 0.05 to 1% by mass, based on the reaction product of monoalcohol and organic polyisocyanate. 1 to 0.1% by mass is more preferable.
  • the amount of the metal salt of the carboxylic acid based on the reaction product is less than 0.05% by mass, the reaction is substantially slow and takes a long time. On the other hand, the use of the metal salt of the carboxylic acid is difficult.
  • the amount of phosphite used is preferably from 0.05 to 1% by mass, more preferably from 0.1 to 0.5% by mass, based on the reaction product of monoalcohol and organic polyisocyanate. preferable.
  • the amount used is less than 0.05% by mass, the effect as a co-catalyst is insufficient.
  • the amount used exceeds 1% by mass, the final product using the product obtained by the reaction is used. May adversely affect product properties There is.
  • the halophanation rate within a range in which 1.8 to 2.0 times the molar amount of isocyanate group is consumed with respect to the hydroxyl group of the monoalcohol.
  • the product obtained by reacting in the range where the conversion rate of isocyanato groups less than 1.8 times the molar amount of hydroxyl groups with respect to the hydroxyl group is consumed is a large amount of monofunctional component, which deteriorates the physical properties of the coating film.
  • isocyanate groups exceeding a double molar amount are consumed, it is considered that an isocyanuration reaction has occurred.
  • the alphaphanation reaction is preferably carried out in the range of 70 to 1550 ° C. If the reaction temperature is less than 70 ° C, the reaction proceeds very slowly. If the reaction temperature exceeds 150 ° C, the color becomes fuzzy.
  • the free unreacted organic polyisocyanate (monomer) present in the allophanatization reaction mixture is extracted with, for example, n-hexane or 10 to 1 OOP a under high vacuum. Remove to a residual content of not more than 1.0% by weight by suitable means such as thin-film distillation at ⁇ 140 ° C.
  • the isocyanuration reaction of the allophanatization reaction product is performed using a known isocyanuration catalyst.
  • the isocyanuration catalyst include triethylamine, N-ethylbiperidine, N, N′-dimethylpiperazine, N-ethylmorpholine, tertiary amine such as phenolic Mannich base, tetramethylammonium Hydroxide of tetraalkylammonium such as tetraethylammonium, tetraptylammonium, organic weak acid salts, trimethylhydroxypropylammonium, trimethylhydroxypropylammonium, triethylhydroxyammonium Hydroxyl ammonium such as humum Hydroxide of humic acid, acetic acid, propionic acid, butyric acid, strength bromic acid, strength purinic acid, valeric acid, isovaleric acid, octylic acid, myristic acid, naphthenic acid, etc. Alkali metal salt of carboxylic acid Etc., and the like. These are simply Can be used alone or in
  • carboxylic acid metal salts of carboxylic acids are preferred.
  • the isocyanuration catalyst is preferably used in an amount of 0.000 "! To 1.0% by weight, in particular 0.001 to 0.1% by weight of 0 / o, based on the organic polyisocyanate.
  • the isocyanuration reaction is preferably carried out in the range of 40 to 90 ° C. When the reaction temperature is below 40 ° C or above 90 ° C, the reaction proceeds very slowly.
  • a terminating agent such as acidic phosphate ester, phosphoric acid or methyl paratoluenesulfonate is added to stop the isocyanuration reaction.
  • the modified isocyanate mixture obtained by the present invention can be diluted with an inert solvent and used as a curing agent for paints and adhesives.
  • inert solvents examples include HAWS (manufactured by Seal Chemicals Japan Co., Ltd., Anilin Point 15 ° C), Suzusol 3 10 (manufactured by Maruzen Oil Co., Ltd., Anilin Point 16 ° C), Etsonaphtha N o.
  • Non-polar organic solvents such as 5 ° C
  • low odor solvents such as isopentane, isohexane, isooctane, and isododecane.
  • Table 1 summarizes the raw materials used, the amounts charged, the reaction conditions, reaction results, and the properties of the modified isocyanate mixture.
  • the residual free HDI content was determined by gas chromatography analysis.
  • the analysis of the modified isocyanate mixture was performed by GPC analysis, IR analysis, and 13 C_NMR analysis.
  • Figure 1 shows this GPC analysis chart.
  • the residual free HDI content was determined by gas chromatography analysis.
  • the analysis of the modified isocyanate mixture was performed by GPC analysis, IR analysis, and '3C-NMR analysis.
  • Figure 2 shows this GPC analysis chart.
  • a drying recorder (RIKEN OPTICAL: current Ricoh Co., Ltd.) was used.
