JPS5968330A - Production of crosslinked amide polymer - Google Patents

Abstract

PURPOSE:To obtain easily a crosslinked amide polymer suitable for use in the production of adhesives, etc., by reacting a linear polymer contg. amide bonds with a compd. having at least two 2-oxazolin-2-yl groups per molecule under heating. CONSTITUTION:A linear polymer contg. amide bonds such as nylon 6 or nylon 12 is reacted with a compd. having at least two 2-oxazolin-2-yl groups per molecule under heating to obtain the desired crosslinked polymer. Examples of the compds. having at least two 2-oxazolin-2-yl groups per molecule are bisoxazoline monomers such as 1,4-bis(2-oxazolin-2-yl)butane, trisoxazoline monomer such as 1,3,5-tris-(2-oxazolin-2-yl)benzene, oligomers having a 2-oxazolin-2-yl group at its terminal, polymers having a 2-oxazolin-2-yl group at its terminal.

Description

[Detailed description of the invention] The present invention relates to a method for producing crosslinked amide polymers.

Conventionally, various methods have been proposed for crosslinking polymers having an amide bond (-CONH-).

For example, epoxy resin or phenol resin is used to crosslink nylon. This crosslinking reaction is due to the amino group (-NH2) present at the end of the nylon.
This is not a cross-linking reaction using amide bonds.

On the other hand, thermosetting acrylic resins contain primary amines. This takes advantage of the fact that 91st-class amide groups easily react with each other when heated, generating ammonia and forming bond bonds. This crosslinking method utilizes the primary amide groups hanging from the polymer even in the trenches. Although a crosslinking method that utilizes the amide group (-〇〇NH-) in the main chain of a polymer has been desired for a long time, few useful methods are known. The only method proposed is to form a slight amide group of nylon with Vdehyde and alcohol (R-○H) and crosslink this by heating. However, this method has various limitations in producing crosslinked precursors. Still, the formation of alkoxymethyl form,
Then, a two-stage operation of crosslinking is required, making the process complicated. Furthermore, during crosslinking, volatile alcohol is generated, which is a major drawback and a major restriction when used in plastics, adhesives, paints, etc.

The present inventors have conducted detailed research on the reactivity of compounds having an amide bond and compounds having 2-oxazolin-2-y/L'M, and have found that 2-oxazolin-2-yl to the amide bond It has been found that the addition reaction of groups can easily occur by heating the thread. When this reaction is used to crosslink a linear polymer having an amide bond, there is no need to process the linear polymer before crosslinking, and even the amide bond in the main chain can be easily crosslinked. , it was found that no low-boiling point compounds were produced at all, and the present invention was completed based on these findings.

That is, the present invention relates to the production of a crosslinked amide polymer, which is characterized by reacting a linear polymer having an amide bond with a compound having two or more 2-oxazolin-2-yl groups in the molecule under heating. It is the law.

The linear polymer having an amide bond used in the present invention may be any linear polymer having an amide bond in the molecule, and specifically, aliphatic nylon,
For example, nylon 6, nylon 11. Nylon 12. J
-Iron 6.6. Nylon 6.10. nylon 6.12
Single nylon or nylon 6/6.6/6 such as
, 10, copolymerized nylons such as nylon 6/12, aromatic nylons, and polymers made from xylylene diamine and adipic acid.

Alternatively, it may be a polymer obtained by reacting a dimer acid with various diamines called dimer acid polyamide. Furthermore, it may be a polyester amide obtained by reacting a bis(2-oxazoline) compound with a bicyclic acid. Examples of pinu(2-oxazoline) compounds used for this purpose include 1,6-(2-oxazolin-2-yl)hexane, 1,3-bis(2-oxazolin-2-yl/I/ ) benzene, 1,4-bis(2-oxazolin-2-yl)benzene, and the like.

Bicyclic haws include, for example, adipic acid, sepatic acid,
Examples include dimer acid and dodecanedioic acid. Furthermore,
It may also be a polyamideimide obtained by a reaction between an aromatic diamine and an aromatic tetracarboxylic dianhydride. Examples of aromatic diamines used for this purpose include 4,4
'-Diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether.

Examples of aromatic tetracarboxylic dianhydrides include 3,3'-diaminodiphenylnurphone, 1,5-naphthalenediamine, metaphenylenediamine, and pyromellitic dianhydride, 3,3'.

4.4'-benzophenone tetracarboxylic dianhydride,
bis-(3,42-cyclodiphenyl)ether dianhydride,
Examples include bis-(3,4-dicarboxyphenylene/v)sulfone dianhydride and 1,2,4,5-naphthalenetetracarboxylic dianhydride. Alternatively, it may be obtained by reaction to give a linear polymer having an amide bond, for example, by anionic polymerization of ε-caprolactam. The linear polymer may be of high molecular weight or may be a low molecular weight oligomer. Among linear polymers having amide bonds, nylons such as aliphatic nylons and copolymerized nylons, and polymers obtained by the reaction of dimer acids and diamines such as dimer acid polyamides are particularly preferred.

