JPH07242588A - Polyoxyalkylene derivative containing carboxyl group - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a modifier for aqueous polyurethane resins or various kinds of polymers. CONSTITUTION:This compound is expressed by formula I [R1 is H or a 1-3C alkyl; R2 is a 1-6C alkylene or a 6-8C arylene; (l) is 0-2; (m) is 0.1 to 35; (n) is 0.1-50; 0.5<(m+n)<50; A is a 4-7C alkylene; B is a 2-6C alkylene]. The compound of formula I is obtained by subjecting a compound of formula II containing an alkylester group of a carboxylic acid and hydroxyl groups to addition polymerization with a 3 or 4-membered cyclic ether and a 5-membered cyclic ether using Lewis acid to afford a polyoxyalkylene derivative containing an alkylester group of carboxylic acid and hydroxyl groups and then, hydrolyzing the resultant compound with a base or an acid. The compound of formula I is an oligomer having low melting point or being liquid at ordinary temperature and can be used as a hydrophilic property-providing agent and modifier for polymers and the resultant aqueous polyurethane resin is excellent in stability and mechanical performance and can be used for coating, adhesive, binder, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyoxyalkylene derivative having a carboxyl group and a hydroxyl group, which is useful as a modifier for an aqueous polyurethane resin or various polymers, and a polyurethane resin using the derivative.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of danger of ignition and explosion due to solvent, toxicity to human body, environmental pollution, etc.
There is an increasing tendency to replace the solvent-based resins used in the past with aqueous resins. In particular, water-based polyurethane resin is a paint because it is possible to obtain a polymer with excellent characteristics from soft elastomers to hard plastics by reacting polyisocyanate compounds with many different structures, polyol compounds, and chain extenders. , Is being investigated in a wide range of fields such as adhesives and impregnants. As the water-based polyurethane resin, anion-type, cation-type, and nonion-type ones are known. However, due to the stability of the water-based polyurethane resin over time, physical performance, and miscibility with other emulsions and various pigments, etc. A self-emulsifying aqueous polyurethane having a carboxyl group introduced into a resin skeleton has been particularly attracting attention. A usual method for introducing a carboxyl group into a polyurethane resin is to react an excess polyisocyanate compound with a polyol compound to synthesize an isocyanate-terminated prepolymer, and then to react at least one carboxyl group and an isocyanate group in the molecule. 2 active hydrogen
It is carried out by reacting a compound containing one of them. As the compound for introducing a carboxyl group into the polyurethane resin skeleton, D.I. Review by Dieterich "Progress in Organic Co
ating, 9 (1981) 281-340 "and the like are known, but all have a high melting point and poor solubility in polyurethane resins and solvents used for polyurethane resins, and resins having a carboxyl group. Among the conventionally known compounds, 2,2'-dimethylolpropionic acid is a compound having a relatively good introduction of the carboxyl group into the polyurethane resin skeleton. ,
Even this compound has a high melting point and poor solubility in a polyurethane resin or a solvent, and it is necessary to use a solvent having a high polarity such as N-methyl-2-pyrrolidone. N-methyl-2, which is a water-soluble high-boiling-point solvent from an aqueous polyurethane resin
-It is difficult to remove pyrrolidone and the like, and the aqueous polyurethane resin obtained by these methods has a problem that it is used while containing a solvent.

[0003]

The present invention has been made in view of the above circumstances, and a first object thereof is to easily introduce a carboxyl group into a polyurethane resin skeleton or the like and to have a low melting point or a liquid state at room temperature. To provide a polyoxyalkylene derivative having at least one carboxyl group and hydroxyl group in the molecule. A second object is to provide a polyurethane resin containing a carboxyl group, which is particularly suitable for an aqueous polyurethane resin comprising the polyoxyalkylene derivative, a polyisocyanate compound, and optionally other polyol compound or a chain extender.

[0004]

Means for Solving the Problems The present inventors have conducted various studies in order to achieve the above-mentioned object, and carried out addition polymerization of a cyclic ether to the hydroxyl group of an alkyl ester of a carboxylic acid and a compound having a hydroxyl group to form a carboxylic acid. A polyoxyalkylene derivative having a carboxyl group and a hydroxyl group is synthesized by synthesizing a polyoxyalkylene derivative having an alkyl ester and a hydroxyl group, and then hydrolyzing the alkyl ester of a carboxylic acid of the polyoxyalkylene derivative. We have found this and completed the present invention.

