JPH0255715A - Storage-stable, hydraulic, one-pack oxazolidine-isocyanate composition - Google Patents

Abstract

PURPOSE: To obtain a one-liquid type composition excellent in storage stability and hydraulic property which is useful as adhesive, coating material or sealant by blending a urethane oxazolidine and an aromatic multifunctional isocyanate.

CONSTITUTION: This one-liquid type composition contains a urethane oxazolidine and an aromatic multifunctional isocyanate or isocyanate prepolymer. The urethane oxazolidine compound has a structural formula represented by the formula. In the formula, R₁ is a 2-6C aliphatic hydrocarbon group; R₂, R₃ are each H, a 1-4C aliphatic hydrocarbon group, a 5-7C alicyclic hydrocarbon group or a 6-10C aromatic hydrocarbon group, or they can form a 5-membered ring together with cyclic carbon atom; R₄ is a 2-6C aliphatic hydrocarbon; R₅ is an organic isocyanate; and (n) is 1-6, preferably 2 or 3. As the urethane oxazolidine, urethane bisoxazolidine is preferably used.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to one-part, storage-stable, moisture-curable adhesive, coating and sealant compositions containing defined oxazolidines and polyfunctional aromatic isocyanates.

BACKGROUND OF THE INVENTION Moisture-curable, isocyanate-terminated urethane prepolymers have long been used in the formulation of adhesives, coatings, and sealant products. The reaction of such formulations with atmospheric moisture is often catalyzed by the addition of t-amines or tin salts to increase the rate of cure. A byproduct of this reaction is carbon dioxide, which when generated in sufficient quantities creates voids in the cured polymer. One way to overcome this problem has been to utilize oxazolidine compounds as curing agents or coreactants. (Example sentence +, fU,
S, P, ni3,661,923.3,743°62
See 6.4,138.545 and 4,002°601. ) The use of oxazolidine compounds in one-component, moisture-curable urethane compositions has generally been limited to systems using aliphatic isocyanates.

(For example, U, S, P, 3,912,691.4,02
4.117.4, 381.388 and 4,417.1
See 02. ) It has been taught in the art that systems containing aromatic polyisocyanates have a very short shelf life.

(For example, U, S, P, Nfi4, 118.

See 376. ) Avoid using blends of aromatic isocyanates and oxazolidines.''
JTechnolog V, ±day, 65. 1977 [Unattractive when long service life of blends is required] and Preprints ofl
) vision of Organic Coati
ngs and plastics.

167th Heetino or America
n Chemical Society, April 1974, p. 739, it is stated that ``only 1 to 2 days of service life are obtained.''

A shelf life or shelf life of 6 months or more is desirable and compositions having such a shelf life are considered shelf stable. The use of aliphatic isocyanates to achieve such storage stability is undesirable because it slows down the curing time and is significantly more expensive.

Therefore, storage stability utilizing aromatic isocyanates,
It is desirable to provide a moisture curable composition.

SUMMARY OF THE INVENTION It has surprisingly been found that aromatic isocyanate compounds can be used in combination with certain oxazolidine compounds to produce storage-stable, water-curable, one-component compositions useful as adhesives, coatings or sealants. discovered. The storage stable, water curable, corrugated composition ball of the present invention is comprised of a urethane oxazolidine and an aromatic polyfunctional isocyanate. The urethane oxasilidine is preferably a urethane bisoxazolidine.

DETAILED DESCRIPTION OF THE INVENTION The urethane oxazolidine compounds of the invention are any organic compounds having at least one, preferably 2 or 3, groups of the formula: (wherein R1 is 2 to 6, preferably 2 or represents an aliphatic hydrocarbon group having 3 carbon atoms; R and R3 may be the same or different; and hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, 5 to 7 R2 and R3 are preferably are the same or different groups and are hydrogen or an aliphatic hydrocarbon group having 1 to 4 carbon atoms: R4 represents an aliphatic hydrocarbon group having 2 to 6 carbon atoms; R5 is represents a group obtained by removing an isocyanate group from an organic isocyanate, preferably a di- or tri-isocyanate; and n represents an integer from 1 to 6, preferably 2 or 3).

