DE2752383A1 - PLASTIC REINFORCED COMPOSITIONS OF A POLYPHENYLENE ETHER RESIN - Google Patents

Description

Polyphenylene ether resin

The invention relates to mineral-reinforced, plasticized Polyphenylene ether compositions, in particular thermoplastic deformable compositions, containing a Polyphenyl ether resin with or without an impact modifier, a plasticizing amount of a plasticizing agent and a mineral reinforcing agent Agent that effects improved stiffness with a noticeably unexpected retention of extensibility.

The polyphenylene ether resins are known as a class of thermoplastics which have a number of outstanding physical properties, oie can generally be prepared by oxidative and non-oxidative methods, such as those described in e.g. B. in US Patents 3,300,874 and 330b 875 by Hay and Uü-PJen 3,257,357 and 3,257,358 by ütamatoff, the disclosure content of which is incorporated into the present application by this reference.

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It is known that the polyphenylene ether resins can be combined with agents for impact modification to to achieve improved impact resistance and other mechanical properties. Suitable agents for impact modification for polyphenylene dyes are described in US Pat. No. 3,383,435 by Cizek, the disclosure of which is incorporated into the present application by this reference.

The term "plasticized" is used herein to describe compositions containing sufficient plasticizing agent to maintain the optimum extrusion temperature _o by at least about 13.9 ° C / and usually from about 13.9 / to about 55 , 6 ° ψ zn lower.

It has now surprisingly been found that plasticized Polyphenylene ether compositions containing a mineral contain reinforcing agent, have increased stiffness, which by the flexural modulus and the flexural strength in comparison measured against other compositions without said agent. In addition, the improvement in rigidity properties was not expected along with any significant preservation of extensibility, as measured by tensile elongation and impact strength, is obtained.

The invention in its broadest scope relates to reinforced plasticized thermoplastic compositions used for Deforming or processing, e.g. B. by compression deformation, Extrusion, calendering and the like are suitable which have improved stiffness compared to corresponding non-reinforced compositions which contain:

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(a) a polyphenylenather resin either alone or in combination with an agent for Impact modification;

(b) a dedicated plasticizing agent in one for lowering the optimal one Extrusion temperature by at least 13 ~ 9 ° C suitable amount; and

(c) a mineral reinforcing agent in an amount sufficient to compare to bring about improved rigidity to corresponding unreinforced compositions.

The polyphenylene ether resins of the compositions come generally from the genus with structural units of the formula:

809826/0555

- Jr-

the one unit in which the ether oxygen atom / with the Benaolkern

the next following structural unit is connected, η a is a positive integer and has at least the value 50,

and each Q is a monovalent substituent selected from water substance, halogen, carbon radicals without a tertiary alpha carbon atom, halogenated hydrocarbon grates with at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbyl oxy radicals and halocarbon oxy radicals with at least two carbon atoms between the halogen atom and the phenyl nucleus, mean t

The polyphenylene ether resins preferably have the above formula, in which each Q is an alkyl group, particularly preferably having 1 to 4 carbon atoms. This class includes, for example, poly (2,6-dimethyl-1,4-phenylene) ether; Poly (2,6-diethyl-1,4-phenylene) * ether; Poly (2-methyl-6-ethyl-1,4-phenylene) ether; Poly (2-methyl-6-propyl-1,4-phenylene) ether; Poly (2,6-dipropyl-1,4-phenylene) ether; Poly (2-ethyl-6-propyl-1,4-phenylene) ether and the like.

Particularly preferred is poly (2,6-dimethyl-1,4-phenylene) ether, preferably with a basic viscosity of about 0.45 Deciliters per gram (dl / g), measured in chloroform at 30 ° C.

The preparation of polyphenylene ether resins according to the above formula is described in the aforementioned patents of US Pat Hay and Stamatoff described.

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The choice of plasticizer is not critical and any conventional means used for the purpose can be employed. The component (b) is preferable Phthalate or phosphate plasticizers and especially phosphate plasticizers.

The phosphate plasticizer is preferably a compound of the formula:

OR ³ P OR ¹

OR ²

12 3
wherein R, R and R are the same or different and are alkyl, haloalkyl, cycloalkyl, ^{halocycloalkyl, aryl, haloaryl, alkyl-substituted aryl, halo a} ger ^ -substituted aryl, aryl-substituted alkyl, haloaryl-substituted alkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, halogen and Mean hydrogen.

For example, called selenium: cresyldiphenyl phosphate, 2-ethylhexyldiphenyl phosphate, Tricresyl phosphate, triisopropylphenyl phosphate, triphenyl phosphate, triethyl phosphate, Dibutylphenyl phosphate, diethyl phosphate, cresyl diphenyl phosphate, isooctyl diphenyl phosphate, tributyl phosphate, 2-ethylhexyl diphenyl phosphate, Isodecyl diphenyl phosphate, isodecyl dicresyl phosphate, didecyl cresyl phosphate, tri-n-hexyl phosphate, di-noctylphenyl phosphate, Di-2-ethylhexylphenyl and tri-2-ethylhexyl phosphate as well as their mixtures. Particularly preferred are aromatic phosphates, e.g. B. triphenyl phosphate.

