WO1983000328A1 - Solid blocked cross-linking agents based on |,4-cyclohexane bis(methylisocyanate) - Google Patents

Solid blocked cross-linking agents based on |,4-cyclohexane bis(methylisocyanate) Download PDF

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Publication number
WO1983000328A1
WO1983000328A1 PCT/GB1982/000219 GB8200219W WO8300328A1 WO 1983000328 A1 WO1983000328 A1 WO 1983000328A1 GB 8200219 W GB8200219 W GB 8200219W WO 8300328 A1 WO8300328 A1 WO 8300328A1
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methylisocyanate
alkyl
chbmi
adducts
compounds according
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French (fr)
Inventor
Limited Kodak
Kodak Company Eastman
George Charles Russell
Paul Mcbride
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Kodak Ltd
Eastman Kodak Co
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Kodak Ltd
Eastman Kodak Co
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    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • This invention relates to new derivatives of 1,4-cyclohexane bis(methylisocyanate) (CHBMI) which are non-reactive under ambient conditions to resins containing active hydrogens, such as those in hydroxyl or amino groups, but which become reactive when subjected to relatively low temperatures for short periods of time.
  • CHBMI 1,4-cyclohexane bis(methylisocyanate)
  • Coating compositions comprising the reaction product of a polyfunctional isocyanate and a resin containing isocyanate-reactive functions such as hydroxyl groups are well known and widely used in industry.
  • the isocyanate generally reacts very quickly with the resin at about room temperature, and therefore these components must be packaged, shipped and stored separately and mixed together only when the cross-linking reaction is desired.
  • the disadvantages of such a system are obvious.
  • Proposed alternatives generally embody the "one-pack" formulation concept, wherein blending and packaging of the isocyanate and resin without premature interaction is the goal.
  • relatively unreactive phenol blocked isocyanate compositions which regenerate free isocyanates upon heating have been used.
  • free phenol is produced upon heating, with attendant undesirable odour, corrosiveness and toxicity.
  • many such blocked isocyanates require high temperatures for commencement of the curing.
  • solid isocyanate adducts of formulae I and II below are highly useful in one-pack formulations, because they become reactive at relatively low temperatures to cross-link hydroxylated resins without attendant odour, corrosiveness and toxicity.
  • These adducts are formed by reacting one mole of unsubstituted or substituted 1,4-cyclohexane bis(methylisocyanate) with two moles of a blocking compound having an active hydrogen, i.e. a precursor of A below, and preferably but not critically in the presence of an amine catalyst and a solvent.
  • the adducts of the present invention have the formulae
  • A is R is O to three of the same or different substituents selected from alkyl, -NR 1 R 2 , -NO 2 , halogen, alkoxy, aryl, alkaryl and cycloalkyl; R 1 and R 2 are the same or different alkyl; R 3 is alkylene of from 2 to 8 carbons; X is selected from alkyl, aryl, and cycloalkyl, such as trimethylol propane, and wherein each of the aforesaid alkyl moieties of R, R 1 , R 2 and X contains from 1 to 10 carbons and is straight or branched; and n is 2, 3 or 4.
  • adducts in general have additional advantages in that they are solids at room temperature and so are easily handled, they are aliphatic and thus less susceptible to thermal yellowing, and they are capable of being used with a wide choice of cure temperature/time schedules based on the blocking agent selected. Furthermore, because of the relatively high -NCO content of the CHBMI per mole in comparison with many commercial isocyanate crosslinkers, less of the blocked CHBMI is required to satisfy the stoichiometry of the hydroxylated resin.