That is, the present invention is as follows. 1. Polyoxyalkylene derivative containing carboxyl group and hydroxyl group represented by the following general formula [Chemical Formula 1]

[0006]

[Chemical 3]

R1; H, C1 to C3 alkyl group R2; C1 to C6 alkylene group, C6 to C8 arylene group l; 0 to 2 m; 0.1 to 35 n; 0.1 to 50 0.5 <(M + n) <50 A; C4-C7 alkylene group B; C2-C6 alkylene group

2. Alkyl ester group of carboxylic acid obtained by addition-polymerizing 3- to 4-membered cyclic ether and 5-membered cyclic ether by using Lewis acid in a compound containing an alkyl ester group of carboxylic acid represented by the following general formula [Chemical Formula 2] and a hydroxyl group And a hydroxyl group-containing polyoxyalkylene derivative, and a method for producing the above-mentioned polyoxyalkylene derivative containing a carboxyl group and a hydroxyl group, wherein the derivative is hydrolyzed in the presence of a base or an acid.

[0009]

[Chemical 4]

R: C1 to C8 alkyl group R1; H, C1 to C3 alkyl group R2; C1 to C6 alkylene group, C6 to C8 arylene group l; integer of 0 to 2

3. A carboxyl group-containing polyurethane resin comprising the polyoxyalkylene derivative having a carboxyl group and a hydroxyl group, a polyisocyanate compound, and optionally other polyol compound or a chain extender.

The compound having an alkyl ester group of carboxylic acid and a hydroxyl group used in the present invention is a compound represented by the following general formula [Chemical Formula 3].

[0013]

[Chemical 5]

R: C1 to C8 alkyl group R1; H, C1 to C3 alkyl group R2; C1 to C6 alkylene group, C6 to C8 arylene group l; integer of 0 to 2

Specific compounds include 2,2-bis (hydroxymethyl) propionic acid and 4,4-bis (4
Examples thereof include C1-C8 alkyl esters of compounds containing one carboxyl group and two hydroxyl groups such as -hydroxyphenyl) pentanoic acid and bis (4-hydroxyphenyl) acetic acid.

Examples of the Lewis acid used in the present invention include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, antimony pentachloride, aluminum chloride, ferric chloride, titanium tetrachloride, tin tetrachloride and hexachloride. Metallic or non-metal halides such as lithium fluorophosphate; solid acids such as silicon dioxide, titanium dioxide, zirconium dioxide and aluminum oxide, and solid acids obtained by impregnating the above halides.
Examples thereof include complexes of boron trifluoride, antimony pentafluoride and the like with chain and cyclic ethers such as dimethyl ether, diethyl ether and tetrahydrofuran.
Particularly, a complex of boron trifluoride and tetrahydrofuran is suitable.

The 3- to 4-membered cyclic ether compound used in the present invention is a 3-membered cyclic ether compound such as ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, and epichlorohydrin. Alkylene oxides, 1,3-propylene oxide, 1,3
Examples include 4-membered cyclic alkylene oxides such as -butylene oxide, 2-methyl-1,3-epoxypropane and 2,2-dimethyl-1,3-epoxypropane. Among them, ethylene oxide and 1,2-propylene oxide are preferable. It is also possible to use two or more types in combination.

Examples of the 5-membered cyclic ether compound used in the present invention include tetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and 2-methyltetrahydrofuran.