  • JISK 5600 a coating resistance test
  • JISK 5600 a coating resistance test
  • the weathering test equipment is manufactured by Q_Pane I, and the cycle condition is 1 cycle: 70 ° ⁇ , only re is 8 r, then 50 ° C, only water spray is 4 hr.
  • each peak is an HDI monoalophanate
  • peak (2) is an isocyanurate consisting of 3 HDI molecules
  • peak (3) is an HD I dialophaneate
  • peak (4) is 3 molecules. It is presumed that each is a isocyanurate form of monodiaphanated HDI.
  • the modified isocyanate mixture P-2 has a peak (2) production of 14.2% of its total (total) peak area, and peak (4) is P_2.
  • the total (total) is almost absent in the peak area
  • the modified isocyanate mixture P_ 1 has a peak (2) production of 3.0% in its total (total) peak area, peak (4) Produced 9.1% of the total peak area of P-1 (total).
  • the modified isocyanate mixture P-2 which is a mixture of HDI mono and diaphanate and isocyanurate consisting of 3 molecules of HDI, isocyanurate consisting of HD I mono and diaphanate and trimolecular HDI.
  • P_ 1 is more tolerant to non-polar organic solvents and low odor solvents.
  • Isocyanurate compound consisting of 3 molecules of monoarophanate HDI is mixed in a proportion (9.1%) with a certain ratio (9.1%). Is estimated to be high.
  • FIG. 2 GPC analysis chart of modified isocyanate mixture P_2.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention a pour objet un procédé de production d'un mélange à base d'isocyanate modifié contenant une liaison allophanate et une liaison isocyanurate, présentant d'excellentes propriétés en matière de durcissabilité, de séchage et de résistance aux intempéries et, en particulier, une excellente tolérance à un solvant organique non polaire ou à un solvant moins odorant et présentant une faible viscosité. La présente invention propose, à cet effet, un procédé de production d'un mélange à base d'isocyanate modifié contenant une liaison allophanate et une liaison isocyanurate, comprenant les étapes consistant à faire réagir un monoalcool avec un excès de polyisocyanate organique en présence d'un catalyseur d'allophanation afin de provoquer l'allophanation du polyisocyanate ; à éliminer le polyisocyanate organique n'ayant pas réagi jusqu'à ce que la teneur en polyisocyanate organique soit inférieure ou égale à 1,0 % en poids ; et à procéder à l'isocyanuration du produit résultant en présence d'un catalyseur d'isocyanuration.
PCT/JP2007/000864 2006-11-27 2007-08-10 Procédé de production d'un mélange à base d'isocyanate modifié contenant une liaison allophanate et une liaison isocyanurate Ceased WO2008065732A1 (fr)

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WO2009130965A1 (fr) * 2008-04-24 2009-10-29 日本ポリウレタン工業株式会社 Composition de polyisocyanate et composition de revêtement de type à deux composants l'utilisant
JP2013532738A (ja) * 2010-07-20 2013-08-19 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 高光反射を有するポリウレタン
WO2015133494A1 (fr) * 2014-03-04 2015-09-11 三井化学株式会社 Composition d'isocyanurate
US9732080B2 (en) 2006-11-03 2017-08-15 Vertex Pharmaceuticals Incorporated Azaindole derivatives as CFTR modulators
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US10058546B2 (en) 2012-07-16 2018-08-28 Vertex Pharmaceuticals Incorporated Pharmaceutical compositions of (R)-1-(2,2-difluorobenzo[D][1,3]dioxo1-5-y1)-N-(1-(2,3-dihydroxypropy1)-6-fluoro-2-(1-hydroxy-2-methylpropan-2-y1)-1H-indol-5-y1) cyclopropanecarbox-amide and administration thereof
US10071979B2 (en) 2010-04-22 2018-09-11 Vertex Pharmaceuticals Incorporated Process of producing cycloalkylcarboxamido-indole compounds
US10081621B2 (en) 2010-03-25 2018-09-25 Vertex Pharmaceuticals Incorporated Solid forms of (R)-1(2,2-difluorobenzo[D][1,3]dioxol-5-yl)-N-(1-(2,3-dihydroxypropyl)-6-fluoro-2-(1-hydroxy-2-methylpropan-2-yl)-1H-indol-5-yl)cyclopropanecarboxamide
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USRE50453E1 (en) 2006-04-07 2025-06-10 Vertex Pharmaceuticals Incorporated Indole derivatives as CFTR modulators

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