JPH0228216A - Production of modified polyamide(imide) - Google Patents

Abstract

PURPOSE:To obtain the title polymer having good resistance to hydrolysis and heat aging by adding a compound having oxazoline ring to a polyamide or polyamideimide prepared by reacting an organic diisocyanate with an organic carboxylic acids. CONSTITUTION:A compound (e.g., 1,3-phenylene-bis-2-oxazoline) having one or more oxazoline rings in one molecule is added to a polyamide or polyamideimide prepared by mutually reacting components selected from compounds consisting of an organic diisocyanate (e.g., 4,4'- diphenylmethanediisocyanate), organic carboxylic acid (e.g., polyester composed of 3-methyl-1,5-pentanediol and adipic acid and having both carboxylic ends and organic carboxylic anhydride (e.g., trimellitic acid) to provide the aimed modified polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to organic diisocyanates, dicarboxylic acids and/or
Or manufacture modified polyamide or modified polyamide-imide that has excellent heat resistance, oil resistance, chemical resistance, hydrolysis resistance, and heat aging resistance from polyamide or polyamide-imide obtained by reacting with acid anhydride. Regarding how to.

[Prior Art] Polyamides obtained by the reaction of diisocyanates and dicarboxylic acids and methods for producing the same are already known (U.S. Pat. Nos. 4,087,481 and 4,12).
No. 9,715, No. 4,156,065, etc.). Also,
A polyamideimide obtained by the reaction of an organic diisocyanate, a dicarboxylic acid, and an acid anhydride and a method for painting the same have already been disclosed in Japanese Patent Application No. 123394/1982.

[Problems to be Solved by the Invention] However, the above-mentioned polyamides or polyamideimides have insufficient performance in applications requiring high hydrolysis resistance and heat aging resistance. Among polyamides or polyamide-imides, those having ester bonds in the molecule have particularly low hydrolysis resistance and heat aging resistance compared to polyamides or polyamide-imides having no such bonds.

In order to improve the hydrolysis resistance, attempts have been made to introduce ether bonds into the molecular chains of polyamides or polyamideimides, but such polyamides or polyamideimides have poor optical properties, mechanical properties, and heat aging resistance. There were problems with gender, etc.

An object of the present invention is to provide a modified polyamide or modified polyamide-imide that has significantly improved hydrolysis resistance, heat aging resistance, etc., without significantly impairing the excellent properties of polyamide-imide. It is.

[Means for Solving the Problem] As a result of intensive studies on improving the hydrolysis resistance and heat aging resistance of polyamide or polyamide-imide, the present inventors found that after the late stage of the polymerization reaction of polyamide or polyamide-imide or during molding processing. The present inventors have discovered that the above object can be achieved by adding and reacting a compound having one or more oxazoline rings in the molecule, and have completed the present invention.

That is, in the present invention, when obtaining an organic diisocyanate component, an organic dicarboxylic acid component, and a polyamide-imide, the polyamide or polyamide-imide obtained by further reacting the organic diisocyanate component, an organic dicarboxylic acid component, and an acid anhydride component has at least one polyamide-imide in the molecule. This is a method for producing modified polyamide or modified polyamide-imide, which is characterized by adding and reacting a compound having an oxazoline ring.

The polyamide subjected to modification in the present invention is obtained by a polycondensation reaction between an organic diisocyanate component and a dicarboxylic acid component, and the polyamideimide is obtained by a polycondensation reaction between an a-organic diisocyanate component, a dicarboxylic acid component, and an acid anhydride component. It is.

At this time, the organic diisocyanate component used is not particularly limited, and typical examples include 4.4
-diphenylmethane diisocyanate, 2.4-tolylene diisocyanate, 2.6-) lylene diisocyanate, phenylene diisocyanate, 1.5-naphthylene diisocyanate, 3.3'-dichloro4.4'-
Aromatic diisocyanates having 8 to 20 carbon atoms such as diphenylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4.4°-dicyclohexylmethane diisocyanate. Examples include aliphatic or cyclic diisocyanates having 8 to 20 carbon atoms such as diisocyanates. In consideration of mechanical properties and heat resistance, aromatic diisocyanates are preferred, particularly preferably 4,4'-diphenylmethane diisocyanate, 2.
4-tolylene diisocyanate, 2.6-tolylene diisocyanate are used.