8 0 9826 / OS5S

μ '

Examples of phthalate plasticizers include dibenzyl phthalate, phenyl cresyl phthalate, diethyl phthalate, Dirnethyl phthalate, phenylbenzyl phthalate, butylbenzyl phthalate, Butyl cyclohexyl phthalate, dibutyl phthalate, octyl cresyl phthalate, diphenyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, butyl octyl phthalate, butyl decyl phthalate, Diisooctyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propyl heptyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate and ditridecyl phthalate.

The plasticizer (b) is added in an amount sufficient to give a plasticized composition to deliver within the meaning of the limit described above. Generally the plasticizer is in amounts of at least about 5 parts per 100 parts of the combined resin components, preferably from about 5 to about 100 parts to 100 parts of resin.

The mineral reinforcing agent / is, for example, talc, aluminum silicate, e.g. B. Toni, H ^ drl / tized, dehydrated or calcined clay, zinc oxide, titanium dioxide, Antimony oxide, barium sulphate, precipitated or natural calcium carbonate, zinc sulphide, and the like · Particularly preferred is hydrated aluminum silicate ·

The amount of mineral reinforcing agent changes depending on the formulation and the particular composition requirements. However, in the preferred compositions there is at least about 5 parts mineral reinforcing agent per 100 parts resin combined

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contain. Particularly preferred compositions contain from about 5 to about 150 parts of mineral reinforcing agent to 100 parts of resin plus plasticizer.

The nature of the impact modifier for the polyphenylene ether or polyphenylene ether / polystyrene haree is not critical and any of the elastomeric polymers and copolymers commonly used to improve the impact properties of thermoplastic compositions can be used. The means for impact modification can be, for example, elastomeric ABA block copolymers in which the end blocks A and A are identical or different and are derived from a vinyl aromatic compound, e.g. B. styrene, ee -Methylstyrene, vinyl toluene, vinyl xylene, vinyl naphthalene and the like, and the central block B of a conjugated diene, z. B. butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like is derived.

These can be produced by organometallically initiated polymerization processes using, for example, sodium or lithium metal or one of their organic derivatives. The diene monomers can be mixed with a monofunctional or difunctional initiator, such as, for. B.! Nhe ^ dy ^ eVaT ^ n ^ recience Publishere, Vol. 23, Part II (1969), pages 553-559. Other methods of making them are shown in US Pat. No. 3,251,905 to Zelinski and US Pat. No. 3,231,635 to Holden et al. described, the disclosure content of which is incorporated into the present application by this reference .

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The relative proportions of the polymer units in the A-B-A block copolymers can be used over a wide range vary. However, the central block B preferably has a larger molecular weight than the combined end blocks, whereby an optimal impact resistance and solvent resistance is achieved. In general that lies The molecular weight of each of the two end blocks is between about 2,000 and about 100,000 and the molecular weight of the central block is between about 65,000 and about 1,000,000.

For example, the "Kraton" resins are available from Shell Chemical Co., Polymer Division, e.g. B. K-1101 (Polystyrene-polybutadiene-polystyrene), K-1102 (polystyrene-polybutadiene-polystyrene) and K-1107 (polystyrene-polyisoprene-polystyrene).

The hydrogenated A-B-A block copolymers are also well known. In general, these are block copolymers of A-B-A types in which the end blocks A and A are equal or are different and which, prior to hydrogenation, include homopolymers and copolymers derived from vinyl aromatic hydrocarbons, especially vinyl aromatics, in which the aromatic moiety is either monocyclic or polycyclic, are derived. Examples of such monomers are styrene, ei-methylstyrene, vinylxylene, ethylvinylxylene, Vinyl naphthalene and the like. The central block B can also derived from a conjugated diene, e.g. B. of butadiene, isoprene, 1,3-pentadiene and the like. The central block is preferably made of polybutadiene or Polyisoprene.

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The preparation of hydrogenated A-B-A block copolymers is described in US Pat. No. 3,431,323 to Jones, whose Disclosure content is incorporated into the present application by this reference.

Examples include the Kraton G resins available from US Pat Shell Chemical Co., Polymers Division, e.g. B. G-GXT-O65O, G-GXT-O772, G-GXT-O782 and G-6521.

Radial teleblock copolyraers from a vinyl aromatic compound, a conjugated diene and a coupler are also suitable agents for impact modification for the compositions according to the invention. this are branched polymers with segments or blocks consisting of a conjugated diene polymer, a vinyl aromatic polymer together with a coupling agent, in which chains of the diene polymer in the copolyra structure radiate outwards from a coupling agent, and each chain at its other end with one Completes block of vinyl aromatic polymer.

The radial teleblock copolymers are known. They are described in "Adhesives Ages ¹ ·, December 1971, pp. 15-20 and" Rubber World ", January 1973, pp. 27-32, the disclosure content of which is incorporated into the present application by this reference. The preparation of these copolymers is described in US Pat. No. 3,281,383 to Zelinski, the disclosure of which is also incorporated into the present application by this reference.

