WO2019104888A1 - 亚胺型季铵盐催化剂、其制备方法及其用于制备多异氰酸酯组合物 - Google Patents

亚胺型季铵盐催化剂、其制备方法及其用于制备多异氰酸酯组合物 Download PDF

Info

Publication number
WO2019104888A1
WO2019104888A1 PCT/CN2018/076687 CN2018076687W WO2019104888A1 WO 2019104888 A1 WO2019104888 A1 WO 2019104888A1 CN 2018076687 W CN2018076687 W CN 2018076687W WO 2019104888 A1 WO2019104888 A1 WO 2019104888A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
group
catalyst
imine
polyisocyanate composition
Prior art date
Application number
PCT/CN2018/076687
Other languages
English (en)
French (fr)
Inventor
王暖程
尚永华
王玉启
石滨
朱智诚
李和甫
黎源
华卫琦
Original Assignee
万华化学集团股份有限公司
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 万华化学集团股份有限公司 filed Critical 万华化学集团股份有限公司
Priority to JP2020528969A priority Critical patent/JP2021504532A/ja
Priority to KR1020207013665A priority patent/KR102456365B1/ko
Priority to EP18884647.1A priority patent/EP3718630A4/en
Priority to US16/762,265 priority patent/US11059772B2/en
Publication of WO2019104888A1 publication Critical patent/WO2019104888A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0241—Imines or enamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • C07C53/06—Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/122—Propionic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C07C63/06—Benzoic acid
    • C07C63/08—Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1896—Compounds having one or more Si-O-acyl linkages
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1858—Catalysts containing secondary or tertiary amines or salts thereof having carbon-to-nitrogen double bonds
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • 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
    • 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane 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
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms 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
    • 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
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7893—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having three nitrogen atoms in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Definitions

