JPH05156004A - Reactive plasticizer for thermosetting resin - Google Patents

Abstract

PURPOSE:To provide the subject plasticizer consisting of a highly low-viscosity liquid material, easily incorporable in a thermosetting resin even in a solventless system, capable of giving cured products with good plasticity and flexibility. CONSTITUTION:The objective plasticizer consisting of an aliphatic polyamidamine composition can be obtained by condensation between (A) a dimer acid component containing >=50wt.% of a chain dimer acid or its lower ester of formula I (R<1> and R<2> are each H or lower alkyl; (m), (n), (p) and (q) are each 0 or an integer of >=1; (m+n)=13, (p+q)=15), (B) a 4-20C alkylenepolyamine, and if needed, (C) a monovalent fatty acid or its ester of formula II (R<3> is 5-21C alkyl or alkenyl; R<4> is H or lower alkyl) at the equivalent ratio of the free or esterified carboxyl group in the component A to the primary amino group in the component B of (1:1) to (1:1.9) and at the molar ratio of the component C to the component A of <=2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel reactive plasticizer for thermosetting resin, and more specifically, it is a liquid material having an extremely low viscosity and can be easily compounded with a thermosetting resin even in a solvent-free system. The present invention relates to a reactive plasticizer for a thermosetting resin, which comprises a dimer acid polyamidoamine composition capable of giving a cured resin having plasticity and flexibility.

[0002]

BACKGROUND OF THE INVENTION Dimer acid is a polyvalent carboxylic acid obtained by polymerization reaction of two or more molecules of unsaturated fatty acid, and is usually obtained as a mixture of two or more kinds, and various applications as a mixture. Have been offered to. This dimer acid is the highest molecular weight dibasic acid which is highly reactive and hydrophobic and which can be obtained industrially, and the polymer derived from it is amorphous and flexible and has good stability at low temperature. It is used in many fields because it shows sex. For example, a non-reactive dimer acid polyamide obtained from dimer acid as a raw material is tough, shows flexibility, and has good adhesive performance, and thus is used as a component of an adhesive, an ink, a surface coating agent, Reactive substances are compounded with epoxy resins as epoxy resin curing agents, and are used for surface coating of metals, plastics, ceramics, etc., or as two-component reactive adhesives.

Such dimer acid has hitherto been used as a catalyst using montmorillonite clay as a catalyst, and unsaturated resin acid as a dimer acid.
It is produced by a method of dimerizing at a high temperature of about 00 to 250 ° C. In this method, since the trans-double bond is generally conjugated to increase the thermal polymerization rate, tall oil fatty acid or soybean oil fatty acid having a high linoleic acid content is used as a raw material, and its industrial process is standardized. Has been done.

By the way, when dimer acid is produced by such a method, the linoleic acid contained in the raw material is dimerized and

[Chemical 4] In addition to the chain dimer acid represented by

[Chemical 5] as well as

[Chemical 6] A mixture containing the cyclic dimer acid represented by is obtained.

However, when the content of the cyclic dimer acid is high, the viscosity and the pour point become high. For example, the one obtained by condensing the cyclic dimer acid with the alkylene polyamine has a high melt viscosity, and it is blended with the resin to produce xylene or It is necessary to dilute with an organic solvent such as alcohol to reduce the viscosity before use.However, if such a diluted product is used, the residual solvent may cause the impact resistance and high temperature stability of the resin to be impaired. The use of organic solvent is not preferable from the viewpoint of environmental pollution and work hygiene.

Therefore, for example, with respect to dimer acid, alkylene polyamine is 2 times mole and fatty acid with a low melting point is 4 times.
A method for producing a low melting point composition using a solvent such as methanol in an amount of about 7 to 7 times has been proposed (JP-A-55-106224 and JP-A-56-8435).
However, since the composition obtained by this method contains a large amount of amino groups having active hydrogen, it has a drawback that a whitening phenomenon (amine brushing) occurs on the resin surface due to moisture and carbon dioxide in the air. However, the use of a large amount of amine also poses a problem in terms of work hygiene.

Generally, in hydrocarbons having the same carbon chain length, compounds having a cyclic structure in the molecule are known to have higher melting points and viscosities than chain structure compounds due to their steric characteristics. Has been. When unsaturated fatty acid containing 78% by weight of oleic acid was used as a raw material and condensed in the presence of a montmorillonite catalyst at a temperature of about 250 ° C., the amount of cyclic structure was reduced to 40% by weight of linear dimer acid. Although it has been reported that a dimer acid composition containing the same can be obtained [[Journal of American Oil Chemistry Society (J. Am. Oil
Chemist's Soc. ) "Volume 51, 52
2 (1974)], no method for increasing the chain dimer acid content to 50% by weight or more has been known so far.

[0008]

DISCLOSURE OF THE INVENTION The present invention has a lower viscosity than conventional ones and high fluidity at low temperatures.
It was made for the purpose of providing a reactive plasticizer for a thermosetting resin, which comprises a dimer acid polyamidoamine composition which can be easily blended with the thermosetting resin without being diluted.