Such oxazolidines are, for example, tl, s, P, 1
llI14.

002.601, in which numerous examples are given.

Ring opening by hydrolysis of these oxazolidines produces one hydroxyl group and one secondary amine group per oxazolidine ring, and even oxazolidines with only one oxazolidine ring can be converted into isocyanates by reaction with water. For the purposes of the addition reaction, it is converted into a compound that is difunctional. However, in order to obtain a relatively large crosslink density in the final cured product, certain N, N'
Preference is given to using urethane oxazolidines containing two oxazolidine rings (hisoxazolidine), such as bis-[(2-isopropyl-1,3-oxazolidin-3-yl)ethoxycarbonyl]-1°6-diamithexane. .

Suitable commercially available hisoxazolidines include:
The aliphatic poly(amino alcohol) based [Hard
ner OZ J.

The free acid promotes early opening of the oxazolidine ring, but
It is theorized that these oxazolidines can impart the desired shelf life because they are non-acidic.

Any organic aromatic polyisocyanate can be used for the preparation of the prepolymer, examples of these include diphenylmethane-2,4'-diisocyanate and/or -4,4'-diisocyanate; tolylene-2,4
Isocyanate groups such as -diisocyanate and -2,6-diisocyanate and mixtures of these isomers may be mentioned by way of example. Other examples include dinaphthalein-
1゜5-diisocyanate; triphenylmethane-4゜4',4''-triisocyanate; phenylene-1,3
-diisocyanate and phenylene-1°4-diisocyanate; dimethyl-3,3'-biphenylene-4,
4'-Diisocyanate: Includes diphenyl isopropyridine-4,4'-diisocyanate; biphenylene diisocyanate; xylene-1,3-diisocyanate and xylene-1,4-diisocyanate.

A list of useful commercially available polyisocyanates can be found in the Encyclopedia of Chemica.
Technology J, 1rk-Othll
er, 2nd edition, Volume 12, pp. 46-47, Inter
Science Pub, N. Y. (1967). Preferred isocyanates include diphenylmethane-4,4'-diisocyanate (MDI) and tolylene-2,4-diisocyanate/tolylene-2
, 6-diisocyanate (TDI>) and mixtures of these isomers.

Liquid mixtures of isocyanate-functional derivatives of MDI and TDI and melting point modifiers <MDI and polycarboimide adducts such as 15onate 143LJ, commercially available from UpjOhn, and Honda CDJ, commercially available from Hobay Chemical. ): high molecular weight diphenylmethane diisocyanates (e.g. commercially available from Llpjohn, rPAPIJ and IPAP (204-
IPAPI 901J series, Hobay Ch
"Hondu" which is commercially available from emica1 company.
r HRJ (“Hondur HR3J and [Ho
ndur HRS-10J, and Rubicon
l'R, commercially available from Chemicals
ubinate HJ; and proketoisocyanate compounds formed by reaction of aromatic isocyanates or isocyanate-functional derivatives described above with blocking agents such as ketooximes. Such blocked isocyanate compounds are conveniently referred to herein as isocyanate-functional derivatives of MDI or TDI.

Polyols suitable for use in the present invention include polytetramethylene oxide glycols, ethylene oxide terminated polypropylene oxide polyols, polypropylene oxide polyols, Ll, S, P, N (as described in 14, 511, 626); Polyethylene oxide polyols, hydroxy-terminated polybutadiene, aliphatic glycols, polyester polyols (
Examples include polyacrylate polyols or polyester polyols), fatty alcohols, and triglycerides (eg, mustard oil). Mixtures of polyols can also be used.

