JPH09227774A - Polymer mixtures containing polyphenylene ethers and hydrogenated diene-vinyl aromatic block copolymers and articles molded therefrom - Google Patents

Abstract

(57) Abstract: To further improve the aging characteristics of a polymer mixture containing a polyphenylene ether and a hydrogenated block copolymer. The present invention is directed to (A) polyphenylene ether, (B) hydrogenated diene-vinyl aromatic block copolymers, and optionally additional components, with the exception of styrene homopolymer and rubber modified polystyrene. ). The polymer mixture of the present invention is particularly suitable for applications where good aging properties are required.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to A. Polyphenylene ether, B.I. Hydrogenated diene-vinyl aromatic block copolymer,
And C.I. It relates to a polymer mixture which optionally comprises additional components, except for homopolymers of styrene and rubber-modified polystyrene.

The invention further relates to an article made from the polymer mixture of the invention, in particular a support structure for a deflection yoke of a television.

[0003]

Polymer mixtures consisting of polyphenylene ethers and hydrogenated block copolymers are known from US Pat. No. 4,167,507. This known polymer mixture comprises a hydrogenated triblock copolymer. The known polymer mixture may also contain homopolymers of styrene and polystyrene modified with rubber. In the examples of US Pat. No. 4,167,507, the use of hydrogenated triblock copolymers in combination with crystalline clear polystyrene instead of rubber modified polystyrene improves the aging properties of the polymer mixture. Have been proved.

[0004]

SUMMARY OF THE INVENTION It has now been found that the aging properties of such a polymer mixture can be further improved without compounding styrene homopolymer or rubber modified polystyrene. However, the polymer mixture of the present invention can include any conventional ingredients and additives. However, the above-mentioned styrene homopolymer and rubber-modified polystyrene are not included.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The polymer mixture of the present invention in any case comprises the following two components: A. Polyphenylene ether. B. Hydrogenated block copolymer. This polymer mixture also contains C.I. It can contain conventional ingredients. However, styrene homopolymer and rubber-modified polystyrene are excluded.

A. Polyphenylene ether Polyphenylene ether is commonly abbreviated as PPE. The PPE used in the present invention is a known polymer containing a plurality of structural units represented by the following formula (I).

[0007]

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Here, Q is independent for each structural unit.
¹ is independently halogen, primary or secondary lower alkyl (ie, alkyl of up to 7 carbon atoms),
Phenyl, haloalkyl, aminoalkyl, hydrocarbon oxy, or at least 2 halogen and oxygen atoms
Is a halohydrocarbonoxy, separated by carbon atoms, wherein each Q ² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl,
Hydrocarbon oxy, or halohydrocarbon oxy as defined for Q ¹ . Most often both Q ¹ are both alkyl or phenyl, especially C _1-4 alkyl, and both Q ² are hydrogen.

Both homopolymer and copolymer PPE are included. Preferred homopolymers are those containing 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include, for example, random copolymers containing the above units in combination with 2,3,6-trimethyl-1,4-phenylene ether units. Also known are PPE containing partial structures prepared by grafting vinyl monomers or polymers such as polystyrene and elastomers, and coupling agents such as low molecular weight polycarbonates, quinones, heterocyclic compounds and formal. Coupled PPE, which is a polymer of increased molecular weight by reacting with the hydroxy groups of the two PPE chains in the above method (provided that a significant proportion of free OH groups must remain), is also included.

PPE generally has a number average molecular weight of about 3,000.
It is in the range of 0 to 40,000 and the weight average molecular weight is in the range of about 20,000 to 80,000. This molecular weight is determined by gel permeation chromatography. P
The intrinsic viscosity of PE is most often in the range of about 0.15-0.6 dl / g as measured in chloroform at 25 ° C. Depending on the application of the polymer mixture of the invention, i.e. where good flow properties are required, an intrinsic viscosity of less than 0.40 dl / g, preferably 0.26 to.
PPE in the range of 0.34 dl / g is preferably used.

Generally, PPE is prepared by oxidatively coupling at least one monohydroxyaromatic compound such as 2,6-xylenol or 2,3,6-trimethylphenol. A catalyst system is usually used for such coupling. A typical catalyst system contains at least one heavy metal compound such as a compound of copper, manganese or cobalt, and usually contains various other substances in combination therewith.