  • the present adducts are conveniently prepared by mixing the active hydrogen compound with a suitable amine catalyst in a solvent such as toluene or acetone, and slowly adding the CHBMI thereto, preferably but not critically in stoichiometric amounts, and preferably but not critically with heating, usually for several hours, until precipitation of the solid product is essentially completed.
  • a temperature of from about 50 to 120°C. is typical, and 80 to 100°C. is preferred.
  • the crude product may then be recrystallized from a suitable solvent such as toluene or acetone to yield the pure adduct.
  • the compounds of formula II above are prepared by first reacting the CHBMI in excess with a polyfunctional hydroxy-containing compound and subsequently blocking the polyisocyanate thus formed with a suitable blocking agent in the manner described hereinabove.
  • the crosslinking of the hydroxylated resins using the present adducts can be catalyzed using known catalysts for isocyanate hydroxyl reactions such as tertiary amines or organo tin or organo zinc compounds.
  • concentration of the adduct is usually about the stoichiometric equivalent for reaction with all of the hydroxyl groups on the polymer, but may be varied widely depending on the cure rate and cured coating properties desired.
  • Typical hydroxylated polymers with which the adducts of the present invention may be used are disclosed in, for example, United States Patent
  • polyesters which contain, in a co-condensed form, aliphatic and aromatic dicarboxylic acids having 4 to 12 carbon atoms and polyols having 2 to 10 carbon atoms and 2 to 4 primary or secondary hydroxyl groups.
  • Saturated and unsaturated polyester resins of this type are described in Houben-Weyl "Makromolekulare Stoffe II" ("Macromolecular Materials II"), volume 14/2, pages 4 to 42.
  • Crosslinking can occur over a broad temperature/time range varying, for example, from about 30 minutes or more at 150°C. to about 10 minutes or less at 180°C. depending on the resin, blocking agent and/or catalyst used. It is obvious that the flexibility in cure schedules allowed by the present adducts renders them useful in areas such as industrial coating applications.
  • 1,4-cyclohexane bis(methylisocyanate) (18.8 g.) over a period of about 30 seconds. The reaction was exothermic and a white precipitate appeared. The mixture was heated and stirred for four hours at
  • CHMBI caprolactam adduct was required per 100 g. of resin for a stoichiometric reaction.
  • the adduct had about 23% of its weight as available -NCO.
  • 36.5 g. of a commercial caprolactam- blocked isophorone diisocyanate (CID) curing agent having an available -NCO content of 11.5% by weight
  • 27.5 g. of a commercial caprolactam-blocked cycloaliphatic isocyanate, having an available -NCO content of 15.3% by weight were required for stoichiometric reactions.
  • Table 2 lists the components of two coating compositions which were based on the same hydroxylated polyester resin.
  • Composition A contained the commercial CID curing agent, and Composition B contained the CHBMI-caprolactam adduct.
  • compositions A and B coated on a steel substrate 0.635 mm. thick and subjected to a curing step for 15 minutes at 180°C. metal temperature are given in the following
  • CHBMI-cured material had superior impact strength, with the other properties being as good or better than those of the coating containing the commercial crosslinker at a much higher concentration.
  • CHBMI (Column C) produced a finished coating having lower orange peel and higher gloss than that obtained using a commercial reduced temperature crosslinker (Column D). From the above examples and tables it can be seen that the blocked CHBMI crosslinkers impart superior properties to the cured coatings in many important areas such as gloss, impact strength and surface appearance. As will be appreciated, these properties are of major importance for commercial coating formulations.

