JPH01242564A - Production of urethane polyol having tertiary amino group - Google Patents

Abstract

PURPOSE:To easily obtain the subject substance useful as a synthetic resin raw material, a surfactant, a water-soluble point, etc., by reacting a urethane diol having secondary amino group with a compound having epoxy group. CONSTITUTION:A compound of formula (R is H or CH3; n is 1-4) is made to react with a compound having epoxy group (e.g., n-butyl glycidyl ether) at room temperature -200 deg.C to obtain the objective compound. The objective compound soluble in a solvent can be produced by using equivalent or less than equivalent amount of epoxy group based on the secondary amino group. The objective substance is a compound having at least 3 OH groups, at least one tertiary amino group and at least 2 urethane bonds. The present process does not require any restriction in the kind of the isocyanate compound used as a starting raw material in contrast with conventional process.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Application Field) The present invention relates to a novel method for producing urethane polyols having tertiary amino groups useful as chemical products such as synthetic resins and surfactants. .

(Prior art) Urethane alcohol having a tertiary amino group utilizes the polarity of the tertiary amino group to make chemicals such as epoxy resins and urethane resins water-soluble, improve water dispersibility, and improve wood-philic properties. It is used to improve adhesion to surfaces, or to improve the reactivity of chemicals due to the catalytic action of tertiary amino groups.

Conventionally, in order to produce this kind of urethane alcohol having a tertiary amino group, it has been a common method to prepare it by reacting a compound having an isocyanate group with a polyol having a tertiary amino group.

However, as compounds having isocyanate groups, phenyl isocyanate, which has low volatility and low toxicity,
Only isocyanates with a large number of carbon atoms, such as tolylene diisocyanate and hexamethylene diisocyanate, can be obtained generally and industrially, and even if special isocyanates are obtained, they are expensive and have safety and hygiene problems. Alternatively, there are problems such as the unavoidable complexity of handling operations.

(Problems to be Solved by the Invention) As a result of intensive studies to solve the drawbacks of the conventional methods for producing urethane alcohols having tertiary amino groups, the present inventors found that The present inventors have discovered that a desired urethane polyol having a tertiary amino group can be obtained from a urethane diol and an epoxy group-containing compound, and have completed the present invention.

An object of the present invention is to provide a method for easily producing a urethane polyol having a tertiary amino group without using isocyanate as a starting material.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention is obtained by reacting a urethanediol having a secondary amino group represented by the following general formula (I) with a compound having an epoxy group. The present invention relates to a method for producing a urethane polyol having a tertiary amino group.

General formula (■): Hereinafter, the configuration of the present invention will be explained in detail.

In the method for producing a urethane polyol having a tertiary amino group according to the present invention,
Urethane diols having a grade amino group can be easily produced without using special isocyanates. That is, the urethane diol component having a secondary amino group represented by the general formula (I) is a polyalkylene polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, or pentaethylene hexamine, and ethylene carbonate and/or propylene. It can be easily produced by reacting 1,3 dioxolan-2-one such as carbonate.

Used in the present invention. Examples of the compound having an epoxy group include n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and styrene oxide.

Phenyl glycidyl ether, cresyl glycidyl ether, 5ee-butylphenyl glycidyl ether, glycidyl (meth)acrylate, vinylcyclohexene monoepoxide, α-pinene oxide, Cardura E (manufactured by Shell Chemical ■, glycidyl ester), ethylene oxide, propylene oxide, etc. Compounds having 1-epoxy group; (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl aniline, bisphenol A-based epoxy resin,
Bisphenol F-based epoxy resin.

Compounds with two epoxy groups such as glycidyl ester resins, cyclopentadiene jepoxy compounds, resorcinol diglycidyl ether; novolac type epoxy resins, tetraglycidyl diaminodiphenylmethane, triglycidyl luminophenol, bisresorcinol tetraglycidyl ether, tetra 3 such as glycidyl xylene diamine, triglycidyl isocyanurate, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and epoxidized soybean oil.
Compounds having more than one epoxy group are used.

In the present invention, the reaction between the urethanediol having a secondary amino group represented by the general formula (I) and the compound having an epoxy group is carried out based on the reaction between the secondary amino group and the epoxy group. . Reaction temperature is room temperature to 200℃
Temperatures of 200° C. or higher are not preferred because the reaction between the hydroxyl groups in the urethane diol and the epoxy groups tends to occur.

In the present invention, in order to produce a polyurethane polyol having a 3R amino group that is soluble in a solvent, 1) If the compound having an epoxy group is a compound having one epoxy group, the secondary amino group is n in the general formula (I) of the urethanediol having 2) epoxy groups is a compound having two epoxy groups, urethanediol having a secondary amino group n in the general formula (I) is 1 to 2, and 3), when the compound having an epoxy group is a compound having three or more epoxy groups, urethane diol having a secondary amino group is It is appropriate that n in the general formula (I) be 1; other combinations tend to prevent dissolution in the solvent.

