JPH06184070A - Alicyclic enamine derivative and moisture curable polyurethane composition comprising the same - Google Patents

Abstract

PURPOSE:To obtain a new compound, capable of producing a secondary diamine by hydrolysis and useful as a curing agent in providing an epoxy resin and an urethane resin. CONSTITUTION:The compound of the formula [A is 1-22C secondary diamine residue; (CR2)n is aliphatic ring; R is H or 1-6C hydrocarbon; (n) is 2-4; E is electrophilic compound residue; B is 1-6C alkyl or E], e.g. 1,4-bis(1-cyclohexyl-2- oyl-N,N'-diphenylurea)piperazine. The compound of the formula is obtained by reacting a secondary amine with an alicyclic ketone compound and then reacting the resultant condensate with an electrophilic compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel substance which produces a secondary diamine by hydrolysis, an alicyclic enamine derivative,
The present invention relates to a moisture-curable polyurethane composition and its use.
The compound that produces a secondary diamine by hydrolysis is
It is a compound useful as a curing agent when obtaining an epoxy resin or a urethane resin.

The present invention relates to an alicyclic enamine derivative and a moisture-curable polyurethane composition utilizing a reaction of hydrolyzing an alicyclic enamine derivative with moisture in the air to produce a secondary diamine.

Furthermore, the present invention relates to a moisture-curable polyurethane composition which is useful for industrial purposes as a sealing material for construction or vehicles, a wall material, a waterproof material, a paint or an adhesive, and its use.

[0004]

2. Description of the Related Art Polyurethane resins are excellent in various properties such as rubber elasticity, abrasion resistance, and durability, and are used as sealing materials, wall materials, waterproof materials, paints, or adhesives.

These polyurethane resins include a one-pack type in which a polyurethane prepolymer having a terminal isocyanate group is cured by water in the atmosphere after application, and a curing agent containing a main agent containing a polyurethane prepolymer having a terminal isocyanate group and a polyol chain. Are roughly classified into a two-component type which is mixed and hardened at the time of construction.

[0006] One-component polyurethane can be used by anyone because of its simple construction method, and has recently been particularly noticed. This one-component polyurethane is called moisture-curable polyurethane, and the following method is known.

(1) Moisture of polyisocyanate
Moisture-curing polyurethane composition utilizing reaction of reaction with, that is, decarboxylation gas of an adduct of isocyanate and water, part of polyisocyanate becomes amine, and generated amine reacts with remaining polyisocyanate and cures (2) Moisture curable composition comprising polyketimine and polyisocyanate (UK Patent No. 1064841
No.), (3) Moisture-curable polyurethane composition comprising polyenamine and isocyanate (JP-A-57-1612).
6), (4) β-amino-β-lactam derivative obtained by reacting enamine with isocyanate is moisture (water).
There is a moisture-curable polyurethane composition (Japanese Unexamined Patent Publication (Kokai) No. 2-168) which utilizes a reaction of the reaction with amine, that is, an amine and an isocyanate residue aldehyde are formed, and the generated amine reacts with polyisocyanate to cure.

However, the composition (1) has a relatively good storage stability in a closed container, but has a drawback that it has a markedly poor curability and foams. An amine catalyst can be used to improve the curability, but it is not suitable for practical use because storage stability is deteriorated and foaming is severe.

In the composition (2), polyketimine reacts with polyisocyanate, and therefore, when used as a moisture-curable polyurethane composition, it is necessary to block isocyanate groups. Further, the blocked polyisocyanate and polyketimine system is characterized by no foaming, but the curability is remarkably slow and is not suitable for practical use.

Also in the composition (3), when an aromatic isocyanate is used as the polyisocyanate in order to react the polyenamine with the polyisocyanate, it is necessary to block the isocyanate group like the polyketimine, and it is practically suitable like the polyketimine. Not a thing.

On the other hand, when a polyisocyanate having a relatively low reactivity, such as an aliphatic or alicyclic polyisocyanate is used, it is known that it can be applied to a sealing material, etc. It has the feature.

However, polyenamine reacts with an aliphatic or alicyclic polyisocyanate, though very gradually, so that the storage stability is poor even if it is stored in a closed container for a long time or at a temperature slightly higher than room temperature. . In addition, there are drawbacks such that the initial physical properties are not maintained during storage, or the thickening becomes severe and the workability is significantly deteriorated.

The composition of (4) has the characteristic of being non-foaming, but since it is very sensitive to humidity and heat, its curability is extremely fast, and the amine reacts with a slight amount of moisture in the compound or at high temperature. Since it is formed and reacts with polyisocyanate, the storage stability tends to deteriorate in the closed container for a long period of time or at a temperature higher than normal temperature.

[0014]

Problems to be Solved by the Invention Overcoming various problems as described above, namely, good storage stability in a closed container, high retention rate of initial physical properties, gelation, etc. It is extremely important performance in this type of polyurethane that it has no viscosity, good viscosity stability, moderately fast curing in the atmospheric humidity, and no foaming. Determine the commercial value of. Also, high storage stability in a closed container,
In other words, there is a strong demand for a moisture-curable polyurethane composition which can be stored for a long period of time with a constant viscosity, is moderately fast in moisture, and does not foam.

[0015]

Means for Solving the Problems As a result of researching the above-mentioned problems, the present inventors have been able to develop a novel alicyclic enamine derivative which produces a secondary diamine by hydrolysis, Arrived Furthermore, by using the alicyclic enamine derivative of the present invention, the storage stability of the moisture-curable polyurethane composition is high, and the curability under moisture can be increased, and it can be developed into various applications. It has become possible.

