EP0000232B1 - Verfahren zur Herstellung von blockierten Polyisocyanaten und danach erhältliche blockierte Polyisocyanate - Google Patents

Verfahren zur Herstellung von blockierten Polyisocyanaten und danach erhältliche blockierte Polyisocyanate Download PDF

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Publication number
EP0000232B1
EP0000232B1 EP78200062A EP78200062A EP0000232B1 EP 0000232 B1 EP0000232 B1 EP 0000232B1 EP 78200062 A EP78200062 A EP 78200062A EP 78200062 A EP78200062 A EP 78200062A EP 0000232 B1 EP0000232 B1 EP 0000232B1
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EP
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Prior art keywords
weight
polyisocyanates
reaction
temperature
parts
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EP78200062A
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German (de)
English (en)
French (fr)
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EP0000232A1 (de
Inventor
Rainer Dr. Gras
Johann Dr. Obendorf
Elmar Dr. Wolf
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Huels AG
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Chemische Werke Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a process for the preparation of new compounds with a high content of latent isocyanate groups and the compounds obtainable by this process and their use.
  • masked isocyanates also called isocyanate releasers
  • isocyanate releasers Tertiary alcohols, phenols, acetoacetates, malonic esters, acetylacetone, phthalimide, imidazole, hydrogen chloride, hydrogen cyanide and E- caprolactam are known as blocking agents.
  • the use of monophenols and e-caprolactam is preferred for this purpose.
  • blocked isocyanates have the property of reacting like isocyanates at elevated temperature. The more acidic the H atom of the masking group is, the easier it is to split off. Such blocked isocyanates are described in DE-A-21 66 423. Terminally blocked isocyanates which additionally contain uretdione groups have also been described in DE-A-25 02 934.
  • the splitting temperature of aliphatic e-caprolactam-blocked polyisocyanates is generally about 180 ° -190 ° C.
  • blocked polyisocyanates in a simple manner, which block at a temperature which is at least 20 ° -30 ° C lower than the isocyanates blocked with the conventional blocking agents, if the process for the preparation of blocked polyisocyanates is carried out by reacting polyisocyanates with N-containing cyclic compounds so that cyclic amidines of the general formula are used as N-containing cyclic compounds uses, where R can be the same or different substituents from the group hydrogen, alkyl, cycloalkyl, aralkyl and aryl radical and the reaction takes place at temperatures of 0-150 ° C, preferably 80-120 ° C.
  • the polyisocyanates and the cyclic amidines are used in amounts such that there is 0.5-1.1, preferably 0.8-1.0 mol of cyclic amidine per isocyanate group.
  • the reaction can be carried out both in solvents, in the melt and in polyisocyanate presented in excess.
  • Suitable starting compounds which can be used for blocking with the cyclic amidines are, for example, polyisocyanates, in particular diisocyanates, such as aliphatic, cycloaliphatic, araliphatic, aryl-substituted aliphatic and / or aromatic diisocyanates, as described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/2, pp. 61-70 and the article by W.
  • the dimeric and trimeric forms of the polyisocyanates such as uretdiones and isocyanurates, which can be prepared by known methods, can of course also be used as starting materials for blocking with the imidazolines described in detail below.
  • polyisocyanates are also understood to mean those which, prior to blocking with the imidazolines, have been subjected to a reaction for molecular enlargement with the so-called chain extenders customary in isocyanate chemistry, such as water, polyols, polyamines and others, the bifunctional or trifunctional chain extender , that is to say compounds having groups which are reactive toward isocyanate groups, such as hydroxyl and / or amino groups, are used in such amounts that the resulting new isocyanate bears at least 2 isocyanate groups on average.
  • chain extenders customary in isocyanate chemistry
  • the bifunctional or trifunctional chain extender that is to say compounds having groups which are reactive toward isocyanate groups, such as hydroxyl and / or amino groups, are used in such amounts that the resulting new isocyanate bears at least 2 isocyanate groups on average.
  • polyisocyanates with one or more urea groups result.
  • Suitable polyols include diols and triols, e.g. Ethylene glycol, propylene glycols such as 1,2- and 1,3-propanediol, 2,2-dimethylpropanediol- (1,3), butanediols such as butanediol- (1,4), hexanediols e.g.
  • polyamines suitable for chain extension or molecular enlargement for example, ethylenediamine 1,2, propylenediamine-1,2 and -1,3, butylenediamine-1,2, -1,3 and -1,4 as well as hexamethylenediamines should be mentioned .
  • reaction of the polyisocyanates before blocking with the chain extenders mentioned in the stated proportions can be carried out at temperatures in the range from 0-150 ° C., preferably 80-120 ° C.
  • Suitable imidazoline derivatives for the purposes of the present invention are, for example, those with optionally aryl-substituted alkyl radicals, with optionally alkyl-substituted aryl radicals, such as 2-methylimidazoline, 2,4-dimethylimidazoline, 2-methyl-4- (n -butyl) -imidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2-phenyl-4- (N-morpholinylmethyl) imidazoline, 2- (o -Tolyl) imidazoline, 2- (p-tolyl) imidazoline, etc.
  • Mixtures of the imidazoline derivatives can also be used according to the invention. This is particularly useful if blocked isocyanates with low melting points or ranges are required.
  • the imidazoline derivatives which can be used according to the invention can be prepared by known processes from optionally substituted geminal diamines and aliphatic or aromatic mononitriles in the presence of elemental sulfur or sulfuryl chloride as a catalyst.
  • FR-A 14 66 282 it is already known to produce 0-1,2-imidazoline-N-carboxyalkyl- or carboxycycloalkylamides by reacting ⁇ -1,2-imidazolines and monoisocyanates for therapeutic purposes.