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Older examples of commercially available radi _v alen teleblock copoly ■ are the Solprenharze the Phillips Petroleum Company, known as Solprene 406 (containing about 60 weight parts of butadiene units and about 40 weight parts of styrene units), Solprene 411 (containing about 70 parts by weight butadiene Units and about 30 parts by weight of styrene units), Solpren 414 (containing about 60 parts by weight of butadiene units and about 40 parts by weight of styrene units), Solpren 417 (containing about 20 parts by weight of butadiene units and about 80 parts by weight of styrene units) and S411P ( containing about 70 parts by weight of butadiene units and 30 parts by weight of styrene units). These materials also contain a relatively small amount of a coupling agent, e.g. B. less than 1 part by weight coupling agent per 100 parts polymer.

Hydrogenated radial teleblock copolymers of a vinyl aromatic compound, a conjugated diene and a coupling agent such as. B. Solpren 512 available from Phillips Petroleum Co.

The means for impact modification can also be made from Resins are made that contain acrylic resin-modified diene rubber. Preferably they are resin compositions of a poly (alkylene methacrylate) which is grafted onto a butadiene-styrene copolymer skeleton or an acrylonitrile-butadiene-styrene terpolymer skeleton, or a resin composition composed of a mixture of a poly (alkyl methacrylate) and a butadiene-styrene -Copolymer or a Acrylonitrile-butadiene-styrene terpolymer.

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- vr- jib

A preferred commercial impact modifier of this type is Acryloid KM 611, available from Rohm and Haas Co., an acrylic / styrene / styrene-butadiene terpolymer.

The aforementioned acrylic resin-modified elastomers can be prepared according to known procedures, as described in US Pat. No. 2,943,074 and US Pat. No. 2,857,360, the disclosure content of which is incorporated into the present application by this reference.

The impact modifier can also be a graft copolymer of a vinyl aromatic compound and a diene, preferably from about 75 to about 10 % by weight of a vinyl aromatic monomer and from about 25 to about 90 % by weight of a conjugated diene. The aromatic monomer can be, for example, styrene, methylstyrene, vinyltoluene, vinylxylene, and the like, and the diene can be, for example, butadiene, isoprene, and the like. Graft copolymers of styrene and styrene-butadiene are preferred.

A preferred commercially available graft copolymer is, for example Blendex 525 available from Marbon Chemical Co.

The compositions of the invention can be prepared by conventional methods. Preferably, each of the components is added as part of a blend premix and the mixture at an extrusion temperature

(500 ⁰ F) n (625 ° F)

from about 260 / to about 330 C / depending on the requirements of the particular composition given by an extruder. The strands coming out of the extruder can

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chilled, cut into pellets and deformed or otherwise shaped into any shape.

The following examples are exemplary of the compositions of the present invention. You are supposed to The invention is not restricted to the particular embodiments described therein. All parts are parts by weight.

Unless otherwise specified, the units of measure for properties in the examples below are as follows follows:

Tensile yield kg / cm (psi) Tear strength (tensile break) kg / cm (psi) Tensile elongation % Flexural modulus kg / cm (psi) Flexural Strength (540 ° f) kg / cm ² (psi) Melt viscosity at 282.2 ⁰ C / 1500 sec ^"1 poise Gloss, 45 ° surface gloss dimensionless

unit

UL-94- Underwriters Laboratories sec / sec

Bulletin 94

Izod impact strength ft.lbs./in.η.

Gardner impact strength in.lbs. Heat resistance ° C (° P)

Linear coefficient of thermal expansion (CLTE) in / in F, measured from 30 ° C to 65 C.

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Examples 1 - 4

Self-extinguishing, plasticized mixtures were made from 78 parts of poly (2,6-dimethyl-1,4-phenylene ether) resin, intrinsic viscosity about 0.45 deciliter / gram, measured in chloroform at 30 ° C, 22 parts triphenyl phosphate flame retardanta Placer, 5 parts styrene-butadiene-styrene block copolymer (Kraton 1101, Shell Chemical Co., Polymers Division), 1.5 parts polyethylene and 20 parts miscellaneous mineral reinforcing agents as indicated, prepared and extruded at a temperature of about 305 C /.

The extrudate was cut into pellets at a temperature

O (520 ⁰ F)

temperature of about 270 C / deformed to test bars and on mechanical and flanun-inhibiting properties investigated. For comparison purposes, a mixture was made with the same components in the same amount but without fillers, the mineral reinforcing agents and the test results are summarized in Table 1.

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Tabel

Example filler

Tensile strength (tensile yield)

Tensile break

Tensile elongation Impact strength after

I2Od Gardner

Bending UL-94

Melting flame · solid viscous test Module sity

1 tone, untreated

2 tone, treated

3 tone, treated

4A * no

675

(9,600) (10,100)

675

(9.6OC) & 0.000)

682

(S, 700) (S, 800)

632

(9,000) (9,100)

242
233
233
243

090 984 3.5OO

(428.OOO) (14.OOO)

21,650 900 2,900

(3O8.OOO (12.8OO)

1.3 / 2.0

1.0 / 2.7

♦ control

a Al-Sil-Ate NFC, Freeport Kaolin Co.