In addition, in order to produce a polyurethane polyol having a tertiary amino group that is soluble in the solvent as described above, the ratio of the secondary amino group of the urethane diol to the epoxy group of the compound having an epoxy group is equivalent to the secondary amino group. or less than an equivalent amount of epoxy groups is suitable.

The urethane polyol having a tertiary amino group of the present invention produced as described above has at least three hydroxyl groups, at least one tertiary amino group, and at least two urethane bonds in the molecule. It is a compound that has

The urethane polyol compound having a tertiary amino group of the present invention can be used without a catalyst itself or with a urethanization catalyst.
Crosslinked urethane resins can be produced by self-condensation, such as by deglycolization, in the presence of catalysts such as organotin compounds, organolead compounds, polyisocyanates, and melamine resins.

A crosslinkable resin can be formed in combination with a crosslinking agent such as a urea resin.

In addition, the general formula (2) used when producing the urethane polyol having 3R amino groups of the present invention
Urethane diol having an amino group is highly aqueous, and if the compound having an epoxy group to be reacted with it is a hydrophobic compound such as Cardura E, epoxidized soybean oil, or epoxy resin, the urethane diol has 5 reactions. Since the product, ie, the urethane polyol having a tertiary amino group of the present invention, has both a parent wood part and a hydrophobic part, it can be used as a water-soluble paint, a surfactant, and the like.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist of the invention is exceeded.

Example 1 1 mol of diethylenetriamine was placed in a 4-volume flask with a thermometer, a stirrer, 9 dropping funnels, and a condenser, and 2 mol of propylene carbonate was added dropwise from the dropping funnel.
As the dripping starts, heat is generated and external temperature is generated, so the dripping is adjusted to maintain the temperature at 80°C.

After the dropwise addition was completed, the temperature was maintained at 80° C. for 2 hours to obtain a pale yellow viscous resinous material. As a result of infrared analysis and nuclear magnetic analysis, this compound was confirmed to have the following structural formula.

To 1 mol of the urethanediol having the secondary amino group,
Cardura E (glycidyl ester with the following structure, Shell Chemical aWi).

As a result of infrared analysis and nuclear magnetic analysis, it was confirmed that the resinous material was a urethane polyol having a tertiary amino group having the following structure.

The urethane polyol is soluble in acetone and butyl acetate.

Example 2 1 mol of diethylenetriamine in Example 1 was replaced with 1 mol of tetraethylenepentane, and 2 mol of propylene carbonate was replaced with 82 mol of ethylene carbonate to react in the same manner as in Example 1, having a secondary amino group with the following structure. Synthesized urethanediol.

Three moles of Cardura E were added to the urethane diol having secondary amino groups, and the reaction was carried out in the same manner as in Example 1 to synthesize a urethane polyol having 5 hydroxyl groups and 3 tertiary amino groups. The urethane polyol is soluble in acetone.

Example 3 In a flask similar to Example 1, diethylenetriamine 2
4 moles of molten ethylene carbonate are added dropwise.At the start of the first drop, it generates a lot of heat and the temperature rises, but adjust the dropping to keep the temperature at 120℃.After the first drop is finished, the temperature rises to 120℃.
6 to obtain a brown crystalline compound at normal temperature for 1 hour.
While melting the mole at 120 ° C., Ebicuron 850 (bisphenol A-based epoxy resin,
Epoxy value equivalent: 190) After 1 hour of adding 2 parts of the same compound, the reaction was kept at 120°C for 2 hours to complete the reaction, and the non-volatile content was 5.
A brown transparent solution of urethane polyol with 0% tertiary amino groups was obtained.

〔Effect of the invention〕

According to the present invention, a urethane polyol having a tertiary amino group can be easily produced from a urethane diol having a specific secondary amino group and an epoxy group-containing compound.

Therefore, compared to the conventional method for producing a urethane polyol having a tertiary amino group from an incyanate group-containing compound and a tertiary amino group-containing compound, the present invention is free from any restrictions on the isocyanate compound as a starting material. do not have.

The urethane polyol having a tertiary amino group produced by the present invention can be combined with other crosslinking agent components to form a crosslinkable resin, or by utilizing its hydrophilicity, it can be used as a water-soluble resin having both an appropriate hydrophilic part and a hydrophobic part. It can be used as a synthetic paint or a surfactant, and is extremely useful.

Claims (1)

[Scope of Claims] A method for producing a urethane polyol having a tertiary amino group, which comprises reacting a urethane diol having a secondary amino group represented by the following general formula (I) with a compound having an epoxy group. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R represents H or CH_3, n represents an integer from 1 to 4, respectively. ]