JPS6334181B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for producing a polyphenylene oxide solidified product. [Background Art] Polyphenylene oxide (also referred to as polyphenylene ether, hereinafter abbreviated as PPO) has attracted attention in recent years due to its excellent high frequency characteristics. Molding methods for PPO include melt extrusion,
There are methods such as the calendar method. However, in the melt extrusion method, since the melting temperature of PPO is high, there is no suitable heat-stable crosslinking agent, and in the calender method, there are disadvantages such as high cost. As a method for forming a film at low temperatures, there is a casting method that uses a solvent, but a resin composition with film-forming properties has not been obtained using PPO alone. For this purpose,
The premise is that a PPO-based composition with film-forming properties can be obtained. [Object of the Invention] In view of the above circumstances, an object of the present invention is to provide a method for producing a PPO solidified product at low cost and at a low temperature. [Disclosure of the invention] In order to achieve the above object, the present invention
In obtaining the PPO-based solidified product, PPO,
A styrenic thermoplastic polymer and triallyl isocyanurate and/or triallyl cyanurate are selected, and the blending ratio of these three is 7% or more by weight or more than 93% by weight of PPO (hereinafter referred to as "%") based on the total of these three. ), 7% to less than 93% of styrenic thermoplastic polymer, and 70% or less of triallyl isocyanurate and/or triallyl isocyanurate, and after dissolving and mixing these raw materials in a solvent, The gist is a method for producing PPO-based solidified products, which is characterized by forming a film by drying in layers. This invention will be explained in detail below. Note that here, the solidified product includes a cured product. The PPO used in this invention is, for example,
The following general formula, (Here, R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same,
May be different. ), and one example thereof is poly(2,6-dimethyl-1,4 phenylene oxide). Such PPO can be synthesized, for example, by the method disclosed in USP 4,059,568. For example, but not limited to,
A polymer having a weight average molecular weight (Mw) of 50,000 and a molecular weight distribution (Mw/Mn) of 4.2 (Mn is the number average molecular weight) is used. The styrene-butadiene copolymer (hereinafter referred to as "styrene thermoplastic polymer") used in this invention is a component that improves film-forming properties, and includes, for example, styrene-butadiene block polymer (SBS) and styrene-butadiene block polymer (SBS). Examples include rubber (SBR). The polymer state may be an elastomer or a rubber, but a high molecular weight rubber state is particularly preferable because it improves film forming properties, and the block state is, for example,
Examples include AB, ABA, ABAB (for example, A is polystyrene and B is polybutadiene). Triallyl isocyanurate (hereinafter abbreviated as TAIC) and triallyl cyanurate (hereinafter abbreviated as TAC) used in this invention are isomers in chemical structure, and have almost the same film forming properties, Because it has compatibility, solubility, reactivity, etc.
Similarly, either one or both can be used. The ratio of blending the above raw materials is 7% or more and less than 93% of PPO and 7% of styrenic thermoplastic polymer to the total of PPO, styrenic thermoplastic polymer, and TAIC and/or TAC.
93% or more, and TAIC and/or
TAC is below 70%. If any of these is out of this range, film formability will be lost,
This makes it impossible to obtain a solidified product, especially a film-like solidified product. Figure 1 shows the raw materials for the PPO solidified product used in this invention, PPO (PPO), styrene thermoplastic polymer (STP), and TAIC.
and/or TAC (TAIC) blending ratio [%]
It shows. As shown in FIG. 1, a region C indicated by diagonal lines upward to the right is the range of the above-mentioned blending ratios. The preferred blending ratio range is the above region C.
Of these, area D is shaded upward to the left, and the more preferable range is PPO of 10% or more 80
% less than 20 to 80 styrenic thermoplastic polymers
% and TAIC and/or TAC is 60
% (in the figure, area E covered by the vertical line in area D). The raw materials according to the above formulation are usually dissolved in a solvent and mixed (solution mixing). In this case, it is preferable that the solid content of the resin is in the range of 10 to 30% based on the solvent. Examples of the solvent include halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, and methylene chloride, aromatic hydrocarbons such as chlorobenzene, benzene, toluene, and xylene, and carbon tetrachloride. Trichloroethylene is particularly preferred, and each of these may be used alone. It is also possible to use a mixture of two or more, but
Not limited to these. The method for producing the PPO solidified product according to the present invention is, for example, as described above, by dissolving the raw materials in a solvent and mixing them, forming a thin layer by casting or coating on an appropriate material, and then drying to remove the solvent. By doing so (casting method), a film-like solidified product can be obtained. That is, according to the method for producing a PPO-based solidified product according to the present invention, a PPO-based solidified product can be produced at a low temperature without using the expensive calendar method. To explain the casting method in detail, a solution prepared by dissolving the raw materials for the PPO solidified product in a solvent is placed on a mirror-treated iron plate or a carrier film for casting to a thickness of, for example, 5 to 700 μm. Casting (or coating)
