JPH08169931A - Polyisocyanate composition - Google Patents

Abstract

PURPOSE: To obtain a polyisocyanate compsn. excellent in reactivity and storage stability by reacting a specific methylene-crosslinked polyphenyl polyisocyanate with an alkanolamine-based polyol. CONSTITUTION: A methylene-bridged polyphenyl polyisocyanate contg. 20-60wt.% diphenylmethane diisocyanate is reacted with a polyol obtd. by the addition reaction of propylene oxide and/or ethylene oxide with an alkanolamine and having an OH value of 20-800mgKOH/g, pref. 100-650mgKOH/g, in an equivalent ratio of NCO group to OH group of 10-200, pref. 50-150. Pref. examples of the alkanolamine are N-methyldiethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, and a mixture of at least two of these amines.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can be handled in the same manner as methylene-crosslinked polyphenyl polyisocyanate (hereinafter referred to as "polymeric MDI"), which is widely known as a polyurethane raw material used for adhesives, paints, binders, etc. The present invention relates to a polyisocyanate composition having improved reactivity and excellent storage stability.

[0002]

2. Description of the Related Art Polymeric MDI which is a raw material for producing polyurethane such as adhesives, paints and binders.
It is well known that an acidic substance contained therein affects its reactivity. Therefore, the acidity is an important index regarding the quality of the polymeric MDI, and various treatment methods for reducing the acidity in the polymeric MDI have been proposed. For example, Japanese Patent Publication No. 55-22473 proposes a method using an epoxy compound.
However, in this patent, satisfactory reactivity is not obtained, and there is a problem in storage stability (viscosity increase with time).

In order to improve the reactivity, N, N,
N ', N'-tetramethylhexamethylenediamine,
N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, N, N '
Dimethylcyclohexylamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, N-
A catalyst such as ethylmorpholine or triethylenediamine may be added, but when these are added to the polymeric MDI, the reactivity is good, but the storage stability is poor,
There are drawbacks such as thickening with time and gelation when heated or stored for a long time.

Further, aliphatic amines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-diaminobutane, o-phenylenediamine, m-phenylenediamine, p-phenylene. Aromatic amines such as diamine, tolylenediamine, triaminobenzene, 4,4'diaminodiphenylmethane, 4,4'diaminodiphenylsulfone, alkanolamines such as triethanolamine, triisopropanolamine, tributanolamine, etc. can be added to polymeric MDI. When reacted with, the reactivity is good,
Insoluble matter is produced.

In order to suppress the formation of insoluble matter, aliphatic amines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, or o-phenylenediamine,
A polyol prepared by adding propylene oxide and / or ethylene oxide to an aromatic amine such as m-phenylenediamine, tolylenediamine, triaminobenzene, 4,4'diaminodiphenylmethane is a polymer M.
When reacted with DI, the resulting polyisocyanate composition has improved reactivity and no formation of insolubles, but is highly viscous and thickens or gels upon heating or long-term storage.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a modified polymer MDI (polyisocyanate composition) having storage stability equivalent to that of general polymer MDI and improved reactivity. That is.

[0007]

The inventors of the present invention arrived at the present invention as a result of various studies to solve such problems. That is, in the present invention, a polymeric MDI containing diphenylmethane diisocyanate (hereinafter referred to as MDI) in an amount of 20 to 60% by weight and a polyol obtained by adding propylene oxide and / or ethylene oxide to alkanolamine are used in an equivalent ratio of NCO groups and OH groups. 10
To a polyisocyanate composition obtained by reacting at about 200.

Polymeric MDI used in the present invention
Contains 20 to 60% by weight of MDI. MD
If the content of I is less than 20% by weight, the viscosity of the polyisocyanate compound will be high, and if it exceeds 60% by weight, MDI will precipitate during storage at low temperatures, making handling difficult. Polymeric MDI containing 20 to 60% by weight of MDI in which a part of the isocyanate groups is urethane-modified, carbodiimide-modified or isocyanurate-modified can also be used.

Alkanolamines used in the present invention include N-methyldiethanolamine, diethanolamine, triethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, diisopropanolamine, triisopropanolamine, N-methyl. Examples thereof include butanolamine, N-ethyldibutanolamine, dibutanolamine, tributanolamine and the like. The alkanolamine is preferably one or more alkanolamines selected from N-methyldiethanolamine, diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine.

