JPS5959724A - Production of modified thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the titled modified resin excellent in affinity for and compatibility with other resins without detriment to the inherent properties, by reacting a polyphenylene ether with a specified 1,2-substituted olefin compound in a substantially solvent-free system at a specified temperature. CONSTITUTION:The titled modified resin is obtained by reacting a polyphenylene ether of the formula, wherein R1 and R2 are each a 1-4C alkyl, or a halogen, and n is an integer representing the degree of polymerization, with at least 0.3pt.wt. carboxyl group-containing 1,2-substituted olefin or an acid anhydride structure-containing 1,2-substituted olefin compound in the presence of 0.1- 5pts.wt., per 100pts.wt. polyphenylene ether, radical generator in a substantially solvent-free system at the temperature range of 220-370 deg.C.

Description

[Detailed description of the invention]

The present invention relates to a method for producing a benign thermoplastic resin, and more particularly to a method for producing a modified polyphenylene ether. In recent years, in the plastics industry, as applications have diversified, there has been a demand for higher added value to resin products by composites with different materials or polymer alloys by combining various existing polymers. Although polyphenylene ether has excellent mechanical properties, it has poor affinity for other types of materials. Therefore, compounding is limited and sufficient effects are not achieved. For example, in reinforced 4frJ resin, which is made by mixing glass fiber with polyphenylene ether or a resin composition containing polyphenylene ether as one component, glass, m's
Due to the lack of adhesive strength between the glass and the resin,
Attempts have been made to treat the surface to improve adhesion, but no significant effect has been achieved. Furthermore, regarding polymer alloying, polyphenylene ether has poor synergism with other resins, resulting in poor mechanical properties of the resulting molded product, so that it was not possible to obtain a product that could be put to practical use. In particular, when alloying with a highly polar resin, such as a polyamide resin, the resulting molded product has an extremely high 1tα and cannot be put to practical use. For this reason, it has been investigated to chemically modify the resin composition by using polynylene ether or polyphenylene ether as one component.
As a modification technique for the same purpose, polyphenylene ether is dissolved in a solvent in the coexistence of a radical generator,
A method in which styrene and maleic anhydride are added at a temperature of ~200°C and polymerized for a long period of time, and a method in which other polymerizable compounds are polymerized have been proposed (Japanese Patent Publication No. 52/1999).
Publication No. 864. (Special Publication No. 52-80991). However, it takes 15
This method requires expensive polymerization equipment, additional equipment is required for solvent removal and polymer purification, and a large amount of energy is required, which is disadvantageous for industrial implementation. In view of the current situation, the inventors of the present invention have arrived at the present invention as a result of extensive research into methods for effectively producing modified resins in a process-saving and energy-saving manner. (However, R,, R2 is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n is an integer representing the degree of polymerization.) To 100 parts by weight of polyphenylene ether, o, x to 22 in a substantially solvent-free system in the presence of 5 parts by weight of a radical generator.
L2 ft! having a carboxyl group of 0.873° or more in the temperature range of 0 to 370°C! This is a method for producing a modified thermal tjJ plastic resin, which is characterized by reacting a J-converted olefin or a 1,2-iq-converted olefin compound having an acid anhydride structure. According to the method of the invention, modification can be carried out using lightly equipped equipment such as a general-purpose twin-screw extruder, and it is possible to modify polyphenylene in a short time without requiring a desolvation step or a polymer purification step. It has been discovered that ether can be modified without impairing its inherent physical property balance. Specific examples of the polyphenylene ether referred to in the present invention include poly(2,6-dimethylphenylene-1,4-ether), poly(2-methyl-6-ethylphenylene-1,
4-ether), poly(2,6-diethylphenylene-
1,4-ether, poly(2-methyl-6-,-propylphenylene-1,4-ether). Ho'J (2-methyl-6-chlorophenylene-1,4
-ether), poly(2-ethyl-6-chlorophenylene-1,4-ether), and the like. It is preferable that the degree of polymerization n is selected from the range of 60 to 300. E. The radical generator included in [1] in the invention represents a known organic peroxide or diazo compound, and specific examples include:
Penzoyl peroquinde, dicumyl peroquine, di-tcrt-butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroper'
: 1 xide, cumene hydroper 4 kind. Examples include azobisisobutyronitrile. These radical generators can also be used in combination of two or more types.
1,2- with mono-substituted olefin or acid anhydride structure
Specific examples of substituted olefin compounds