Examples of compounds having two or more 2-oxazolin-2-yl groups in the molecule used in the present invention include monomers such as bisoxazoline and trisoxazoline, and 2-oxazoline-2-yl) V groups at the terminal. Examples include oligomers and polymers with

As a monomer of bisoxazoline, for example, 1.4-
Bis(2-oxazolin-2-yl)butane, ■, 6-
Bis(2-oxazolin-2-i/L/)hegisan, 1
．． Compounds in which an oxazoline ring is bonded to an alkyl) V chain such as 8-bis(2-oxazolin-2-yl)octane,
For example, 1,3-bis(2-oxazolin-2-yl)
Two oxazolines in the aromatic nucleus such as benzene, 1,4-bis(2-oxazolin-2-yl)benzene, 3-bis(5-methy/l/-2-oxazolin-2-y)benzene Rings are bonded together, or 2.2'-bis(2-oxazoline), 2. Sr-bis(4-methy/l
'-2-oxazoline), 2.2'-(5-methy/M-
2-oxazoline), etc.

Examples of trisoxazoline monomers include 1, 3.
5-) Lis(2-oxazolin-2-yl)benzene and the like.

Oligomers and polymers having a 2-oxazolin-2-yl group at the end can be obtained by the method described below. For example, a polyester amide can be easily obtained by reacting a polycarboxylic acid with a bisoxazoline, but if oxazolinyl groups are used in excess of the acid groups during this reaction, a polyester amide having an oxazoline ring at the end can be obtained. By changing the type of acid and oxazoline used, the number of functional groups, and the amount used, compounds with various molecular weights and functional groups can be easily obtained.

Among the polycarboxylic acids used for this purpose, examples of dibasic acids include succinic acid and adipic acid.

Examples include aliphatic dibasic acids such as azelaic acid, sepanic acid, dodecanoic acid, and dimer acid, and aromatic dibasic acids such as phthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Examples of tri- or higher polybasic acids include trimellitic acid and butane-1,2,3,4-tetracarboxylic acid. As the oxazoline, for example, 1,6-(2-oxazoline-2-i/I/
) hexane, 1,3-bis(2-oxazoline-2-i/L/)benzene, l,4-bis(2-oxazoline-
2-I/I/) Bisoxazolines such as benzene are mentioned.

Furthermore, oligomers and polymers having two or more 2-oxazolin-2-yl groups can also be obtained by reacting acid-terminated oligomers and polymers with bis- or trinuoxazoline. Examples of acid-terminated compounds that can be used for this purpose include acid-terminated butadiene oligomers, acid-terminated acrylonitrile-butadiene oligomers, and acid-terminated polyesters.

A linear polymer with an amide bond and two or more 2
A crosslinked amide polymer is obtained by mixing the mixture with a compound having an -oxazolin-2-yl group and then heating the mixture.

Generally, linear polymers having an amide bond and compounds having two or more 2-oxazolin-2-yl groups in the molecule are often solid. In that case, for example, the two components may be weighed and mixed at the same time in a container kept below a temperature at which no reaction occurs, each component may be added while being dissolved one after another, or the components may be added in advance in another container. They may be mixed in a molten state, or if they have a high softening point or melting point and there is a risk of gelation during mixing, they may be dissolved in a solvent and then mixed by removing the solvent. The amount of the compound having two or more 2-oxazolin-2-yl groups in the molecule for the linear polymer having an amide bond may be any amount as long as it is greater than the amount for crosslinking the amide bond of the linear polymer. , any amount can be used depending on the required properties.

Usually, the proportion is about 0.5% by weight or more, preferably about 1% by weight or more, based on the linear polymer having an amide bond.

In the present invention, it is preferable to use, for example, the following catalysts in the heating reaction, since crosslinking can be carried out quickly.

Examples of the catalyst include triphenyl phosphite, trisulfite (nonylpheni/l/), triethyl phosphite, tri-n-butyl phosphite, trisulfite (2-
ethylhexy/L/), tristearyl phosphite, diphenylmonodecyl phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(
tridecy) V) Pentaerythritol tetraphosphite, diphenyl phosphite, phosphorous (p 4 , 4'-butylidene bis(3-methy/l/-6-t-butylphenyl-di-tridecy) V) Pentaerythritol honupite and phosphorous acid esters such as Trieste/I/. Among the above, phosphite esters containing ferulate groups or substituted ferulate groups are particularly preferred. The amount of phosphite melon is about 0.05% by weight or more, preferably about 0.5% by weight based on the total amount of the two components.
% by weight or more.

The reaction temperature may be higher than the temperature at which the crosslinking reaction progresses, but
Preferably, the culm degree is about 150°C to 220°C. Although the curing time varies depending on the type and amount ratio of the two components, the curing temperature, the type and amount of the catalyst, etc., curing can be performed in about several tens of seconds.