The polyol used in the present invention has an OH value of 20 mgKOH / g or more, 800 mgKOH / g, preferably 100 mgKOH / g or more, 650 mgKOH / g.
g of polyol. When a polyol having an OH value of 20 mgKOH / g or less is used, the reactivity is not improved. When a polyol having an OH value of 800 mgKOH / g or more is used, the reactivity is improved, but the polyisocyanate composition has Insoluble matter is produced.

In the present invention, the ratio of the polymeric MDI to the polyol is such that the equivalent ratio of the NCO group of the polymeric MDI to the OH group of the polyol is 10 to 200, preferably 5
Reacts from 0 to 150. Equivalent ratio of NCO group and OH group is 1
When it is 0 or less, the viscosity of the isocyanate composition becomes high, and the apparent isocyanate group content in the isocyanate composition decreases, so that the polyurethane manufacturer is restricted in use. If the equivalent ratio of NCO group to OH group is 200 or more, the reactivity is not improved.

The polyisocyanate composition of the present invention can be produced by adding the above-mentioned polymeric MDI to a nitrogen gas atmosphere,
0.5-2 at 40-120 ° C by adding polyol in the previous period
It can be easily obtained by reacting for 4 hours, preferably 1 to 4 hours at 50 to 80 ° C., and then cooling to room temperature.

[0013]

EXAMPLES The present invention will now be described with reference to Examples and Comparative Examples in order to more specifically describe the present invention, but the present invention is not limited to these Examples.

The methods for measuring the viscosity and the isocyanate group content of the polymeric MDI and the isocyanate composition are in accordance with JIS standard K1603. Method for evaluating reactivity Polyisocyanate composition 4 in 200 cc poly cup
0 g, methylene chloride 10 g, and benzylated phenol resin 50 g were inserted, and after stirring and mixing for 1 minute, the mixture was allowed to stand, and the cured state of the mixture was judged by the stickiness of the surface,
The shorter the time from the start of mixing to the time when tackiness disappears (tack free time), the better the reactivity is judged to be. In this test, the liquid temperature and temperature of each raw material before mixing are 23 ± 1 ° C. Storage stability evaluation method Insert 180 g of the polyisocyanate composition into a 200 cc glass bottle with a stopper, measure the content of isocyanate group (NCO group) and the viscosity after storage in a high temperature tank at 60 ° C. for 2 weeks after sealing. However, it is judged that the smaller the rate of change, the better the storage stability.

Raw materials used Cosmonate M-50: Polymeric MDI manufactured by Mitsui Toatsu Chemicals Inc. NCO group content 31.8% Viscosity 85 cps / 25 ° C. MDI content 53% Cosmonate M-200: Polymeric manufactured by Mitsui Toatsu Chemicals MDI NCO group content 31.3% Viscosity 190 cps / 25 ° C MDI content 42% Cosmonate M-700: Mitsui Toatsu Chemical Co., Ltd. Polymeric MDI NCO group content 30.6% Viscosity 750 cps / 25 ° C MDI content 35 % Cosmonate LK: Carbodiimide-modified MDI NCO group content of Mitsui Toatsu Chemicals, Inc. 28.3% Viscosity 75 cps / 25 ° C. MDI content 70%

Epiol P: Phenylglycidyl ether manufactured by NOF Corporation 155 Epoxy equivalent 155 triethanolamine: Wako Pure Chemical Industries, Ltd. Purity 99% OH value 1122 mgKOH / g Ethylenediamine: Wako Pure Chemical Industries, Ltd. Purity 99% OH value 3740 mgKOH / g

Polyol A: PO of triethanolamine
Addition polyol OH number 550mgKOH / g Viscosity 430cps / 25 ° C Polyol B: Triethanolamine PO
Addition polyol OH value 350 mg KOH / g Viscosity 280 cps / 25 ° C Polyol C: Diethanolamine PO addition polyol OH value 112 mgKOH / g Viscosity 300 cps / 25 ° C Polyol D: Ethylenediamine PO addition polyol OH value 760 mgKOH / g Viscosity 49000 cps / 25 ° C Polyol E : PO of m-tolylenediamine
Addition polyol OH value 490mgKOH / g Viscosity 500000cps / 25 ℃