In addition, the organic dicarboxylic acid component is not particularly limited, and one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and double-terminated carboxylic acid polyesters.
More than one species can be used.

Typical organic dicarboxylic acids include those having 4 to 54 carbon atoms, such as glutaric acid, adipic acid, azelaic acid, pimelic acid, sebacic acid, decanniic acid, dodecanniic acid, and dimer acid.
aliphatic dicarboxylic acids and isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acids, etc. having 8 or more carbon atoms
20 aromatic dicarboxylic acids are mentioned. Among these low molecular weight dicarboxylic acids, aliphatic dicarboxylic acids are more preferably used than aromatic dicarboxylic acids from the viewpoint of moldability.

Examples of the double-terminated carboxylic acid polyester include polyhexane adipate dicarboxylic acid, polyhexane azelate dicarboxylic acid, poly3-methyl-1,5-bentanediol adipate dicarboxylic acid, and poly3-methyl-1
, 5-bentanediol azelate dicarboxylic acid, poly 2-methyl-18-octanol azelate dicarboxylic acid, poly 2-methyl-1,8-octanol azelate dicarboxylic acid, poly 1,9-nonane diol adipate dicarboxylic acid , poly 1,9-nonanediol azelate dicarboxylic acid, poly 2-methyl-1,8-octanediol/1,9-nonanediol adipate dicarboxylic acid, poly 2-methyl-1,8-octanediol/
1. Aliphatic polyester dicarboxylic acids such as 9-nonane diacelate nocarboxylic acid, aromatic dicarboxylic acids such as polyethylene terephthalate dicarboxylic acid, polybutylene ethylene terephthalate dicarboxylic acid, and β-proviola, chthone, and pivalarolactone. , γ-valerolactone,
ε-caprolactone, methyl-ε-caprolactone, δ
-valerolactone, β-methyl-δ-valerolactone,
Examples include polyesternocarboxylic acids derived from ring-opening polymers of one or more lactones such as δ-caprolactone.

In the present invention, in order to obtain a product with particularly excellent hydrolysis resistance, 3-methyl-1,5-pentanol, 2
- It is preferable to use diols such as methyl-1,8-octanediol and 1,9-nonanediol singly or in combination, and it is particularly desirable to select 2-methyl-1,8-octanediol because it significantly improves the low-temperature properties. . These diols are preferably used in an amount of 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more of the total diol components. In addition, β-methyl-δ-valerolactone was used as the carboxylic acid polyester at both ends.
It is also preferable to use a polyester obtained by ring-opening polymerization of a lactone monomer containing 0 mol% or more, since the hydrolysis resistance becomes particularly good.

The above-mentioned double-terminated carboxylic acid polyester can be obtained by a conventionally known method for producing polyester. for example,
A polyester diol having hydroxyl groups at both ends obtained by polycondensing an excess amount of a dicarboxylic acid component with a diol component and by ring-opening polymerization of a lactone using a compound having active hydrogen such as ethylene glycol as an initiator. can be reacted with dicarboxylic acid or its anhydride to obtain a double-terminated carboxylic acid polyester.

As the dicarboxylic acid component used in producing the polyamide in the present invention, it is preferable to use an aliphatic dicarboxylic acid and a double-terminated carboxylic acid polyester in combination, considering the moldability and flexibility of the resulting polyamide.
Furthermore, in 100 mol% of the dicarboxylic acid component, it is preferable that 10 mol% or more of the carboxylic acid polyester at both ends is contained as dicarboxylic acid.