b OX-1 coated clay, Freeport Kaolin Co,

c OX-2 coated clay, Freeport Kaolin Co,

TS3

cn r> o co oo co

Qo

Examples 5-10

Self-extinguishing, plasticized compounds were made from 78 parts of poly (2,6-dimethyl-1,4-phenylene ether), 22 parts Triphenyl phosphate flame retardant plasticizer, 5 Parts of styrene-butadiene-styrene block copolymer (Shell's Kraton 1101), 1.5 parts of polyethylene and a clay filler (Al-Sil-Ate NCP, Freeport Kaolin Co.) in the specified Quantities produced and shaped as in Examples 1. The physical properties are in Table 2 summarized:

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Tabel

At- Phr
game (weight

Impact strength

after

Tensile (tensile tensile yield) break elongation Izod Gardner module

Firm
speed

UL - 94 CLTE

cn
cn
«Η

5
6th
7th
8th
9

10
10

11.1 (10)

25 (20)

33 (25)

43 (30)

67 (40)

(50)
no

645 (9200)

696 (9900)

717 (10200)

710 (lolOO)

794 (11300)

893 (12700)

6.19 (8800)

654 (9300)

689 (9800)

696 (9900)

682 (9700)

766 (1O9O0)

893 (12700)

661 (9400)

65 64 50 39 21 8 72

10.1 7.0 2.5 1.4 1.3

28 190 984

345I8 ¹ - ⁰⁰⁰ Io ₀₇ ⁴

⁴⁷

, 1562.000) 116.100) T673.OOOrTI6.4OO)

^5θ4 .9 ° 7.0ΟθΡΐΐ7.80Ο) 0.7 less than

7.8 243 23 ^ 5O _{6 <ooo)} 9 _t O _3i4oo)

1.3 / 5.7 4.0 χ 1 / 3.3 3.4 χ 2/6

2.3 / 13 2.8 χ

1.7 / 10.7 3/45

1.7 / 3 4.8 χ

control

<-. indicates: parts of clay per 100 parts of resin plus plasticizer ^; near thermal expansion coefficient cn

OO CJ

to.

It has been shown that even with a reinforcement of 67 phr (40 %) in Example 9, a considerable degree of extensibility, measured by the tensile elongation and the impact strength, is retained in comparison with the unreinforced control (10 A *).

Examples 11-13

Mixtures of poly (2,6-dimethyl-1,4-phenylene ether) resin, Mineral oil, styrene-butadiene-styrene block copolymer (Kraton 1101), polyethylene and clay as a reinforcing filler were produced and shaped as in Examples 1-4. The compositions and physical properties are summarized in table 3:

Table 3

Example JJ. TIA * 12 V3 13A *

Components (parts by weight)

Poly (2,6-dimethyl-1,4-

phenylene ether) 78 78 78 85 85

Mineral oil (Kaydol) 22 22 22 15 15

Styrene butadiene styrene

Block copolynier

Kraton 1101 5 5 5 5 5

Polyethylene 1.5 1.5 1.5 _{1f5 1f5}

Sound as reinforcing

Filler (NCF, Freeport

Kaolin) 25 - 43 43 -

control

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- * β -

Table continued 3

example 11 Examples 11 A * 12th 801 13A * properties (11,400) tensile strenght 598 64Ο 598 8Ol 766 (tensile yield) (8,500) (9.1ΟΟ) (8,500) (11.4ΟΟ) (1Ο.9ΟΟ) Tear resistance 591 562 591 71 682 (tensile strength
a break) (8,4OO) (8,000) (8,4oo) (9,7OO) Tensile elongation 39 52 24 6O (tensile elongation! 2.0 Impact strength after Izod 3.5 7.4 2.4 5.8 (Izod impact) 42 Impact strength after Gardner 163 282 122 42,7OO 272 (Gardner impact) (6Ο8.ΟΟΟ) Bending module 32,100 21,900 38,500 1265 24,6OO (flexural modulus) (457.OOO) (312,000) (547,000) (18.OOO) (35Ο.ΟΟΟ) Flexural strength 956 878 1OO5 1Ο33 (flexural strength) (13.60O) (12,500) (14,300) 130.6
(267) (14,700) Heat resistant speed 111,
(heat distortion temp.) (232) 1 110.0
(230) 116.1
(24i! 122.8
(253! *
control 14-19

Mixtures of 78 parts of poly (2,6-dimethyl-1,4-phenylene ether) resin, 22 parts of triphenyl phosphate flame-retardant plasticizer, 1.5 parts of polyethylene, 0.5 parts of tridecyl phosphite, 0.15 parts Zinc sulfide, 0.15 part zinc oxide, 43 parts clay as a reinforcing filler (NCF, Freeport Kaolin) and various Impact modifiers in the various amounts indicated were prepared, extruded and used in the examples 1-4 deformed. The physical properties are summarized in Table 4.