  • the invention relates to the field of preparation of polyisocyanates, in particular to an imine-type quaternary ammonium salt catalyst for preparing a polyisocyanate composition, a preparation method of the catalyst, and a polyisocyanate prepared by using the catalyst.
  • Aliphatic diisocyanates have an irreplaceable advantage in the synthesis of anti-yellowing coatings and coatings and are widely used in the coatings industry.
  • the low vapor pressure of the monomeric aliphatic isocyanate makes it a large limitation in application, so it is more common to modify it into a polyisocyanate, increase the biotolerance of the process, and further obtain a product with excellent performance.
  • isocyanurate Since isocyanurate has high thermal stability, strong radiation resistance, low viscosity and high crosslink density, isocyanate self-polymerization has been extensively studied in the past. The research focuses on how to find a highly efficient form of catalyst structure that can effectively reduce the amount of additives used in industrial processes to achieve high quality polyisocyanate products.
  • the catalyst generally used for the isocyanate self-polymerization has the following structural features:
  • the cation form may have an alkali metal ion, an alkaline earth metal ion, and an ionic group structure having N, P as a core and having the following characteristics:
  • R 1 , R 2 , R 3 , and R 4 may be the same or different, and are optionally selected from an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group, such as US 673062, US 6,800,714, and US 700,1973, all of which are derived from R 1 containing a benzene derivative.
  • the structure, R2 and R3 are alkyl or substituted alkyl or cycloalkyl
  • R4 is an alkyl or cycloalkyl or alkoxy quaternary ammonium salt cation, which enables efficient product synthesis.
  • its color number control still cannot meet the requirements of industrial production for low color polyisocyanate compounds.
  • US5489663 also uses a variety of cation designs to achieve the desired color control effect, but its catalyst design results in lower reactivity and requires higher reaction temperature control. When the temperature control is lower, the reaction time is multiplied.
  • the anions commonly used in the quaternary ammonium salt form are R 5 COO - , OH - , F - , which can obtain the trimeric structure of the ideal structure.
  • US 5124427 adopts the design of anion of OH - and F - , and the product color number is controlled at 40- Between 80.
  • Patent CN101927184 discloses the use of a quaternary ammonium/phosphine salt in combination with a six-membered heterocyclic compound of a weakly basic nitrogen-containing compound to efficiently prepare a light-colored polyisocyanate compound.
  • One of the objects of the present invention is to provide an imine-type quaternary ammonium salt type catalyst. From the design of the catalyst, by introducing an imine structure, on the basis of ensuring high catalytic activity, it has the properties of pyrolysis and deactivation. And in the synthesis of polyisocyanate, it can effectively prevent the risk of uncontrolled reaction and cause the accumulation of pollution.
  • Another object of the present invention is to provide a method for preparing an imine-type quaternary ammonium salt type catalyst, which can effectively prevent the risk of occurrence of agglomeration caused by uncontrolled reaction in the synthesis of polyisocyanate.
  • Still another object of the present invention is to provide a polyisocyanate composition prepared by using the above catalyst.
  • the imine-type quaternary ammonium salt type catalyst provided by the present invention adopts the following technical scheme:
  • the catalyst has the structural formula shown by Formula I below:
  • R 1 and R 2 are each independently selected from a linear C1-C20 (such as C3, C5, C8, C10, C12 or C15) alkyl group or a branched C3-C20 (such as C5, C8, C10, C12). Or C15) alkyl and C1-C20 (such as C3, C5, C8, C10, C12 or C15) hydroxyalkyl (also known as hydroxyalkyl), C3-C8 (such as C4 or C6) cycloalkyl, and aromatic Fat base
  • R 3 is a linear or branched alkyl, cycloalkyl or aryl group; for example, a linear C1-C13 alkyl group (such as a linear C1, C3, C7, C9 or C13 alkyl group), or a branched C3- a C15 alkyl group (such as a branched C5, C8, C10, C12 or C15 alkyl group), or a C3-C8 cycloalkyl group (such as a C4, C5 or C6 cycloalkyl group), or a phenyl group or a benzyl group.
  • Aryl a linear C1-C13 alkyl group (such as a linear C1, C3, C7, C9 or C13 alkyl group), or a branched C3- a C15 alkyl group (such as a branched C5, C8, C10, C12 or C15 alkyl group), or a C3-C8 cycloalkyl group
  • R 4 is hydrogen, aryl, linear C1-C15 (such as C3, C5, C8, C10 or C12) alkyl or branched C3-C15 (such as C5, C8, C10 or C12) alkyl.
  • the preparation method of the imine-type quaternary ammonium salt type catalyst provided by the present invention adopts the following technical scheme:
  • a method for preparing an imine quaternary ammonium salt catalyst comprises the following steps:
  • Trimethylchlorosilane was gradually added to the disubstituted secondary amine under ice water bath conditions, and the reaction was resumed to room temperature after the completion of the addition, and the reaction was completed, and then quenched by adding ice water to the reaction solution, and the intermediate product was isolated. ;
  • the imine-type quaternary ammonium salt catalyst has the structural formula shown in Formula I above.
  • optional removal means removal or non-removal, and it is understood by those skilled in the art that it can be actually determined depending on the target concentration of the catalyst.
  • the molar amount of the trimethylchlorosilane is not less than the molar amount of the secondary amine, preferably the molar amount of the secondary amine.
  • the intermediate product can be separated by extraction, for example, after extraction with an extractant, drying, and distillation to obtain an intermediate product a; wherein the extracting agent is preferably selected from the group consisting of dichloromethane and acetic acid.
  • the drying is preferably carried out by adding a drying agent such as anhydrous sodium sulfate and/or anhydrous magnesium sulfate.
  • the reaction in the step (1) is controlled to be carried out at a temperature of from 0.5 to 2 h, such as 1 or 1.5 h, after returning to room temperature and before quenching.
  • the trimethylchlorosilane is used in a molar amount of not less than the molar amount of the carboxylic acid, preferably 1 to the molar amount of the carboxylic acid.
  • the intermediate product can be separated by extraction, for example, after extraction with an extractant, drying, and distillation to obtain an intermediate product b; wherein the extracting agent is preferably selected from the group consisting of dichloromethane and acetic acid.
  • the drying is preferably carried out by adding a drying agent such as anhydrous sodium sulfate and/or anhydrous magnesium sulfate.
  • the reaction in the step (2) is controlled to be carried out at 0.5 to 1 h after returning to room temperature and continuing the reaction before quenching.
  • the intermediate product a, the intermediate product b, and the dimethyl acetal are fed in substantially equimolar amounts; in the present invention, “substantially equimolar amount” It means that the difference between the molar amounts of the two materials is not more than 10%, preferably 5%, further preferably 2%, of the lesser ones.
  • the reaction in the step (3) is preferably carried out at 50 to 80 ° C, for example, 60 or 70 ° C for 3 to 8 hours, such as 4, 5 or 6 hours.