[7. maleic anhydride, itaconic anhydride, glutaconic anhydride,
citraconic anhydride, aconitic anhydride, hymic anhydride, 5-norbornene-2-methyl-2-carboxylic acid,
Examples include phthalic acid. '; In the A invention, the radical generator is used in an amount of 0.1 to 5 parts, preferably 0.3 to a part, per 100 parts of polyphenylene ether. When the amount of stool is less than 0.1 parts by weight The properties of polymer alloys or reinforced resins using the obtained Yugai body t]1; no improvement was observed, -10,000, modification 11,
(2) is not preferable because it produces a gel-like 11 coalescence. In the present invention, the 1,2-substituted olefin having a carboxyl group or the 1,2-substituted olefin compound having an acid anhydride is used in an amount of 0.8 parts by weight or more, preferably 0.8 parts by weight or more, preferably 1 lls or more of 05 binder, per 100 parts of polyphenylene ether. If the amount used is less than 0.3 parts heavy, the same performance as above due to modification will not be observed in polymer alloys or reinforced resins using the obtained modified product. On the other hand, even if it is used in excess of 5 parts by weight, no further improvement in performance will be seen and it is not economical, so the preferred amount used is 0.3 to 5 parts by weight.
The particularly preferred amount used is 0.6 to 4 parts. In the present invention, the ratio of the radical generator used h to the use h of the 1,2-substituted olefin compound having carboxyl group, 2-substituted olefin or acid anhydride structure is 0.2 to 1.0. Preferably, the present invention is conducted in a substantially solvent-free system at 220 to 370
The reaction time is preferably 20 seconds to 80 minutes, particularly preferably 40 seconds to 5 minutes. 22
At a temperature of 0.degree. C., the melt viscosity of the modified product becomes high, resulting in poor doughability, while at a tiA temperature of over 870.degree. C., a gel-like modified product tends to be produced, which is not preferable. The present invention may be carried out by any method as long as each component is brought into contact with each other while melt-kneading for 1 m, and an extruder with appropriate noise is used to improve the quality of green parts. It is preferable to employ a continuous method using an internal mixer, kneader, etc. In the practice of the present invention, glass fiber, carbon fiber. asbestos fiber, aramid fiber, phenolic resin fiber,
Metal carbides at A'f8, calcium carbonate, carbon black, fillers such as silica, plasticizers, steel (fuels, pigments, other polymers, etc. can also be added to the reaction system).
). In order to improve the strength and impact resistance of polyphenylene ether, styrene thread (νJ I!u or olefinic wax A resin is added to the practice of the invention. In addition, styrene thread resin or olefin resin can be added after modification.According to the present invention, a modified product of Holif J-nylene ether can be produced by a convenient method. Thus, the modified product obtained by the method of the present invention has excellent performance compared to (ν' fat Δ\), and is also excellent in compatibility and compatibility with other 4i'd fats, etc. It is used in numerous industrial applications as a base polymer for reinforced resins or as a polymer alloy with other resins, T1 drawn products, filaments, and films.The following 1
The present invention will be explained in more detail with reference to Examples. Example 1 Intrinsic viscosity measured at 25°C using chloroporm 0.9
1 d e/y'l dog (2,6-dimethyJl/
7 jl-,1: L/ y -1,4-ether) powder and 'Jl! I = 2 og of water maleic acid. After tri-blending dicumyl peroxide lof at room temperature, screw diameter 29 mm, L/D = 25
Using a rotary rotary force type vented extruder, the cylinder temperature was 300°C and the screw rotation speed was 15 (l rpm).
After passing through a cooling bath, it was pelletized. Collect 5 g of this pellet, grind it to a powder using a 4-pump machine, and heat it for 4 s in a Soxhlet extractor using 1 (10 ml of ethanol). After drying under pressure for an hour, the polymer
A sample was obtained. The existence of a CO2 pattern originating from the reaction with maleic anhydride in this polymer is the absorption peak between 1600 and 18 GO cm in the Fourier infrared absorption spectrum! l'i! By analysis! ＋'I acknowledge it. Ratio 1 Example 1 The same poly(2,6-dimethylphenylene-1 as in Example 1)
, 4-ether) powder and maleic anhydride 2 (
After triblending with 1 and 1, it was treated under the same denaturing conditions as in Example 1. 52 of the obtained pellets were collected and used in Example 1.