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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)
  • Paints Or Removers (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des nouveaux produits d'addition sont préparés à partir de 1,4-cyclohexane bis(méthylisocyanate), qui peut être substitué dans l'anneau de cyclohexane, et à partir de composés actifs contenant de l'hydrogène, tels que des phénols, des lactames, des oximes, et des acylacétates d'alkyle et des alkoxycarbonylacétates. Ces produits d'addition peuvent être incorporés dans des résines contenant des groupes réagissant à l'isocyanate, tels que des groupes hydroxyle, pour donner des compositions qui sont polymérisées par chauffage.New adducts are prepared from 1,4-cyclohexane bis (methylisocyanate), which may be substituted in the cyclohexane ring, and from active compounds containing hydrogen, such as phenols, lactams, oximes, and alkyl acylacetates and alkoxycarbonylacetates. These adducts can be incorporated into resins containing isocyanate reacting groups, such as hydroxyl groups, to give compositions which are polymerized by heating.

Description

SOLID BLOCKED CROSSLINKING AGENTS BASED ON 1,4-CYCLOHEXANE BIS(METHYLISOCTANATE)
This invention relates to new derivatives of 1,4-cyclohexane bis(methylisocyanate) (CHBMI) which are non-reactive under ambient conditions to resins containing active hydrogens, such as those in hydroxyl or amino groups, but which become reactive when subjected to relatively low temperatures for short periods of time. These new compounds readily gel hydroxylated resins and thus are useful as crosslinkers for such resins in industrial coatings and related uses.
Coating compositions comprising the reaction product of a polyfunctional isocyanate and a resin containing isocyanate-reactive functions such as hydroxyl groups are well known and widely used in industry. The isocyanate generally reacts very quickly with the resin at about room temperature, and therefore these components must be packaged, shipped and stored separately and mixed together only when the cross-linking reaction is desired. The disadvantages of such a system are obvious.
Proposed alternatives generally embody the "one-pack" formulation concept, wherein blending and packaging of the isocyanate and resin without premature interaction is the goal. In one such approach, relatively unreactive phenol blocked isocyanate compositions which regenerate free isocyanates upon heating have been used. With such formulations, however, free phenol is produced upon heating, with attendant undesirable odour, corrosiveness and toxicity. Moreover, many such blocked isocyanates require high temperatures for commencement of the curing. Thus, it is highly desirable to provide blocked isocyanate formulations which become reactive at low temperatures and without the liberation of undesirable by-products.
It has now been found that solid isocyanate adducts of formulae I and II below are highly useful in one-pack formulations, because they become reactive at relatively low temperatures to cross-link hydroxylated resins without attendant odour, corrosiveness and toxicity. These adducts are formed by reacting one mole of unsubstituted or substituted 1,4-cyclohexane bis(methylisocyanate) with two moles of a blocking compound having an active hydrogen, i.e. a precursor of A below, and preferably but not critically in the presence of an amine catalyst and a solvent.
The adducts of the present invention have the formulae
Figure imgf000004_0001
wherein A is
Figure imgf000004_0002
R is O to three of the same or different substituents selected from alkyl, -NR1R2, -NO2, halogen, alkoxy, aryl, alkaryl and cycloalkyl; R1 and R2 are the same or different alkyl; R3 is alkylene of from 2 to 8 carbons; X is selected from alkyl, aryl, and cycloalkyl, such as trimethylol propane, and wherein each of the aforesaid alkyl moieties of R, R1, R2 and X contains from 1 to 10 carbons and is straight or branched; and n is 2, 3 or 4. These adducts in general have additional advantages in that they are solids at room temperature and so are easily handled, they are aliphatic and thus less susceptible to thermal yellowing, and they are capable of being used with a wide choice of cure temperature/time schedules based on the blocking agent selected. Furthermore, because of the relatively high -NCO content of the CHBMI per mole in comparison with many commercial isocyanate crosslinkers, less of the blocked CHBMI is required to satisfy the stoichiometry of the hydroxylated resin. The present adducts are conveniently prepared by mixing the active hydrogen compound with a suitable amine catalyst in a solvent such as toluene or acetone, and slowly adding the CHBMI thereto, preferably but not critically in stoichiometric amounts, and preferably but not critically with heating, usually for several hours, until precipitation of the solid product is essentially completed. A temperature of from about 50 to 120°C. is typical, and 80 to 100°C. is preferred. The crude product may then be recrystallized from a suitable solvent such as toluene or acetone to yield the pure adduct.
The compounds of formula II above are prepared by first reacting the CHBMI in excess with a polyfunctional hydroxy-containing compound and subsequently blocking the polyisocyanate thus formed with a suitable blocking agent in the manner described hereinabove.
If desired, the crosslinking of the hydroxylated resins using the present adducts can be catalyzed using known catalysts for isocyanate hydroxyl reactions such as tertiary amines or organo tin or organo zinc compounds. The concentration of the adduct is usually about the stoichiometric equivalent for reaction with all of the hydroxyl groups on the polymer, but may be varied widely depending on the cure rate and cured coating properties desired.