  • the alcohol solvent is a monohydric alcohol and/or a diol; wherein the monohydric alcohol is preferably selected from a C1-C10 aliphatic, alicyclic, araliphatic or aromatic alcohol or phenol.
  • the alcohol is preferably present in the form of a linear, branched or cyclic alcohol or a phenol; the diol is not limited to the following, and examples thereof include ethylene glycol, 1,3-propanediol, and 1,2-propanediol.
  • the present invention also provides a polyisocyanate composition prepared by using the above catalyst; preferably, the following technical solution is adopted:
  • a polyisocyanate composition wherein the polyisocyanate composition has an isocyanurate, a urethane, an allophanate, and an iminooxadiazinedione group, wherein the allophanate
  • the molar ratio of the base / (isocyanurate group + allophanate group) is from 0.1 to 0.8, preferably from 0.2 to 0.6, such as 0.3, 0.4 or 0.5; the allophanate group / (urea group)
  • the molar ratio of the acid ester group + carbamate group is from 0.1 to 0.7, preferably from 0.2 to 0.5, such as 0.3 or 0.4; the molar ratio of the iminooxadiazinedione group / the isocyanurate group It is 0.0005-0.15, preferably 0.01-0.1, such as 0.02, 0.05 or 0.08.
  • composition according to the invention wherein the at least one isocyanate monomer having an NCO functionality of >1 is prepared by oligomerization in the presence of the above-described imine-type quaternary ammonium salt catalyst.
  • the oligomerization reaction is well known in the art, for example, a polymerization reaction that does not exceed tetramerization.
  • the isocyanate monomer is selected from the group consisting of aliphatic diisocyanates, preferably hexamethylene diisocyanate (HDI), 2-methylpentane-1,5-diisocyanate, 2 , 4,4-trimethyl-1,6-hexane diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, 4-isocyanatomethyl-1,8- Octane diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate (IPDI), 1,3- and 1,4-double (iso) Cyanate methyl)benzene (XDI), and one or more of 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H 6 XDI).
  • HDI hexamethylene diisocyanate
  • 2-methylpentane-1,5-diisocyanate 2
  • the catalyst is added in the form of an alcohol solution, preferably, the mass concentration of the catalyst in the alcohol is from 0.25% to 50%, such as 1%, 5%, 10%, 15%, 20%, 30% or 40%; the catalyst is used in an amount of 0.001 to 5%, preferably 0.002 to 2%, such as 0.1%, 0.5, of the mass of the organic isocyanate. %, 1% or 1.5%.
  • the oligomerization reaction is carried out in a temperature range of from 0 ° C to 100 ° C, preferably from 20 to 90 ° C, such as 30, 50 or 70.
  • the oligomerization reaction is terminated after converting from 5 to 80% by weight, preferably from 10 to 70% by weight, such as 40% by weight or 50% by weight of the isocyanate monomer; further preferably, the oligomerization is carried out.
  • the reaction is stopped by deactivating the catalyst, further preferably by deactivating by thermal decomposition or by adding an acid or an acid derivative, wherein an acid or an acid derivative such as benzoyl chloride is added, and phosphorus or sulfur is added. Acidic esters of acids, these acids themselves, are particularly preferably thermally deactivated.
  • the organic isocyanate of the unreacted monomer can be separated from the reaction mixture for recycling.
  • the positive effect of the invention is that, from the design of the catalyst, by introducing an imine structure, on the basis of ensuring high catalytic activity, it has the properties of pyrolysis and deactivation, and can be effectively prevented in application to polyisocyanate synthesis.
  • the polyisocyanate composition prepared by the above catalyst using the above catalyst has a certain proportion of isocyanurate, urethane, allophanate, iminooxadiazinedione, and shows excellent Moisture resistance and thin stability characteristics.
  • the invention measures the NCO content according to the method of GB/T 12009.4-1989.
  • the invention tests the product color number according to the method of GB/T 3143-1982.
  • the respective molar ratios of the isocyanurate group, the urethane group, the allophanate group, and the iminooxadiazinedione group in the polyisocyanate composition of the present invention are used.
  • the AVANCE 400 manufactured by Bruker Biospin was subjected to deuterated chloroform CDCl 3 as a solvent, and a 13 C nuclear magnetic resonance spectrum was measured by using a sample (polyisocyanate composition) concentration of 60% by mass, 100 MHz, and scanning overnight.
  • the dynamic viscosity of the design of the present invention is obtained by a Brookfield DV-I Prime viscometer using an S21 rotor at 25 ° C.
  • the shear rate of the polyisocyanate according to the present invention can be ensured according to different shear rates. Ideal fluid behavior, so the shear rate is not specifically given here.
  • the reagents used in the synthesis of the present invention were purchased from Sigma-Aldrich and were analytically pure unless otherwise specified.
  • Catalyst I The structure of Catalyst I is as follows:
  • Catalyst II is as follows:
  • Catalyst III is as follows:
  • Catalyst IV is as follows:
  • Catalyst V is as follows:
  • the molar ratio of allophanate groups/(isocyanurate groups + allophanate groups) in the prepared curing agent is 0.1; allophanate groups / (ureido groups + amino groups)
  • the molar ratio of the formate group is 0.7; the molar ratio of the iminooxadiazinedione group / the isocyanurate group is 0.1.
  • the molar ratio of allophanate groups/(isocyanurate groups + allophanate groups) in the prepared curing agent is 0.1; allophanate groups / (ureido groups + amino groups)
  • the molar ratio of the formate group is 0.7; the molar ratio of the iminooxadiazinedione group / the isocyanurate group is 0.1.
  • the molar ratio of allophanate groups/(isocyanurate groups + allophanate groups) in the prepared curing agent is 0.3; allophanate groups / (ureido groups + amino groups)
  • the molar ratio of the formate group was 0.6; the molar ratio of the iminooxadiazinedione group / the isocyanurate group was 0.08.
  • the molar ratio of allophanate groups/(isocyanurate groups + allophanate groups) in the prepared curing agent is 0.65; allophanate groups / (ureido groups + amino groups)
  • the molar ratio of the formate group was 0.65; the molar ratio of the iminooxadiazinedione group / the isocyanurate group was 0.12.
  • the molar ratio of allophanate groups/(isocyanurate groups + allophanate groups) in the prepared curing agent is 0.52; allophanate groups / (ureido groups + amino groups)
  • the molar ratio of the formate group is 0.5; the molar ratio of the iminooxadiazinedione group / the isocyanurate group is 0.1.
  • Example 7 product 3.0h
  • Example 8 product 5h
  • Example 9 product 4.5h
  • Example 10 product 4h Comparative Example 1 product 2h
  • the polyisocyanate composition of the invention exhibits excellent moisture resistance and thinning stability characteristics.
  • the preparation process starts from the design of the catalyst, and the catalyst has a high temperature (100 ° C) decomposition and deactivation property by introducing an imine structure. Therefore, in the application to polyisocyanate synthesis, the risk of occurrence of exudation can be effectively prevented by uncontrolled reaction, and at the same time, the catalyst still maintains high catalytic activity in the normal reaction temperature range.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种亚胺型季铵盐催化剂，该催化剂具有如下式I所示的结构通式，式中，R1、R2分别独立地选自C1-C20直链烷基或支链的C3-C20烷基和C1-C20羟基烷基、C3-C8环烷基，和芳脂基；R3为直链或支链的烷基、环烷基或芳基；R4为氢、芳基、直链C1-C15烷基或支链的C3-C15烷基。还提供了该催化剂的制备方法以及利用其制备得到的多异氰酸酯组合物。通过引入亚胺结构，在保证催化剂高催化活性的基础上，使其具备高温分解、失活的性质，并应用至多异氰酸酯合成中，能有效防止反应失控而引发的暴聚的风险。