Example 1 A reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 1000 g of Cosmonate M-50 was charged, and the polyol B1 was added thereto.
0 g was added at room temperature with stirring under a nitrogen gas atmosphere,
After mixing and stirring for 10 minutes, heat up to 80 ° C in 30 minutes,
After reacting for 3 hours at room temperature, it was cooled to room temperature to obtain a polyisocyanate composition. The polyisocyanate compound obtained is
NCO group content: 31.1%, viscosity: 105 cps / 25 ° C,
Reactivity (tack free time): 6 minutes. In addition, the properties of this polyisocyanate compound after being left for 2 weeks in a constant temperature bath at 60 ° C. are as follows: NCO group content: 31.0
%, The viscosity was 120 cps / 25 ° C., and showed excellent storage stability.

Examples 2-3 As Cosmonate M-200 as a polymeric MDI,
A polyisocyanate composition was obtained in the same manner as in Example 1 except that Cosmonate M-700 was used.
The properties of the obtained polyisocyanate composition are shown in Table 1.

Example 4 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 800 g of Cosmonate M-200 and 200 g of Cosmonate LK were used as the polymeric MDI. The properties of the obtained polyisocyanate composition are shown in Table 1.

Examples 5 to 6 Polyisocyanate compositions were obtained in the same manner as in Example 1, except that the amounts of the polyol B added were 30 g and 50 g, respectively. The properties of the obtained polyisocyanate composition are shown in Table 1.

Example 7 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 30 g of polyol C was added instead of polyol B. The properties of the obtained polyisocyanate composition are shown in Table 1.

Example 8 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 10 g of Polyol A was added instead of Polyol B. The properties of the obtained polyisocyanate composition are shown in Table 1.

Comparative Example 1 Cosmonate M-20 as a general-purpose polymer MDI
The properties of No. 0 are shown in Table 2. Comparative Examples 2-3 The same operation as in Example 1 was performed except that 10 g of polyol D and polyol E were added instead of polyol B,
A polyisocyanate composition was obtained. Table 2 shows the properties of the obtained polyisocyanate composition.

Comparative Example 4 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 5 g of triethanolamine was added instead of the polyol B. Table 2 shows the properties of the obtained polyisocyanate composition. Comparative Example 5 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 2 g of ethylenediamine was added instead of the polyol B. Table 2 shows the properties of the obtained polyisocyanate composition. Comparative Example 6 A polyisocyanate composition was obtained in the same manner as in Example 1 except that 5 g of Epiol P was added instead of the polyol B. Table 2 shows the properties of the obtained polyisocyanate composition.

[0026]

[Table 1]

[0027]

[Table 2]

Unlike the comparative examples, the polyisocyanate compositions obtained in Examples 1 to 7 were brown transparent liquids, and no insoluble matter was formed. Also, 60
The NCO content and the viscosity after 2 weeks at C did not change much compared with the values immediately after the production, and the storage stability was good as compared with the case of the comparative example. The tack free time of Cosmonate M-200, which is a general-purpose polymeric MDI shown in Comparative Example 1, is 180 minutes, whereas the polyisocyanate compositions obtained in Examples 1 to 7 all have a tack free time of 1. Very short (up to 6 minutes) and excellent in reactivity.

[0029]

EFFECT OF THE INVENTION The isocyanate composition of the present invention has an excellent reactivity as compared with the conventional polymeric MDI and does not affect the storage stability.
It is extremely useful as a raw material for polyurethane production.

Claims (4)

[Claims] 1. A diphenylmethane diisocyanate containing 2
The equivalent ratio of NCO group and OH group is methylene-bridged polyphenyl polyisocyanate containing 0 to 60% by weight and a polyol having an OH value of 20 to 800 mgKOH / g obtained by adding propylene oxide and / or ethylene oxide to an alkanolamine. A polyisocyanate composition obtained by reacting at 10 to 200. 2. The polyisocyanate composition according to claim 1, wherein the alkanolamine is one or a mixture of two or more selected from N-methyldiethanolamine, diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine. 3. The OH number of the polyol is 100 to 650 m.
The polyisocyanate composition according to claim 1, which is gKOH / g. 4. The equivalent ratio of NCO groups to OH groups is 50 to 15.
The polyisocyanate composition according to claim 1, which is 0.