That is, the present invention has the general formula (I)

[0017]

[Chemical 8]

[A is a branched or cyclic group having 1 to 22 carbon atoms.
It is a residue of secondary diamine, and (CR ₂)_nIs an aliphatic ring
Represent. R is a hydrogen atom or a linear or branched chain having 1 to 6 carbon atoms
Or, it is a cyclic hydrocarbon. E is a residue of an electrophilic compound
Is. B is a linear, branched or cyclic carbon atom having 1 to 6 carbon atoms.
A rukyl group or E, where n is adjacent to the 1-position and the 1-position
Represents the number of carbon atoms forming an aliphatic ring excluding
Is an integer of ~ 4. ] An alicyclic enamine derivative represented by
And the alicyclic enamine derivative and polyisocyanate
And / or isocyanate-terminated polyurethane
Moisture curable polyurethane composition comprising a prepolymer
Regarding Also, moisture-curable polyurethane composition and filler
To a moisture-curable polyurethane waterproof material.

Next, the present invention will be specifically described. The alicyclic enamine derivative of the present invention is a compound represented by the general formula (I), and specifically, 1,4-bis (1-cyclohexyl-2-oil-N, N'-diphenylurea). Piperazine, 1,4-bis (1-cyclohexyl-
2-oil-N, N'-dimethylurea) piperazine,
1,4-bis (1-cyclohexyl-2-oil-N,
N'-diethylurea) piperazine, 1,4-bis (1
-Cyclohexyl-2-oil-N, N'-dipropylurea) piperazine, 1,4-bis (1-cyclohexyl-2-oil-N, N'-dioctadecylurea) piperazine, 1,4-bis [1 -Cyclohexyl-2-oil-N, N'-di (2-ethylhexylurea)] piperazine, 1,4-bis [1-cyclohexyl-2-oil-N, N'-di (2-ethoxyethoxy) ethoxycarbonyl Amino-O-tolylurea] piperazine, and further 1,4-bis [2,6-bis (2-methoxycarbonylethyl) -1-cyclohexenyl] piperazine

[0020]

[Chemical 9]

1,4-bis [2,6-bis (2-methoxycarbonylpropyl) -1-cyclohexenyl] piperazine

[0022]

[Chemical 10]

1,4-bis [2,6-bis (2-cyanoethyl) -1-cyclohexenyl] piperazine

[0024]

[Chemical 11]

N, N'-bis [2,6-bis (2-methoxycarbonylethyl) -1-cyclohexenyl]-
N, N 'dimethylethylenediamine

[0026]

[Chemical 12]

1,3-bis {1- [2,6-bis (2-
Methoxycarbonylethyl) -1-cyclohexenyl]
Piperidin-4-yl} propane

[0028]

[Chemical 13]

1,4-bis [2- (2-methoxycarbonylethyl) -6-methyl-1-cyclohexenyl] piperazine (with 2,6-position isomers)

[0030]

[Chemical 14]

1,4-bis (2,6 diacetyl-1-cyclohexenyl) piperazine

[0032]

[Chemical 15]

And the like. The alicyclic enamine derivative of the present invention is obtained by reacting an electrophilic compound with a condensate obtained by reacting a secondary diamine and an alicyclic ketone compound.

The secondary diamine in the portion A used in the production of the alicyclic enamine derivative (I) of the present invention has 1 carbon atom.
To 22 are branched or cyclic secondary diamines, and specifically, for example, the following general formulas (II), (III) or (I
It is a compound of an aliphatic secondary diamine represented by V).

[0035]

[Chemical 16]

[0036]

[Chemical 17]

[0037]

[Chemical 18]

[0038] (wherein, R _1, R ₂ are each 1-8C alkyl carbons, cycloalkyl or aryl group, R _3,
R ₄ is a hydrogen atom or a chain, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. Also, X has 1 to 10 carbon atoms.
It is an alkylene, cycloalkylene or arylene group, G is CH or N, and when G is CH, X can be excluded. ) Suitable secondary diamines are, for example, N, N 'as secondary diamines of the type of formula (II) above.
-Dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-dicyclohexylethylenediamine, N, N'-diphenyldiamine N, N'-dimethyl-1,4-diaminocyclohexane, N, N'-diisobutyl-2,2,4- Trimethylhexamethylenediamine, N, N'-dimethyl-p-phenylenediamine and the like.

Examples of the secondary diamine of the type of the above formula (III) include 4,4'-dipiperidyl propane and 4,4 '.
-Dipiperidylethane, 4,4'-dipiperidyl, 4,
4'-dipiperazyl propane, N, N'-dipiperazyl methane and the like.

The secondary diamine of the formula (IV) type is, for example, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-cyclohexylpiperazine and the like.

The part containing (CR ₂ ) _n used in the production of the alicyclic enamine derivative (I) of the present invention is an alicyclic ketone compound. n is 2 to 4, but the case of 4 is preferable. The alicyclic ketone compound is a monoalicyclic ketone, and specifically, for example, cyclopentanone, methylcyclopentanone, dimethylcyclopentanone, cyclohexanone, methylcyclohexanone, dimethylhexanone, ethylhexanone, cycloheptanone, methyl Examples include cycloheptanone, dimethylcycloheptanone (including isomers and various mixtures of isomers), and the like.

The electrophilic compound of the E moiety used in the production of the alicyclic enamine derivative (I) of the present invention is
Examples thereof include isocyanate compounds, (meth) acrylic acid or its esters, compounds having an acrylic group such as acrylonitrile, acetyl compounds such as acetic anhydride, alkyl halides, allyl halides and acid halides.
Examples of the isocyanate compound include aliphatic, alicyclic, and aromatic isocyanates.