Particularly useful PPE for many purposes are those consisting of molecules having at least one end group containing aminoalkyl. The aminoalkyl group is typically ortho to the hydroxy group. To obtain a product containing such end groups, a suitable primary or secondary monoamine (eg, di-n-butylamine, dimethylamine, etc.) is used as one of the components of the oxidative coupling reaction mixture. It may be blended. Also, 4-hydroxybiphenyl end groups are often present, which are typically obtained from reaction mixtures in which the by-product diphenoquinone is present, especially copper-halide-secondary or tertiary. Obtained when using a system consisting of amines. A significant proportion of the polymer molecules, usually those which also make up about 90% by weight of the polymer, may contain at least one of the aminoalkyl-containing end groups or 4-hydroxybiphenyl end groups described above.

As will be apparent to those skilled in the art from the above, the polyphenylene ethers considered to be used in the present invention are those currently known regardless of the difference in the structural unit or the chemical characteristics associated therewith. All are included. B. Hydrogenated Block Copolymers Hydrogenated block copolymers are known products and are commercially available. All known hydrogenated block copolymers can be used in the polymer mixtures according to the invention. Suitable block copolymers include hydrogenated diblock copolymers and hydrogenated triblock copolymers.

Particularly suitable are hydrogenated block copolymers of the ABA type, where each A before hydrogenation is about 4,000.
Is a polymerized vinyl aromatic block having a molecular weight of ˜115,000 and B is about 20,000 to 450,000.
It is a polymerized conjugated hydrocarbon block having an average molecular weight of zero. Also, the end block is 8,000-
Having an average molecular weight of 60,000 and having a polybutadiene polymer block of 50,000 to 300,000.
More preferably, it has an average molecular weight of zero. The amount of this end block is preferably 2 to 33% by weight, more preferably 5 to 30% by weight, based on the whole block copolymer. After hydrogenation, the unsaturation of block B is 3
It is reduced to less than 0%, preferably less than 10%. Most preferred are block copolymers in which block B is 100% hydrogenated or almost 100% hydrogenated. The two A blocks can be the same or different with respect to their chemical composition or molecular weight.

Particularly preferred is US Pat. No. 3,431,
No. 323 hydrogenated triblock copolymer ABA. The pre-hydrogenation end blocks of these copolymers consist of homopolymers or copolymers prepared from vinyl aromatic hydrocarbons (aromatic component may be monocyclic or polycyclic). Typical monomers include styrene, α-methylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, etc. or mixtures thereof. These end blocks may be the same or different. The central block may be derived from polyisoprene or polybutadiene, for example.

These block copolymers are formed by techniques well known to those skilled in the art. For hydrogenation, various hydrogenation catalysts (for example, nickel or diatomaceous earth, Raney catalyst, copper chromate, molybdenum sulfide or finely divided platinum or other noble metal supported on a low surface area carrier) are used. Can be implemented. Hydrogenation is carried out at a desired temperature / pressure, for example, atmospheric pressure to about 20 MPa, at a temperature of 19 ° C or higher,
It can be carried out for 0.1 to 24 hours, preferably 0.2 to 8 hours.

C. Additional Components In addition to components A, B described above, the polymer mixture of the present invention may include other components commonly used in polymer mixtures containing PPE. However, homopolymers of styrene and polystyrene modified with rubber are excluded. Particularly suitable additional components are reinforcing fibers, fillers, flame retardants, plasticizers and stabilizers.

The preferred reinforcing fiber is glass fiber,
A suitable filler is mica flake. The combination of glass fiber and mica flakes is advantageous for certain applications.
As flame retardants, it is possible to use all customary flame retardants for polymer mixtures containing polyphenylene ethers. Particularly suitable are phosphate-based compounds. Most commonly used phosphates have a plasticizing effect.

Polymer mixtures containing polyphenylene ether, reinforcing fibers and a polyethyloxazoline binder with good aging properties are described in US Pat. No. 5,019,61.
No. 6 is known. The known composition may additionally contain polystyrene, clay, mica, talc and flame retardants. In the case of the preferred compositions of the invention, the polymer mixture is 88 to 96 parts by weight of component A and 12 to 4 parts by weight of component B, calculated per 100 parts by weight of A + B.

The polymer mixture according to the invention is particularly suitable for producing a support member for a deflection yoke of a television. A particularly preferred polymer mixture for this purpose comprises, as component C,
Glass fiber (5-20 parts by weight), mica flakes (5-2)
0 parts by weight) and a flame-retardant compound mainly containing an organic phosphate (10 to 30 parts by weight). Further, conventional stabilizers such as organic phosphite, zinc sulfide and magnesium oxide (0.5 to 2.0 in total) are added.
Preference is given to adding (in parts by weight). All amounts given for component C are based on 100 parts by weight of A + B.