  • the blocking of diisocyanates with 0-1,2-imidazolines is not yet known.
  • the blocking can also be carried out in solvents.
  • suitable solvents for this reaction are only those which do not react with the polyisocyanates, for example ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and others; Aromatics such as benzene, toluene, xylenes, chlorobenzene, nitrobenzene and others; cyclic ethers such as tetrahydrofuran, dioxane and others; Esters such as methyl acetate, n-butyl acetate and others; aliphatic chlorinated hydrocarbons such as chloroform, carbon tetrachloride and others; and aprotic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
  • the reaction mixtures are kept at the stated temperatures until the NCO content of the reaction mixture has dropped to values below 0.2% NCO, otherwise until a constant is reached NCO value.
  • Another object of the present invention is the subsequent implementation of a group of blocked polyisocyanates, namely those in which cyclic amidines have been used in substoichiometric amounts, i.e. the ratio of cyclic amidine to isocyanate groups was ⁇ 1: 1 with the same chain extenders that have previously been described as molecular enlargement agents.
  • the reaction also takes place at temperatures in the range from 0-150 ° C., preferably 80-120 ° C., but below the deblocking temperature of the blocked polyisocyanate.
  • This process variant allows the product range of the blocked polyisocyanates to be adapted to practical requirements within very wide limits.
  • This process variant is of particular interest for polyisocyanates with differently reactive NCO groups, i.e. asymmetric polyisocyanates.
  • the invention also relates to the adducts obtainable by the processes described. These are generally compounds of the molecular weight range from 300-2,500, preferably from 300-1,000.
  • the process products have a melting range in the temperature range from 30-220 ° C., preferably 80-160 ° C.
  • the polyisocyanates blocked with the cyclic amidines are further characterized by a content of terminal isocyanate groups present in blocked form (calculated as NCO) of 4-25% by weight, preferably 10-21% by weight.
  • R is the same or different substituents from the group hydrogen, alkyl, cycloalkyl, aralkyl and R 'is the divalent organic radical of a compound with 2 OH groups.
  • the compounds of the invention described above are particularly suitable because of their melting points and at the same time higher molecular weights as catalysts for the anionic polymerization of E- caprolactam.
  • the compounds can also be used to produce wire enamels.
  • IPDI Isophorone diisocyanate
  • anhydrous acetone 300 parts by weight at room temperature.
  • 2-phenylimidazoline which in 500 parts by weight. anhydrous acetone were dissolved, added dropwise. After the 2-phenylimidazoline addition was complete, the mixture was heated at 50 ° C. for one hour. The acetone was distilled off. The last residues of acetone were removed by drying the reaction product at 60 ° C. in a vacuum drying cabinet.
  • the IPDI blocked with 2-phenylimidazoline is a white powder with a melting range of 98-106 ° C, a glass transition temperature (DTA) of 63-80 ° C and a splitting temperature of approx. 120 ° C.
  • the IR spectrum of this blocked polyisocyanate is shown in Fig. 1.
  • the reaction product is a white crystalline powder with a melting range of 95-98 ° C, a glass transition temperature (DTA) of 65-85 ° C and a splitting temperature of approx. 140 ° C.
  • the IR spectrum of the blocked polyisocyanate is shown in Fig. 2.
  • Fig. 4 shows the IR spectrum of the blocked polyisocyanate.
  • Example 4 a To 556 parts by weight of the IPDI diethylene glycol adduct described in Example 4 a are 320 parts by weight at 100 ° C. 2-Phenyl-4-methylimidazoline added so that the temperature of the reaction mixture did not rise above 110 ° C. To complete the reaction, the reaction mixture was heated at 110 ° for a further 2 hours.
  • the reaction product is a white powder with a melting range of 95-100 ° C, a glass transition temperature (DTA) of 60-85 ° C and a splitting temperature of approx. 150 ° C. NCO could no longer be detected in the reaction product.
  • DTA glass transition temperature
  • Fig. 5 shows the IR spectrum of the blocked polyisocyanate.
  • reaction product is a colorless product with a melting range of 100-107 ° C, a glass transition temperature (DTA) of 60-95 ° C and a splitting temperature of approx. 170 ° C.
  • Fig. 6 shows the IR spectrum of the blocked polyisocyanate.
  • the reaction product is a white crystalline powder with a melting range of 107-110 ° C, a glass transition point (DTA) of 82-89 ° C and a splitting temperature of approx. 150 ° C.
  • Example 4 a To 556 parts by weight of the adduct of 2 moles of IPDI and 1 mole of diethylene glycol described in Example 4 a was 168 parts by weight at 120 ° C. 2-Methylimidazoline added so that the temperature of the reaction mixture did not rise above 110 ° C. To complete the reaction, the reaction mixture was heated at 110 ° C. for a further 2 h. The reaction mixture is a white powder with a melting range of 109-112 ° C, a glass transition point (DTA) of 83-91 ° C and a splitting temperature of 160 ° C.
  • DTA glass transition point
  • Fig. 8 shows the IR spectrum of the blocked polyisocyanate.
  • the reaction product is a white crystalline powder with a melting range of 90-103 ° C, a glass transition temperature (DTA) of 78-90 ° C and a splitting temperature of approx. 130 ° C.
  • the diisocyanate blocked with 2,4-dimethylimidazoline is a white powder with a melting range of 85-105 ° C, a glass transition temperature (DTA) of 70-91 ° C and a splitting temperature of approx. 150 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP78200062A 1977-07-01 1978-06-27 Verfahren zur Herstellung von blockierten Polyisocyanaten und danach erhältliche blockierte Polyisocyanate Expired EP0000232B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2729704 1977-07-01
DE19772729704 DE2729704A1 (de) 1977-07-01 1977-07-01 Verfahren zur herstellung von blockierten polyisocyanaten