Specific examples thereof include compounds represented by the following general formula (V).

[0044]

[Chemical 19]

In the formula, Z is a residue of an aliphatic, alicyclic or aromatic monoisocyanate, and n is 1 or 2.
Specifically, 1) monoisocyanates such as phenyl isocyanate, o-tolyl isocyanate, ρ-tolyl isocyanate, methyl isocyanate, and butyl isocyanate, 2) tolylene diisocyanate (including various mixtures of isomers, hereinafter referred to as TDI). , Diphenylmethane isocyanate (including various mixtures of isomers; hereinafter referred to as MDI), 3,3'-dimethyl-4,4'-
Biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylene diisocyanate (hereinafter XD
Called I. ), Tetramethylxylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as HDI), dicyclohexylmethane isocyanate, isoporone diisocyanate, hydrogenated xylylene isocyanate, 1,4-cyclohexyl diisocyanate,
1-methyl-2,4-isocyanatocyclohexane,
2,2,4-trimethyl-1,6 diisocyanate Diisocyanate such as hexane and a compound having active hydrogen, for example, a secondary amine or a primary or secondary alcohol obtained by reacting the following general formula ( Isocyanates represented by VI) or (VII) can be used.

[0046]

[Chemical 20]

R ₆ OCONH-Y- (VII) In the formula, R ₅ is a linear or branched alkyl group having 1 to 1000 carbon atoms, an alkoxy (polyoxyalkylene) alkyl group, and R ₆ is 1 to 1 carbon atoms. 1000 linear or branched alkyl groups, alkoxy (polyoxyalkylene) alkyl groups, and Y is a residue of isocyanate. Preferably, R ₅ is a butyl group and R ₆ is an isopropyl group, a butyl group, a 2-ethylhexyl group, an octyl group, a 2- (2-ethoxy-ethoxy) ethyl group or a polyether group. Y is a residue of hexamethylene diisocyanate, tolylene diisocyanate or isophorone diisocyanate.

As the compound having an acrylic group, 2-
Examples thereof include compounds having an (alkoxycarbonyl) ethyl group or a 2-cyanoethyl group. Here, the hydrogen atom on the carbon at the 1-position or 2-position of the 2- (alkoxycarbonyl) ethyl group may be substituted with a methyl group, a nitro group or a cyano group. Specifically, examples of the residue of the compound having an acrylic group include a residue of the compound represented by the general formula (VIII) or (IX), and acrylic acid or methacrylic acid methyl, ethyl, propyl, butyl. , Esters such as allyl, acrylonitrile and the like.

[0049]

[Chemical 21]

—CH ₂ CH ₂ CN (IX) In the formula, R ₇ is a residue of acrylic acid ester or methacrylic acid ester excluding an acrylic group or a methacrylic group. R ₈ is a hydrogen atom or a methyl group. ) Further, examples of the acetyl compound include a residue of the compound represented by the general formula (X) such as acetic anhydride.

-COCH ₃ (X) As the electrophilic compound, as described above, other halogenated alkyls, allyl halides, acid halides and the like can be mentioned, and the residue E thereof is -R (R is an alkyl group). Represents), —CH ₂ CH═CH ₂ , and —COR (R represents an alkyl group).

In the alicyclic enamine derivative of the present invention, the secondary diamine and the alicyclic ketone are subjected to an azeotropic dehydration reaction using a solvent such as cyclohexane, benzene, toluene or xylene. The alicyclic enamine, which is a condensate, is thus obtained, and the alicyclic enamine is obtained by further dropping the above electrophilic compound under stirring and reacting. In this case, the electrophilic compound corresponding to the substituent E is added to the carbon adjacent to the 1-position of the cycloalkene ring of the alicyclic enamine. When the alicyclic ketone compound has no substituent on the aliphatic ring, for example, when cyclohexanone is used, 1
Substituent E is often added to the two carbons adjacent to position 1, but when the alicyclic ketone compound has a substituent on the carbon adjacent to position 1 of the aliphatic ring, for example, when methylhexanone is used. Often, the substituent E is often not added to the carbon.

The polyurethane prepolymer used in the present invention is a compound having two or more isocyanate groups, and a prepolymer prepared by a conventional method with an organic polyisocyanate and an organic polyhydroxyl compound in excess of isocyanate, and It is the organic polyisocyanate itself.

As the organic polyisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene Examples thereof include aromatic diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures of two or more thereof.

The organic polyhydroxyl compounds used in the present invention are polyether polyols, polyester polyols, other polyols and mixed polyols thereof. For example, a polyol produced using a metal cyanide compound as a catalyst is also included.

As the polyether polyol, one or more polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, sucrose and propylene oxide and ethylene can be used. Examples thereof include polyols and polyoxytetramethylene polyols obtained by adding one kind or two or more kinds of oxides, butylene oxides, styrene oxides and the like.

As the polyester polyol, ethylene glycol, propylene glycol, butanediol,
One or more of pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane or other low molecular weight polyols and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, Dimer acid,
Examples thereof include condensation polymers with hydrogenated dimer acid or one or more low molecular weight dicarboxylic acids and oligomer acids, and ring-opening polymers such as propiolactone, caprolactone and valerolactone.

Other polyols include polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol and the like. Further, low molecular weight polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol glycerin, trimethylolpropane, glucose, sorbitol and sucrose are also included.

Examples of the plasticizer include dibutyl phthalate and dioctyl phthalate. Examples of stabilizers include antioxidants and ultraviolet absorbers.