Description

[根据细则37.2由ISA制定的发明名称]　亚胺型季铵盐催化剂、其制备方法及其用于制备多异氰酸酯组合物 技术领域
本发明涉及多异氰酸酯制备领域，具体的涉及一种用于制备多异氰酸酯组合物的亚胺型季铵盐催化剂、该催化剂的制备方法，以及利用该催化剂制备得到的多异氰酸酯。
背景技术
脂肪族二异氰酸酯类化合物在合成抗黄变涂层和涂料方面有不可替代的优势，被广泛用于涂层工业。但单体脂肪族异氰酸酯的低蒸汽压使其在应用上有较大的限制，因此更常见的是将其改性为多异氰酸酯，增加加工过程的生物耐受性，进一步获得性能优异的产品。
由于异氰脲酸酯具有较高的热稳定性，较强的耐辐射性，较低的粘度和高交联密度，异氰酸酯自聚反应在过去被广泛的研究。研究重点集中在如何寻求一种高效的催化剂结构形式，能够有效降低工业化过程中的助剂用量，从而获得高品质的多异氰酸酯产品。
一般用于异氰酸酯自聚的催化剂具有如下结构特点：
M n+R 5 n-
其中阳离子形式可以有碱金属离子，碱土金属离子，以N、P为核心的具有下述特征的离子团结构：
M n+＝[R 1R 2R 3Z +R 4],n＝1
其中，R 1、R 2、R 3、R 4可以相同或不同，任选自具有1-20个碳原子的烷基或取代烷基，比如US673062、US6800714、US7001973均采用R 1含有苯系衍生物结构、R2和R3为烷基或取代烷基或环烷基、R4为烷基或环烷基或烷氧基的季铵盐阳离子，能够高效的进行产品合成。但需要指出的是，其色号控制仍不能满足工业生产对低色号多异氰酸酯化合物的要求。而US5489663同样采用多样的阳离子设计获得理想的色度控制效果，但其催化剂设计导致反应活性较低，需要较高的反应温度控制，而当温度控制较低时，其反应时间成倍延长。
季铵盐形式中常用的阴离子为R 5COO -、OH -、F -，能够获得理想结构的三聚体结构，如US5124427采用阴离子为OH -、F -的设计，产品色号控制在40-80之间。
专利CN101927184中公开了使用季铵/膦盐与一种弱碱性含氮化合物的六元杂环类化合物复配时能够高效制备浅色好的多异氰酸酯化合物。
然而，需要指出的是，上述专利所报道的制备过程，均在低聚阶段进行终止再经过单体脱出得到合格样品。从工艺安全角度出发，该反应存在潜在的、巨大的热累计效应，工艺过程控制中一旦发生失控，会造成巨大的经济损失和威胁人员安全。
发明内容
本发明的目的之一在于提供一种亚胺型季铵盐型催化剂，从催化剂的设计出发，通过引入亚胺结构，在保证高催化活性的基础上，使其具备高温分解、失活的性质，并在多异氰酸酯合成中，能有效防止反应失控而引发暴聚的风险。
本发明另一目的在于提供一种亚胺型季铵盐型催化剂的制备方法，其制备得到的催化剂，能有效防止多异氰酸酯合成中反应失控而引发暴聚的风险。
本发明的再一目的在于提供利用上述催化剂制备得到的多异氰酸酯组合物。
为实现上述目的的一个方面，本发明提供的亚胺型季铵盐型催化剂采用如下技术方案：
一种亚胺型季铵盐催化剂，其中，
所述催化剂具有如下式I所示的结构通式：
Figure PCTCN2018076687-appb-000001
式中，R 1、R 2分别独立地选自直链C1-C20(比如C3、C5、C8、C10、C12或C15)烷基或支链的C3-C20(比如C5、C8、C10、C12或C15)烷基和C1-C20(比如C3、C5、C8、C10、C12或C15)羟基烷基(也称为 羟烷基)、C3-C8(比如C4或C6)环烷基，和芳脂基；
R 3为直链或支链的烷基、环烷基或芳基；例如直链C1-C13烷基(比如直链C1、C3、C7、C9或C13烷基)，或支链的C3-C15烷基(比如支链的C5、C8、C10、C12或C15烷基)，或C3-C8环烷基(比如C4、C5或C6环烷基)，或为诸如苯基、苯甲基的芳基；
R 4为氢、芳基、直链C1-C15(比如C3、C5、C8、C10或C12)烷基或支链的C3-C15(比如C5、C8、C10或C12)烷基。
为实现上述目的的另一方面，本发明提供的亚胺型季铵盐型催化剂的制备方法采用如下技术方案：
一种亚胺型季铵盐催化剂的制备方法，包括以下步骤：
(1)冰水浴条件下向二取代的仲胺中逐步加入三甲基氯硅烷，加入完毕后恢复至室温继续反应，反应完成后向反应溶液中加入冰水淬灭，并分离得到中间产物a；
Figure PCTCN2018076687-appb-000002
(2)冰水浴条件下向羧酸中逐步加入三甲基氯硅烷，加入完毕后恢复至室温继续反应，反应完成后向反应溶液中加入冰水淬灭，并分离得到中间产物b；
Figure PCTCN2018076687-appb-000003
(3)将分离得到的中间产物a、中间产物b及二甲基缩醛溶于醇溶剂中，在50-80℃下进行反应，反应完成后任选的除去部分所述醇溶剂，得到含目标浓度的所述亚胺型季铵盐催化剂的醇溶液；
Figure PCTCN2018076687-appb-000004
优选地，所述亚胺型季铵盐催化剂具有如上式I所示的结构通式。
其中，“任选的除去”表示除去或不除去，本领域技术人员理解，可以根据催化剂的目标浓度来实际确定。
根据本发明的催化剂制备方法，优选地，步骤(1)中，所述三甲基氯硅烷的摩尔用量不少于所述仲胺的摩尔用量，优选为所述仲胺的摩尔量的1-1.2倍；在一种实施方式中，中间产物可以通过萃取的方式进行分离，例如使用萃取剂萃取后、干燥、蒸馏分离得到中间产物a；其中，所述萃取剂优选选自二氯甲烷、乙酸乙酯和氯仿中的一种或多种；所述干燥优选通过加入干燥剂诸如无水硫酸钠和/或无水硫酸镁进行。
根据本发明的催化剂制备方法，优选地，步骤(1)中的反应，在恢复至室温后、淬灭前继续反应的时间控制在0.5-2h，比如1或1.5h。
根据本发明的催化剂制备方法，优选地，步骤(2)中，所述三甲基氯硅烷的摩尔用量不少于所述羧酸的摩尔量，优选为所述羧酸的摩尔量的1-1.2倍；在一种实施方式中，中间产物可以通过萃取的方式进行分离，例如使用萃取剂萃取后、干燥、蒸馏分离得到中间产物b；其中，所述萃取剂优选选自二氯甲烷、乙酸乙酯和氯仿中的一种或多种；所述干燥优选通过加入干燥剂诸如无水硫酸钠和/或无水硫酸镁进行。
根据本发明的催化剂制备方法，优选地，步骤(2)中的反应，在恢复至室温后、淬灭前继续反应的时间控制在0.5-1h。
根据本发明的催化剂制备方法，优选地，步骤(3)中，所述中间产物a、中间产品b及二甲基缩醛采用基本等摩尔量投料；在本发明中，“基本等摩尔量”是指该三种物料的两两之间的摩尔投料量之差不超过其中较少一方的10％，优选5％，进一步优选2％。
根据本发明的催化剂制备方法，步骤(3)中的反应，优选地在50-80℃，比如60或70℃下进行3-8h，比如4、5或6h的反应。
优选地，所述醇溶剂为一元醇和/或二元醇；其中，所述的一元醇优选选自C1-C10的脂肪族、脂环族、芳脂族或芳香族的醇或酚，该一元醇优选以直链、支链或环状醇或酚的形式存在；所述的二元醇，不限定于以下，例如可列举出，乙二醇、1,3-丙二醇、1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、新戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、二乙二醇、聚乙二醇、聚丙二醇、聚四亚甲基二醇、2-甲 基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-甲基-1,8-辛二醇以及2,2-二乙基-1,3-丙二醇。
为实现上述目的的再一方面，本发明还提供了利用上述催化剂制备得到的多异氰酸酯组合物；优选采用如下技术方案：
一种多异氰酸酯组合物，其中，所述多异氰酸酯组合物具有异氰脲酸酯、氨基甲酸酯、脲基甲酸酯和亚氨基噁二嗪二酮基，其中所述脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.1-0.8，优先0.2-0.6，比如0.3、0.4或0.5；所述脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.1-0.7，优先0.2-0.5，比如0.3或0.4；所述亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.0005-0.15，优先0.01-0.1，比如0.02、0.05或0.08。
根据本发明的组合物，其中，由NCO官能度>1的至少一种异氰酸酯单体，在上述亚胺型季铵盐催化剂的存在下进行低聚反应制备。所述低聚反应为本领域熟知，例如不超过四聚的聚合反应。
根据本发明的组合物，优选地，所述异氰酸酯单体选自脂族的二异氰酸酯，优选为六亚甲基二异氰酸酯(HDI)、2-甲基戊烷-1,5-二异氰酸酯、2,4,4-三甲基-1,6-己烷二异氰酸酯、2,2,4-三甲基-1,6-己烷二异氰酸酯、4-异氰酸根合甲基-1,8-辛烷二异氰酸酯、3(4)-异氰酸根合甲基-1-甲基环己基异氰酸酯(IMCI)、异佛尔酮二异氰酸酯(IPDI)、1,3-和1,4-双(异氰酸根合甲基)苯(XDI)，以及1,3-和1,4-双(异氰酸根合甲基)环己烷(H 6XDI)中的一种或多种。
为更好的促进目标反应，根据本发明的组合物，优选地，制备过程中，所述催化剂以醇溶液的形式加入，优选地，催化剂在醇中的质量浓度为0.25％-50％，比如1％、5％、10％、15％、20％、30％或40％；所述催化剂的使用量为所述有机异氰酸酯质量的0.001-5％，优选0.002-2％，比如0.1％、0.5％、1％或1.5％。
根据本发明的组合物，优选地，所述低聚反应在0℃-100℃，优选20-90℃的温度范围中进行，比如30、50或70。
根据本发明的组合物，优选地，所述低聚反应在转化5-80wt％，优 选10-70wt％，比如40wt％或50wt％的异氰酸酯单体的之后中止；进一步优选地，所述低聚反应通过使所述催化剂失活而中止，进一步优选通过热分解失活或添加酸或酸衍生物使所述催化剂失活，其中添加酸或酸衍生物例如苯甲酰氯，添加包含磷或硫的酸的酸性酯、这些酸本身，特别优选热分解失活。本发明中，反应中止后，可以将未反应的单体的有机异氰酸酯从所述反应混合物中分离出，以便循环利用。
本发明的积极效果在于：从催化剂的设计出发，通过引入亚胺结构，在保证高催化活性的基础上，使其具备高温分解、失活的性质，并在应用至多异氰酸酯合成中，能有效防止反应失控而引发暴聚的风险；
同时，本发明利用上述催化剂制备得到的多异氰酸酯组合物具有一定范围配比的异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、亚氨基噁二嗪二酮基，并显示优良的耐潮、开稀稳定性特征。
具体实施方式
下面结合实施例对本发明作进一步的说明，需要说明的是，实施例并不构成对本发明要求保护范围的限制。
本发明中涉及的所有百分数，除特别说明外，均为质量百分数。
本发明按照GB/T 12009.4-1989的方法测定NCO含量。
本发明按照GB/T 3143-1982的方法测试产品色号。
本发明的多异氰酸酯组合物(也即异氰酸酯固化剂)中的异氰脲酸酯基、氨基甲酸酯基、脲基甲酸酯基以及亚氨基噁二嗪二酮基团的各摩尔比使用Bruker Biospin制造的AVANCE400，以氘代氯仿CDCl 3为溶剂，以试样(多异氰酸酯组合物)浓度60质量％、100MHz、扫描过夜测定 13C核磁共振谱。
需要说明的是，在上述测定中，将以下的信号的积分值除以测定的碳的数量，由其值求出各摩尔比率。
异氰脲酸酯基：148.6ppm附近
脲基甲酸酯基：154ppm附近
氨基甲酸酯基：156.5ppm附近
亚氨基噁二嗪二酮基：137.3ppm附近
摩尔比1：脲基甲酸酯基/(脲基甲酸酯基+异氰脲酸酯基)＝(154ppm附近的信号面积)/(154ppm附近的信号面积+148.6附近的信号面积/3)
摩尔比2：脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)＝(154ppm附近的信号面积)/(154ppm附近的信号面积+156.5ppm附近的信号面积)
