WO2020133067A1 - Procédé pour la préparation de polyisocyanate contenant un groupe uretdione - Google Patents

Procédé pour la préparation de polyisocyanate contenant un groupe uretdione Download PDF

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Publication number
WO2020133067A1
WO2020133067A1 PCT/CN2018/124363 CN2018124363W WO2020133067A1 WO 2020133067 A1 WO2020133067 A1 WO 2020133067A1 CN 2018124363 W CN2018124363 W CN 2018124363W WO 2020133067 A1 WO2020133067 A1 WO 2020133067A1
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Prior art keywords
diisocyanate monomer
diisocyanate
preparation
reaction
content
Prior art date
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Ceased
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PCT/CN2018/124363
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English (en)
Chinese (zh)
Inventor
朱智诚
石滨
尚永华
严成岳
李晶
刘照
刘伟
李海军
王暖程
黎源
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Publication of WO2020133067A1 publication Critical patent/WO2020133067A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
    • 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

Definitions

  • the invention belongs to the technical field of preparing isocyanate, and particularly relates to a preparation method of uretdione polyisocyanate.
  • the isocyanate homopolymer containing uretdione group has a very low viscosity, therefore, it has excellent application performance as a crosslinking agent component in a low-solvent, high-solids coating composition.
  • US8134014 discloses a method for preparing polyisocyanates containing uretdione groups using fused ring-substituted aminopyridines as catalysts.
  • the isocyanate homopolymers prepared therefrom have a high content of uretdione groups and are suitable for suitable isocyanates. There are no special restrictions, but pyridine compounds are likely to cause product coloration.
  • DE-A 3030513 discloses the preparation of polyisocyanates with high uretdione content as tri-(dialkylamino)phosphines either alone or in combination with cocatalysts (DE-A-3437635) as oligomerization catalysts.
  • their technical use is threatened by phosphorus oxide with a high potential carcinogenic risk, for example, hexamethylphosphoric triamide.
  • the uretdione polyisocyanate prepared by tertiary phosphine has a high product color number, and the product is prone to turbidity when stored at a low temperature ( ⁇ 0°C).
  • the present invention provides a method for preparing a polyisocyanate containing a uretdione group.
  • a polyisocyanate with high long-term low-temperature storage stability is obtained.
  • the invention provides a method for preparing a polyisocyanate containing a uretdione group.
  • a diisocyanate monomer with a total mass of M in the reaction system is polymerized under the catalyst of tertiary phosphine to prepare a polyisocyanate containing a uretdione group.
  • the reaction is terminated, and the unreacted diisocyanate monomer in the system is removed and reused
  • the content of phosphine oxide in the unreacted diisocyanate monomer is controlled not to exceed 1 wt% , Preferably not more than 0.5 wt%.
  • the preparation method of the present invention controls the content of phosphine oxide in the recycling part not to exceed the unreacted diisocyanate monomer in the recycling part 1wt%, which further improves the storage stability of its products.
  • the reaction is terminated.
  • the tertiary phosphine has the following structure:
  • R 1 , R 2 , and R 3 are independently selected from aliphatic substituents or aromatic substituents.
  • the aliphatic substituent is selected from linear alkyl, branched alkyl, or cycloalkyl, and the aromatic substituent is preferably a C 7 -C 10 aromatic substituent, such as, Benzyl; the aliphatic substituent is preferably C 1 -C 10 linear alkyl, C 3 -C 10 branched alkyl, C 3 -C 10 cycloalkyl; the aromatic substitution The group is preferably benzyl.
  • the tertiary phosphine is selected from trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, dicyclopentylbutyl Phosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, tribenzylphosphine, benzyldimethylphosphine, tricyclohexylphosphine, tri-n-octylphosphine.
  • the amount of tertiary phosphine is 0.01-5 wt% of the diisocyanate monomer, preferably 0.1-3 wt%, for example, 0.3 wt%, 0.5 wt%.
  • the above-mentioned catalyst tertiary phosphine used in the present invention is a nucleophilic reagent, for example, trioctylphosphine is a relatively weak base, and the solvent must be strictly deoxygenated during use, and it needs to be protected with an inert gas, which will occur if exposed to air The violent oxidation reaction generates trioctylphosphine oxide.
  • the inventors found that tertiary phosphine as a catalyst may cause the content of phosphine oxide in the system to increase when it is used. The content of phosphine oxide may even exceed 1%. If it is not removed, it will result in high levels of phosphine oxide remaining in the product. It will affect the stability of the product's long-term low-temperature storage.
  • catalyst poisons can be added to the system to terminate the reaction.
  • the catalyst poison used is dimethyl sulfate, phosphate, acid chloride, sulfur, or peroxide.
  • the amount of catalyst poison required for the termination of the reaction depends on the amount of catalyst in the system. The amount is equimolar to the amount of catalyst used in the system. Considering the various losses of the catalyst during the reaction, 60-90% of the catalyst poison equivalent to the amount of catalyst used in the system is sufficient to terminate the reaction.
  • the unreacted diisocyanate monomer in the reaction system is removed and the phosphine oxide content in the part of the removal system is determined.
  • gas chromatography can be used to detect the removal system The content of phosphine oxide in the part.