Examples of the catalyst include tertiary amines and organometallic compounds. The moisture-curable polyurethane composition of the present invention is a sealing material for construction or vehicles,
It can be used as a wall material, a waterproof material, a paint, an adhesive or the like. It is especially useful as a waterproof material.

The waterproof material comprises the moisture-curable polyurethane composition of the present invention and a filler. Examples of the filler include calcium carbonate, titanium oxide, calcium hydroxide, calcium oxide, talc, clay, aluminum sulfate, vinyl chloride paste resin and the like. These may be used alone or in combination of one or more.

[0062]

EXAMPLES The urethane prepolymers used in the examples are as follows. In the examples, “part” means “part by weight”.

<Urethane Prepolymer a> 1501 parts of polyoxypropylene glycol (molecular weight 3000) produced with a calcium hydroxide catalyst, 3095 parts of polyoxypropylene triol (molecular weight 5000) and 404 parts of 2,4-tolylene diisocyanate. , At 100 ℃ 1
The reaction was carried out for 0 hours to obtain a urethane prepolymer. Terminal N
CO group is 1.5%, viscosity is 59,000 cps / 25 ° C
Met.

<Urethane Prepolymer b> 2550 parts of polyoxypropylene glycol (molecular weight 5100) produced using a metal cyanide complex as a catalyst and 172 parts of 2,4-tolylene diisocyanate are reacted at 100 ° C. for 10 hours, A urethane prepolymer was obtained. Terminal NCO
The group was 1.5% and the viscosity was 61,000 cps / 25 ° C.

<Urethane Prepolymer c> 3000 parts of neopentyl glycol, butylene glycol, polyester glycol of adipic acid (molecular weight 3000),
2,4-tolylene diisocyanate with 348 parts of 10
The reaction was carried out at 0 ° C for 5 hours to obtain a urethane prepolymer.

When diluted with toluene, the terminal NCO group is 1.6
%, The viscosity was 10,000 cps / 25 ° C. <Urethane prepolymer d> 1750 parts of polyoxypropylene glycol (molecular weight 2000) and polyoxyethylene propylene triol (molecular weight 7000) 199
A urethane prepolymer was obtained by reacting 0 part, 655 parts of diphenylmethane diisocyanate and 489 parts of xylene at 100 ° C. for 10 hours.

Terminal NCO group is 2.3%, viscosity is 5000
cps / 25 ° C. Curability is JIS-A5758
The time until becoming tack-free was measured according to item 6-10 of (1986).

The alicyclic dienamine used in the examples was prepared as follows. <Alicyclic Dienamine BCP-1> Piperazine 86.1
Parts (1.0 mol) are mixed with 196.2 parts (2.0 mol) of cyclohexanone and 200 parts of toluene and heated under nitrogen in a water drop separator.

After 5 hours, half the amount of water and after 20 hours the calculated amount of water had separated. When the solvent toluene was distilled off and the residue was recrystallized with 200 parts of dehydrated acetone, plate-like crystals were deposited. When this was filtered, a colorless transparent solid was obtained.

[0070]

[Chemical formula 22]

This product is 1,4-bis (1-cyclohexenyl) piperazine and is abbreviated as BCP-1. The elemental analysis results of this compound were as follows. <Alicyclic Dienamine BCP-2> 4-methylcyclohexanone 22 instead of cyclohexanone of BCP-1
When the same operation as that for BCP-1 was carried out except that 6.2 parts were used, a colorless transparent solid was obtained.

This product is 1,4-bis (4-methyl-1-cyclohexenyl) piperazine, which is abbreviated as BCP-2 below. The elemental analysis results of this compound were as follows.

[0073] <Alicyclic Dienamine BCP-3> The same operation as in BCP-1 was performed except that 111.1 parts of 2-methyl-piperazine was used instead of piperazine of BCP-1, and a colorless transparent solid was obtained. It was

This product is 1,4-bis (1-cyclohexenyl) 2-methylpiperazine, and is abbreviated as BCP-3 below. The elemental analysis results of this compound were as follows.

[0075] Examples of enamine derivatives will be shown below.

Example 1 An alicyclic dienamine BCP-1 was placed in a reaction vessel having an internal volume of 1 liter.
61.5 parts (0.25 mol) and 200 g of toluene were charged. Phenylisocyanate 119.2 parts (1 m
ol) was transferred to a dropping funnel, and the dropping funnel was attached to the reactor.

While stirring at room temperature in a nitrogen stream,
The dropping was started while paying attention to heat generation, and the dropping was performed for 1 hour.
After the dropping was completed, stirring was continued at 50 ° C. for 20 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is lost, the target compound was precipitated as a crystalline compound. This infrared absorption spectrum is shown in FIG. The precipitate is filtered,
The target compound was obtained by vacuum drying at 50 ° C. for 20 hours. Hereinafter, this compound is referred to as AAU-1.
This is 1,4-bis (1-cyclohexyl-oil-
N, N'-diphenylurea) piperazine.

Example 2 The same operation as in Example 1 was carried out by using 69 parts of BCP-2 instead of BCP-1 of Example 1. The compound obtained is called AAU-2.

Example 3 Instead of BCP-1 of Example 1, BCP-3 65.2 was used.
The same operation as in Example 1 was performed using the parts. The compound obtained is called AAU-3.