The molecular weight of the carboxylic acid polyester at both ends is 300 to 8.
．． It is preferably within the range of 000, more preferably from 500 to
5,000. If the molecular weight is 300, molding processability deteriorates, and if it exceeds 8,000, mechanical properties and transparency deteriorate, which is not preferable.

The organic carboxylic acid anhydride component used in obtaining the polyamide-imide of the present invention may be any of those conventionally used in the production of polyamide-imide or polyimide. For example, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, diphenylsulfone-3,3°, 4,4'-tetracarboxylic dianhydride,
Examples include biphenyltetracarboxylic dianhydride,
Trimellitic anhydride is particularly preferably used.

Generally, the reaction between an organic noisocyanate and an organic dicarboxylic acid or acid dianhydride is represented by the following formula.

nα:N-R-NGO organic dicarboxylic acid residue, R” is the residue of acid dianhydride represent

In this reaction, isonoan and carboxylic acid and Equivalent ratio of acid anhydride Preferably below. death Ku Even more preferable Ku is 0.98 or more The upper limit is 1.02 or less.

If the equivalent ratio is less than 0.97, the degree of polymerization will not increase and good mechanical properties will not be obtained at all. On the other hand, the corresponding amount ratio is 1.
If it exceeds 0.03, gelation occurs and polymerization itself becomes difficult.

In the present invention, the polymerization reaction is carried out in the presence of an inert organic solvent,
Or it can be carried out in the absence, or it can be carried out in the presence of a catalyst. Here, the preferred catalyst is 1
-Methyl-2-phosphosine-l-oquinodo, 1-phenyl-2-phosphorene-l-oquindo, l-phenyl-2
Examples include, but are not limited to, -phosphosine-3-methyl-1-oxide. In addition, an inert organic solvent refers to an organic solvent that does not react with either the reactants or the catalyst under the reaction conditions. Examples of such inert organic solvents include toluene, quinolene, tetralin, hexane, tetrahydrofuran, nomethylsulfoquinde, N,N
-dimethylformamide, N,N-trimethylacetamide, N-methyl-2-pyrrolidone, tetramethylene sulfone, tetramethylurea, hexamethylphosphoramide,
Examples include dioxane.

In the present invention, it is important to add and react a compound having at least one oxazoline ring in the molecule (hereinafter sometimes simply referred to as an oxazoline compound) to the polyamide or polyamideimide.

The compound having an oxazoline ring is not particularly limited as long as it has at least one oxazoline ring in the molecule. Typical oxasily compounds include phenyl-2oxazoline, 2-phenylcarbamoyl-2-oxazoline, 2.2°-bis-2-
Examples include oxazoline and 1,3-phenylene-bis-2-oxazoline, which can be used alone or in combination. A preferred oxazoline compound is 1,3-phenylenebis-2-oxazoline, but is not limited thereto.

The amount of the oxazoline compound added is preferably about 0.2 to 10% by weight based on the total amount of polyamide and polyamideimide. If it is less than 0.2% by weight, the performance improvement required by the present invention will not be achieved. When a trifunctional or higher functional oxazoline compound is used, an increase in molecular weight is observed, which is favorable for mechanical properties.

The added amount of the oxazoline compound is sufficient to exhibit its effect at about IO weight %, but if it is more than that, various physical properties may deteriorate.

The reaction between the polyamide or polyamideimide and the oxazoline compound may be carried out by adding the oxazoline compound to the molten resin, or by adding the oxazoline compound to the molten resin, as long as the polyamide or polyamideimide and the oxazoline compound are well mixed. Alternatively, an oxazoline compound may be added to the solution.

The reaction temperature is carried out in a solution state or in a molten state;
Various ranges can be taken depending on the composition of polyamide and polyamideimide. For example, in a solution state, 100℃
The above is preferable, and the temperature in the molten state may be at least the melting point of the polyamide and polyamideimide used. Further, the reaction may be carried out either in the presence or absence of a catalyst.

When the reaction is carried out in a solution state, the inert organic solvent used in the above-mentioned polymerization reaction can be used as is.