摩尔比3：亚氨基噁二嗪二酮基/异氰脲酸酯基＝137.3ppm附近的信号面积/(148.6附近的信号面积/3)
本发明设计的动力学粘度采用BrookField DV-I Prime粘度计，采用S21转子于25℃获得，根据文献报道(CN200710180169.X)，不同剪切速率可以保证本发明所述的多异氰酸酯流变性数据符合理想流体行为，所以这里不特别给出剪切速率。
本发明合成过程使用的试剂均购买自Sigma-Aldrich，如未特别说明，均为分析纯。
实施例1：
催化剂I的制备
(1)冰水浴条件下向5份二甲胺中逐滴加入12份(重量份，下同)三甲基氯硅烷，滴加完毕后恢复至室温继续反应0.5h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物I-a；
(2)冰水浴条件下向16份2-乙基己酸中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应1h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物I-b；
(3)将分离得到的中间产品I-a、中间产品I-b及13份二甲基缩正丁醛溶于243份正己醇溶液中，50℃反应5h，反应完成后得到10％催化剂I正己醇溶液。
催化剂I的结构如下：
Figure PCTCN2018076687-appb-000005
实施例2：
催化剂II的制备
(1)冰水浴条件下向6.5份甲基乙基胺中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应0.5h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物II-a；
(2)冰水浴条件下向16份2-乙基己酸中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应1h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物II-b；
(3)将分离得到的中间产品a、中间产品b及16.8份二甲基缩苯甲醛溶于32份甲醇溶液中，50℃反应8h，反应完成后得到50％催化剂II甲醇溶液。
催化剂II的结构如下：
Figure PCTCN2018076687-appb-000006
实施例3：
催化剂III的制备
(1)冰水浴条件下向15份N-(4-乙基苄基)乙胺中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应3h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物III-a；
(2)冰水浴条件下向4.24份甲酸中逐滴加入12份三甲基氯硅烷， 滴加完毕后恢复至室温继续反应1h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物III-b；
(3)将分离得到的中间产品a、中间产品b及8.3份二甲基缩乙醛溶于2144份1,3-丁二醇溶液中，70℃反应8h，反应完成后得到1％催化剂III的1,3-丁二醇溶液。
催化剂III的结构如下：
Figure PCTCN2018076687-appb-000007
实施例4：
催化剂IV的制备
(1)冰水浴条件下向16份N-甲基-2-茚满中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应1.5h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物IV-a；
(2)冰水浴条件下向8.1份丁酸中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应1h，反应完成后向反应溶液中加入50份冰水淬灭，使用二氯甲烷萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物IV-b；
(3)将分离得到的中间产品a、中间产品b及15.9份二甲基缩环戊基醛溶于133.2份2-乙基己醇溶液中，80℃反应8h，反应完成后得到20％催化剂IV的2-乙基己醇溶液。
催化剂IV的结构如下：
Figure PCTCN2018076687-appb-000008
实施例5：
催化剂V的制备
(1)冰水浴条件下向5份二甲胺中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应0.5h，反应完成后向反应溶液中加入50份冰水淬灭，使用乙酸乙酯萃取后得到有机相、向有机相中加入10份无水硫酸钠干燥、减压蒸走溶剂得到中间产物V-a；
(2)冰水浴条件下向13.5份苯甲酸中逐滴加入12份三甲基氯硅烷，滴加完毕后恢复至室温继续反应1h，反应完成后向反应溶液中加入50份冰水淬灭，使用乙酸乙酯萃取后得到有机相、向有机相中加入10份无水硫酸镁干燥、减压蒸走溶剂得到中间产物V-b；
(3)将分离得到的中间产品a、中间产品b及8.3份二甲基缩乙醛溶于4269份乙二醇和4269份正丁醇溶液中，60℃反应8h，反应完成后得到0.25％催化剂V的混合醇溶液。
催化剂V的结构如下：
Figure PCTCN2018076687-appb-000009
实施例6：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将1.2g10％催化剂I的己醇溶液逐滴加入至HDI中，控制体系温度为60-65℃，反应过程监控NCO％变化，当NCO％值降为38时，加入0.12g磷酸终止反应。反应液经过薄膜蒸发脱除剩余单体得到约260g异氰酸酯固化剂。
产品指标：
粘度：1650cp/25℃
NCO％：22.2％
色号：20Hazen
游离单体：0.03％
制备的固化剂中，脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.1；脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.7；亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.1。
实施例7：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将4.0g3％催化剂II的己醇溶液逐滴加入至HDI中，控制体系温度为60-65℃，反应过程监控NCO％变化，当NCO％值降为38时，反应20min内升温至100℃，此后1h内，NCO％不再发生变化，催化剂受热失活，反应终止。反应液经过薄膜蒸发脱除剩余单体得到约260g异氰酸酯固化剂。
产品指标：
粘度：1700cp/25℃
NCO％：22.1％
色号：20Hazen
游离单体：0.04％
制备的固化剂中，脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.1；脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.7；亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.1。
实施例8：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将6g1％催化剂III的1,3-丁二醇溶液逐滴加入至HDI中，控制体系温度为60-65℃，反应过程监控NCO％变化，当NCO％值降为38时，反应20min内升温至100℃，此后1h内，NCO％不再发生变化，催化剂受热失活，反应终止。反应液经过薄膜蒸发脱除剩余单体得到约240g异氰酸酯固化剂。
产品指标：
粘度：2800cp/25℃
NCO％：21.0％
色号：18Hazen
游离单体：0.03％
制备的固化剂中，脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.3；脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.6；亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.08。
实施例9：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将30g0.2％催化剂IV的2-乙基己醇溶液逐滴加入至HDI中，控制体系温度为70-75℃，反应过程监控NCO％变化，当NCO％值降为36时，反应20min内升温至100℃，此后1h内，NCO％不再发生变化，催化剂受热失活，反应终止。反应液经过薄膜蒸发脱除剩余单体得到约260g异氰酸酯固化剂。
产品指标：
粘度：600cp/25℃
NCO％：19.8％
色号：16Hazen
游离单体：0.03％
制备的固化剂中，脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.65；脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.65；亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.12。
实施例10：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将20g0.5％催化剂IV的2-乙基-1,3-己二醇溶液逐滴加入至HDI中，控制体系温度为60-65℃，反应过程监控NCO％变化，当NCO％值降为30时，反应20min内升温至100℃，此后1h内，NCO％不再发生变化，催化剂受热失活，反应终止。反应液经过薄膜蒸 发脱除剩余单体得到约360g异氰酸酯固化剂。
产品指标：
粘度：8000cp/25℃
NCO％：18.5％
色号：21Hazen
游离单体：0.03％
制备的固化剂中，脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.52；脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.5；亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.1。
对比实施例1：
20℃/50mbar条件下，对600gHDI进行脱气处理10min。氮气保护下，处理后的HDI预热至60℃，将0.3g40％的商品化的N,N,N-三甲基-N-苄基氢氧化铵的甲醇溶液逐滴加入至HDI中，控制体系温度为60-65℃，反应过程监控NCO％变化，当NCO％值降为42时，加入0.06g磷酸终止反应。反应液经过薄膜蒸发脱除剩余单体得到约230g异氰酸酯固化剂。
产品指标：
粘度：2000cp/25℃
NCO％：22.0％
色号：22Hazen
游离单体：0.05％
实施例11：
分别称取30g实施例6、7、8、9和10制备的产品和对比实施例1制备的产品装入不同玻璃瓶中(玻璃瓶容量150ml)，然后分别加入70g含水量为1000ppm的乙酸丁酯和0.05gDBTL，搅拌均匀后，将容器密封放置于35℃恒温箱中，观察产品凝胶时间。
样品名称 凝胶时间
实施例6产品 3.5h
实施例7产品 3.0h
实施例8产品 5h
实施例9产品 4.5h
实施例10产品 4h
对比实施例1产品 2h
上述实施例可以看出：
本发明的多异氰酸酯组合物显示优良的耐潮、开稀稳定性特征，同时，其制备工艺从催化剂的设计出发，通过引入亚胺结构，使催化剂具备高温(100℃)分解、失活的性质，因此，在应用至多异氰酸酯合成中，能有效防止反应失控而引发暴聚的风险，同时，正常反应温度段，催化剂仍然保持很高的催化活性。