Example 4 61.5 parts (0.25 mol) of BCP-1 and 200 parts of toluene were charged to a reactor having a content of 1 liter. 295.5 parts (1 mol) of octadecyl isocyanate was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring in a nitrogen stream at room temperature, dropping was started while paying attention to heat generation, and the dropping was performed for 1 hour. After completion of dropping, 8
The mixture was stirred at 0 ° C. for 50 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. 50 this solution
Vacuum drying was performed at 20 ° C. for 20 hours to obtain the target compound. This compound is designated as AAU-4.

Example 5 61.5 parts (0.25 mol) of BCP-1 and 200 parts of toluene were charged to a reactor having a content of 1 liter. Tolylene diisocyanate (isomer ratio 2,4 / 2,6 = 80 /
20) 174 parts (1 mol), 2- (2-ethoxyethoxy) ethanol 134 parts (1 mol) and toluene 10
0 parts were uniformly mixed and reacted at room temperature for 7 hours in a nitrogen stream to obtain a reaction product having an NCO group-containing weight% of 10.3.

The reaction product was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring at room temperature in a nitrogen stream, start dropping while paying attention to heat generation,
It was added dropwise for 1 hour. After the completion of dropping, the mixture was stirred at 80 ° C. for 30 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. When 10 parts of this solution was mixed with 100 parts of dehydrated toluene, a crystalline compound was deposited. The precipitate was filtered and vacuum dried at 50 ° C. for 20 hours to obtain about 5 parts of product. This is AA
U-5.

Example 6 61.5 parts (0.25 mol) of BCP-1 and 200 parts of toluene were charged to a reactor having a content of 1 liter. 222 parts (1 mol) of isophorone diisocyanate, 134 parts (1 mol) of 2- (2-ethoxyethoxy) ethanol (1 mol) and 100 parts of toluene were uniformly mixed and reacted at room temperature in a nitrogen stream for 7 hours to obtain a NCO group-containing weight%. A reaction product of 9.2 was obtained.

The reaction product was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring at room temperature in a nitrogen stream, start dropping while paying attention to heat generation,
It was added dropwise for 1 hour. After the completion of dropping, the mixture was stirred at 80 ° C. for 30 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. When 10 parts of this solution was mixed with 100 parts of dehydrated toluene, a crystalline compound was deposited. The precipitate was filtered and vacuum dried at 50 ° C. for 20 hours to obtain about 5 parts of product. This is AA
U-6.

Example 7 BCP-1 (61.5 parts, 0.25 mol) and cellosolve acetate (200 parts) were charged to a reactor having a content of 1 liter. 168 parts of hexamethylene diisocyanate (1mo
1), 129 parts (1 mol) of dibutylamine and 100 parts of cellosolve acetate were uniformly mixed and reacted at 20 ° C. for 2 hours in a nitrogen stream to obtain a reaction product having an NCO group-containing weight% of 10.6.

The reaction product was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring at room temperature in a nitrogen stream, start dropping while paying attention to heat generation,
It was added dropwise for 1 hour. After the completion of dropping, the mixture was stirred at 80 ° C. for 50 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. When 10 parts of this solution was mixed with 100 parts of dehydrated toluene, a crystalline compound was deposited. The precipitate was filtered and vacuum dried at 50 ° C. for 20 hours to obtain about 5 parts of product. This is AA
U-7.

Example 8 BCP-1 (62 parts) (0.25 mol) and toluene 20
0 parts and 0 parts were charged to a reactor having a content of 1 l. 174 parts (1 mol) of 2,4-tolylene diisocyanate, 74 parts (1 mol) of 1-butanol and 100 parts of toluene were uniformly mixed and reacted at room temperature in a nitrogen stream for 7 hours to give an NCO group-containing weight% 12.1 The reaction product of

The reaction product was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring at room temperature in a nitrogen stream, while paying attention to heat generation, dropping was started and dropping was performed for 1 hour. After dropping, 30 at 80 ℃
The mixture was stirred for an hour and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. When 10 parts of this solution was mixed with 100 parts of dehydrated toluene, a crystalline compound was deposited. The precipitate was filtered and vacuum dried at 50 ° C. for 20 hours to obtain about 5 parts of product. This is AA
U-8.

Example 9 62 parts (0.25 mol) of BCP-1 and 20 parts of toluene
0 parts and 0 parts were charged to a reactor having a content of 1 l. 174 parts (1 mol) of 2,4-tolylene diisocyanate, 60 parts (1 mol) of 2-propanol and 100 parts of toluene were uniformly mixed and reacted at room temperature in a nitrogen stream for 7 hours to obtain NCO.
A reaction product with a group-containing weight% of 12.6 was obtained.

The reaction product was transferred to a dropping funnel, and the dropping funnel was attached to the reactor. While stirring at room temperature in a nitrogen stream, start dropping while paying attention to heat generation,
It was added dropwise for 1 hour. After the completion of dropping, the mixture was stirred at 80 ° C. for 30 hours and left at room temperature for 16 hours.

When the infrared absorption spectrum was measured,
Characteristic absorption at ^2230cm-1 of the NCO is disappeared to obtain a toluene solution of the objective compound. When 10 parts of this solution was mixed with 100 parts of dehydrated toluene, a crystalline compound was deposited. The precipitate was filtered and vacuum dried at 50 ° C. for 20 hours to obtain about 5 parts of product. This is AA
U-9.

Example 10 123 parts of BCP-1 (0.5 m
ol) and 200 parts of dehydrated methanol were charged. 172 parts (2 mol) of methyl acrylate was transferred to the dropping funnel, and the dropping funnel was attached to the reactor.

