JPH02311453A - Vinyl compound containing ketimine group and its production - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is H or lower alkyl; R', R'' and R''' are lower alkyl; A is group of formula II, C(=O)-OCH2CH2 or CO] and formula III ((n) is 4 or 5). USE:A raw material for industrial production. Useful as a raw material in the fields of organic synthesis and polymer production. PREPARATION:The objective compound of formula I or formula III is produced by reacting an isocyanate compound of formula IV with a ketimine-containing hydroxyl compound of formula V or formula VI. The reaction is carried out generally at <=120 deg.C, preferably 0 to 90 deg.C. In order to suppress the progress of side reactions, it is preferable to dissolve the compound of formula V or formula VI in an inert solvent and dropping an inert solvent solution of the compound of formula IV very slowly to the above solution.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a ketimine group-containing vinyl compound and a method for producing the same, particularly because of its excellent reactivity, as a raw material in the fields of organic synthesis and polymer production. It has a wide range of uses.

General formula (I) R... (I) C)12=CR" ^ -N)l-C-〇 -R'-11=COR... or general formula (II) R... (II) CI+2=C (wherein, R is hydrogen or a lower alkyl group, R', R''
and R″°° is a lower alkyl group, n is an integer of 4 or 5, and 4.^ is a H3 CXC group or a C-0CH20H2 group or a C group l
II II
This invention relates to a novel ketimine group-containing vinyl compound represented by CH300 and a method for producing the same.

(Prior Art) Vinyl compounds containing ketimine groups can be widely used in the field of polymer chemistry because of their excellent reactivity. That is, this ketimine group-containing vinyl compound (I) or (
I[> is a polymerizable carbon-
It is a compound that has both a carbon unsaturated group and a ketimine group, which is easily hydrolyzed by water and converted into a primary amine group, in the same molecule. In other words, the ketimine group can be regarded as an active group equivalent to a primary amine group, and this means that the carbon-carbon unsaturated group of the ketimine group-containing vinyl compound (I) or (II) can be subjected to various reactions, such as radical reactions. A ketimine group-containing compound equivalent to a primary amine group can be synthesized by carrying out polymerization, anionic polymerization, trimerization, trimerization, polar addition, active hydrogen addition, etc. Furthermore, a particularly useful application is that a polymer containing a ketimine group equivalent to a primary amino group can be easily synthesized.

This high molecular weight polymer containing a ketimine group equivalent to a primary amino group can be subjected to various crosslinking reactions as it is or after being hydrolyzed. The ketimine group-containing polymer can be used in adhesives and coatings. In addition, even without being subjected to a crosslinking reaction, the cationic nature of the amine group can be used to apply it as a flocculant, a retention aid for paper, a fixing agent for dyeing agents, etc.

Conventionally, methods for synthesizing polymers containing such primary amino groups include JP-A-48-34294 and JP-A-50-
24331, a method using alkyleneimine as in JP-A-55-58260, or JP-A-56-1
No. 00842, a method using hydrazine hittride as in JP-A-56-103203, or JP-A-61-1
As described in No. 26181, a method has been proposed in which a polymer containing glycidyl (meth)acrylate as a copolymerization component is reacted with ammonia to produce a polymer containing a primary amino group. The method using alkyleneimine has the problem of being difficult to handle due to its toxicity, and the method using hydrazine hydride can basically only be applied to water-based polymers and has problems in terms of stability. . In addition, the production method by reacting a polymer containing glycidyl (meth)acrylate as a copolymerization component with ammonia has problems such as an excessive amount of ammonia and a high-pressure reaction, which increases the cost in terms of production equipment.

(Problems to be Solved by the Invention) The present invention provides a vinyl compound containing a ketimine group equivalent to a primary amino group and a method for producing the same. A primary amine group can be easily introduced.

An object of the present invention is to provide a vinyl compound containing a ketimine group equivalent to a primary amino group and a method for producing the same.