Because of their hydrolytic stability in the cured compositions of the present invention, preferred classes of polyols include polypropylene oxide polyols, ethylene oxide-terminated polypropylene oxide polyols and polytetramethylene oxide glycols, especially about 500-600
It has a number average molecular weight of 0. Suitable commercially available polytetramethylene oxide glycols include commercially available polytetramethylene oxide glycols [QOPolyme (l j 650.100
0 or 2000 series and E, 1. du pon
Terathane J65, commercially available from Ne1O1lrS & Co, Inc.
0.1000 or 2000 series. suitable,
Commercially available polypropylene oxide polyols include N1axJ Series IPPGJ, [LH
Includes TJ and [LHGJ. Ethylene oxide end group polypropylene oxide polyol is 0li
n Commercially available from CheliCalS.
This is the Po1y GJ series.

The oxazolidine:isocyanate equivalence should preferably be from about 0.1 to about 1.2:1.0. Decreasing the amount of oxazolidine reduces the carbon dioxide suppression effect, while increasing its amount results in an excess of unreacted oxazolidine, all of which are undesirable characteristics such as reduced strength of the cured composition, excessive tackiness. and rubbery cysts.

The compositions of the invention can contain other ingredients or adjuvants if desired. For example, extenders or reinforcing fillers (e.g. carbon black, metal oxides such as zinc oxide, and inorganics such as talc, clays, silicas, silicates, etc.) can be included to impart special characteristics to the composition. can.

Partially hydrogenated terphenyls such as Hon5an
rHB-40, commercially available from Hob.
Plasticizers such as dioctyl phthalate, dibutyl phthalate, diisodecyl phthalate or tricresyl phosphate, commercially available from the company Ay Che++1ca1, can also be used in the compositions of the invention.

Toluene, xylene, methyl ethyl ketone, acetone,
Other suitable materials free of solvent and isocyanate-reactive moieties such as ethyl acetate, mineral sulfur and VM and P naphtha may also be used in the compositions of the present invention.

In addition, the compositions contain antioxidants, pigments, UV absorbers, adhesion promoters (silanes such as mercaptosilanes or aminosilanes or tackifying resins such as terpene phenolic resins), desiccants (such as sodium molecular sieves such as aluminum silicates and desiccants such as zeolites).

The prepolymers of the present invention can be made using conventional methods. Typically, these can be made by reacting an excess of one or more polyisocyanates with one or more polyols to form a prepolymer with residual isocyanate functionality.

The compositions of the present invention when properly formulated have utility as adhesives, coatings and sealants, and can be applied to glass, metals, plastics, wood, leather, masonry (Ha
It can be applied to various articles and substrates, such as articles (sonary), woven or knitted fabrics, or base materials. They find particular utility where low shrinkage, void-free compositions are required, such as in concrete joints for sealing.

The invention is further illustrated by the following non-limiting examples, in which all parts are by weight unless otherwise specified.

Large] 16.49 parts (11 parts) (16.49 parts)
13,2 NGO equivalents) flaked MDI, 21.06
parts (1,008 equivalents) of polypropylene oxide polyol (1”N1axLHT-28J, Union
The compositions of the present invention were prepared by adding the following: Stirring was started and the mixture was heated to 60°C. Then 52.45 parts (5,20H equivalent) of polytetramethylene ether glycol, MW200
0(rPoly*eg 2000J Quaker 0
ATS) and 10.0 parts of partially hydrogenated terphenyl (rHB-40J Hon5anto) were added.

The mixture was held at 60°C for 3 hours, then allowed to cool to about 55°C and stored in a tight container.