After performing the same purification as in Example 1, analyze it using an infrared absorption spectrum as in Example 1. -'', but no absorption peak derived from -CO2- was observed. Comparative Example 2 The same poly(2,6-dimethylphenylene-1 as in Example 1)
．． A tri-blend of 1 kF of 4-c-chill powder and 10 f of dicumyl peroxide was prepared, and the pellets were treated under the same benign conditions as in Example 1. Tail/use row 1 Each pellet of Example 1 and Comparative Example 1.2 was blended with nylon 6 as shown below, a molded article was obtained from the blend '%+, and the physical properties of the obtained molded article were compared. . Nylon 6 has a relative viscosity of 2.6 (96% sulfuric acid, 25°C, 1
% concentration jJl] was used. That is, the modified polyphenylene ether of Example 1 100ffif? With the part, nylon 6 pellets L-110
After triblending the surface metal with a weight loss of 0, it was dried under reduced pressure at 105 u for 24 hours. After drying, the cylinder temperature was 275°C using the same Bentoy twin-screw extruder as used in Example 1.
After bath melt kneading at a screw rotation speed of 150 rpln,
I picked up pellets. After drying this pellet under reduced pressure at 105°C for 24 hours. A sample piece with a thickness of 1/8 inch was obtained at 270°C according to a conventional method using an injection molding machine with a screw diameter of 25 mm. The pellets of Examples 1 and 2 were also blended with nylon 6 and sample pieces were obtained under backward bath melt kneading and molding conditions. Table 1 shows the physical properties of the sample pieces. The sample pieces of the comparative examples were easily broken and extremely brittle, but the examples were notable for improved physical properties, especially improvements in bending strength and impact strength. From the above examples, it is clear that polyphenylene ether can be modified by a simple process and an extremely short reaction time without the need for a removal solvent step, and the resulting modified product is extremely effective as a component of polymer alloys. That is clear. Examples Poly(2,6-
(dimethylphenylene-1,4-ether) powder 5k
'c! ,: t 150 g of maleic anhydride, 100 g of di-tert-butyl perkind, and polystyrene (manufactured by Mitsui Toatsu Co., Ltd., trade name: TOBOLEX 550)
After blending 4kg with Dora R, 29rnmφ
Twin screw extrusion with vent Q5
C. and a screw rotation speed of 15 Or pm to obtain pellets. Extrusion force: 11 tons of 80 pellets, 20 pieces of chopped strand glass fiber of 2 mm length, and a weight of 2 mm.
A glass fiber mixed hatsumode was obtained by i. A molded article was molded from this mixed material, and the physical properties of the obtained molded piece were measured 1.
No. For comparison, a similar test was conducted using unmodified poly(2,6-dimethylphenylene-1,4-ether). The results are shown in Table-2. Table-2 Examples 3-5. Comparative Examples 4 to 8 70 parts by weight of poly(2,6-dimethylphenylene-1.4-ether) powder having an intrinsic viscosity of 1.08 d e/9 and ABSMl mf (Mitsui East EE cylinder, trade name Li)
A mixture was prepared from 80.7 MM parts of maleic anhydride and di-tert-butyl peroxide in the amounts shown in Table 8. PJ LafLt knee to own QlfVt') ') -L
- Diameter 48 mm, cylinder temperature 260°C using a rotary force type vented extruder with '/B = 86 directions.
The pellets were kneaded under the conditions of a screw rotation Mi5ar pill and extruded through a cooling bath to obtain pellets with a pellet tiger.
6 (measured with sulfuric acid having a relative viscosity of 2.4.96% at 25°C and a concentration of 1%), 60 pieces of pellets were triblended and then dried under reduced pressure at 105°C for 24 hours. After drying, the temperature of the cylinder was 275°C using the above-mentioned vented twin-screw extruder.
Pellets were obtained after melt mixing at a screw rotation speed of 150 r IJm. After drying the pellets I at 105°C for 24 hours, a j5 (1/8 inch) molded product was obtained and its physical properties were measured. The results are shown in Table 3. It is clear from the results shown in Table 3 that it is necessary to keep the addition ratio of acid within a proper range, and that it is necessary to use a radical generator. This makes it possible to produce new polymer alloys that can be put to practical use in a variety of applications.ゝ゛＼7. '' , /゛,, / '-, Pa\, \,-1 Table-3;

Claims (1)

[Scope of Claims] Polyphenylene ether 100]ji having a carboxyl group of 0.8 M star part or more in the temperature range of 220 to 870°C in a substantially solvent-free system in the coexistence of 1 to 5 parts of a radical generator, A method for producing a modified thermoplastic resin, which comprises reacting a 1,2-substituted olefin or a 1,2-g-substituted olefin compound having an acid anhydride structure.