(Means for Solving the Problem) In order to solve the above problems, the inventors of the present invention have conducted intensive research and found that the general formula (II[) C1+2=C...(I[[> ^- N = C = 0 (wherein, R is hydrogen or a lower alkyl group, A is a C group of C row, or C-, 0C112C11゜ group or C
Group I II llCl
+30 0) and the incyanate compound represented by the general formula (TV) R''HO-R'-N = C... (IV) ■ Ro゛ or the general formula (V) (wherein, Ro, R" and R゛°° each represent a lower alkyl group, and n represents an integer of 4 or 5.) A getimine group-containing hydroxy compound represented by the formula (I) R...(I) CH2 =CR" \ I A -NH-C-0-R'-N =C OR"' or general formula (II) R...(II) C12=C (wherein, R is hydrogen or a lower alkyl group , It', R
” and R゛°° are lower alkyl groups, n is 4 or 5
is an integer of 8 is <Etc group or C-0CR2ct+2 group or C group I II
A ketimine group-containing vinyl compound and a method for producing the same have been completed, which are characterized by obtaining a ketimine group-containing vinyl compound represented by IICH300.

More specifically, the incyanate group-containing vinyl compound of general formula (I[[) used in the present invention is isocyanate ethyl methacrylate (Dov
S, AProduct name XAS-10743,00), m-
Inbrohenyl-α,α-dimethylbenzyl isocyanate (translated by Yakuhin Kogyo Co., Ltd., product name m-TM I)
, methacryloyl isocyanate (Nippon Paint Co., Ltd.)
For example, methacryloyl isocyanate is combined with methacrylamide as described in JP-A-62-238254, JP-A-61-260048, and JP-A-61-263953. It can be obtained by thermally decomposing a reaction product with oxalyl halide, but at present, the above-mentioned compound is manufactured by each manufacturer.9 General formula (IV) used in the present invention
R"HO-R'-N = C... (IV) Ro゛.

or general formula (V) (wherein Ro, R" and R"° represent a lower alkyl group, n
represents an integer of 4 or 5) A getimine group-containing hydroxy compound represented by the general formula (Vl) HO-R--NH2=-if) (wherein Ro represents a lower alkyl group) and a hydroxyalkylamine compound having the general formula (■) R''0=C...(VU) Ro゛.

or with a ketone compound represented by the general formula (■) ... (■) (wherein R゛, R'' and R゛'° represent a lower alkyl group, and rl represents an integer of 4 or 5) For example, dehydration condensation is produced by a known technique by dehydration condensation, as described in Japanese Patent Application Laid-open No. 1986-
As described in the Examples of No. 263216, it is generally prepared from a hydroxyalkylamine compound (Vl) and an excess of a ketone compound (■) or (■).

The hydroxyalkylamine compound (Vl
) includes, for example, ethanolamine, 2-aminopropanol-1,2-aminobutanol-1,3-aminobutanol-1,4-aminobutanol-1, and the like.

As the ketone compound (■) or (■) used in the present invention, for example, acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, etc. can be used.

In the production of the ketimine group-containing vinyl compound of general formula (I) or (It) of the present invention, an isocyanate group, a ketimine group, a hydroxyl group, a vinyl group and an inert solvent,
For example, aliphatic hydrocarbons such as pentane, hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, hydrocarbon solvents such as petroleum ether, petroleum benzene, etc. , carbon tetrachloride, chloroform, 1
．． Halogenated hydrocarbon solvents such as 2-dichloroethane, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and isophorone, ethyl acetate, It may be appropriately selected from esters such as butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc., and these may be used alone or in a mixture, or may not be used.

A ketimine group-containing vinyl compound (I> or (I
In the production of I), the reaction is generally carried out at a temperature not exceeding 120°C, more preferably at a temperature of 0 to 90°C, since side reactions may occur if the temperature exceeds 120°C. At low temperatures, the reaction slows down, which is industrially disadvantageous.

During the reaction, dibutyltin laurate, dimethyltin chloride, tri-n-butyltin acetate, tetra-
Either a tin-based catalyst such as n-butyltin, an amine-based catalyst such as triethylamine or triethylenediamine, or a catalyst such as cobalt naphthenate may be used alone or in a mixture, or may not be used. .

