Poly(alkenyl substituted aromatic) and elastomer containing polymer compositions and process for their preparation

• US 5,079,268 A
• Filed: 05/30/1990
• Issued: 01/07/1992
• Est. Priority Date: 06/23/1989
• Status: Expired due to Term

• Current Assignee: Shell Research Limited (Shell Plc)
• Original Assignee: Shell Research Limited (Shell Plc)
• Inventors: De Koning, Gerardus J. M., Nelissen, Laurentius N. I. H., Zijderveld, Johannes M.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Hamilton, III, Thomas
• Application Number:
  US07/528,881
• Time in Patent Office: 587 Days
• Field of Search: 525/149, 525/152, 525/391, 525/392, 525/905, 521/81
• US Class Current: 521/81
• CPC Class Codes: C08F 255/06 on to ethene-propene-diene terpolymers C08F255/023 takes precedence
• CPC Class Codes: C08F 283/08 on to polyphenylene oxides
• CPC Class Codes: C08F 287/00 Macromolecular compounds obtained by polymerising monomers on to block polymers
• CPC Class Codes: Y10S 525/905 Polyphenylene oxide

Abstract

Poly(alkenyl substituted aromatic) and elastomer containing polymer compositions, obtainable by a process comprising:

(a) conversion of polyphenylene ether or a structurally related polymer thereof with an acid halide, an acid anhydride or ketene, in at least one alkenyl substituted aromatic monomer;

(b) dissolution of at least one EPDM rubber and an optionally partially hydrogenated diblock copolymer A--B, optionally mixed with minor amounts of triblock copolymers ABA, wherein A represents a poly(alkenyl aromatic) block and B represents an optionally, partially hydrogenated poly conjugated diene block;

(c) prepolymerization of the obtained mixture until a polymerization degree of from 5 to 20%;

(d) suspending the prepolymerized mass into an aqueous medium;

(e) polymerization by thermal initiation or by initiation by means of at least one free radical initiator, optionally in the presence of an expanding agent;

and a process for the preparation of such polymer compositions.

Claims

1. Poly(alkenyl substituted aromatic) containing polymer compositions, obtained by a process comprising:

(a) reacting a polyphenylene ether or a structurally related polymer thereof of the formula ##STR6## wherein R₁ and R₄ each may represent hydrogen, halogen, a phenyl group, alkenyl group, alkadienyl group, an aryloxy group, or wherein R₁ and R₄ each may represent an alkyl group or an alkoxy group, each of the latter containing 12 or less carbon atoms and each optionally substituted by halogen, cyano, hydroxy, phenyl or amino, whereas alkyl or alkoxy groups attached to the terminal phenol nucleus of the chain may be substituted by an amino, dialkylamino or a di(alkanoyl) amide group, wherein the alkyl groups each contain 4 or less carbon atoms, wherein R₂ and R₃ each may represent hydrogen, halogen, a phenyl group, alkenyl group, alkadienyl group, aryloxy group or wherein R₂ and R₃ each may represent a primary or secondary alkyl group or alkoxy group as defined for R₁ and R₄, optionally substituted by halogen, cyano, hydroxy, phenyl, and wherein R₁, R₂, R₃ and R₄ may represent different or the same groups in one repeating unit, and n represents an integer having a value of at least 50 and more preferably 100 to 500, with an acid halide, an acid anhydride or ketene, in at least one alkenyl substituted aromatic monomer, the amount of polyphenylene ether or structurally related polymer in the reaction mixture being in the range of from 5 to 30% by weight calculated on the complete final composition;

(b) dissolving at least one ethylenepropylenediene monomer (EPDM) rubber having a specific density in the range of from 0.85 to 0.95, a Mooney viscosity (ML(1+4) 125°

C.) in the range of from 30 to 80, an ethylene content in the range of from 50 to 70% by weight, in the reaction mixture of step (a) in an amount of from 5 to 20% by weight together with a diblock copolymer A--B which is optionally partially hydrogenated, optionally mixed with minor amounts of triblock copolymers A--B--A, wherein A represents a poly(alkenyl aromatic) block and B represents an optionally, partially hydrogenated poly (conjugated diene) block, having a number average molecular weight in the range of from 10,000 to 1,000,000 and showing a glass transition temperature of -20°

C. or below, said diblock copolymer being added to the reaction mixture of step (a) in an amount of from 1 to 5% by weight calculated on the weight of the complete final composition;

(c) prepolymerizing the obtained mixture until a prepolymerized mass is formed having a degree of polymerization of from 5 to 20%;

(d) suspending the resulting prepolymerized mass in an aqueous medium; and

(e) polymerizing by thermal initiation or by means of at least one free radical initiator, optionally in the presence of an expanding agent, the prepolymerized mass of step (d).

2. Polymer compositions according to claim 1, obtained by said process, step (a) of which is carried out in a predominantly styrene monomer containing mixture.

3. Polymer compositions according to claim 1, obtained by said process, step (a) of which is carried out with an acid halide or a non-cyclic acid anhydride as capping agent selected from compounds of the formulae:

##STR7## wherein X₁ represent halogen or an alkyl group containing 1 to 4 carbon atoms, and which may optionally be substituted by halogen, wherein X₂ represents halogen, and wherein R₅ and R₆ each independently represent an alkyl, alkenyl, aryl or aralkyl group, containing from 1 to 12 carbon atoms and optionally being substituted by hydroxy, halogen, alkyl containing 1 to 4 carbon atoms, or a free or esterified carboxyl group, in the presence of a catalyst of the formula;

##STR8## wherein R₉ and R₁₀ both represent alkyl groups containing from 1 to 4 carbon atoms, optionally substituted by at most one phenyl group and wherein R₇ and R₈ represent hydrogen, halogen or lower alkyl, while R₉ and R₁₀ may represent different or the same groups, and optionally in the presence of a neutralizing agent.