In carrying out the present invention, depending on the molecular structure and molecular weight of the target polyoxyalkylene derivative,
When a 5-membered cyclic ether is added to the hydroxyl group for which the type and amount of the compound having an alkyl ester group of the carboxylic acid and the hydroxyl group, the cyclic ether compound and the catalyst have to be set, the Lewis acid catalyst alone does not cause addition polymerization. Since it does not proceed, a 5-membered cyclic ether is added to and dissolved in a compound containing an alkyl ester group and a hydroxyl group of a carboxylic acid, and then 3 to 4 is added to a mixed solution containing a Lewis acid.
It is carried out by gradually dropping reaction of a member cyclic ether with stirring. The quantitative ratio of each component used to hydroxyl group is 0.01 to 2 mol of Lewis acid, preferably 0.04 mol.
Is 0.5 to 50 mol, 3 to 4 membered cyclic ether is 0.5 to 50 mol, preferably 1 to 10 mol, and 5 membered cyclic ether is determined in relation to the amount of 3 to 4 membered cyclic ether to be used.
Usually, the solvent is also used in excess and the unreacted material is recovered and reused after the polymerization reaction. When it is necessary to improve the solubility of the product, an inert organic solvent such as toluene, xylene, diethyl ether or dibutyl ether may be used. The reaction is -20 to 60 ° C, preferably 0 to 40
It is preferable to carry out the treatment under a substantially anhydrous condition at ℃ under a stream of dry nitrogen. The reaction time is 1 to 15 hours in the above temperature range, and 0 to 1
Two to six hours at 0 ° C is sufficient.

The polymerization completed liquid is neutralized with an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, etc., unreacted cyclic ether is removed by distillation, etc., and then an aqueous layer containing a catalytic decomposition product is separated. . When the solid acid or the like is not required to be neutralized, the catalyst component is separated by subjecting it to adsorption filtration as it is, and then the unreacted cyclic ether is recovered. The organic layer containing the polymer is purified by a known method such as washing with water, adsorption and filtration to obtain the polyoxyalkylene derivative having an alkyl ester group and a hydroxyl group of the carboxylic acid of the present invention. The polyoxyalkylene derivative having a carboxyl group and a hydroxyl group of the present invention is obtained by adding an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to the polyoxyalkylene derivative having a carboxylic acid alkyl ester group and a hydroxyl group obtained by the above method. , Hydrolysis reaction (saponification reaction). For the hydrolysis reaction, an alkali of equimolar or more with respect to the alkyl ester group of carboxylic acid is used, and if necessary, a lower alcohol such as ethanol or a water-soluble solvent such as tetrahydrofuran is added to give 60 to 10
It proceeds efficiently at 0 ° C. This hydrolysis reaction can also be carried out in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid or solid acid.

The polyisocyanate compound used in the present invention is not particularly limited, and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3'-dimethyldiphenylmethane-4,4 'diisocyanate, p-phenylene diisocyanate, 1,5
-Naphthalene diisocyanate, m-xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4
Aliphatic, aromatic and alicyclic diisocyanates such as tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 4,4'-dicyclohexylmethane diisocyanate, 1,4-bisisocyanatomethylcyclohexane A compound can be mentioned.

Polyols such as polyoxypropylene polyol, polyoxytetramethylene glycol, and the like, polyester polyols such as polybutylene adipate polyol, polyhexamethylene adipate polyol, polycaprolactone polyol, and polyhexamethylene carbonate are used as polyols in the present invention. Examples of polyols and chain extenders include glycols such as ethylene glycol and butanediol, and diamine compounds such as ethylenediamine, isophoronediamine and hydrazine.

The polyurethane resin using the polyoxyalkylene derivative having a carboxyl group and a hydroxyl group of the present invention, as a concrete example, an aqueous polyurethane resin is carried out by the following method. That is, a conventionally known polyol is reacted with an excess amount of a polyisocyanate compound in the presence or absence of a solvent to synthesize an isocyanate-terminated prepolymer, and then a polyoxyalkylene derivative containing a carboxyl group and a hydroxyl group of the present invention is reacted. To synthesize an isocyanate-terminated prepolymer having a carboxyl group. This prepolymer is mechanically dispersed in deionized water containing an inorganic base such as sodium hydroxide, an organic base such as triethylamine, tributylamine, dimethylethanolamine, and morpholine, and optionally a chain extender such as ethylenediamine and isophoronediamine. It is synthesized by dispersion emulsification. Isocyanate-terminated prepolymer containing a carboxyl group is polymerized by reacting with a chain extender such as ethylenediamine in the presence of a solvent to polymerize, and the carboxyl group is salted with an organic base such as triethylamine, and then machined in deionized water. It is also possible to dispersively emulsify and synthesize. In any case, conventionally known polyol 0 to 0.50, polyisocyanate compound 0.50 to 0.67, chain extender in equivalent ratio to the polyoxyalkylene derivative 0.02 to 0.50 of the present invention 0-0.5
It can be used in a ratio of 0.