The crosslinked amide polymer obtained by the present invention has high mechanical strength and adhesive performance, and is also excellent in heat resistance and chemical resistance. By appropriately changing the type and quantity ratio of a linear polymer having an amide bond or a compound having two or more 2-oxazoline-2-ifV groups in the molecule, crosslinked polymers with a wide range of properties can be obtained. I can do it. This crosslinked amide polymer can be used, for example, in adhesives, baking paints, powder coatings, plastic materials, heat-resistant varnishes, etc., depending on its properties.

EXAMPLES The present invention will be explained in more detail with reference to Examples and Usage Examples below.

Examples / 1.4-bis(2-oxazolin-2-y/I/)benzene, 1,3-bis(2-oxazolin-2-yl)benzene, dodecanoic acid and dimer acid (Versagym 2889 manufactured by Henkel Japan) ) Acid value obtained from 5. Polyesteramide 5C1,1,3-bis(2-oxazoline-
2-a) v) Benzene LOG' was weighed into a stainless steel beaker, mixed well, and kept at 190°C. Then, 2.0 g of triphenysulfite/I/sulfite was added and mixed. After 5 minutes, the mixture gelled and an insoluble and infusible cured product was obtained.

The three components of Usage Example/Example/ were thoroughly mixed at 150°C, and the mixture was sandwiched between two copper plates and bonded together at a contact pressure of 200°C for 30 minutes. Tensile shear adhesive strength was measured at 23°C and 80°C. For comparison purposes, we also investigated the adhesive strength of polyesteramide alone.

Tensile shear adhesive strength (kVcIT12) 23℃
80 Examples/162 73 Polyesteramide alone 108 20
Examples 133 g of dimer acid and 1,3-bis(
2-Oxazoline-2-i/I/) 100 g of benzene was reacted at 190° C. for 1 hour to obtain a polyesteramide oligomer having an oxazoline ring at the end. Oxazoline oligomer 2 (1,1,4-bis(
Acid value 8. obtained from 2-oxazolin-2-yl)benzene, 1,3-bis(2-oxazolin-2-y)V)benzene, dodecanoic acid and dimer acid (Versadime 288). Weigh polyester amide 50f7 with a fi original viscosity of 0.45 into a reaction container, mix well, and add 190
It was kept at ℃. Then, 1.5 q of triphenyl phosphite was added and mixed. After 12 minutes, it gelled and an insoluble and infusible cured product was obtained.

Usage example λ! ,! The three materials used in Example Y were mixed in advance at 140° C., and this was sandwiched between two materials, a steel plate and an aluminum plate, and the mixture was bonded at a contact pressure of 200 for 30 minutes.

For the aluminum plate, we measured the adhesive force of the foil, and for the steel plate test piece, we hung a heavy foil with a constant load (500 g) and left it in an open room maintained at a constant temperature, and examined the temperature at which the adhesive part peeled off. was designated as heat resistant.

Peeling adhesive strength 1 Heat resistance example 2 15'g/25mm 2
502. Polyesteramide only 6kg/
25 mm 120°C Example 3 25 g of dimer acid holamide with a softening point of 140'C and a reduced viscosity of 0.38 and 1,3-bis(2-oxazoline-2
-I/l/) 5 g of benzene and bisphenol/l/A pentaerythritol phosphite 1. Oq 1901:
The mixture was weighed and mixed in a reaction container.

After 8 minutes, gelation occurred to obtain an insoluble and infusible cured product.

Example copolymerized nylon (Higashishi 842-P) 2(l) and 1.3-bis(2-oxazolin-2-yl)benzene 0.59.
Triphenylsulfite) VQ, 59 was weighed and mixed in a reaction vessel at 190°C. After 1 minute and 30 seconds, it gelled and an insoluble and infusible cured product was obtained.

Example! Timer acid (Enhaul 1024i manufactured by Emery) 65
q and 1,3-bis(2-oxazoline-2-i/L/)
50 g of benzene was reacted at 200 tE for 30 minutes, weighed into a polyester reaction vessel with oxazoline at the end, mixed well, and then 1.2 g of bisphenol A bexacillin-2-i) v) benzene. Add 2g to the reaction container, mix well, and heat to 2o5''C.
I kept it.

Then tris phosphite (nonylphenyl/L/) o, 9q
was added and mixed. After 2 minutes and 30 seconds, the mixture gelled to obtain an insoluble cured product.

Example 7 Powder 309 of Nai T"11 and 3 g of 1,4-bis(2-oxazolin-2-i)V)benzene were mixed, placed in a stainless steel beaker, and heated to bring the internal temperature to 200°C. The contents were once melted, but gradually gelled. Thus, m-cresol-insoluble crosslinked nylon 11 having no irA point was obtained.

Comparative Example 30g of Nylon 11 powder was placed in a stainless steel beaker, heated and kept at an internal temperature of 200°C for 1 hour. Once dissolved, it was completely dissolved. That is, nylon 1
1 is a linear polymer! Met.

Claims (1)

[Claims] A linear polymer with an amide bond and two or more 2
- A method for producing a crosslinked amide polymer, which comprises reacting a compound having an oxazolin-2-yl group under heating.