[0021]

Description of Examples Example I and Comparative Example A Two different polymer blends were prepared using the following ingredients. PPE: Poly (2,6-dimethylphenylene-) having an intrinsic viscosity of about 0.3 dl / g measured in chloroform at 25 ° C.
1,4-ether). ccPS: A styrene homopolymer having a weight average molecular weight of about 260,000. SEBS: Hydrogenated styrene-butadiene-styrene triblock copolymer. The molecular weight of the styrene block is about 18,000 and the molecular weight of the hydrogenated butadiene block is about 80,000. The total content of styrene is about 31% by weight. Glass: Glass fiber having an average length of about 4.5 mm and a diameter of 14 μm. Mica: Mica flakes. RDP: resorcinol bis (diphenyl phosphate) and higher oligomers (weight ratio about 65: 3)
5). MgO: Magnesium oxide. ZnS: zinc sulfide. Ph: Blend of trisnonylphenyl phosphite and diphenyldecyl phosphite.

[Werner Pfleider
The above components were compounded with a twin-screw extruder (er). The average temperature setting was 280 ° C. The polymer mixture thus compounded was extruded and pelletized. The following test pieces were molded from these pellets. Vicat (ISO 306 method B, heating rate 120 ° C./hour), melt viscosity (DIN 54811,
280 ° C., 1500 / sec), impact strength with Izod notch (ISO 180 method 1A, room temperature), tensile strength (ISO527, crosshead speed 5 mm / min).

Tensile strength was measured both before aging the test bars and after several aging periods up to 3600 hours in an air circulating oven at 130 ° C. 3600
The retention of tensile strength after time aging was calculated as a percentage (%) to the original tensile strength. The amount used and the properties measured are shown in the following table (Table A). Table A Example A I Composition (parts by weight) PPE 60.4 60.4 ccPS 4 - SEBS 5 5 Glass 10 10 Mica 10 10 RDP 10 14 MgO 0.6 0.6 ZnS Ph characteristics Vicat B / 120 (° C. ) 151 141 Melt viscosity (1500 sec ^-1 ) (Pa.s) 300 222 Izod notch impact (kJ / m ² ) 23 26 Tensile strength retention rate (%) 89 97 From the results of this table, the results of Example I It can be seen that the absence of styrene homopolymer (ccPS) in the composition improves the aging properties (compared to the composition of Example A). Replacing the rubber-modified polystyrene with a combination of a homopolymer of styrene and a partially hydrogenated block copolymer improves the aging properties, as described in US Pat. No. 4,167,507. Especially already demonstrated in Example A). In the polymer mixture of the present invention, the aging properties were further improved by eliminating the styrene homopolymer.

All patents cited herein are hereby incorporated by reference.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location // (C08L 71/12 53:02) (72) Inventor Ferdinand Geraldas F. Grimelt Netherlands , 5751, Zet Dühne Plantage, Berse 58 (72) Inventor Johannes Maria Heremons Holland, 4725, Ager Wouth Plantage, Kerkstraat 12A (no address) ( 72) Inventor Henricus Cornelis Zimmermanns Netherlands, 4613, Die Bergen op Zoom, Narcissenberg, No. 27

Claims (9)

[Claims] 1. A. First Embodiment Polyphenylene ether, B.I. Hydrogenated diene-vinyl aromatic block copolymers, and C.I. A polymer mixture that optionally includes additional components, except homopolymers of styrene and rubber-modified polystyrene. 2. 88 to 9 per 100 parts by weight of A + B.
Containing 6 parts by weight A and 12-4 parts by weight B,
The polymer mixture according to claim 1. 3. The polymer mixture of claim 1, wherein the polyphenylene ether has an intrinsic viscosity of less than 0.40 dl / g measured at 25 ° C. in chloroform. 4. A polymer mixture as claimed in claim 1, which comprises, as component C, one or more of reinforcing fibers, fillers, flame retardants, plasticizers and stabilizers. 5. Containing glass fibers as component C,
The polymer mixture according to claim 1. 6. A polymer mixture as claimed in claim 1, which contains mica flakes as component C. 7. A polymer mixture as claimed in claim 1, which comprises a phosphate compound as component C. 8. An article made from the polymer mixture of claim 1. 9. A deflection yoke for a television having a support member made from the polymer mixture of claim 1.