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Funds for
Impact strength example modification

Tensile yield

14th

15th

16

17th

18th

19th

5 parts of styrene-butadiene-styrene block copolymer

10 parts of styrene-butadiene-styrene block copolymer

5 parts of styrene-buta-alien-styrene block copolymer ^e

5 parts of hydrogenated styrene-butadiene-styrene block copolymer

5 parts of acrylic-styrene-styrene-butadiene terpolymer ^ß

5 parts graft
copolymer from
Styrene and sty
rol-butadiene ⁿ

738 (10500)

689 (9800)

745 (10600)

632 (9000)

738 (10500)

731 (10400)

Tabel

Tear resistance
(tensile train break) elongation

675 (9600)

646 (9200)

727 (10200)

619 (8800)

675 (9600)

675 (9600)

49 51 50

33 46 49

Bending impact strength *

Izod Gardner modulus of strength

1.8 203 40980 1120 (583000) (16000)

2.7 212 37820 1033 (538000) (14700)

2.0 185 40770 1019 (580000) (14500)

2.4 190 36200 956 (515000) (13600)

1.3 195 41690 1054 (593000) (15100)

1.3 195 43 230 1076 (615000) (15300)

e K1101, Shell Chera. Co., Polymers Diν.

f KG 6521, Shell Chem. Co., Polymers Div.

g Acryloid KM 611, Rohm & Haas Co.

h Blendex 525, Marbon Chem. Co ₇

Examples 20-38

Mixtures of 78 parts of poly (2,6-dimethyl-1,4-phenylene ether), 22 parts of triphenyl phosphate, 5 parts of acrylic-styrene-styrene-butadiene terpolymer (Acryloid KM 611, Rohm & Haas Co.), 1.5 parts of polyethylene, 0.5 part of tridecyl phosphite, 0.15 part of zinc sulfide, 0.15 part of zinc oxide and 43 parts of various mineral reinforcing agents were prepared, extruded and shaped as in Examples 1-4. The mineral reinforcing agents and test results are summarized in Tables 5, 5A and 5B.

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Tabel

^ ο cn σι αϊ

Example filler

20 21 22 23 24 25 26

Calcium carbonate

Calcium carbonate * '

Antimony oxide

Volume*

Tone ^J tone ^;

volume

26A * no

Tensile strength (tensile yield break)

661 (9,4OO) 548 (7,8OO)

668 (9,500) 534 (7.6ΟΟ)

597 (8,500) 569 (8,1OO)

710 (10.10O) 640 (9.10O)

710 (10.100) 605 (8.6OO)

727 (1Ο.2ΟΟ) 623 (8,900)

773 (11,000) 654 (9,300)

654 (9,3OO) 619 (8,800)

Impact ability Izod Gardner Bending UL-94 after fewer Firming Flame test Train- 0.9 as Modulus stretch 10 1.2 / 20 1.0 10 31.7OO 998 16 (451.OOO) (14.20O) 1 / 2.3 7.4 240 32.41Ο 1Ο4Ο 21 (461,000) (14,800) 1.3 / 5.3 1.6 150 24,6OO 851 76 fewer (350.OOO) (12.10O) 1.7 / 4.7 1.0 as 36,270 1-47 29 10 (516.OOO) (14.9ΟΟ) 1.7 / 2 ^ζ 1.1 140 4Ο.63Ο 1054 25th (578.OOO) (15.OOO) 1/3 1.4 260 39.37Ο 1069 34 (560.00O) (15.2ΟΟ) 1.3 / 2 20.4 300 45.130 1124 36 (642.OOO) (16.OOO) 1.7 / 3 22.29Ο 907 90 (317,000) (12,900)

^ Control

i Carbium, Diamond Shamrock Co., precipitated calcium carbonate

j Carbium MM, Diamond Shamrock Co., precipitated calcium carbonate

k Al-Sil-Ate W, Freeport Kaolin Co.

Al-Sil-Ate LO, Freeport Kaolin Co.

m Al-Sil-Ate H02, Freeport Kaolin Co.

η Al-Sil-Ate NC, Freeport Kaolin Co.

INJ CO OO

Table 5 A Tensile strength tear resistance

Example filler ( tensile yield) (tensile break) Zj

27 barium sulfate 654 or 300) 562 (8.ex »)

28 calcium 619 (8,800) 499 (7,100)

carbonate

29 calcium 625 (8,900) 505 (7,200)

carbonate

fo 30 calcium _{6 33 (9,000) 506 (7,100} ) _o carbonate

co 31 calcium ₆ 4o (9,100) 505 (7,200) 00 carbonates

£ 31A no 647 (9,200) 645 (9,200)

Impact strength according to Gardner £ Izod 83 61 1.5 10 23 1.2 75 25th 1.3 31 25th 1.2 52 28 1.3 202 86 3.3

tn ³ ^ control
⁰¹

π <- 1 bariteββ, Charles Pfizer Co.
η Marblewhite 325 »Charles Pfizer Co., a powdered natural calcium carbonate
ο Vicron 15 - 15, Charles Pfizer Co · »a ground natural calcium carbonate
ρ Vicron 25 - 11, Charles Pfizer Co., a ground natural calcium carbonate

q Vicron 41 - 8, Charles Pfizer Co., a ground natural calcium carbonate

cn ro co 00

Table 5 B

cn cn «n

Tensile strength example filler (tensile yield) Impact strength tensile strength tensile to (tensile break) Elongation Izod Gardner module strength

Γ 39,710

32 33 34 35 36 37 37 A.

volume

ICiUBf

carbonate ⁵

lkUpT

Talc ¹ TaXkW TaIkW None

668 (9,500)

562 (8,000)

689 (9,800)

645 (9,200)

682 (9,700)

717 (1O.2OO)

548 (7,800)

(7.6ΟΟ) (6,700) (7,500) (9,200) (9.7ΟΟ) (8,6OO) (7,700)

r s t η ▼ w

P * eej> ort Kaolin Co, Wianofil 5, HJI Co. Emtal '996, Bnglehard Co · MP 45 π ft, 0> ρ? Α · β Pfieer Co. MP $ 5 * 38, Charles Pfiaex Co. MP 12 ^ 50, (ÄMries Pfieer Op.