The oxazoline compound may be added at any time after the late stage of the polymerization reaction. For example, it is also possible to pelletize polyamide or polyamide-imide after the polymerization reaction and melt-mold the pellets while adding an oxazoline compound at the time of molding. Here, the latter stage of the polymerization reaction is the time after the organic diisocyanate component, dicarboxylic acid component, and acid anhydride have disappeared by about 90%, preferably 95%. Even if the oxazoline compound is added at a time when polymerization has not progressed much, good results cannot be obtained because hydrolysis resistance is not developed.

The modified polyamide or modified polyamide-imide obtained by the present invention has characteristics such as excellent hydrolysis resistance, mechanical properties, and heat aging resistance, so it can be used in various applications that have not been used conventionally, such as sheets and films. ,tube,
It can be used for hoses, roll gears, backing materials, vibration isolation materials, belt laminate products, automobile parts, sporting goods, industrial machinery parts, etc.

[Example code] The present invention will be specifically explained below with reference to Examples.

In the examples, the tensile strength was measured by punching out a 100 μm thick film obtained by hot pressing or casting with a DMF solution using a dumbbell.

Hydrolysis resistance was evaluated by jungle test.

The jungle test is carried out at 70°C and 95% relative humidity.
A film with a thickness of 00 uo+ was left for 28 days, and the tensile strength retention rate of the film before and after the jungle test was measured, and the retention rate was evaluated.

A double-terminated carboxylic acid polyester, which is a raw material used in the examples, was synthesized according to the following synthesis example, and its composition and molecular weight are summarized in Table I.

Synthesis Example 1 1.7 3-methyl-1,5-bentanediol in the reactor
70g (15 mol) adipic acid 2,781g (19
, [15 mol)] and the esterification reaction was started at 150° C. with stirring. The temperature was gradually raised to 200°C over about 3 hours to complete the esterification reaction. Water distilled out at this stage. Then, the reaction was accelerated while gradually reducing the pressure in the system, and when the terminal hydroxyl groups were almost completely eliminated, the reaction was terminated to obtain a double-terminated carboxylic acid polyester (A). The average molecular weight determined from the acid value was 980.

Synthesis Examples 2.3.4 and 5 In the same manner as in Synthesis Example 1, both terminal carboxylic acid polyesters (B, C, D, E) listed in Table I were obtained.

Synthesis Example 6 Contents 5Q with stirring device, dropping funnel, and gas inlet/outlet
After thoroughly purging the OmQ Mitsuro flask with dry nitrogen gas, 12.4 g of ethylene glycol was added to the flask.
(0.2 mol) and 0.13 g of butyllithium were charged, and while stirring vigorously, 150 g of B-methyl-δ valerolactone was added at once from the dropping funnel. The reaction was stopped by adding 200 g of water for 1 hour. 200g toluene
In addition, water was washed three times by fractional immersion, and toluene and a trace amount of water were distilled off using an evaporator to obtain a viscous liquid. Transfer this liquid to another flask with a content of 500 + IQ and 20 toluene.
0 g and 42 g (0.42 mol) of succinic anhydride were added thereto and heated to 100° C. with stirring, and the reaction was completed after 4 hours. Toluene was distilled off using an evaporator, and the product was further purified by molecular distillation to obtain a double-terminated carboxylic acid polyester F. The acid value is 106.7KoHmg/g, the hydroxyl value is 0.2KoHmg/g, and the average molecular weight calculated from these is 1. It was Q10.

Synthesis Example 7 In the same manner as in Synthesis Example 6, a double-terminated carboxylic acid polyester (G) shown in Table I was obtained.

Example 1 In a beaker, put the double-terminated carboxylic acid polyester A prepared in Synthesis Example 1 (198 g, 0.2 mol) and azelaic acid (56.4 g, 10.3 mol), heat it to 120°C to melt it, Dehydrated under reduced pressure for minutes. Then, the melted 4,4′-diphenylmethane diisonoanate (
125 g, 0.5 mol) was added at once and stirred vigorously for about 20 minutes. At this point, 70% of the isocyanate
had disappeared.