While stirring in a nitrogen stream at 50 ° C., the dropping was started while paying attention to heat generation, and the dropping was carried out for 1 hour. After the dropping, stirring was continued for 8 hours under reflux. After cooling to room temperature, the solvent was removed under reduced pressure. A yellow-red-brown solid was obtained, which was recrystallized from dehydrated acetone. Filtered,
By vacuum drying, colorless needle crystals were obtained. Measurement of the infrared absorption spectrum, was observed a characteristic absorption of an ester to ^1740cm-1, characteristic absorption of enamine was observed in ^1640cm-1. The formation of the target compound was also confirmed from the NMR spectrum. The infrared absorption spectrum and the NMR spectrum are shown in FIGS. 2 and 3. The abbreviation of this compound is BC
P4MA. The analysis results are shown in Tables 1 and 2.

Example 11 123 parts (0.5 mol) of BCP-1 obtained in Example 1
And 200 parts (2 mol) of methyl methacrylate in Example 1
The reaction was performed in the same manner as in. The product becomes a reddish brown liquid,
In the measurement of infrared absorption spectrum, was observed a characteristic absorption of an ester to ^1740cm-1, characteristic absorption of enamine was observed in ^1640cm-1. The abbreviation for this compound is BCP4MM. The analysis results are shown in Tables 1 and 2.

Example 12 123 parts (0.5 mol) of BCP-1 obtained in Example 1
And 106 parts (2 mol) of acrylonitrile were reacted in the same manner as in Example 1. The product is, after recrystallization from DMF,
It becomes a white solid, and in the infrared absorption spectrum measurement,
Characteristic absorption of nitrile was observed at 2260 cm ^-1 , 1640
The characteristic absorption of enamine was observed at cm ^-1 . The abbreviation for this compound is BCP4AN. The analysis results are shown in Tables 1 and 2.

Example 13 A liquid enamine derivative BCDA was obtained by the same reaction as in Example 1 except that N, N'-dimethylethylenediamine was used instead of piperazine. This product was subjected to the addition reaction of methyl acrylate as in Example 1 without any special purification. After removing the solvent, vacuum distillation was performed to obtain a transparent bright liquid having a boiling point of 84 ° C./0.1 mmHg. When the infrared absorption spectrum was measured, it was 1740.
characteristic absorption of ester in ^cm-1 was observed, the characteristic absorption of enamine was seen to ^1640cm-1. The abbreviation of this compound is BC
DA4MA. The analysis results are shown in Tables 3 and 4.

Example 14 The reaction was carried out in the same manner as in Example 1 except that 1,3- (4,4'-dipiperidyl) propane was used instead of piperazine to obtain a solid enamine derivative BCDP. This product was subjected to the addition reaction of methyl acrylate as in Example 1 without any special purification. After removing the solvent,
Recrystallization from dehydrated acetone gave white crystals. Measurement of the infrared absorption spectrum, was observed a characteristic absorption of an ester to ^1740cm-1, characteristic absorption of enamine was observed in ^1640cm-1. The abbreviation of this compound is BCDP4
Let's call it MA. The analysis results are shown in Tables 3 and 4.

Example 15 As a result of dehydration condensation in the same manner as in Example 1 except that 224 parts of 2-methylcyclohexanone was used instead of cyclohexanone of Example 1, 1,4-bis (2-methylcyclohexene-1) was obtained. The product BMCP, which is mainly composed of (-yl) piperazine, was obtained. Further, as a result of addition reaction of methyl acrylate to this BMCP, a product having a structure in which 2 mol of methyl acrylate was added was obtained. The abbreviation for this compound is BMCP2MA. The analysis results are shown in Tables 3 and 4.

Example 16 123 parts (0.5 mol) of BCP-1 obtained in Example 1
And 204 parts (2 mol) of acetic anhydride in dioxane 240
A part was used as a solvent and similarly reacted. The product was recrystallized from THF to give a clear solid. The measurement of the infrared absorption spectrum was observed a characteristic absorption of enamine to 1640 cm ^-1 is observed a characteristic absorption of an acetyl group in 1700 cm ^-1. As shown in FIG. The abbreviation for this compound is BCP-4AC. The analysis results are shown in Tables 3 and 4.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4] Examples and comparative examples of the moisture-curable polyurethane composition comprising the enamine derivative and the urethane prepolymer will be shown below.

Example 17 AAU-1 was added to a 70% dimethylacetamide solution in 220%.
Parts and 1214 parts of urethane prepolymer a were mixed, sealed and stored at room temperature for 6 months, but no change was observed. After storage, it was applied on a glass plate and left at room temperature in a room with a relative humidity of 50% to be tack-free.

Examples 18 to 25 Similar to Example 17, AAU-1, AAU-2, AAU
Each 70% dimethylacetamide solution of No. -3 and urethane prepolymers a, b, and c were mixed according to the formulation shown in Table 5.

[0112]

[Table 5] The formulations of the respective Examples were tightly stoppered and stored at room temperature for 6 months. In all cases, the increase in viscosity was within 50% and no gelation was observed. After storage, it was applied on a glass plate and left at room temperature in a room with a relative humidity of 50%. Table 3 shows the tack-free time when the surface was cured. The curability is JIS-A57.
The time until becoming tack free was measured according to Item 6-10 of 58 (1986). This is shown in Table 7.

Comparative Examples 1, 2 and 3 Urethane prepolymers a, b and c were coated on a glass plate and left at room temperature in a room with a relative humidity of 50%. 5
It didn't become tack free even after hours. This is shown in Table 7.

Comparative Examples 4 to 12 AAU-1, AAU-2 and AAU-3 of Examples 4 to 12
Table 6 shows the formulations of comparative examples using BCP-1, BCP-2, and BCP-3, respectively, instead of.