Note that even if the ketimine group-containing hydroxy compound (TV) or (V) is added to the incyanate group-containing vinyl compound (I [[>), the isocyanate group-containing vinyl compound (III) is Either may be added to compound (IV) or (V), but from the viewpoint of preventing the progress of side reactions, the ketimine group-containing hydroxy compound (TV) or (V) is dissolved in an inert solvent. It is preferable to react by dropping a solution of the isocyanate group-containing vinyl compound (III) in an inert solvent little by little.

(Function) As is clear from the above explanation, the incyanate group-containing compound (II[) and the ketimine group-containing hydroxy compound (IV) or (V), which is equivalent to a primary amine, are more easily Vinyl compound (I) or (II) can be produced.

Here, the produced ketimine group-containing vinyl compound (I)
Or (II) generally has high solubility and is soluble in most common organic solvents. In addition, as shown in the following formula, this ketimine group-containing vinyl compound (I) or (If) has a primary amino group that appears when hydrolyzed with water, so it exhibits highly reactive effects with various compounds. It is something.

CH2=CR・・＼IA-NHC-
0-R'-N =C0H20OR... ↓ CH2=CR... \IA
-NHC-0-R'-N112+0 =COR"' Or, CH2:C ■ ■ CH2=C In the above formula, the carbon-carbon unsaturated group has polymerization reactivity, and therefore the ketimine group-containing vinyl compound (I) or (II) can be used to produce homopolymers and copolymers.

For example, it can be used to modify graft-polymerized synthetic resins, synthetic fibers, natural polymers, etc., or it can be used to modify graft-polymerized synthetic resins, synthetic fibers, natural polymers, etc. ) acrylamide, etc.) and can be used to produce paints, adhesives, flocculants, dye fixatives, plastics, elastomers, etc. Note that radical polymerization is advantageous in the polymerization, and examples of catalysts include azobisisobutyronitrile, benzoyl peroxide, and di-tert-butyl peroxide.

The urethane moiety of the ketimine group-containing vinyl compound (I) or (II) has high intermolecular cohesive force and intermolecular hydrogen bond forming ability, and the polymer obtained using the ketimine group-containing vinyl compound (I) or (n) contributes to exhibiting excellent properties in terms of toughness, adhesion, dispersion, etc.

Rather than using the ketimine moiety of the ketimine group-containing vinyl compound (I> or (II)) while crafting the ketimine group in the polymer obtained using the ketimine group-containing vinyl compound (I) or (If), In many cases, it is more useful to actively hydrolyze it with water to convert it into a primary amine group graft polymer.

In other words, primary amino groups hydrolyzed by water can contribute to reactions with epoxy compounds, active ester compounds, acryloyl group-containing compounds, carbonyl compounds, organic acids, etc. Furthermore, when these polyvalent compounds are used, undergoes a crosslinking reaction to obtain a cured product, and by actively utilizing these crosslinking reactions, durability can be improved in paint and adhesive applications.

Furthermore, it is also possible to use the primary amine group as a dye fixing agent, a surface treatment agent, a flocculant, etc.

Grafted getimine group was hydrolyzed using aqueous solutions of various organic acids and inorganic acids, or hydrolyzed in advance with water 1
When a class amino group is neutralized with various organic acids or 8M-free acids, the neutralized portion basically becomes water-soluble, and if there are many neutralized portions, the entire resin can be made water-soluble.

As described above, the ketimine group-containing vinyl compound (I) or (■) has a wide range of uses as a raw material for industrial production.

In addition, in order to improve the storage stability of the ketimine group-containing vinyl compound (I>, tnaha (II)) obtained according to the present invention, hydroquinone, p-methoxyphenol, 4-t-butylcatechol is used as a polymerization inhibitor. , p-nitrophenol, etc. are used.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the following Examples.

In addition, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively.

Example 1 305 parts (5 moles) of monoethanolamine and 1000 parts (10 moles) of methyl isobutyl getone were charged into a reactor equipped with a stirrer, a cooling tube, a distilled water separator, and a thermometer, and heated while stirring. (approximately 100-110°C), the temperature was gradually increased to maintain reflux.