Claims (11)

  1. 一种用于制备多异氰酸酯组合物的亚胺型季铵盐催化剂，其特征在于，
    所述催化剂具有如下式I所示的结构通式：
    Figure PCTCN2018076687-appb-100001
    式中，R 1、R 2分别独立地选自直链C1-C20烷基或支链的C3-C20烷基和C1-C20羟基烷基、C3-C8环烷基，和芳脂基；
    R 3为直链或支链的烷基、环烷基或芳基；
    R 4为氢、芳基、直链C1-C15烷基或支链的C3-C15烷基。
  2. 一种亚胺型季铵盐催化剂的制备方法，包括以下步骤：
    (1)冰水浴条件下向二取代的仲胺中逐步加入三甲基氯硅烷，加入完毕后恢复至室温继续反应，反应完成后向反应溶液中加入冰水淬灭，并分离得到中间产物a；
    (2)冰水浴条件下向羧酸中逐步加入三甲基氯硅烷，加入完毕后恢复至室温继续反应，反应完成后向反应溶液中加入冰水淬灭，并分离得到中间产物b；
    (3)将分离得到的中间产物a、中间产物b及二甲基缩醛溶于醇溶剂中，在50-80℃下进行反应，反应完成后任选的除去部分所述醇溶剂，得到含目标浓度的所述亚胺型季铵盐催化剂的醇溶液；
    优选地，所述亚胺型季铵盐催化剂具有式I所示的结构通式。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述三甲基氯硅烷的摩尔用量不少于所述仲胺的摩尔用量，优选为所述仲胺的摩尔量的1-1.2倍；
    步骤(2)中，所述三甲基氯硅烷的摩尔用量不少于所述羧酸的摩尔量，优选为所述羧酸的摩尔量的1-1.2倍；
    步骤(3)中，所述中间产物a、中间产品b及二甲基缩醛采用基本等摩尔量投料。
  4. 根据权利要求2或3所述的制备方法，其特征在于，步骤(1)中的反应，在恢复至室温后、淬灭前继续反应0.5-2h；
    步骤(2)中的反应，在恢复至室温后、淬灭前继续反应0.5-1h；
    步骤(3)中的反应，在50-80℃下进行3-8h的反应，所述醇溶剂为一元醇和/或二元醇。
  5. 一种多异氰酸酯组合物，其特征在于，所述多异氰酸酯组合物具有异氰脲酸酯、氨基甲酸酯、脲基甲酸酯和亚氨基噁二嗪二酮基，其中所述脲基甲酸酯基/(异氰脲酸酯基+脲基甲酸酯基)的摩尔比为0.1-0.8，优先0.2-0.6；所述脲基甲酸酯基/(脲基甲酸酯基+氨基甲酸酯基)的摩尔比为0.1-0.7，优先0.2-0.5；所述亚氨基噁二嗪二酮基/所述异氰脲酸酯基的摩尔比率为0.0005-0.15，优先0.01-0.1。
  6. 根据权利要求5所述的多异氰酸酯组合物，其特征在于，所述多异氰酸酯组合物由NCO官能度>1的至少一种异氰酸酯单体，在根据权利要求1所述的亚胺型季铵盐催化剂或根据权利要求2-4中任一项制备得到的亚胺型季铵盐催化剂的存在下进行低聚反应制备。
  7. 根据权利要求6所述的多异氰酸酯组合物，其特征在于，所述异氰酸酯单体选自脂族的二异氰酸酯，优选为六亚甲基二异氰酸酯、2-甲基戊烷-1,5-二异氰酸酯、2,4,4-三甲基-1,6-己烷二异氰酸酯、2,2,4-三甲基-1,6-己烷二异氰酸酯、4-异氰酸根合甲基-1,8-辛烷二异氰酸酯、3(4)-异氰酸根合甲基-1-甲基环己基异氰酸酯、异佛尔酮二异氰酸酯、1,3-和 1,4-双(异氰酸根合甲基)苯，以及1,3-和1,4-双(异氰酸根合甲基)环己烷中的一种或多种。
  8. 根据权利要求6或7所述的多异氰酸酯组合物，其特征在于，制备过程中，所述催化剂以醇溶液的形式加入，优选地，所述催化剂在醇中的质量浓度为0.25％-50％；
    所述催化剂的使用量为所述异氰酸酯单体质量的0.001-5％，优选0.002-2％。
  9. 根据权利要求6-8中任一项所述的多异氰酸酯组合物，其特征在于，所述低聚反应的反应温度为0℃-100℃，优选20-90℃。
  10. 根据权利要求6-9中任一项所述的多异氰酸酯组合物，其特征在于，所述低聚反应在转化5-80wt％，优选10-70wt％的异氰酸酯单体的之后中止；
    优选地，所述低聚反应通过使所述催化剂失活而中止，进一步优选通过添加酸或酸衍生物使所述催化剂失活。
  11. 利用根据权利要求1所述的亚胺型季铵盐催化剂或根据权利要求2-4中任一项制备得到的亚胺型季铵盐催化剂制备得到的多异氰酸酯组合物。
PCT/CN2018/076687 2017-11-30 2018-02-13 亚胺型季铵盐催化剂、其制备方法及其用于制备多异氰酸酯组合物 WO2019104888A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020528969A JP2021504532A (ja) 2017-11-30 2018-02-13 イミン型第四級アンモニウム塩触媒、その調製方法、およびポリイソシアネート組成物の調製のためのその使用
KR1020207013665A KR102456365B1 (ko) 2017-11-30 2018-02-13 이민형 4급 암모늄염 촉매, 그의 제조방법 및 폴리이소시아네이트 조성물의 제조를 위한 그의 용도
EP18884647.1A EP3718630A4 (en) 2017-11-30 2018-02-13 IMINE-TYPE QUARTERLY AMMONIUM SALT CATALYST, PROCESS FOR ITS PREPARATION AND ITS USE IN THE PREPARATION OF A POLYISOCYANAE COMPOSITION
US16/762,265 US11059772B2 (en) 2017-11-30 2018-02-13 Imine-type quaternary ammonium salt catalyst, preparation method thereof and use thereof for preparation of polyisocyanate composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711243688.6 2017-11-30
CN201711243688.6A CN107913730B (zh) 2017-11-30 2017-11-30 亚胺型季铵盐催化剂、其制备方法及多异氰酸酯组合物

