JPH03106934A - Cross-linking polyphenylene ether having capped reactive terminal - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION As is already known, polyphenylene ethers have many valuable properties, such as high plasticization temperatures, low dielectric loss factors and good ductility.

However, the solvent resistance of polyphenylene ether is somewhat lower than desired. This makes it difficult to use polyphenylene ether as a printed circuit board material. This is because the board is often passed through a chlorinated solvent cleaning bath prior to the required copper lamination. Therefore,
It is desired to obtain modified polyphenylene ethers which on the one hand maintain favorable properties and on the other hand have good solvent resistance.

In the present invention, "polyphenylene ether" is defined as, for example, U.S. Pat. No. 3,306,874 by Alan S. Hay.
No. 3,306,875 or U.S. Pat. No. 3,257,357 and U.S. Pat. 257. It is understood that the term refers not only to polymers such as those described in each specification of No. 358, but also to copolymers mainly composed of phenylene ether units.

It is known to further convert polyphenylene ethers after production. For example, European Patent Publication No. 54,140
A method for preparing polyphenylene ethers substituted with groups readily available for graft polymerization, in particular isobrobyl groups, is described in the specification. Styrene or methyl methacrylate can then be polymerized onto this polyphenylene ether to form a graft copolymer. However, the terminal hydroxyl groups of polyphenylene ether are not involved. According to European Patent No. 172.516, a graft copolymer in which the main chain is a copolymer of styrene and acrylonitrile is also produced using polyphenylene ether as a graft monomer. In specific embodiments, the polyphenylene ether always comprises less than 50% by weight of the total polymer. Polyphenylene ethers are either bound to the chloromethyl groups of copolymers, or polyphenylene ethers are first converted with chloromethylstyrene derivatives and then end-grouped in this way, polymerized with nitrile monomers. . A graft copolymer is thus formed in each case. In practice, polyphenylene ethers are often capped with trimellitic anhydride. Crosslinking of polyphenylene ether is substandard.

The present invention provides that when polyphenylene ethers are provided with end groups derived from unsaturated acids of the acrylic acid series, products containing such end groups still have substantially unchanged properties, but when heated. It is based on the recognition of the fact that polymerization reactions that lead to chain elongation, branching and/or crosslinking are entered into, resulting in resistance to solvents for which efforts have been made.

The invention therefore relates to a material based on polyphenylene ether containing polymerizable end groups, characterized in that the crosslinkable end groups are optionally substituted acrylic acid groups.

The other properties that make polyphenylene ethers suitable for printed circuit boards are maintained upon introduction of end groups and polymerization.

The introduction of acrylic groups or substituted acrylic groups into the terminal hydroxyl groups of the polyphenylene ether can be carried out, if necessary, with the acid itself or preferably with its reactive derivative, especially the acid chloride. The simplest compounds of the acid series are preferred, namely acryloyl chloride or methacryloyl chloride, so the terminal groups are preferably acrylic or methacrylic acid groups.

Conventional high temperature shaping processes, such as compression or extrusion, further cause reactions and render the product solvent resistant. Alternatively, the product containing the end groups can be cast from solution to form a film, which is then cured at a moderate temperature, such as by peroxide or ultraviolet light.

Very tough, but still stretchable films are thus obtained with an otherwise unobtainable high molecular weight.

The materials of the invention may further be used in addition to the materials conventionally used in this building material, such as fillers, reinforcing fibers, stabilizers, pigments and dyes, plasticizers, mold release agents, notched impact modifiers and flame retardants. It should be noted that one or more additives may be included.

The present invention will be explained in more detail with reference to the following specific examples.

Example 1 Introduction of End Groups Experiments were carried out in a double-walled glass 1 liter reactor heated to 80° C. and continuously stirred.

1500 g of a 30% by weight solution of polyphenylene ether (hereinafter abbreviated as PPE) in toluene was charged into the reactor.

To this solution was first added 8.7 g dimethylbutylamine and mixed well with the solution. Then 6.8 g of methacryloyl chloride was added.

The mixture was stirred for 2 hours to obtain complete conversion. As measured by infrared spectroscopy, in a typical case the initial
Conversion was complete when the signal of the OH groups, which was between 00 and 800 ppo+, decreased to less than 50 ppa+. The PPE thus end-grouped was isolated by precipitation with an anti-solvent, preferably methanol, deposited again in clean anti-solvent and dried at 120° C. under reduced pressure.

The intrinsic viscosity of the polymer containing the end groups did not change from the starting product within the accuracy of the measurement. Typical values for both the starting product and the product containing end groups were 0.43 dI/g.

Example 2 Samples of PPH containing methacryloyl end groups were heated in a press for various times. Molecule m of each sample
(Mw) and intrinsic viscosity (IV) were measured in chloroform. The results are shown in the table below.

Example 3 Various PPE samples were tested for dissolution in trichloroethene.

The results are shown in the table below.

From the above results it is clear that although a high percentage of glass fibers has no effect on the time to visual dissolution of PPH, the introduction of end groups according to the invention has a surprising effect in this respect.

Claims (1)

[Scope of Claims] (1) A material based on polyphenylene ether containing a polymerizable terminal group, characterized in that the polymerizable terminal group is an optionally substituted acrylic acid group. Materials to be used. (2) The polyphenylene ether containing a polymerizable terminal group according to claim 1, wherein the terminal group is an acrylic acid or methacrylic acid group. (3) Articles, especially printed circuit boards and foils, made using the material of claim 1 or 2. (4) converting the terminal phenolic hydroxyl groups of the polyphenylene ether into phenolate groups and reacting the resulting product with optionally substituted acrylic acid or a reactive derivative thereof, A method for producing a polyphenylene ether containing a polymerizable terminal group according to claim 1 or 2. (5) The production method according to claim 4, wherein (meth)acryloyl chloride is selected as the reactive derivative. (6) Claim 1 or 2
A process for producing molded articles from polyphenylene ethers with increased solvent resistance, characterized in that the polyphenylene ethers containing the described end groups are subjected to a molding treatment using heat and pressure. (7) An enhanced polyphenylene ether comprising forming a polyphenylene ether containing end groups according to claim 1 or 2 from a solution to form a foil, and further polymerizing the foil with a peroxide catalyst or with actinic radiation. A method for producing foil from polyphenylene ether having high solvent resistance.