[0115]

[Table 6] For each comparative example, an increase in viscosity was observed during mixing, and gelation occurred within 5 hours.

[0116]

[Table 7] Example 26 Calcium carbonate 124 in a 4 l planetary mixer
9 parts, 144 parts of titanium oxide, and 16 parts of weathering stabilizer (Irganox 1010) were charged, and the mixture was stirred at room temperature for 15 minutes, and subsequently, the mixture was kneaded at 100 ° C. and dehydrated in vacuum for 1 hour. went. Next, polyurethane prepolymer d
1214 parts, alicyclic enamine derivative AA of Example 1
230 parts of a 70% dimethylacetamide solution of U-1 was charged and kneaded at room temperature for 15 minutes. In addition, xylene 3
45 parts were charged and the mixture was stirred at room temperature for 10 minutes in vacuum to obtain a one-pack type polyurethane composition. For this composition,
Table 9 shows the results of the storage stability and the cured sheet.

The storage stability was determined by measuring the viscosity with a BM type rotational viscometer after the one-pack type polyurethane composition was sealed and stored for a certain period. After the construction, the mechanical properties of the cured sheet were measured according to JIS-K6301.

That is, the hardness, the tensile strength and the elongation were measured when the sample was left to stand at 23 ° C. and 50% relative humidity for 7 days after the construction and further left to stand at 50 ° C. for 7 days. Examples 27 to 32 Similar to Example 26, instead of AAU-1, AAU-
4, AAU-5, AAU-6, AAU-7, AAU-
8 and AAU-9 were kneaded. The formulation of each example is shown in Table 8. The compounding amounts of the raw materials other than AAU are the same as in Example 26.

[0119]

[Table 8] Comparative Example 13 Example 26 except that AAU-1 of Example 26 was not used.
The same preparation as above was performed. Table 10 shows the storage stability and cured sheet results for this composition.

[0120]

[Table 9] In the table, the storage stability shows the stability after 14 days.

[0121]

[Table 10] The storage stability in the table shows the stability after 14 days.

From Table 9 and Table 10, Examples 26 to 32 cure faster than Comparative Example 13, there is no problem of stability after sealed storage, and foaming is observed in the cured product after application. Therefore, it can be seen that the mechanical properties are excellent.

Example 33 59 parts of BCP4MA obtained in Example 10 was mixed with 5 parts of xylene.
After dissolving in 9 parts of urethane prepolymer a, it was mixed with 560 parts of urethane prepolymer a, sealed and stored at room temperature for 6 months, but no change was observed. After storage, apply on glass plate, relative humidity 5
When left in a 0% room at room temperature, the surface hardened in 3 hours and became tack-free. The results are shown in Table 11.

Example 34 In Example 33, the urethane prepolymer a was changed to the urethane prepolymer b, and treated in the same manner as in Example 7 with the formulation shown in Table 11. The results show that, as shown in Table 11, the composition showed good curability even after long-term storage of the composition.

Example 35 In Example 33, the urethane prepolymer a was changed to the urethane prepolymer c and treated in the same manner as in Example 7 with the formulation shown in Table 11. The results show that, as shown in Table 11, the composition showed good curability even after long-term storage of the composition.

Examples 36 to 41 BCP4MM and BCP4AN obtained in Examples 11 to 16
BCDA4MA, BCDP4MA, BCDP4MA, B
Each of MCP2MA and BCP4AC was treated in the same manner as in Example 33 except that urethane prepolymer a was blended as shown in Tables 11 and 12. The formulations of the respective Examples were stored at room temperature for 6 months, but in all cases, the increase in viscosity was within 50% and no gelation was observed. After storage, it was applied on a glass plate and left at room temperature in a room with a relative humidity of 50%. Table 11 and Table 12 show the tack-free time when the surface was cured.

Comparative Examples 14 to 16 The urethane prepolymer a used in Examples 33 to 35,
b and c are applied individually on a glass plate, and the relative humidity is 5
It was left at room temperature in a 0% room. It didn't become tack free even after 5 hours. The results are shown in Table 13.

Comparative Example 17 BCP-1 was used instead of BCP4MA of Example 33 and blended as shown in Table 13. An increase in viscosity was observed during mixing, and gelation occurred within 5 hours.

[0129]

[Table 11]

[0130]

[Table 12]

[0131]

[Table 13] Examples and comparative examples of polyurethane waterproof materials containing a filler will be described below.

Example 42 Calcium carbonate 124 was added to a 4 l planetary mixer.
9 parts, 144 parts of titanium oxide, and 16 parts of weathering stabilizer (Irganox 1010) were charged, and the mixture was stirred at room temperature for 15 minutes, and subsequently dehydrated by vacuum while kneading at 100 ° C. I went for an hour. Next, polyurethane prepolymer d1214 parts and alicyclic enamine derivative BCP4MA 5
290 parts of 0% xylene solution was charged and kneaded at room temperature for 15 minutes. Further, 345 parts of xylene was charged and stirred in a vacuum at room temperature for 10 minutes to obtain a one-component polyurethane waterproof material of the present invention. Table 14 shows the storage stability and the results of the cured sheet for this waterproof material.

Regarding the storage stability, the one-component polyurethane waterproof material was hermetically stored for 14 days, and then the viscosity was measured by a BM type rotational viscometer. After the construction, the mechanical properties of the cured sheet were measured according to JIS-K6301. That is, the hardness, the tensile strength and the elongation were measured when the sample was left to stand at 23 ° C. and 50% relative humidity for 7 days after the construction and further left to stand at 50 ° C. for 7 days.