The polyoxyalkylene derivative having a carboxyl group and a hydroxyl group of the present invention is liquid or has a low melting point at room temperature and can be reacted with an isocyanate-terminated prepolymer without using any solvent. In addition, a carboxyl group-containing polyurethane resin can be easily produced by a conventionally known method for producing a polyurethane resin, and can be used for a solvent type adhesive or a solventless thermoplastic urethane ionomer.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts indicate parts by weight. In this example, the hydroxyl value is a value measured by the pyridine-acetic anhydride method. Gel permeation chromatography (GPC) uses high performance chromatography manufactured by Toyo Soda Co., Ltd., column; TSK-G2
500HX / G4000HX, solvent: It carried out on condition of tetrahydrofuran. The number average molecular weight by GPC was calculated from a calibration curve obtained using a commercially available polyethylene glycol standard reagent. In addition, 1H-NMR, 13C-NMR
Analysis is made by JEOL Ltd. GSX-400, FT-NM
Performed by R.

[Example 1] 57 parts of 2,2-dimethylolpropionic acid n-butyl ester and 144.2 parts of tetrahydrofuran were placed in a nitrogen-substituted 500 cc four-necked flask equipped with a stirrer, a thermometer and a silica gel tube. The mixture was kept under cooling in an ice-cooled bath with stirring, then 7.0 parts of boron trifluoride-tetrahydrofuran complex was added, and then 58.1 parts of propylene oxide was gradually added in a dropping funnel at 5 to 10 ° C over 2 hours. did. Then, after carrying out a polymerization reaction at 5 to 10 ° C. for 4 hours, 320 parts of a 10 wt% sodium carbonate aqueous solution was added to terminate the polymerization. Next, a distillation apparatus was set in the flask and heated to distill the unreacted tetrahydrofuran. After cooling and standing still, the lower aqueous layer was removed. Next, 200 parts of toluene and 100 parts of water were added, the temperature was raised to 60 ° C., washing with stirring was carried out, and the mixture was allowed to cool and allowed to stand, and the lower layer was removed. Add 150 parts of water, 60
After the operation of washing with water at 0 ° C. was repeated 4 times, toluene was distilled from the organic layer at 100 ° C. under reduced pressure to obtain 199 parts of a colorless and transparent polymer at room temperature. This polymer had a hydroxyl value (mgKOH / g) of 151 and an acid value of 0.8. As a result of GPC and NMR analysis, 2,2-dimethylolpropionic acid n-butyl ester as a raw material disappeared and the average molecular weight was 7
It was a copolymer polyol of 38 with tetrahydrofuran and propylene oxide added.

Example 2 In a 1000 CC four-necked flask equipped with a stirrer, a thermometer, and a condenser, 150 parts of the copolymerized diol synthesized in Example 1 and 150 toluene.
Parts, THF (50 parts) and 30% by weight sodium hydroxide aqueous solution (200 parts) were charged, and hydrolysis was carried out in a hot water bath at 80 ° C. for 3 hours. After cooling, the mixture was neutralized with 4N hydrochloric acid, allowed to stand while cooling and separated, and the lower layer was extracted. Next, the operation of adding 100 parts of water and stirring and washing with water for 20 minutes at 60 ° C. is repeated 4 times,
Toluene and tetrahydrofuran were removed from the final organic layer under reduced pressure to obtain 121.5 parts of a transparent liquid polymer having a viscosity of 1260 cps / 22 ° C. The acid value of this polymer was 69, the hydroxyl value was 137, and the average molecular weight by GPC analysis was 817. As a result of NMR analysis, this polymer was obtained by adding 3.1 mol of tetrahydrofuran and 2.1 mol of propylene oxide to 1 equivalent of the hydroxyl group of 2,2-dimethylolpropionic acid.