[0009]

Means for Solving the Problems The inventors of the present invention previously contained 50% by weight or more of a chain dimer acid or its ester or both by dimerizing a specific raw material under specific conditions. We succeeded in obtaining a dimer acid mixture with low viscosity and good low temperature fluidity (Japanese Patent Application No. 2-184).
294), and as a result of further research, it was found that the objective can be achieved by using a mixture of this dimer acid mixture with a specific alkylene polyamine as a reactive plasticizer for thermosetting resin. The present invention has been completed based on this finding.

That is, the present invention provides (A) the general formula

[Chemical 7] (In the formula, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and they may be the same or different, and m, n, p and q are 0 or 1 or more. An integer of m + n = 13 and p + q = 15), and a dimer acid component containing at least 50% by weight of at least one selected from the chain dimer acid and its ester, and (B) having 4 carbon atoms. ~ 20 alkylene polyamine, the equivalent ratio of the free or esterified carboxyl group in the component (A) to the primary amino group in the component (B) is in the range of 1: 1 to 1: 1.9. In addition, if necessary, (C) general formula

[Chemical 8] (In the formula, R ³ is an alkyl group or alkenyl group having 5 to 21 carbon atoms, R ⁴ is a hydrogen atom or a lower alkyl group), and a monovalent fatty acid or an ester thereof is used at a molar ratio of 2 or less to the dimer acid component. The present invention provides a reactive plasticizer for thermosetting resin, which comprises a fatty acid polyamidoamine composition obtained by a condensation reaction.

The dimer acid component used in the present invention is
Any of the dimer acid represented by the above general formula, its monoester, diester, and a mixture thereof may be used.
In addition, trimer acid or its ester may be produced as a by-product during the production of this dimer acid, and such a dimer acid may be used as it is.

The dimer acid component has a carbon number of 1
The unsaturated dimer of 8 unsaturated fatty acids such as oleic acid, linoleic acid and lower alkyl esters thereof such as methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester and tert-butyl ester may be mentioned. it can. These may be a single component or a mixed component containing two or more kinds.

The dimer acid component is obtained by polymerizing an unsaturated fatty acid or an ester thereof in the presence of a Lewis acid type or Bronsted acid type catalyst having high acid strength, and further hydrolyzing the ester when used as a raw material. As a raw material, oleic acid and its lower alkyl ester 70 can be obtained.
Those obtained by using an unsaturated fatty acid or a lower alkyl ester thereof containing at least wt% are preferable.

The dimer acid component thus obtained usually contains monomer components such as unreacted components and by-produced branched fatty acids, so these are removed by vacuum distillation, and then the distillation residue is separated into molecules. It may be purified by distillation and used, or may be used in a state in which the monomer component is contained.

Examples of the alkylene polyamine having 4 to 20 carbon atoms for the condensation reaction with the dimer acid component include diethylene triamine, triethylene pentamine, tetraethylene pentamine, pentaethylene hexamine, and hexaethylene heptamine. These may be used alone or in combination of two or more.

Next, as the monovalent fatty acid represented by the above general formula or its ester for further condensing the condensation product of the dimer acid component and the alkylene polyamine, if necessary, for example, caproic acid, caprylic acid, pelargone. Acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid and their methyl esters, ethyl esters, n-propyl Examples include esters, isopropyl esters, n-butyl esters, isobutyl esters, tert-butyl esters and the like. These may be used alone or in combination of two or more.

In the present invention, the dimer acid component and the alkylene polyamine are used in an equivalent ratio of the former free or esterified carboxyl group to the latter primary amino group of 1: 1 to 1: 1.9. It is necessary to condense at a rate that falls within the range. Further, it is necessary to use the monovalent fatty acid represented by the general formula or its ester in an amount of not more than 2 times, preferably 1 to 2 times the mol of the dimer acid component. This monovalent fatty acid or its ester is used to block the terminal amino group and suppress the curing action.

The reactive plasticizer of the present invention is prepared by condensing the dimer acid component (A) and the alkylene polyamine (B) in a required ratio, or by further adding a monovalent fatty acid or its ester (C) thereto. Is carried out by reacting the monovalent fatty acid or the ester thereof with the dimer acid component (A) and the alkylene polyamine (B) with the monovalent fatty acid or the ester thereof (C). You can also make them react at once.

The condensation reaction is usually carried out at 120 to 250 under normal pressure.
C., preferably by heating at a temperature in the range 180 to 230.degree. Further, in order to prevent coloring of the product, it is advantageous to carry out under an atmosphere of an inert gas such as nitrogen gas. The reaction time depends on the reaction temperature and the type of raw material used and cannot be determined unconditionally, but usually about 2 to 5 hours is sufficient. Further, it is desirable that the reaction be aged under a reduced pressure for an appropriate time before the completion of the reaction. Although the viscosity of the reaction solution increases with the progress of the reaction, the reaction product does not solidify even after the completion of the reaction, and the transfer from the reaction container to the storage container is easy even at room temperature. Also,
If desired, at the end of the reaction, a solvent such as xylene or alcohol may be added as in the conventional products.