45 50 24

17th

22nd

22nd

102

1.2 1.0 1.1 1.0 1.1 1.2 2.6

less than (565.ooo) (I4.ioo)

10 10 10 40 60 293

26,850 (382,000) (12.OOO) 45.980 1Ö26 (654.OOO) (14.60O)

41.690 (593.OOO) (13.80O) 45.7OO Io2o (650,000) (14.60O) 47,380 1Ο3Ο (674,000) (14.70O) 19,890 (283,000) (10,950)

CJl »si

Examples 38-43

Molded compositions of poly (2 _f 6-dimethyl-1,4-phenyfather) resin, triphenyl phosphate and various mineral reinforcing agents as indicated were prepared as in Examples 1-4 and the physical properties examined. The compositions and physical properties are summarized in Tables 6 and 6A, respectively.

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Table 6

ro cn * ^

example

Ingredients (parts by weight) poly (2,6-dimethyl-1,4-phenylene ether) triphenyl phosphate clay

Titanium dioxide zinc oxide 38 39 40 41 42 43

55 55 55 63 63 63

15 15 15 17 17 17

30 - 20 -

30 - 20 -

30 - - 20

N HI

β Ο + »!

B JQ O Ui

, 950 , 150 , 980 , 050 , 250 .300 CM i-l CM CM CM in
O I. m
VO 52.5 I. 64.7

«0

Ti

4 »4»

• β

■ oil 3

•oil oil • »I

- 26 -

8 ο Q QQQ

Q Ö O O O

K) ^ ¹ VO r - in in m «m ^ i in

O · O cn a

O · O · O

rtC> icricD μ Ο φΐητ-ΐΓ-σ »ρ

SCDr "f * 1 CD" -i OCDCTtCTi

m ο ^ co Vf ^^ "t ^ rn

τί-'d · - 'CM »- Π - CN ^ - (N ^

O O O

T-T-O

K CVi

8 2

O \ O \ 00 O CXk O OOO τ- o T ^

cn cn f-I m en 00 cn SO r «- VO

8 8 8 8

Ot

QE) 00 CD Oi QO

νβ tO

ό ο β

S- β-. ff

IA V *

r «

t'3 C 'O

* n r »^ r

ff

809826/0555 ORIGINAL INSPECTED

Examples 44-48

Molded compositions of poly (2,6-dimethyl-1,4-phenylene ether), Triphenyl phosphate, mineral reinforcing agent and an agent for impact modification were prepared as in Examples 1-4. The composition and physical properties are in Table 7 and 7 A summarized.

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Table 7

Example U 45 46 47 48

Components (parts by weight)

_β poly (2,6-dimethyl-1,4- _α phenylene ether ^ triphenyl phosphate Nj clay

5 titanium dioxide - 30 30 40 50

^ Styrene / styrene-butadiene - (^ copolymer (Blendex 525 »
to Marbon Chem. Co.) 5 5-55

Acrylic resin modified

Styrene-butadiene copolymer

(Acryloid KM 611, Rohm & Haas Co.) -5

55 55 55 47 39 15th 15th 15th 13th 11 30th _ _

Table 7A

σ to co

O cn tn

Tensile, tear and impact strength

strength strength after

Bei- (tensile (tensile tensile

game yield) break) elongation Izod Gardner

44

46 47 48

675 (9.6ΟΟ) 576 (8.2ΟΟ)

626 (8,900) 626 (8,9OO)

626 (8,900) 640 (9,10O)

612 (8.7ΟΟ) 583 (8.3OO)

612 (8,700) 576 (8.2ΟΟ)

45

⁸⁰

83

55

42

1.7 183 7.0 232 7.5 242 4.8 222 3.9 183

Bending

Strength modulus

38,380 1OO5

(546,000) (14,300)

25,520 893

(363,000) (12,700)

24,680 9OO

(351,000) (12,800)

27,840 931

(396,000) (13,250)

32,900 949

(468,000) (13.50O)

shiny Formbe
constant
speed in
the warmth UL-94
Flame
test 41.0 209 V-O 60.5 206 V-O 60.5 - V-O 57.5 206 V-O 50.5 202 V-O

Examples 49-50

Mixtures of poly (2,6-dimethyl-1,4-phenylene ether) resin, triphenyl phosphate, clay (NCP, Preeport Kaolin), a styrene-butadiene-styrene block copolymer (Kraton 1101), polyethylene, tridecyl phosphite, zinc sulfide and zinc oxide were used as prepared, extruded and molded in Examples 1-4. The molded compositions were examined for their physical properties in their original state, after heat aging and after water treatment. The compositions and test results are summarized in Tables θ, θ A, 8 B and 8 C.