[Example 3] A hydroxyl value of 5 was added to a 500 CC four-necked flask equipped with a stirrer, a thermometer, and a silica gel tube.
28.7 parts of hexamethylene diisocyanate (HDI manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 152.1 parts of polyhexamethylene carbonate diol (N-960R manufactured by Nippon Polyurethane Industry Co., Ltd.) of 4.2, and the mixture was heated under a nitrogen stream at 85
After reacting at 5 ° C for 5 hours, the acid value of 6 synthesized in Example 2
9, polyoxyalkylene derivative 3 having a hydroxyl value of 137
9.9 parts were added, and the mixture was reacted at 85 ° C. for 5 hours to obtain a carboxyl group-containing isocyanate-terminated prepolymer.
Next, 10 parts of hydrazine monohydrate was added to this prepolymer.
Acetone solution containing 4.9 parts by weight and acetone 150
After adding 1 part and reacting at 40 ° C. for 1 hour, 5.9 parts of triethylamine was added and stirred at 40 ° C. for 10 minutes to form a salt. 360 parts of this prepolymer was forcibly emulsified in 250 parts of water with stirring with a homomixer. Acetone in the obtained polyurethane emulsion was distilled off under heating and reduced pressure, followed by aging for 5 days. The obtained polyurethane emulsion had a solid content of 36.5% by weight and a viscosity of 3800 cps / 2.
It was a product showing good mechanical stability at 0 ° C and pH 7.5. Approximately 200, which was produced at room temperature and heat treated at 80 ° C for 30 minutes
Normal state (20 ℃, 65RH) measured using μ thick film
%) And the tensile properties at the time of immersion in water (20 ° C./24 hrs.) Are shown in [Table 1]. Tensile properties were measured by Tensilon UTM-III-100 manufactured by Orientec Co., Ltd.
It was measured in mm / min.

[0029]

[Table 1]

[Comparative Example 1] In Example 3, 2,2-dimethylolpropionic acid was used in place of the polyoxyalkylene derivative of the present invention, and the ratio of isocyanate group / hydroxyl group as a raw material constituting the polyurethane resin and polyurethane were used. 152.1 parts of polyhexamethylene carbonate, 26.8 parts of hexamethylene diisocyanate, and 5.5 parts of dimethylolpropionic acid were charged so that the carboxylic acid contents in the resin would be the same, and otherwise the same reaction was carried out. . As a result, dimethylolpropionic acid was partially dissolved but most was not dissolved. This prepolymer was forcibly emulsified in water using a homomixer,
No good polyurethane emulsion was obtained.

[0031]

EFFECTS OF THE INVENTION The polyoxyalkylene derivative of the present invention is an oligomer having functional groups having different hydroxyl groups and carboxyl groups and having a low melting point or a liquid at room temperature, and can be used as a hydrophilicity-imparting agent or modifier for polymers. it can.
The carboxyl group-containing polyurethane of the present invention can be particularly preferably used for an aqueous polyurethane resin, and the obtained aqueous polyurethane resin has excellent stability and mechanical performance and can be used for paints, coatings, adhesives, binders and the like.

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Claims (3)

[Claims] 1. A polyoxyalkylene derivative containing a carboxyl group and a hydroxyl group represented by the following general formula [Chemical formula 1] R1, H, C1-C3 alkyl group R2; C1-C6 alkylene group, C6-C8 arylene group l; 0-2 m; 0.1-35 n; 0.1-50 0.5 <(m + n ) <50 A; C4-C7 alkylene group B; C2-C6 alkylene group 2. A carboxylic acid obtained by addition-polymerizing a 3- to 4-membered cyclic ether and a 5-membered cyclic ether by using a Lewis acid to a compound containing an alkyl ester group and a hydroxyl group of a carboxylic acid represented by the following general formula [Chemical Formula 2]. A method for producing a polyoxyalkylene derivative according to claim 1, which comprises a polyoxyalkylene derivative containing an alkyl ester group of an acid and a hydroxyl group and a carboxyl group and a hydroxyl group obtained by hydrolyzing the derivative in the presence of a base or an acid. [Chemical 2] R; C1 to C8 alkyl group R1; H, C1 to C3 alkyl group R2; C1 to C6 alkylene group, C6 to C8 arylene group l; integer of 0 to 2 3. A carboxyl group-containing polyurethane resin comprising the polyoxyalkylene derivative containing a carboxyl group and a hydroxyl group according to claim 1, a polyisocyanate compound, and optionally another polyol compound or a chain extender.