  • vacuum distillation or rectification can be performed under conditions of 130-150°C and absolute pressure of 0.5-3 kPa to remove the content of phosphine oxide in the removed portion.
  • the temperature of the polymerization reaction is 0-150°C, preferably 25-80°C.
  • the diisocyanate monomer is selected from hexamethylene diisocyanate (English abbreviated as HDI), 2-methylpentane-1,5-diisocyanate, isophorone diisocyanate (English abbreviation) IPDI), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, norbornane dimethylene isocyanate, 2,2 One or more of 4,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.
  • HDI hexamethylene diisocyanate
  • 2-methylpentane-1,5-diisocyanate isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • 1,3-bis(isocyanatomethyl)cyclohexane 1,4-bis
  • a suitable co-catalyst can be used in the method of the present invention together with the catalyst.
  • Suitable cocatalysts include especially low molecular weight monovalent or polyvalent fatty alcohols, preferably alcohol compounds with a relative molecular weight of 32-200.
  • the above alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-1-hexanol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol , Isomerized butanediol, hexanediol or octanediol, diethylene glycol, dipropylene glycol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethylpentane
  • One or more of diol, glycerin or trimethylolpropane, and the amount of the aforementioned co-catalyst is 0-5 wt% of the total mass M of the diisocyanate monomer in the reaction system, preferably 0.01-3 wt%.
  • stabilizers and additives may be added at any desired time, which are conventional in the field of polyisocyanate chemistry.
  • antioxidants such as sterically hindered phenol (2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol); light stabilizers, such as HALS amine, triazole, etc. .
  • the present invention has the following advantages:
  • the preparation method of the present invention is based on the prior art, by controlling the content of phosphine oxide in the unreacted monomers recycled to the system not to exceed 1 wt%, so that the obtained polyisocyanate containing uretdione group is not easy to store at low temperature
  • the appearance of turbidity improves the stability of its low-temperature storage.
  • Viscosity measurement method The dynamic mechanical viscosity is measured using a BrookField DV-I Prime viscometer, using an S21 rotor at 25°C.
  • the raw material information used is as follows:
  • Hexamethylene diisocyanate Wanhua Chemical, purity>99%
  • Tri-n-octylphosphine Sigma reagent, purity>95%
  • Tricyclohexylphosphine Aladdin reagent, purity 96%;
  • Dimethyl sulfate Aladdin reagent, purity 98.5%.
  • reaction solution was kept under the protection of dry nitrogen until the addition of the catalyst and the entire reaction.
  • Hexamethylene diisocyanate (abbreviated as HDI) with a total mass M of 1000g, 20g of 2-ethyl-1,3-hexanediol and 3g of tri-n-octylphosphine were successively added at 50°C under stirring, and quantitatively monitored by gel chromatography The proportion of HDI consumption mass M1 in the reaction system to the total mass M of HDI added;
  • the detected phosphine oxide content in the removed portion accounted for 0.98wt% of the unreacted HDI content; when the above 19 times were repeated, the phosphine oxide content in the removed portion was detected 1.2wt% of the unreacted HDI content;
  • Viscosity 162mPas/25°C;
  • Viscosity 168mPas/25°C
  • Hexamethylene diisocyanate (HDI) with a total mass M of 1000g was added to 20g of 2-ethyl-1,3-hexanediol and 3g of tricyclohexylphosphine in turn at 50°C, followed by quantitative monitoring by gel chromatography The proportion of HDI consumption mass M1 in the reaction system to the total mass M of HDI added;
  • the detected phosphine oxide content in the removed portion accounted for 0.98wt% of the unreacted HDI content; when reused to 20 times, the phosphine oxide content in the removed portion was 1.5wt %
  • Viscosity 165mPas/25°C
  • Hexamethylene diisocyanate (abbreviated as HDI) with a total mass M of 1000g is stirred at a temperature of 50°C, and 20g of 2-ethyl-1,3-hexanediol and 3g of tri-n-octylphosphine are sequentially added for reaction, and Quantitatively monitor the ratio of HDI consumption mass M1 in the reaction system to the total mass M of HDI added by gel chromatography;
  • Viscosity 178mPas/25°C
  • the resulting polyisocyanate product containing uretdione groups will not be cloudy when stored at -10°C
  • the phenomenon improves the low temperature stability of uretdione polyisocyanate products prepared by tertiary phosphine catalysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé pour la préparation d'un polyisocyanate contenant un groupe uretdione. Le polyisocyanate contenant un groupe uretdione est préparé à partir d'un monomère diisocyanate ayant une masse totale M dans un système réactionnel au moyen d'une réaction de polymérisation sous la catalyse d'une tert-phosphine. Dans le procédé, la réaction est arrêtée lorsque le rapport de la masse consommée M1 du monomère diisocyanate à la masse totale M du monomère diisocyanate dans le système atteint une proportion souhaitée et le monomère diisocyanate n'ayant pas réagi présent dans le système est retiré et recyclé vers le système, la teneur d'un oxyde de phosphine dans le monomère diisocyanate n'ayant pas réagi étant réglée à pas plus de 1 % en poids, de préférence pas plus de 0,5 % en poids avant que le monomère diisocyanate n'ayant pas réagi retiré du système soit recyclé vers le système. L'homopolymère d'isocyanate d'uretdione obtenu par le procédé selon la présente invention présente une faible coloration et le produit présente une bonne stabilité au stockage.
PCT/CN2018/124363 2018-12-26 2018-12-27 Procédé pour la préparation de polyisocyanate contenant un groupe uretdione Ceased WO2020133067A1 (fr)