50 parts of fumed silica (rCab-0-3il) was added to 535 parts of this prepolymer under nitrogen and with stirring.
TS-720J Cabot), 40 parts titanium dioxide, 160 parts talc ([Histron RC3J
, Cyprus Industrial Minera
ls), 7.5 parts of γ-mercaptopropyl trimethoxysilane (r 5ilane A-189J Ll
nion Carbide), 100 parts of alkyl sulfonic acid ester of phenol (1°
all J Hobay Chea+1ca1 company), 4
7.3 parts of urethane gas oxazolidine ([Hardn
erOZJ (Hobay Chemica 1) and 20 parts of toluene, the 6iR product was transferred to a conventional plastic caulking cartridge. The sealant could be dispensed using a manual caulking gun, and the composition maintained a caulkable viscosity for more than 6 months when stored at about 25°C in a plastic container.

Example 2 A reaction vessel equipped with a nitrogen inlet, a stirrer and a thermometer was
10.72 parts (19.7 NGO equivalents) of tolylene-2
,4-diisocyanate and tolylene-2,6-diisocyanate and 9.99 parts of toluene, 21.03 parts (3,30H equivalent) of polypropylene oxide glycol, MW 2000, (r N1
axho +) All P PG -2025J Unio
n Carbile) and 58.19 parts <6.60
8 equivalents) of polypropylene oxide polyol (r
N1ax LHT-42Jtlnion Carbi
de) was added with stirring. The reaction mixture was gradually heated to 80°C, held at the same temperature for about 3 hours, and then allowed to cool to about 52°C. Next, add 0.07 parts of dibutyltin dilaurate and mix and cool for about 1
It lasted for hours.

The resulting prepolymer was stored in a self-closed container.

Under nitrogen and with stirring, this prepolymer 45.
6 parts, 2.7 parts titanium dioxide: 2.7 parts zinc oxide; 20.7 parts talc; 0.06 parts carbon black (Raven 410Jc; ttes 5ervic
Company e); 8.3 parts of terpene phenolic resin (Pic
cofyn A-135, Hercules);1.
9 parts of fumed silica: 2. O part urethane bisoxazolidine; 1.1 parts silane-containing primer [161
(biuret of hexamethylene diisocyanate (l)
r Desw+odur N-75JHobay Ch
emica 1), 427 g of silane and 1.3 g of dimethylpiperazine were prepared by stirring at 80° C. for 2 hours in a 31 four-way resin flask equipped with a mechanical stirrer, reflux condenser, and nitrogen inlet. ] and 15.2 parts of 1-methoxy-2-acetoxypropane were added.

This composition was applied to concrete as a sealant. This composition is set at 15 1/23x of concrete.
5 1/2 aRX 1.51 between blocks of 5cIa
poured into the gap. The composition was cured at 25°C, 50% R,H for 7 days and then at 49°C for 2 days. The cured sealant was relatively void-free when cut and inspected.

Example 3 and Comparative Examples 1-3 These examples demonstrate the storage stability of compositions of the present invention utilizing urethane bisoxazolidines and the storage stability of the same prepolymers using conventional urethane catalysts such as amines and tin salts. Explain stability.

Four single wave moisture curable compositions were prepared and evaluated using the prepolymer of Example 1. Example 3 used 8.54 parts of Hardner OZJ. Comparative Example 1 used 0.2 parts of 1-Niax A-99J (a tertiary amine catalyst, commercially available from Union Carbide). ). In Comparative Examples 2 and 3, 0.8 parts and 0.1 parts of diptyltin dilaurate (DBTDL) were added, respectively. Tables 1 to 4 below show the Figure 3 shows viscosity measurements after exposing the container to various temperatures.

Centipoise (cps) was measured on a Brookfield RVF viscometer using a #6 spindle and a speed of 4 RPH with a sample temperature of approximately 23°C.

Example 3 = Prepolymer + 8.54 parts Hardner
Ol Comparative Example 1 = 0.2 parts of prepolymer 1,000 NIAX ^-99 Comparative Example 2 = Prepolymer + 0.8 parts DBTDL Comparative Example 3 = Prepolymer + 0.1 parts DBTDL Table 1 - Viscosity at 24°C (C1lS ) Example 3 so oo.