Publications (1)

Publication Number Publication Date
WO2019104888A1 true WO2019104888A1 (zh) 2019-06-06

Family

ID=61898086

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/076687 WO2019104888A1 (zh) 2017-11-30 2018-02-13 亚胺型季铵盐催化剂、其制备方法及其用于制备多异氰酸酯组合物

Country Status (6)

Country Link
US (1) US11059772B2 (zh)
EP (1) EP3718630A4 (zh)
JP (2) JP2021504532A (zh)
KR (1) KR102456365B1 (zh)
CN (1) CN107913730B (zh)
WO (1) WO2019104888A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163611B (zh) * 2016-10-14 2023-08-11 旭化成株式会社 多异氰酸酯组合物、封端多异氰酸酯组合物、亲水性多异氰酸酯组合物、涂料组合物和涂膜
CN109749036B (zh) * 2018-12-25 2021-06-29 万华化学集团股份有限公司 亚胺型季铵盐催化剂及其制备方法和由该催化剂制备的低粘度多异氰酸酯组合物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US673062A (en) 1900-05-02 1901-04-30 Hans Reisert Rotary water-meter.
US5124427A (en) 1991-01-22 1992-06-23 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions
US5489663A (en) 1994-02-17 1996-02-06 Basf Aktiengesellschaft Preparation of polyisocyanates containing isocyanurate groups and use thereof
US20030153714A1 (en) * 1999-09-16 2003-08-14 Degusa Ag Catalyst and process for preparing color-reduced polyisocyanates containing isocyanurate groups
US7001973B2 (en) 2000-12-23 2006-02-21 Degussa Ag Catalyst and process for preparing low-viscosity and color-reduced polyisocyanates containing isocyanurate groups
CN101927184A (zh) 2010-08-16 2010-12-29 烟台万华聚氨酯股份有限公司 一种复合催化剂以及采用该复合催化剂制备多异氰酸酯的方法
CN102718683A (zh) * 2012-06-05 2012-10-10 烟台万华聚氨酯股份有限公司 一种制备低色数异氰酸酯的方法及由其制得的异氰酸酯
CN105964301A (zh) * 2016-05-06 2016-09-28 万华化学集团股份有限公司 一种水杨醛亚胺席夫碱金属配合物催化剂及其制备方法和应用
WO2017029266A1 (de) * 2015-08-17 2017-02-23 Covestro Deutschland Ag Verfahren zur modifizierung von isocyanaten unter verwendung von cyclischen ammoniumsalzen als katalysator