This prepolymer was placed in a Plastograph (manufactured by Brabender) maintained at 260°C to drive polymerization, and approximately 10 minutes after being charged into the Plastograph, when 96% or more of the isocyanate and carboxylic acid had disappeared, 1. After adding 2 parts by weight (2 PHR) of 3-phenylene-bis-2-oxazoline to 100 parts by weight of the total resin and kneading for another 5 minutes, the mixture was taken out to obtain modified polyamide H, and various evaluations were performed. . The results are shown in Table ■.

The obtained modified polyamide gave good results in all of tensile strength, elongation, hydrolysis resistance, and heat aging resistance, as is clear from Table 3.

Examples 2 to 7 Modified polyamides 1 to N were obtained in the same manner or in accordance with Example 1 with the compositions shown in Table 1, and various evaluations were performed. The results are shown in Table H. Similar to Example 1, the modified polyamides of Examples 2 to 7 also showed good results in terms of tensile strength, elongation, hydrolysis resistance, and heat aging resistance.

Example 8 Under a nitrogen atmosphere, 80 g (0,04
), trimellitic anhydride 15.36g (
0.08 mol), 376 g of tetramethylene sulfone and l-methyl-2-phosphosine-1-oxide O,O'9
g of the mixture was charged and heated to 200'C with stirring. Further, 30 g (0.12 mol) of 4.4'-diphenylmethane diisocyanate was added and reacted for 3 hours, followed by 2.3 g of 1.3-phenylene-bis-2-year-old xacillin.
GI was added and the reaction was allowed to proceed for 30 minutes. The reaction solution was
It was poured into methanol (Q), reprecipitated, and dried under reduced pressure to obtain a pale yellow modified polyamide 0, which was subjected to various evaluations.

As is clear from the table, the obtained modified polyamide-imide gave good results in all of tensile strength, elongation, hydrolysis resistance, and heat aging resistance.

Examples 9 and 10 Modified polyamideimides (P and Q) were obtained in the same manner as in Example 8 or according to the compositions shown in Table 1. The results of various performance evaluations are shown in Table ■.

For the modified polyamideimides obtained in Examples 9 and 1O, good results were obtained in all of the tensile strength, elongation, hydrolysis resistance, and heat aging resistance, as shown in Table (2).

Comparative Example 1 A polyamide was obtained in the same manner as in Comparative Example 5 except that 1,3-phenylene-bis-2oxazoline was not added, and various evaluations were performed. The results are shown in Table ■.

When no oxazoline compound was added, satisfactory results were not obtained in both hydrolysis resistance and heat aging resistance.

[Results of the Invention] The modified polyamide and modified polyamide-imide of the present invention are endowed with excellent hydrolysis resistance, heat aging resistance, etc. without impairing the properties of conventional polyamides and polyamide-imides.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Scope of Claims] (1) For polyamide or polyamideimide obtained by reacting with a component selected from the group consisting of organic diisocyanate, organic carboxylic acid, and organic carboxylic acid anhydride, A method for producing modified polyamide or modified polyamide-imide, which comprises adding a compound having one or more oxazoline rings. (2) Any stage after the latter stage of the polymerization reaction when producing polyamide or polyamide-imide through a polymerization reaction with a component selected from the group consisting of organic diisocyanate, organic carboxylic acid, and organic carboxylic acid anhydride. A method for producing modified polyamide or modified polyamide-imide, which comprises adding a compound having one or more oxazoline rings in the molecule. (3) The manufacturing method according to claim 1 or 2, wherein the compound having an oxazoline ring is a compound having two oxazoline rings in the molecule. (4) The manufacturing method according to claim 3, wherein the compound having an oxazoline ring is 1,3-phenylene-bis-2-oxazoline. (5) Addition amount of compound having an oxazoline ring is 0.2
The manufacturing method according to any one of claims 1 to 4, wherein the content is within the range of ~10% by weight.