Table 8 Example 49 Components (parts by weight)

Poly (2,6-dimethyl-1,4-phenylene ether)

Triphenyl phosphate

Styrene-butadiene-styrene block copolymer (Kraton 1101) volume

Polyethylene Tridecyl phosphate Zinc sulfide

zinc oxide

55 67 15th 13th 5 5 30th 20th 1.5 1.5 0.5 0.5 0.15 0.15 0.15 0.15

809826/0555

- vr-

Tabel 8A. Original physical elite PBchfcfttn

example 65Θ 12th 641 Ϊ 66 properties 476 448 58 ρ
Tensile strength kg / cm
(tensile yield), (psi) (9,360) 22.8 ° C (73 ° F) (6,770) 2 700) 65.5 ° C (150 ⁰ F) 200) Strain, % 41 (9,120) 22.8 ° C (73 ° F) 977 39 893 (6,370) .600) 65.5 ° C (150 ⁰ F) 590 576 .000) Flexural Strength, (psi,) kg / cm (13,900) 22.8 ° C (73 ⁰ F) .290 (8,400) 29,500 6th 65.5 ° C (150 ⁰ F) .350 24,820 1 Flexural modulus, (psi ) ₂
22.8 ° C ^k « ^{/ cn} 39 (558,900) (12. 65.5 ° C (150 ⁰ F) 31 (446,000) ( 8th. Notched impact strength
to Izod ft. lbs / in 22.8 ° C (73 ° F) 3.3 (419 -40 ° C (-40 ⁰ F) 0.8 (353 Impact strength according to
Gardner, in. Lbs. 22.8 ° C 83 β, -40 ° C (-40 ⁰ F) 10 1. 252 45

809826/0555

Table 8B. Physical properties after heat aging at 65 ° C and 115 ° C

at 65 ° C at 115 ° C

Tensile tear tensile tear

2 strength strength strength strength

S At- number (tensile (tensile tensile number (tensile (tensile tensile

oo game 49 of the days a lot d) break) stretching stroke of the days yield) break) stretching sleep

cn η 41 45.3 0 41 45 _f 3

^ ^U 661 (9.400) 590 ( ^8.400 ) * * JtJ ₆₆₁ (9,400) 590 (8,400)

<" ¹ 668 (9,500) 569 (8,100) ^{34 41} ' ^{5 1} _{696 (9. 9} oo) 548 (7,800) ^ ^ *'

¹⁰ 703 (lo.ooo) 583 (8.3000) _J2 ^ _{5 10} _ J ₀ , 0

S 30 ⁷¹ ° (10 * 100) 612 (8,700) 37 4 ^ _{9 2} 0 759 (10,800) 682 (9,70O ^ 18? 7.6

> G _{9 752 (10,700) 633 (9,000} ) 2 9 39.3 30 829 (11,800) 829 (11,800) 16 24.2

z to

m 90 ^{773 ( 11,000) 639} < ^{9 100} ) 32 4.4.3 59 844 (12,000) 844 (12,000) 8 23 &

Q (Sj

m '^ o

O 822 (11.70O) 675 (9.600) _β36 (Π.900) 835 (11.9O0) OO

^Löü 25 32.0 90 8 234

Tabel 8B (Continuation)

at 65 ° C at 115 ° C

Pull- Tear- To- Tear-

At- Number strength strength Number strength strength

Qo game of (tensile (tensile tensile) der (tensile (tensile tensile

° 49 days yield) break) stretching stroke days yield) break) stretching stroke

OO

Ki 637 ° (9.10O) 612 (8.7OO) ^ 8 63.7 O _{637 (9. 10,} o) 612 (8.7O0)

68 63 , 7 0 60 61 , 0 1 52 60 , 7 10

68 63 , 7 Ο » ι I. 41 48 , 3 I.
I.

O 1 675 (9.6OO) 605 (8.6ΟΟ) 60 61.0 1 703 (lO.OOO) 569 (8.1ΟΟ)

cn tn

^m 10 689 (9,800) 590 (8,4OO) 52 60.7 10 - - - 39.2

30,682 (9.7OO) 562 (8.0O0) 54 62.1 20 787 (11.2ΟΟ) 598 (8,500) 22 35.8

59 696 (9,900) 583 (8,300) 34 59.4 30 ⁸¹⁵ (11,600) 717 (10,20O) 29 28.2

90 745 (10,600) 640 (9,100) 50 57.0 59 ⁸ ^ S (12,300) 696 (9,900) 19 21.8 , S ₀

180 780 (11,100) 668 (9,500) 45 53.8 90 ^9o7 (12,9007 905 (12,900) 13 25.7 (sj

OO CO

Table 8C. Physical properties after immersion in water at 93.5 ° C (200 ^e F)