The reaction continued for 5 hours, and after obtaining 90 parts of distilled water, the temperature was increased to 50°C.
Next, a distillation apparatus was set, and the pressure was gradually reduced and heated to distill off unreacted methyl isobutyl ketone, and the vapor pressure was 35 to 40! Iw+H(1, boiling point 101~1
The fraction at 05°C was separated to obtain 430 parts of ketimine from monoethanolamine and methyl isobutyl ketone.

Next, 71.5 parts of ketimine obtained by the above operation was charged into a reactor equipped with a stirrer, a thermometer, and a dry air blowing tube, and the m-in Propenyl-α,α-dimethyl isocyanate (trade name m-TMI).

100.5 parts (manufactured by Tadashi Yakuhin Kogyo Co., Ltd.) were added dropwise over 50 minutes. During this time, the reaction temperature gradually increased to 85-90°
After the completion of the 6 dropwise additions of C, the mixture was aged at 85° C. for 30 minutes to obtain a ketimine adduct of m-isopropenyl-α,α-dimethyl isocyanate. This substance has a melting point of 8
It is a solid at 0℃, and the target m-
It was not identified that isopropenyl-α,α-dimethyl isocyanate and ketimine were added through a urethane bond.

In the IR spectrum, vNH1 at 3370 cm-1
1660cm”, vc=o (urethane bond), 15
An amide ■ absorption band at 20 cm-1 and an amide ■ absorption band at 1240 cm'' were observed.In addition, in the IR spectrum, N=C=OII from 2400 to 2200 cm-1
Almost no absorption band was observed.

H-NMR (H(1)l)l')acetone-D6)20.

95ppl (d:C・H3), o, 97ppn
(d: CH3), t, 51) pIl (s: cH3
>, 1.68 ppra (s:CH3), 1.7
2pI) TI (s:CH3), 1.7-1.91
)DIl (m: 2H1IH), 2.1SDI)TI
(s:CH3>, 3.5~4.oppn (
m: 4H), 4.5+) I) II (s: IH),
5.29DIl (d: 2H, J=0.3cps), 7
．． 301111 (s: 3H), 7.5pp11
(s: IH) Example 2 In the same manner as in Example 1, 71.5 parts of ketimine synthesized from monoethanolamine and methyl isobutyl ketone and 100 ml of chloroform were added to a stirrer, a thermometer, and a dry air blowing tube. The mixture was charged into a reactor and cooled with water.

Next, isocyanate ethyl methacrylate (trade name XAS-10743,00,0014Ch
77.5 parts of enical (produced by Company U, S, Company A) were added dropwise over 2 hours. During this time, the reaction temperature did not exceed 10°C. After the completion of one drop, aging was carried out at about 10°C for 1 hour. After aging, chloroform was distilled off under reduced pressure to obtain a ketimine adduct of incyanate ethyl methacrylate. This substance is an active pale yellow oily substance, IR,
By NMR, it was identified that the target incyanate ethyl methacrylate and ketimine were added through a urethane bond. In the IR spectrum, 3
350cm'', vNH11720cm-', vc=
0 (urethane bond), amide ■ absorption band at 1640 cm-' and amide ■ absorption band at 1530 cm-1 and 12
An amide ■ absorption band was observed at 60 cm.

In addition, in the IR spectrum, 2400-2200c
Almost no absorption band of N=C=O of m'' was observed.

H-NMR (H (ppm) acetone Da): O
-95p1)l (d:CH3), 0.971)fu
ll (d:cH>, 1.541)l)II (S
:CH3), t, 7-1, 9111)l (m, 2H
1IH), 1.951)E)II(s:CH3),
3.4-3.81) p41 (m:4H), 4.0-
4.3pu (t: 4H), 5.25pprg
(s: IH), 5.91) pII (d
: 2H, J=0°6 cps) Example 3 Methacryloyl isocyanate was synthesized according to JP-A No. 62-238254. That is, in a reactor equipped with a stirrer and a thermometer, 69.8 parts of oxalyl chloride and 0.
- 200 parts of dichlorobenzene was charged and water-cooled,
42.6 parts of methacrylamide was added over 40 minutes. During this time, the reaction temperature did not exceed 10°C. After adding methacrylamide, the temperature was raised to 40°C and aged for 2 hours. When the mixture was cooled to 10°C or lower, crystals were precipitated.