Typical hydroxylated polymers with which the adducts of the present invention may be used are disclosed in, for example, United States Patent
Specifications Nos. 3,659,003; 3,857,818; 3,912,691; and particularly No. 4,132,843 at columns 4 and 5. Particularly important are the polyesters which contain, in a co-condensed form, aliphatic and aromatic dicarboxylic acids having 4 to 12 carbon atoms and polyols having 2 to 10 carbon atoms and 2 to 4 primary or secondary hydroxyl groups. Saturated and unsaturated polyester resins of this type are described in Houben-Weyl "Makromolekulare Stoffe II" ("Macromolecular Materials II"), volume 14/2, pages 4 to 42. Crosslinking can occur over a broad temperature/time range varying, for example, from about 30 minutes or more at 150°C. to about 10 minutes or less at 180°C. depending on the resin, blocking agent and/or catalyst used. It is obvious that the flexibility in cure schedules allowed by the present adducts renders them useful in areas such as industrial coating applications.
The present compounds, their preparation and use are illustrated in greater detail in the following examples which are illustrative only and are not intended to limit the invention in any way.
Example 1 - Synthesis of the Acetone Oxime Adduct of CHBMI
A mixture of acetone oxime (14.6 g.), triethylamine (0.8 g.) and toluene (25 ml.) was stirred at about 18°C. To this solution was added
1,4-cyclohexane bis(methylisocyanate) (18.8 g.) over a period of about 30 seconds. The reaction was exothermic and a white precipitate appeared. The mixture was heated and stirred for four hours at
80°C. to ensure a complete reaction, and was then filtered and recrystallized from toluene (50 ml.), leaving a white microcrystalline solid having the structure
Figure imgf000007_0001
Example 2 - Synthesis of the Acetoacetic Ester Adduct of CHBMI
A mixture of ethyl acetoacetate (52 g), triethylamine (1.0 g.), and toluene (25 ml.) was stirred at room temperature. To this solution was added 1,4-cyclohexane bis(methylisocyanate) (18.8 g.), with continued stirring over a period of about 30 seconds. The mixture was then heated to between
80-100°C. for three hours, cooled, filtered and washed with ethyl acetate (27 ml). The fine crystalline solid product was dried under reduced pressure and then recrystallized from acetone
(50 ml.). The product was a white microcrystalline solid having the structure
Figure imgf000007_0002
Example 3 - Evaluation of CHBMI Adducts as Cross- linkers for Hydroxylated Resins
A hydroxylated polyester based on trimethyl pentanediol, trimethylol propane, isophthalic acid and adipic acid, having a Number Average Molecular
Weight (Mn) of 1,700 and a HydroxylNumber of 127 was used as the resin to be crosslinked. Mixes were made using this resin and a stoichiometric equivalent of each adduct, both with and without 2% by weight of a 1:1 molar mixture of dibutyl tin diacetate and hexadecyl trimethylammonium stearate as catalyst. The gel times for mixes at 140°C were determined using a Ferranti-Shirley melt viscometer and are shown in Table 1.
Figure imgf000008_0001
*The CHBMI-caprolactam adduct gelled the polyester in approximately 10 minutes at 180°C.
Example 4 - Relative Amounts, by Weight of Crosslinkers Required to Satisfy Stoichio metries of Hydroxylated Resins
When used in a powder coating based on commercially available hydroxylated polyester resin having a Hydroxyl Number of 56, only 20.5 g. of the
CHMBI caprolactam adduct was required per 100 g. of resin for a stoichiometric reaction. The adduct had about 23% of its weight as available -NCO. By comparison, 36.5 g. of a commercial caprolactam- blocked isophorone diisocyanate (CID) curing agent having an available -NCO content of 11.5% by weight, and 27.5 g. of a commercial caprolactam-blocked cycloaliphatic isocyanate, having an available -NCO content of 15.3% by weight, were required for stoichiometric reactions.
Table 2 lists the components of two coating compositions which were based on the same hydroxylated polyester resin. Composition A contained the commercial CID curing agent, and Composition B contained the CHBMI-caprolactam adduct.
Figure imgf000009_0001
The performances of compositions A and B coated on a steel substrate 0.635 mm. thick and subjected to a curing step for 15 minutes at 180°C. metal temperature are given in the following
Table 3, the measurements for each sample being obtained on the same test equipment by the same procedure.
Figure imgf000010_0001
Flexibility No cracking No cracking
*[The front/reverse impact strength measurements were made in accordance with ASTM D 2794-69. The testing machine had a weight measured in pounds falling through a distance measured in inches, and the results are given in inch-pounds. (One pound = 454 grams, one inch = 25.4 mm.). However, these results are used to compare the impact strength of the CHBMI-cured material with that of other materials : the units in which they are expressed are immaterial for this purpose.]
From Table 3, it can be seen that the
CHBMI-cured material had superior impact strength, with the other properties being as good or better than those of the coating containing the commercial crosslinker at a much higher concentration.
Example 5 - Curing Properties of DIBK (Di-Isobutyl Ketoxime) Blocked CHBMI at Different Temperatures
As shown below in Tables 4 and 5, when used in a powder coating with hydroxylated polyester resin having a Hydroxyl Number of 59, DIBK blocked
CHBMI (Column C) produced a finished coating having lower orange peel and higher gloss than that obtained using a commercial reduced temperature crosslinker (Column D).
Figure imgf000011_0001
From the above examples and tables it can be seen that the blocked CHBMI crosslinkers impart superior properties to the cured coatings in many important areas such as gloss, impact strength and surface appearance. As will be appreciated, these properties are of major importance for commercial coating formulations.