Then, the film is obtained by sufficiently drying to remove the solvent. Note that the term "film" here includes what is called a sheet, membrane, tape, etc., and there are no particular limitations on the extent of the surface perpendicular to the thickness direction or the length, and the thickness can be set in various ways depending on the application. It is possible to do so. The carrier film for casting is not particularly limited, but it is preferably one that is insoluble in the above solvent, such as polyethylene terephthalate (hereinafter abbreviated as PET) film, polyethylene film, polypropylene film, or polyimide film. Preferably, it is mold-treated. The solvent is removed from the raw material solution of the PPO solidified product casted (or coated) on a carrier film for casting by air drying and/or drying with hot air. The upper limit of the set temperature during drying is preferably lower than the boiling point of the solvent or lower than the heat-resistant temperature of the carrier film for casting (when drying is performed on the carrier film for casting); The lower limit is determined by drying time, processability, etc. For example, if trichlorethylene is used as a solvent,
When a PET film is used as a carrier film for casting, the temperature range is preferably from room temperature to 80°C, and if the temperature is raised within this range, the drying time can be shortened. The PPO solidified product prepared in this way can be thermally crosslinked using a radical initiator, photocrosslinked,
By performing crosslinking using radiation, etc., tensile strength, impact strength, bursting strength, heat resistance, etc. can be further improved. PPO in advance
It is also possible to add an initiator or the like to the raw material of the solidified product. Examples are shown below along with comparative examples, but the invention is not limited to the examples. (Example 1) Into the reactor equipped with a defoaming device in step 2, 110 g of PPO was added at the blending ratio as shown in Table 1-1, and styrene-butadiene block copolymer SBS (Asahi Kasei Corporation) was added as a styrene-based thermoplastic polymer. Made of Solprene T
-411) 80g, TAIC (Musashino Chemical Co., Ltd.) 10g,
Add 800g of trichlorethylene (trichloroethylene manufactured by Toagosei Chemical Industry Co., Ltd.),
The mixture was thoroughly stirred and mixed until a homogeneous solution was obtained. Thereafter, defoaming was performed, and the obtained solution of the PPO-based solidified material raw material was coated onto a PET film to a thickness of 500 μm using a coating machine. Let it air dry, then
After drying at 50℃, the resulting film is PET
The film was released from the mold and further dried at 120°C for 30 minutes. The thickness of the PPO solidified film after drying was approximately 100 μm. The physical properties of this film were determined by examining the uniformity as good (〇) and poor (x), the surface stickiness as absent (〇) and present (x), and the tensile strength using an autograph. , and whether or not a film-like solidified product was formed is shown in Table 2-1, along with the presence (○) and absence (x) of film formability. (Examples 2 to 13) A film-like solidified PPO product was obtained in the same manner as in Example 1, except that the blending ratio of the raw materials for the PPO solidified product and the solvent were changed as shown in Table 1-1.
The films of each example were examined using the same evaluation method, and the results are shown in Table 2. (Comparative Examples 1 to 5) Solutions were obtained in the same manner as in Example 1 using the blending ratios shown in Table 1-1. Each solution was applied to a PET film and dried in the same manner as in Example 1, but no film-like solidified product was obtained. The results are shown in Table 2-1 along with the raw material formulation. In addition, FIG. 1 shows Examples 1 to 13 and Comparative Example 1.
The blending ratio of each raw material for 5 to 5 was plotted. The black circles are examples, and the black squares are comparative examples. (Examples 14 to 26 and Comparative Examples 6 to 9) In Examples 1 to 13 and Comparative Examples 2 to 5, film-like solidified products were obtained by changing the raw material solution formulation as shown in Table 1-2. The results of each are shown in the second
It is shown in Table 2. (Examples 27 to 30) In Example 1, the composition of the raw material solution was changed as shown in Tables 1-3 to obtain a film-like solidified product.
The results are shown in Table 2-3.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

〔Effect of the invention〕

As seen above, the method for producing PPO-based solidified products according to the present invention has the raw material composition within the above-mentioned range, so it does not require the costly calendar method, and moreover, it can produce PPO-based solidified products at low temperatures, especially A film-like solidified product can be obtained.

[Brief explanation of the drawing]

FIG. 1 shows triangular coordinates showing the mixing ratio of raw materials in the method for producing a PPO-based solidified product according to the present invention. PPO…weight% of polyphenylene oxide,
STP…weight% of styrenic thermoplastic polymer,
TAIC...% by weight of triallyl isocyanurate and/or triallyl cyanurate.

Claims (1)

[Claims] 1. In obtaining the polyphenylene oxide solidified product, polyphenylene oxide,
Select a styrene-butadiene copolymer and triallyl isocyanurate and/or triallyl cyanurate, and set the blending ratio of these three to the total of these three to 7% by weight or more and less than 93% by weight of polyphenylene oxide. , 7% to less than 93% by weight of styrene-butadiene copolymer, and 70% by weight or less of triallyl isocyanurate and/or triallyl cyanurate, and after dissolving and mixing these raw materials in a solvent, thin A method for producing a polyphenylene oxide solidified product, which is characterized by forming a film by drying in layers.