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CN201811597900.3A CN109761903B (zh) 2018-12-26 2018-12-26 一种含有脲二酮基团的多异氰酸酯的制备方法
CN201811597900.3 2018-12-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026109427A1 (fr) 2024-11-22 2026-05-28 Basf Se Compositions stables à la dérive de couleur contenant des polyisocyanates dérivés de diisocyanates (cyclo)aliphatiques

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110305294B (zh) * 2019-07-15 2021-04-20 万华化学集团股份有限公司 一种存储稳定的含有脲二酮基团的多异氰酸酯的制备方法
CN110372846B (zh) * 2019-07-15 2021-06-25 万华化学集团股份有限公司 一种色值稳定的含有脲二酮基团的多异氰酸酯的制备方法
CN111040101B (zh) * 2019-12-23 2021-09-07 万华化学集团股份有限公司 色值稳定的含有脲二酮基团的多异氰酸酯及其制备方法
CN111072917B (zh) 2020-01-02 2021-06-29 万华化学集团股份有限公司 一种存储稳定的多异氰酸酯组合物及制备方法
CN111303373B (zh) * 2020-02-25 2022-07-12 万华化学集团股份有限公司 一种低色度脲基甲酸酯组合物及其制备方法和应用

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US4994541A (en) * 1989-01-03 1991-02-19 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing uretdione and isocyanurate groups, the polyisocyanates obtained by this process and their use in two-component polyurethane coatings
CN1334264A (zh) * 2000-07-19 2002-02-06 拜尔公司 制备具有改进的单体稳定性的脲二酮多异氰酸酯的方法
CN1511858A (zh) * 2002-12-05 2004-07-14 拜尔公司 含有脲二酮基团的低单体含量多异氰酸酯
CN1517336A (zh) * 2003-01-28 2004-08-04 三菱瓦斯化学株式会社 多异氰酸酯化合物、该化合物制造方法、加成聚合组合物以及粉末涂料
CN101209983A (zh) * 2006-12-27 2008-07-02 拜尔材料科学股份公司 调节异氰酸酯的方法
CN105061709A (zh) * 2015-08-26 2015-11-18 华南理工大学 一种基于甲苯二异氰酸酯二聚体的聚氨酯固化剂及其制法
CN108047428A (zh) * 2017-11-24 2018-05-18 万华化学集团股份有限公司 一种低粘度缩二脲聚异氰酸酯及其制备方法和用途

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DE3432081A1 (de) * 1984-08-31 1986-03-06 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von oligomeren polyisocyanaten und ihre verwendung bei der herstellung von polyurethankunststoffen
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US4994541A (en) * 1989-01-03 1991-02-19 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing uretdione and isocyanurate groups, the polyisocyanates obtained by this process and their use in two-component polyurethane coatings
CN1334264A (zh) * 2000-07-19 2002-02-06 拜尔公司 制备具有改进的单体稳定性的脲二酮多异氰酸酯的方法
CN1511858A (zh) * 2002-12-05 2004-07-14 拜尔公司 含有脲二酮基团的低单体含量多异氰酸酯
CN1517336A (zh) * 2003-01-28 2004-08-04 三菱瓦斯化学株式会社 多异氰酸酯化合物、该化合物制造方法、加成聚合组合物以及粉末涂料
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CN105061709A (zh) * 2015-08-26 2015-11-18 华南理工大学 一种基于甲苯二异氰酸酯二聚体的聚氨酯固化剂及其制法
CN108047428A (zh) * 2017-11-24 2018-05-18 万华化学集团股份有限公司 一种低粘度缩二脲聚异氰酸酯及其制备方法和用途

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026109427A1 (fr) 2024-11-22 2026-05-28 Basf Se Compositions stables à la dérive de couleur contenant des polyisocyanates dérivés de diisocyanates (cyclo)aliphatiques

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