Example 49 number
the day Accessibility
(tensile yield) Tear resistance
(■ tensile break) Zue-Dehnun " Izod
Ski; 8098 0
10 661 (9,400)
640 (9,100) 590 (8,400)
555 (7,900) 41
40 3.3
3.1 ro ssso / s 20th
30th 640 (9,100)
654 (9,300) 541 (7,700)
548 (7,800) 31
31 3.0
3.5 40 675 (9,600) 583 (8,300) 27 3.6 50 675 (9,500) 583 (8,300) 24 3.5 59 696 (9,900) 590 (8,400) 23 3.5 90 703 (10,000) 555 (7,900) 27 3.2

ro -j tn

Ni Ca) OO CO

Table 8C (continued) Number Tensile Strength Tear Strength Izod Example 50 of the tensile yield (tensile break) tensile-elongation blow

oo 10

• 20th

ο 30

«" 40

50 59

90

639 (9,100) 612 (8,700) 68 8.6 639 (9,100) 597 (8,500) 88 3.9 668 (9,500) 562 (8,000) 40 3.8 675 (9,600) 569 (8,100) 59 4.1 689 (9,800) 576 (8,200) 56 4.3 710 (10,100) 583 (8,300) 40 3.8 717 ((10,200) 583 (8,300) 28 3.7 752 (10,700) 612 (8,700) 23 3.3

K> CO OO CJ

Claims (1)

Pk - - - "*" "rc" QAnLr 6000 Frankfurt / Main 1, November 23, 1977 Dr. rer. near Horst Schuler ω «*« «. 4i Dr.sch / m / Hk PATfNTANWAlT ^ / Ö ^ J 0 J ^^ ^ ^ ₅ Telex: 04-16759 mopat d Postsdieck-Accounti 282420-602 Frankfurt / M. Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. 4531-8CH-2424 GENERAL ELECTRIC COMPANY 1, River Road Schenectady, N.Y., U.S.A. Claims e A reinforced »plasticized thermoplastic composition with improved stiffness properties, characterized in that it contains: (a) a. Polyphenylene ether resin alone or in combination with an impact modifier; (b) a specific plasticizing agent in an amount that is at least sufficient to remove the lower the optimal extrusion temperature by at least 13.9 ° C; and (c) a mineral reinforcing agent in an amount at least sufficient to im To achieve an improved rigidity compared to a corresponding unreinforced composition. Composition according to Claim 1, characterized in that it comprises at least 5 parts of plasticizing agent Contains parts by weight of resin. 809826/0558 3. Composition according to claim 1 or 2, characterized ι that it contains at least 5 parts of mineral Contains reinforcing agent per 100 parts of resin. 4. assembly according to claim 1 to 3, characterized in that the mineral reinforcing agent Is aluminum silicate. 5. Composition according to claim 1 to 4, characterized in that the polyphenylene ether resin from itself repeating structural units of the formula consists in which the ether-oxygen atom of a unit connected to the benzene nucleus of the next following structural unit, η is a positive integer and has at least the value 50, and each Q is a monovalent one Substituent is selected from hydrogen, halogen, hydrocarbon radicals without a tertiary alpha carbon atom, Halocarbon and halocarbon oxy radicals with at least two carbon atoms between 809826/0555 the halogen atom and the phenyl nucleus and hydrocarbon oxy radicals 6. The composition of claim 5, characterized in that in the polyphenylene ether resin each Q is alkyl having 1 to 4 carbon atoms. 7. Composition according to claim 1 to 6, characterized in that the polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether. 8. Composition according to claim 1 to 7, characterized in that the impact strength modifier is a non-hydrogenated or hydrogenated elastomeric A-B-A block copolymer is 9. The composition of claim Θ, characterized in that the impact strength modifier is a block copolymer of styrene and butadiene. 10. The composition of claim 8, characterized in that the impact strength modifier is a block copolymer of styrene and isoprene. 11. The composition of claim 1 to 8, characterized in that the impact strength modifier is a radial teleblock copolymer vinyl aromatic compound, a conjugated Serve and is a coupling agent. 8098? 6/0 ^r 12. The composition according to claim 1 to 8, characterized in that the agent for impact modification is a resin which contains an acrylic resin-modified diene rubber. 13. The composition according to claim 12, characterized in that the resin containing an acrylic resin-modified diene rubber is a resin composition consisting of a butadiene-styrene skeleton or an acrylonitrile-butadiene-styrene skeleton grafted poly (alkyl methacrylate)) or from a mixture of a poly (alkyl methacrylate) and a butadiene-styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer « 14. Composition according to claim 1 to 8, characterized in that the agent for impact modification is a graft copolymer of a vinyl aromatic compound and a diene compound. 15. Composition according to claim 1 to 14, characterized in that the agent for impact modification is a compound of the formula 3 "1 RO -P-OR Or ² 809826 / 0S56 12 3
wherein R, R and R ^ are the same or different and alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl-substituted aryl, haloalkyl-substituted aryl, aryl-substituted Alkyl, halogenaryl-substituted alkyl, hydroxyalkyl, Hydroxyaryl, hydroxyalkaryl, halogen and hydrogen mean. 16. Composition according to claim 1 to 15, characterized in that indicates that the plasticizer is an aromatic phosphate plasticizer. 17. Composition according to claim 1 to 16, characterized in that the aromatic phosphate is triphenyl phosphate. 18. Composition according to claim 1, characterized in that the plasticizing agent is a flame retardant Means is. 19. Composition according to claim 1 to 18, characterized in that the mineral reinforcing agent is anhydrous aluminum silicate or hydrous aluminum silicate. 20. Composition according to claim 1 to 3 and 5 to 18, characterized in that the mineral reinforcing agent is talc, zinc oxide, titanium dioxide, antimony oxide, barium sulfate, calcium carbonate or zinc sulfide. 809826/0555