Examples 43 to 48 Similar to Example 42, BCP4MA, BCP4MM, B
CP4AN, BCDA4MA, BCDP4MA, BMC
Each of P4MA and BCP4AC was kneaded. The formulations of each example are shown in Tables 14 and 15. BCP4A
Only in the case of N, the same as in Example 42 except that dimethylformamide was used as the solvent and the blending amount of each enamine derivative.

The storage stability of these one-component polyurethane waterproof materials and the evaluation results of the cured sheets are shown in Tables 14 and 15. Comparative Example 18 The same adjustment as in Example 42 was performed except that BCP4MA of Example 42 was not used. Table 15 shows the storage stability of this waterproof material and the evaluation results of the cured sheet.

[0136]

[Table 14]

[0137]

[Table 15] Compared to the comparative examples, the examples according to the present invention showed faster curing, no problem of stability after sealed storage, no foaming was observed in the cured product after application, and mechanical properties were also good. It was

[0138]

The one-pack moisture-curable composition according to the present invention comprises:
Good storage stability, even if stored for a long time at relatively high temperature,
In the cured product after moisture curing, stable physical properties can be obtained, and it can be cured by the moisture in the constructed air.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the enamine derivative AAU-1 of the present invention.

FIG. 2 is an infrared absorption spectrum diagram of the enamine derivative BCP4MA of the present invention.

FIG. 3 is a nuclear magnetic resonance spectrum of the enamine derivative BCP4MA of the present invention.

FIG. 4 is an infrared absorption spectrum diagram of the enamine derivative BCP4AC of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 295/14 Z C08G 18/06 8620-4J C09K 3/10 D // C09K 3/18 101 8318 -4H

Claims (13)

[Claims] 1. A compound represented by the general formula (I):[A is a branched or cyclic secondary diamid having 1 to 22 carbon atoms.
Residue of (CR ₂)_nRepresents an aliphatic ring. R is
Hydrogen atom or C1-C6 linear, branched or cyclic carbon
It is hydrogen chloride. E is the residue of the electrophilic compound. B is
A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or
Is E and n is excluding the 1-position and the carbon adjacent to the 1-position
It represents the number of carbon atoms forming an aliphatic ring, and is an integer of 2 to 4.
is there. ] The alicyclic enamine derivative shown by these. 2. A is represented by the following formula (II), (III) or (I
V) [Chemical 2] [Chemical 3] [Chemical 4] (In the formula, R ₁ and R ₂ are each an alkyl, cycloalkyl or aryl group having 1 to 8 carbon atoms, and R ₃ and R ₄ are hydrogen atoms or a chain, branched or cyclic group having 1 to 6 carbon atoms. X is an alkylene, cycloalkylene or arylene group having 1 to 10 carbon atoms, G is CH or N, and when G is CH, X can be excluded.). The alicyclic enamine derivative according to claim 1, which is a residue of a secondary diamine. 3. The alicyclic enamine derivative according to claim 1 or 2, wherein E is a residue of an isocyanate compound, a residue of a compound having an acrylic group, or a residue of an acetyl compound. 4. A residue of an isocyanate compound is represented by the following formula (V): (In the formula, Z is a residue of an aliphatic, alicyclic or aromatic monoisocyanate, and n is 1 or 2.) The alicyclic enamine according to claim 3. Derivative. 5. Z is represented by the following formula (VI) or (VII): _{R 6 OCONH-Y- (VII)} [ wherein, R ₅ is a linear or branched alkyl group of 1 to 1,000 carbon atoms, an alkoxy (polyoxyalkylene) alkyl group, R ₆ has a carbon number of 1 to 1000 A linear or branched alkyl group, an alkoxy (polyoxyalkylene) alkyl group, and Y is a residue of hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. ] It is shown by these, The alicyclic enamine derivative of Claim 4 characterized by the above-mentioned. 6. The residue of the compound having an acrylic group is 2-
The alicyclic enamine derivative according to claim 3, which is a residue of a compound having an (alkoxycarbonyl) ethyl group or a 2-cyanoethyl group. 7. A 2- (alkoxycarbonyl) ethyl group is represented by the following formula (VIII): (R ₇ is a residue excluding an acrylic group or a methacrylic group of an acrylic ester or a methacrylic ester.
R ₈ is a hydrogen atom or a methyl group. ) Are shown, The alicyclic enamine derivative of Claim 6 characterized by the above-mentioned. 8. The alicyclic enamine derivative according to claim 6, wherein the 2-cyanoethyl group is represented by the following formula (IX). -CH ₂ CH ₂ CN (IX) 9. The alicyclic enamine derivative according to claim 3, wherein the residue of the acetyl compound is represented by the following formula (X) —COCH ₃ (X). 10. A moisture-curable polyurethane composition comprising the alicyclic enamine derivative represented by the general formula (I) according to claim 1 and a polyisocyanate and / or a polyurethane prepolymer having an isocyanate group. 11. The moisture-curable polyurethane composition according to claim 10, wherein the polyurethane prepolymer is terminated with an isocyanate group obtained from polyoxyalkylene polyol and tolylene diisocyanate and / or diphenylmethane diisocyanate. 12. A moisture-curable polyurethane waterproof material comprising the moisture-curable polyurethane composition according to claim 10 and a filler. 13. The filler is calcium carbonate, titanium oxide,
Calcium hydroxide, calcium oxide, talc, clay,
The moisture-curable polyurethane waterproof material according to claim 12, which is one or more selected from the group consisting of aluminum sulfate and vinyl chloride paste resin.