Claims

1. Compounds having the formulae
Figure imgf000013_0004
wherein A is selected from
Figure imgf000013_0003
R is O to three of the same or different substituents selected from alkyl, -NR1R2, -NO2, halogen, alkoxy, aryl, alkaryl and cycloalkyl; R1 and R2 are alkyl, wherein each of the aforesaid alkyl moieties of R, R1 and R2 contains from 1 to 10 carbons and is straight or branched; R3 is alkylene of from 2 to 8 carbons; X is selected from alkyl, aryl and cycloalkyl; and n is 2, 3 or 4.
2. Compounds according to Claim 1 wherein A is
Figure imgf000013_0001
3. Compounds according to Claim 1 wherein A is
Figure imgf000013_0002
4. Compounds according to Claim 1 wherein A is
Figure imgf000014_0002
5. Compounds according to Claim 1 wherein A is
Figure imgf000014_0001
6. A method of curing hydroxylated polymeric material comprising mixing therewith a compound as claimed in Claim 1 in a concentration sufficient to react with a substantial number of hydroxyl groups of the polymer, and thereafter heating the mixture to cause such reaction to take place.
7. A method as claimed in Claim 6, wherein the polymeric material is a polyester.
8. Polymeric material which has been cured by a method as claimed in Claim 6.
PCT/GB1982/000219 1981-07-22 1982-07-22 Solid blocked cross-linking agents based on |,4-cyclohexane bis(methylisocyanate) Ceased WO1983000328A1 (en)

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US4442270A (en) * 1981-06-29 1984-04-10 Eastman Kodak Company Thermosetting powder coating compositions
DE3337394A1 (en) * 1983-10-14 1985-05-02 Herberts Gmbh, 5600 Wuppertal STONE SCRAP PROTECTIVE LACQUER, METHOD FOR THE PRODUCTION AND USE THEREOF
DE3337395A1 (en) * 1983-10-14 1985-05-02 Herberts Gmbh, 5600 Wuppertal NON-AQUEOUS VARNISH WITH HIGH STONE IMPACT PROTECTION, METHOD FOR THE PRODUCTION AND USE THEREOF
DE4240330A1 (en) * 1992-12-01 1994-06-09 Bayer Ag Polyisocyanate mixtures, a process for their preparation and their use
DE4327573A1 (en) * 1993-08-17 1995-02-23 Bayer Ag Uretdione powder coating crosslinker with low melt viscosity
DE19500403A1 (en) * 1995-01-09 1996-07-11 Bayer Ag Dimer diol modified uretdione powder coating crosslinkers
DE19604581A1 (en) 1996-02-08 1997-08-14 Bayer Ag Polyurethane powder matt lacquers
US6291624B1 (en) * 1996-07-30 2001-09-18 Rhodia Chimie Composition which is useful for obtaining a matt or satin coating, use of this composition and coating thus obtained
WO1999005194A1 (en) 1997-07-22 1999-02-04 Basf Coatings Ag Coating agent and method for producing same
US6248843B1 (en) 1998-09-18 2001-06-19 Mcwhorter Technologies, Inc. Powder coatings based on branched oligoesters and triazole blocked polyisocyanates
US6255523B1 (en) * 1998-09-18 2001-07-03 Mcwhorter Technologies, Inc. Power coatings based on branched oligoesters and non-emissive uretdione polyisocyanates
DE19855152C2 (en) * 1998-11-30 2001-02-01 Basf Coatings Ag Coating agent and process for its production
US6762272B1 (en) 2000-02-03 2004-07-13 Rhodia Chimie Compositions useful for obtaining high gloss coatings, methods of using such compositions and coatings thus obtained
PL238230B1 (en) 2016-09-20 2021-07-26 Politechnika Rzeszowska Im Ignacego Lukasiewicza Blocked polyisocyanates, method of their production and applications
CN110582524B (en) * 2017-05-11 2022-03-29 三井化学株式会社 Polyurethane resin, method for producing polyurethane resin, and molded article

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EP0031730A2 (en) * 1979-12-28 1981-07-08 Teijin Limited The improved semipermeable composite membranes and process for their production

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Title
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