Publications (2)

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EP0000232A1 EP0000232A1 (de) 1979-01-10
EP0000232B1 true EP0000232B1 (de) 1981-12-09

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EP78200062A Expired EP0000232B1 (de) 1977-07-01 1978-06-27 Verfahren zur Herstellung von blockierten Polyisocyanaten und danach erhältliche blockierte Polyisocyanate

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Country Link
US (1) US4200725A (it)
EP (1) EP0000232B1 (it)
JP (1) JPS5444670A (it)
DE (2) DE2729704A1 (it)
DK (1) DK297978A (it)
IT (1) IT1096841B (it)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4322327A (en) * 1979-10-19 1982-03-30 Mitsubishi Petrochemical Co., Ltd. Slow-curing water-curable urethane prepolymer composition
JPS56152130U (it) * 1980-04-11 1981-11-14
DE3128733A1 (de) * 1981-07-21 1983-02-24 Hoechst Ag, 6000 Frankfurt "elastifiziertes additionsprodukt aus polyalkylenaether-polyolen und polyisocyanaten, dieses enthaltende mischungen und deren verwendung"
DE3403500A1 (de) * 1984-02-02 1985-08-08 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von stabilisierten polyisocyanaten, stabilisierte isocyanate ratardierter reaktivitaet und ihre verwendung zur polyurethanherstellung
DE3610758A1 (de) * 1986-03-29 1987-10-01 Huels Chemische Werke Ag Pulverfoermige ueberzugsmittel auf basis von 1.2-epoxidverbindungen
GB9520317D0 (en) * 1995-10-05 1995-12-06 Baxenden Chem Ltd Water dispersable blocked isocyanates
EP2274359B1 (de) 2008-04-30 2012-03-07 Sika Technology AG Aktivator für epoxidharzzusammensetzungen
WO2014133041A1 (ja) * 2013-02-26 2014-09-04 富士フイルム株式会社 セルロースアシレートフィルム、新規化合物、偏光板および液晶表示装置
CN105384951B (zh) 2014-09-03 2020-09-18 富士胶片株式会社 聚合物膜、偏振片及液晶显示装置
WO2018102333A1 (en) * 2016-11-30 2018-06-07 Dow Global Technologies Llc Isocyanate-blocked amidines as latent polyurethane catalysts
JP7436374B2 (ja) * 2018-09-28 2024-02-21 広栄化学株式会社 アミデート化合物の製造方法及びアミデート化合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952665A (en) * 1955-12-08 1960-09-13 Mobay Chemical Corp High molecular weight cyclic trimers containing blocked isocyanate groups
BE654888A (it) * 1963-10-29 1965-02-15
FR1466282A (fr) * 1964-07-03 1967-01-20 Basf Ag Formamidino-nu-carboxalcoyl- et -cycloalcoylamides, et procédé pour leur fabrication
US3855235A (en) * 1973-07-16 1974-12-17 Ashland Oil Inc Quaternary ammonium derivatives of bisimidazoline compounds
US4046744A (en) * 1976-07-28 1977-09-06 Rohm And Haas Company Thermosetting coatings based on ketoxime-blocked isocyanates and oxazolidines

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Publication number Publication date
IT7825168A0 (it) 1978-06-30
IT1096841B (it) 1985-08-26
DE2729704A1 (de) 1979-01-11
DE2861432D1 (en) 1982-02-04
EP0000232A1 (de) 1979-01-10
US4200725A (en) 1980-04-29
DK297978A (da) 1979-01-02
JPS5444670A (en) 1979-04-09

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