After adding 120 parts of O-dichlorobenzene and 300 parts of hexane to this reaction solution, it was filtered and the crystals were separated from P. The obtained crystals and 0.4 parts of phenethiazine were charged into a reactor equipped with a stirrer, a thermometer, and a cooling tube, and then a mixed solution of 0-dichlorobenzene and hexane (mixing ratio 0-dichlorobenzene/hexane = 2/3) was added. ), add 400 parts and raise the temperature in an oil bath while stirring until the oil bath temperature is 120-13
The temperature was set to 0°C. At this time, the reaction temperature was 70 to 75°C,
This state was maintained for 1.5 hours for thermal decomposition.

Then, by distillation, methacryloyl isocyanate 15
Next, in the same manner as in Example 1, 3 was synthesized from monoethanolamine and methyl imbutyl ketone.
214.3 parts of methacryloyl isocyanate and 80 ml of chloroform were placed in a reactor equipped with a stirrer, a dry air blowing tube, and a cooling tube. -Chloroethane 80ml
A mixed solution was added dropwise. During this time, the reaction temperature did not exceed 10° C., which was the end of 0 dropwise addition, t*iooC, and the reaction was carried out for 1 hour.

After aging, chloroform and 1,2-dichloroethane were distilled off under pressure to obtain a getimin adduct of methacryloyl isocyanate. This one is IR.

From NMR4, it was identified that the desired methacryloyl isocyanate and getimine were added through a urethane bond.

The IR spectrum is also υNH11 at 3310 cm-1.
770 cm”, vc=o (urethane bond), 1
vc=o (methacryloylcarbonyl group) at 710 cm'', an amide ■ absorption band at 1520 cm'' and an amide ■ absorption band at 1215 cm''. In addition, in the IR spectrum, 2400 to 2200 cm-
Almost no N=C=OII absorption band of 1 was observed.

H-NMR (H (ppm) acetone-Da):
0.

95pl)l (d: cH3>, o, 97pf
)l (d: CH3), 1.541)I)TI
(S:CH3), 1.7-19pDIl (m
, 2H, LH), 1.95pDm(s: CH3
), 3.4-3.81) l) In (m + 4H
), 5.2ppra (s:IH), 5.91)H(d
:2H, J=0. (6 cps) (Effects of the Invention) As is clear from the examples, the present invention enables easier organic synthesis of the incyanate group-containing vinyl compound (III) and the getimine group-containing hydroxy compound (IV) or (V). The object of the present invention is to provide a ketimine group-containing vinyl compound (I) or (II) which has a wide range of uses as a raw material in the field of polymer production.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) or general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R is hydrogen or a lower alkyl group, R', R''
and R''' is a lower alkyl group, n is an integer of 4 or 5, and A is a ▲mathematical formula, chemical formula, table, etc.▼ group, or ▲a mathematical formula, chemical formula, table, etc.▼group or ▲mathematical formula , chemical formula, table, etc. ▼ indicates the group) A ketimine group-containing vinyl compound. (2) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, R is hydrogen or a lower alkyl group, and A is ▲There are mathematical formulas, chemical formulas, tables, etc.) Isocyanate compounds represented by ▼ group or ▲ mathematical formula, chemical formula, table, etc. ▼ group or ▲ mathematical formula, chemical formula, table, etc.) and general formula (IV) ▲ mathematical formula, chemical formula, table, etc. There is ▼...(IV) or general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) (In the formula, R', R'' and R''' are lower alkyl groups,
n represents an integer of 4 or 5. ) is reacted with a ketimine group-containing hydroxy compound represented by General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) or General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼...(II) (In the formula, R is hydrogen or a lower alkyl group, R', R''
and R''' is a lower alkyl group, n is an integer of 4 or 5, and A is a ▲mathematical formula, chemical formula, table, etc.▼ group, or ▲a mathematical formula, chemical formula, table, etc.▼group or ▲mathematical formula A method for producing a ketimine group-containing vinyl compound, which is characterized by obtaining a ketimine group-containing vinyl compound represented by , chemical formula, table, etc.