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2531081A1 (fr) * 1982-07-29 1984-02-03 Centre Nat Rech Scient Procede de stabilisation d'imines reactives, sels d'iminium stables obtenus par ce procede et application de ces sels
DE19611849A1 (de) * 1996-03-26 1997-10-02 Bayer Ag Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung
DE10123416A1 (de) 2001-05-14 2002-11-21 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten
JP4005801B2 (ja) * 2001-12-10 2007-11-14 高砂香料工業株式会社 新規なホスフィン配位子
CN101291970B (zh) * 2005-10-21 2011-06-22 旭化成化学株式会社 高交联性、低粘度聚异氰酸酯组合物及含有其的涂料组合物
US8530534B2 (en) * 2006-05-04 2013-09-10 Air Products And Chemicals, Inc. Trimerization catalysts from sterically hindered salts
EP2050775B1 (en) * 2006-08-11 2013-08-14 Tosoh Corporation Catalyst composition for polyurethane resin production and method for producing polyurethane resin
CN101254474B (zh) * 2008-03-19 2010-06-02 安徽师范大学 用于异氰酸酯三聚的催化剂及其制备、使用方法
JP5410425B2 (ja) * 2008-06-30 2014-02-05 三井化学株式会社 ポリチオウレタン系光学材料用重合性組成物、該重合性組成物より得られるポリチオウレタン系光学材料及びポリチオウレタン系光学材料用重合触媒
DE102009008949A1 (de) * 2009-02-13 2010-08-19 Bayer Materialscience Ag Wässrige Beschichtungssysteme auf Basis physikalisch trocknender Urethanacrylate
CN104130686B (zh) * 2013-04-30 2017-09-19 旭化成株式会社 多异氰酸酯组合物及涂料组合物
US9938369B2 (en) * 2013-07-25 2018-04-10 Covestro Deutschland Ag Use of succinonitrile in the production of polyisocyanates comprising iminooxadiazinedione groups
EP2883895B1 (de) * 2013-12-10 2017-09-13 Covestro Deutschland AG Iminooxadiazindion-Polyisocyanate
CN106604944B (zh) 2014-09-04 2019-03-15 旭化成株式会社 多异氰酸酯组合物、涂料组合物、涂膜及其制造方法、以及潮湿稳定化方法
JP2017082076A (ja) * 2015-10-27 2017-05-18 旭化成株式会社 ポリイソシアネート組成物、塗料組成物及び塗装方法
CN114163611B (zh) * 2016-10-14 2023-08-11 旭化成株式会社 多异氰酸酯组合物、封端多异氰酸酯组合物、亲水性多异氰酸酯组合物、涂料组合物和涂膜
CN106634784A (zh) * 2016-11-09 2017-05-10 万华化学集团股份有限公司 一种双组份聚氨酯发泡胶黏剂

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US673062A (en) 1900-05-02 1901-04-30 Hans Reisert Rotary water-meter.
US5124427A (en) 1991-01-22 1992-06-23 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production and their use in two-component coating compositions
US5489663A (en) 1994-02-17 1996-02-06 Basf Aktiengesellschaft Preparation of polyisocyanates containing isocyanurate groups and use thereof
US20030153714A1 (en) * 1999-09-16 2003-08-14 Degusa Ag Catalyst and process for preparing color-reduced polyisocyanates containing isocyanurate groups
US6800714B2 (en) 1999-09-16 2004-10-05 Degussa Ag Catalyst and process for preparing color-reduced polyisocyanates containing isocyanurate groups
US7001973B2 (en) 2000-12-23 2006-02-21 Degussa Ag Catalyst and process for preparing low-viscosity and color-reduced polyisocyanates containing isocyanurate groups
CN101927184A (zh) 2010-08-16 2010-12-29 烟台万华聚氨酯股份有限公司 一种复合催化剂以及采用该复合催化剂制备多异氰酸酯的方法
CN102718683A (zh) * 2012-06-05 2012-10-10 烟台万华聚氨酯股份有限公司 一种制备低色数异氰酸酯的方法及由其制得的异氰酸酯
WO2017029266A1 (de) * 2015-08-17 2017-02-23 Covestro Deutschland Ag Verfahren zur modifizierung von isocyanaten unter verwendung von cyclischen ammoniumsalzen als katalysator
CN105964301A (zh) * 2016-05-06 2016-09-28 万华化学集团股份有限公司 一种水杨醛亚胺席夫碱金属配合物催化剂及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3718630A4

Also Published As

Publication number Publication date
EP3718630A4 (en) 2022-05-04
KR20200073252A (ko) 2020-06-23
US20200377445A1 (en) 2020-12-03
CN107913730B (zh) 2020-04-10
JP7202427B2 (ja) 2023-01-11
JP2021504532A (ja) 2021-02-15
US11059772B2 (en) 2021-07-13
JP2021185238A (ja) 2021-12-09
EP3718630A1 (en) 2020-10-07
KR102456365B1 (ko) 2022-10-20
CN107913730A (zh) 2018-04-17

Similar Documents

Publication Publication Date Title
US4487928A (en) Process for the preparation of polyisocyanates containing isocyanurate groups, and the use of the products of the process as isocyanate component in the production of polyurethanes
JP7202427B2 (ja) イミン型第四級アンモニウム塩触媒、その調製方法、およびポリイソシアネート組成物の調製のためのその使用
JP5972538B2 (ja) ポリイソシアネートの製造方法およびその使用
US9376403B2 (en) Process for trimerising cycloaliphatic diisocyanates
JP2000086640A (ja) イミノオキサジアジンジオン基を有するポリイソシアネ―トの製造方法
JP7025162B2 (ja) キシリレンジイソシアネート組成物、および、イソシアヌレートの製造方法
JPH0215543B2 (zh)
JP7245166B2 (ja) スピロ環式アンモニウム塩を触媒として用いて少なくともペンタメチレンジイソシアネートを修飾するための方法
WO2018027999A1 (zh) 异氰酸酯聚合催化剂及其制备方法，及其用于制备聚异氰酸酯的方法
WO2020133067A1 (zh) 一种含有脲二酮基团的多异氰酸酯的制备方法
JPH0357132B2 (zh)
US9434807B2 (en) Carbodiimide-containing compositions and method for the production and use thereof
US2954365A (en) Process for the production of isocyanate polymerization products
CN109749036B (zh) 亚胺型季铵盐催化剂及其制备方法和由该催化剂制备的低粘度多异氰酸酯组合物
CN113631605B (zh) 制备具有二聚体、三聚体和/或脲基甲酸酯和任选的氨基甲酸酯结构的多异氰酸酯的方法
JP6705175B2 (ja) Ｍｄｉから誘導されるアロファネート基を含有するポリイソシアネートプレポリマの製造方法
JP6891086B2 (ja) イソシアヌレートの製造方法
JP6891085B2 (ja) イソシアヌレートの製造方法
JP5476962B2 (ja) アシルウレア変性ポリイソシアネート組成物の製造方法
KR101786528B1 (ko) 저장성이 향상된 무황변 폴리이소시아누레이트의 제조방법
CN117467103A (zh) 一种弹性聚氨酯树脂原料、弹性聚氨酯树脂
JP4529676B2 (ja) 反応性安定化ポリカーボネートポリオールの製造方法及び反応性安定化ポリカーボネートポリオールを用いたポリウレタン樹脂
EP4098678A1 (en) Process for modifying isocyanates with use of difluorosilicate salts as catalyst
CN115819702A (zh) 一种异氰酸酯自聚催化剂及其制备方法和一种多异氰酸酯组合物及其制备方法
CN114874129A (zh) 一种可低温高效解封的封闭型异氰酸酯的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18884647

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20207013665

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2020528969

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018884647

Country of ref document: EP

Effective date: 20200630