The dimer acid polyamidoamine condensation product thus obtained has a viscosity at 40 ° C. of 10,
It is 000 cp or less, and has an extremely low viscosity as compared with the conventional one. And this thing can be mix | blended easily with thermosetting resin, such as a phenol resin and an epoxy resin, and it acts as a reactive plasticizer.

[0021]

The reactive plasticizer of the present invention has a low viscosity and can be easily mixed with a thermosetting resin such as a phenol resin or an epoxy resin without diluting with an organic solvent. It does not deteriorate the physical properties due to the inclusion of, and is very advantageous in terms of prevention of environmental pollution and work hygiene.

[0022]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 55% by weight of linear dimer acid obtained by polymerizing oleic acid,
A dimer acid component (A) consisting of 20% by weight of cyclic dimer acid and 25% by weight of trimer acid, and a monovalent fatty acid mixture (C) consisting of 10% by weight of stearic acid, 75% by weight of oleic acid and 15% by weight of linoleic acid. , (C) component /
The components (A) are mixed so that the molar ratio is 1.5, and then, a mixed alkylene polyamine (B) of 50% by weight of diethylenetriamine and 50% by weight of triethylenetetramine is added to the mixture, and a primary amino group / carboxyl group. The equivalent ratio of the groups is 1.9, and added under a nitrogen atmosphere.
The reaction was carried out at 230 ° C. for 2.5 hours and at 230 ° C. and 5 mmHg for 1 hour to obtain a dimer acid polyamidoamine composition. The viscosity of this composition at 25 ° C. was 1200 cp.
Next, when this composition was added to an epoxy resin, it had good compatibility with the resin and the cured product was excellent in crosslinkability, flexibility and plasticity.

Examples 2 to 4 and Comparative Examples 1 to 3 Example 1 was repeated except that the raw materials of the types and amounts shown in Table 1 were used. The results are shown in Table 1. In addition, the compositions of the examples have good compatibility with the epoxy resin,
The cured product was excellent in crosslinkability, flexibility and plasticity.

[Table 1]

Example 5 55% by weight of linear dimer acid obtained by polymerizing oleic acid,
A dimer acid component (A) consisting of 20% by weight of cyclic dimer acid and 25% by weight of trimer acid and tetraethylenepentamine (B) are mixed at a ratio of the equivalent ratio of primary amino group / carboxyl group of 1.5. Then, the reaction was performed in the same manner as in Example 1 to obtain a dimer acid polyamidoamine composition having a viscosity of 2,000 cp at 25 ° C. This product had a good compatibility with an epoxy resin and gave a composition excellent in crosslinkability, flexibility and plasticity.

Example 6 A dimer acid component (A) comprising 55% by weight of linear diethyl dimer acid obtained by polymerizing ethyl oleate, 20% by weight of cyclic dimer acid diethyl and 25 parts by weight of triethyl trimerate was added to stearic acid. An ester mixture (C) consisting of ethyl, ethyl oleate and ethyl linoleate,
The components (C) / (A) are mixed in a molar ratio of 1.5, and the mixture is mixed with diethylenetriamine 50.
An alkylenepolyamine component (B) consisting of 50% by weight of triethyltetramine and 50% by weight of triethyltetramine in an amount such that the equivalent ratio of primary amino group / ethoxycarbonyl group is 1.9,
A condensation reaction was carried out in the same manner as in Example 1. The viscosity of the obtained dimer acid polyamidoamine composition at 25 ° C. was 1,050 cp. It showed a good compatibility with the epoxy resin.

Claims (2)

[Claims] 1. (A) General formula: (In the formula, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and they may be the same or different, and m, n, p and q are 0 or 1 or more. An integer of m + n = 13 and p + q = 15), and a dimer acid component containing at least 50% by weight of at least one selected from the chain dimer acid and its ester, and (B) having 4 carbon atoms. ~ 20 alkylene polyamine, the equivalent ratio of the free or esterified carboxyl group in the component (A) to the primary amino group in the component (B) is in the range of 1: 1 to 1: 1.9. A reactive plasticizer for a thermosetting resin, which is composed of an aliphatic polyamidoamine composition obtained by condensation in the following ratio. 2. (A) General formula: (In the formula, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and they may be the same or different, and m, n, p and q are 0 or 1 or more. An integer of m + n = 13 and p + q = 15), and a dimer acid component containing at least 50% by weight of at least one selected from the chain dimer acid and its ester, and (B) having 4 carbon atoms. ~ 20 alkylene polyamine, the equivalent ratio of the free or esterified carboxyl group in the component (A) to the primary amino group in the component (B) is in the range of 1: 1 to 1: 1.9. At a rate of
Furthermore, (C) general formula: (In the formula, R ³ is an alkyl group or alkenyl group having 5 to 21 carbon atoms, R ⁴ is a hydrogen atom or a lower alkyl group), and a monovalent fatty acid or an ester thereof is used at a molar ratio of 2 or less to the dimer acid component. A reactive plasticizer for thermosetting resin, comprising a fatty acid polyamidoamine composition obtained by a condensation reaction.