Comparative example 1 Comparative example 2 so　oooo　　so　oo.

50000 9B 250 53.750 375000 57500 >500000 67,500 gelled Comparative example 3 50,000 So　oo.

52,500 53,750 57.500 Table 3 - Viscosity at 49°C (cps) Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 348.750
50,000 50,000 50,0001
12.000 75,000 Gelled 100.
000193.750 375,000 1
85,000235000 >500000
250000290,000 Gelled -
->500.000 - Gelled Table 2 - Viscosity at 38°C (CDS) Example 3 Comparative Example 1 48.750 50,000 56.250 56,250 61.250 61,250 62.500 62500 78.750 72,500 88.750 77.500 85.000 87,500 98.750 102,500 122.500 136,250 310.000 >500,000 Comparative Example 2 so, oo.

>500.000 Gelled Comparative Example 3 50.000 55.000 82.500 107, 500 470.000 Table 4 -60℃ degrees (C3) Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 348, γ5 (
] 50,000 50,000 50000
82.500 72,500 Gelled 88.
750210.000 131,250 1
81250375,000 Gelled -390
,000>500,000 ->
500,000 Gelled -- The gelled composition of the invention, Example 3, performed better or equal to Comparative Examples 1-3 at all temperatures tested. Additionally, all of Comparative Examples 1-3 produced undesirable CO2 that precluded void-free coatings.

Comparative Example 4 This comparative example illustrates the reduced storage stability of a composition using an adipate-based bisoxazolidine.

The prepolymer of Example 1 and 6.83 parts (1 equivalent) of adipate-based suoxazolidine (rQM-100
Moisture curable compositions were prepared and evaluated as in Example 3 using a moisture curable composition (commercially available from Rohm & Haas, Inc.).

Viscosity measurements are shown in Table 5 below.

First 24 hours 1 week 2 weeks 3 weeks 4 weeks 5 weeks 6 times 7 weeks 11 weeks 24°C 82.500 98.750 123.750 112.500 135.000 140.000 Table 5 - Viscosity 38°C degrees (cps) 49°C 60°C 131.250 158,750 132.500 315,000 178.750 >500.000 265.000 Gelled >500000 Gelled This seems to support the theory of decreasing stability.

Claims (8)

[Claims] (1) A storage-stable, water-curable, one-component composition comprising a urethane oxazolidine and an aromatic polyfunctional isocyanate or an isocyanate prepolymer. (2) The above urethane oxazolidine has a structural formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an aliphatic hydrocarbon group having 2 to 6, preferably 2 or 3 carbon atoms; R_2 and R_3 may be the same or different, hydrogen, aliphatic hydrocarbon group having 1 to 4 carbon atoms, 5 to
represents an alicyclic hydrocarbon group having 7 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, or can represent a five-membered ring together with the ring carbon atoms, R_2 and R_3 Preferably they are the same or different groups and are hydrogen or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R_4 represents an aliphatic hydrocarbon group having 2 to 6 carbon atoms; R_5 is 2. A composition according to claim 1, wherein n represents a group obtained by removing an isocyanate group from an organic isocyanate, preferably a di- or tri-isocyanate; n represents an integer from 1 to 6, preferably 2 or 3. thing. (3) The composition according to claim 1, wherein the urethane oxazolidine is urethane bisoxazolidine. 4. The composition of claim 1, wherein the oxazolidine to isocyanate equivalent is between about 0.1 and 1.2:1.0. 5. The composition of claim 4, wherein the oxazolidine to isocyanate equivalent is between about 0.25 and 1.0:1.0. (6) A polyurethane material formed by contacting the composition of claim 1 with water. (7) The high molecular weight urethane material according to claim 6, wherein said oxazolidine is bisoxazolidine. (8) A product characterized in that it consists of a support having, at least in part, a coating of the polyurethane material of claim 6.