4. Polymer compositions according to claim 3, obtained by said process, step (a) of which is carried out with a capping agent selected from the group consisting of parabromomethylphenylsulphonyl bromide, parabromomethylphenylsulphonyl chloride, acetic anhydride, benzoic anhydride and bromoacetic anhydride.

5. Polymer compositions according to claim 4, obtained by said process, step (a) of which is carried out with an acetic anhydride capping agent.

6. Polymer compositions according to claim 1, obtained by said process, step (a) of which is carried out with N,N-dimethyl-4-amino pyridine as catalyst.

7. Polymer compositions according to claim 1, obtained by said process, step (a) of which is carried out with an acid halide and an additional acid neutralizing agent.

8. Polymer compositions according to claim 7, obtained by said process, step (a) of which is carried out with a parabromomethylphenylsulphonyl bromide capping agent, N,N-dimethyl-4-amino pyridine as catalyst and triethylamine or tri-n-propylamine.

9. Polymer compositions according to claim 1, obtained by said process, step (a) of which is carried out with a capping agent selected from the formula ##STR9## wherein Y represents a bivalent radical of the formulae:

##STR10## wherein m represents an integer in the range of from 2 to 8 and wherein R₁₁ and R₁₂ may each independently represent an alkyl group of 1 to 4 carbon atoms, a phenyl group or an aralkyl group or wherein R₁₁ and R₁₂ together with the carbon atoms of the double carbon-carbon bond may form a cycloalkenyl, cycloalkadienyl or aryl group, in the presence of a non nucleophilic base.

10. Polymer compositions according to claim 9, obtained by said process, step (a) of which is carried out with maleic anhydride and sodium hydride.

11. Polymer compositions according to claim 1, wherein R₁ and R₄ in formula I represent methyl, optionally substituted when attached to the terminal phenol nucleus with amino or dialkylamino, and R₂ and R₃ represent hydrogen.

12. Polymer compositions according to claim 1, obtained by said process wherein in step (a) said polyphenylene ether or structurally related polymer is added in an amount in the range of from 10 to 25% by weight, relative to the weight of complete final composition.

13. Polymer compositions according to claim 1, obtained by said process, wherein in step (c) a prepolymerization degree of from 8 to 15% is achieved.

14. Polymer compositions according to claim 1, obtained by said process, in step (b) of which EDPM copolymers are employed, which contain from 50 to 705 by weight ethylene, and from 0.5 to 12% by weight of a norbornene derivative and exhibit a number average molecular weight in the range of from 40 to 90 kg/mole and an Mw/Mn ratio in the range of from 2.0 to 4.0.

15. Polymer compositions according to claim 1, obtained by said process, in step (b) of which diblock A--B copolymers are employed, having a number average molecular weight in the range of from 50,000 to 800,000 and which have a content of the alkenyl substituted aromatic in the range of from 20 to 40% by weight.

16. Process for the preparation of poly(alkenyl substituted aromatic) containing polymer compositions comprising:

(a) reacting a polyphenylene ether or a structurally related polymer thereof of the formula ##STR11## wherein R₁ and R₄ each may represent hydrogen, halogen, a phenyl group, alkenyl group, alkadienyl group, an aryloxy group, or wherein R₁ and R₄ each may represent an alkyl group or an alkoxy group, each of the latter containing 12 or less carbon atoms and each optionally substituted by halogen, cyano, hydroxy, phenyl or amino, with alkyl or alkoxy groups attached to the terminal phenol nucleus of the chain optionally being substituted by an amino, dialkylamino or a di(alkanoyl) amide group, wherein the alkyl groups each contain 4 or less carbon atoms, wherein R₂ and R₃ each represent hydrogen, halogen, a phenyl group, alkenyl group, alkadienyl group, aryloxy group or wherein R₂ and R₃ each represent a primary or secondary alkyl group or alkoxy group as defined for R₁ and R₄, optionally substituted by halogen, cyano, hydroxy, phenyl, and wherein R₁, R₂, R₃ and R₄ represent different or the same groups in one repeating unit, and n represents an integer having a value of at least 50, with an acid halide, an acid anhydride or ketene, in at least one alkenyl substituted aromatic monomer, the amount of polyphenylene ether or structurally related polymer in the reaction mixture being in the range of from 5 to 35% by weight calculated on the complete final composition;

(b) dissolving at least one EPDM rubber having a specific density in the range of from 0.85 to 0.95, a Mooney viscosity (ML(1+4) 125°

C.) in the range of from 30 to 80, an ethylene content in the range of rom 50 to 70% by weight, in the reaction mixture of step (a) in an amount of from 5 to 20% by weight together with a diblock copolymer A--B which is optionally partially hydrogenated, optionally mixed with minor amounts of triblock copolymer A--B--A, wherein A represents a poly(alkenyl aromatic) block and B represents an optionally, partially hydrogenated poly conjugated diene block, having a number average molecular weight in the range of from 10,000 to 1,000,000 and exhibiting a glass transition temperature of -20°

C. or below, said diblock copolymer being present in an amount of from 1 to 5% by weight calculated on the weight of the complete final composition;

(c) prepolymerizing the obtained mixture until a prepolymerization mass is formed having a degree of polymerization of from 5 to 20%;

(d) suspending the prepolymerized mass in an aqueous medium; and

(e) polymerizing by thermal initiation or by means of at least one free radical initiator, optionally in the presence of an expanding agent, the prepolymerized mass of step (d).