Silane vulcanized thermoplastic elastomers

Abstract

The present invention relates to novel polymer compositions, particularly in the form of thermoplastic Vulcanisates, said compositions comprising the reaction product of a first polymer (rubber phase); a second polymer (thermoplastic phase); a carboxylic acid anhydride; either a vinylsilane in combination with a peroxide or a sulphursilane; and whereby said silane is allowed to react with the polymers first. The invention further provides for processes of manufacturing such compositions and for articles comprising such compositions.

Claims

1. A thermoplastic vulcanisate (TPV) composition comprising the reaction product of (a) a first polymer (rubber phase); (b) a second polymer (thermoplastic phase); (c) a carboxylic acid anhydride; (d) either (d1) a vinyl-silane in combination with a peroxide or (d2) a sulphursilane; and whereby component (d) is first added to a polymer melt comprising components (a) and (b), followed by the addition of component (c).

2. The composition according to claim 1, wherein component (a) is a Polyethylene or an Ethylene-Propylene-Diene-Rubber.

3. The composition according to claim 1, wherein component (b) is a Polypropylene.

4. The composition according to claim 1, wherein component (c) is maleic acid anhydride.

5. The composition according to claim 1, wherein component (d1) is vinyltrimethoxy-silane in combination with 2,5-dimethyl-2,5-di(tert.butylperoxy) hexane (DHBP) or wherein component (d2) is Bis(triethoxy-silylpropyl) polysulfide.

6. The composition according to claim 1 wherein (a) is present in an amount of 50-90 wt %; (b) is present in an amount of 5-40 wt %; (c) is present in an amount of 0.2-5 wt %; and/or (d) is present in an amount of 0.2-5 wt %; wherein the wt % is based on the total amount of polymer present.

7. The composition according to claim 1, wherein the gel content is 5-40 wt %; and/or the tensile strength is 3-40 MPa; and/or the elongation break is 100-1500%; and/or the melt index is 0.1-20 g/10 min at 190 C./5 kg; and/or the shore hardness is 20 A-80 D.

8. The composition according to claim 1, wherein component (d) is selected from (d1), component (a) is selected from the group consisting of ethylene propylene copolymer (EPR), ethylene propylene diene terpolymer (EPDM), butyl rubber (BR), natural rubber (NR), chlorinated polyethylenes (CPE), isoprene rubber (IR), silicone rubber, chlorinated rubbers, styrene-butadiene rubber (SBR), nitrile rubber (NBR), ethylene-vinyl acetate (EVA), ethylene methacrylate (EMA), ethylene butylacrylate (EBA), ethylene ethylacrylate (EEA), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE) and component (b) is selected from the group consisting of polypropylene and its copolymers, thermoplastic polyolefins (TPO's), thermoplastic polypropylene, polyethylene and its copolymers, silane copolymers, polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), polycarbonate (PC), and polyamide (PA).

9. The composition according to claim 1, wherein component (d) is selected from (d2), component (a) is selected from the group consisting of EPR, EPDM, BR, NR, CPE, IR, SBR, NBR, chlorinated rubbers and PVC ethylene propylene copolymer (EPR), ethylene propylene diene terpolymer (EPDM), butyl rubber (BR), natural rubber (NR), chlorinated polyethylenes (CPE), isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), chlorinated rubbers and polyvinyl chloride (PVC); and component (b) is selected from the group consisting of polypropylene and its copolymers, polyethylene and its copolymers, polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile (SAN), polymethylmethacrylate (PMMA), thermoplastic polyesters (PET, PBT), polycarbonate (PC), and polyamide (PA).

10. A process for manufacturing a composition according to claim 1, said process comprising the steps of: method A, where component (d1) is used: proving a homogeneous mixture of components (a) and (b), and then adding component (d1), either simultaneously or subsequently and then adding component (c); or method (B), where component (d2) is used: proving a homogeneous mixture of components (a) and (b) and then adding component (d2), and then adding component (c).

11. The process of claim 10 method (A), wherein the vinylsilane is added first, followed by addition of the peroxide.

12. An article consisting of a composition according to claim 1, said article being selected from the group of pipes, profiles, molded parts, foamed parts and sheet-like articles.

13. An automotive device consisting of a composition according to claim 1.

14. An aircraft device consisting of a composition according to claim 1.

15. A healthcare device consisting of a composition according to claim 1.

16. A power cable comprising a composition according to claim 1.

Description

EXAMPLE 1

Silane Thermoplastic Vulcanised Elastomers, Peroxide Curable

(1) The experiments were carried out on a Brabender Plasticorder having a mixing chamber from 50 CC and equipped with Sigma mixing knives. The setting temperature was 190 C. and mixing speed used was 120 RPM.

EXAMPLE 1.1

(2) TABLE-US-00001 Ingredient component % Engage 8452 rubber phase (a) 75.00 VLDPE ex DOW Chemical Melt Index 3 gr/10 min density 0.875 g/cm.sup.3 Eltex P HF 100 thermopl. phase (b) 22.50 Polypropylene homopolymer ex Solvay Melt index 0.9 gr/10 min density 0.900 g/cm.sup.3 DHBP (d1) 0.05 ex Degussa Vinyltrimethoxysilane (d1) 1.50 Maleic Anhydride anhydride (c) 0.95

(3) The total amount of ingredients will be 50 gr by weighted according the example 1.1. Engage 8452 (very low density polyethylene (VLDPE) and Eltex P HF 100 polypropylene homopolymer are introduced in the mixing chamber and mixed until homogenisation. Vinyltrimethoxysilane/DHBP mixture are injected in the mixing chamber, after 5 minutes grafting/compounding time the Brabender Torque reached a value from 5 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 minutes. The Brabender Torque value increased to 12 Nm after 7 minutes and dropped at 6 Nm after 10 minutes, which indicated that, the cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 Bars, having the following characteristics:

(4) TABLE-US-00002 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [MPa] 28 at break Elongation at break ISO 37 .sup.1) [%] 820 Melt Index ISO 1872-1, [g/10 min] 2.0 (190 C./5 kg) No 18T Shore hardness A ISO 868 86 Gel content ISO 6427 [%] 36 .sup.1) 50 mm/min pulling speed

(5) The above data show, that this specimen shows characteristics of a TPV. Further, the specimen is transparent and odourless.

EXAMPLE 1.2

Comparison

(6) TABLE-US-00003 Ingredient component % Engage 8452 rubber phase (a) 75.00 Eltex P HF 100 thermopl. phase (b) 22.50 DHBP (d1) Vinyltrimethoxysilane (d1) Maleic Anhydride anhydride (c) 1.00

(7) The total amount of ingredients will be 50 gr by weighted according the example 1.1. Engage 8452 and Eltex P HF 100 are introduced in the mixing chamber and mixed until homogenisation. After 5 minutes grafting/compounding time the Brabender Torque reached a value from 6 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 minutes. The Brabender Torque value increased to 6 Nm after 6 minutes and remains at 5 Nm, which indicated that, no cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 Bars, having the following characteristics:

(8) TABLE-US-00004 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [MPa] 13 at break Elongation at break ISO 37 .sup.1) [%] 800 Melt Index ISO 1872-1, [g/10 min] 8.5 (190 C./5 kg) No 18T Shore hardness A ISO 868 82 Gel content ISO 6427 [%] 0 .sup.1) 50 mm/min pulling speed

(9) The above data show, that this specimen shows NOT characteristics of a TPV. Further, the specimen is transparent and odourless.

EXAMPLE 1.3

(10) TABLE-US-00005 Ingredient component % Engage 8842 rubber phase (a) 75.00 UVLDPE ex DOW Chemical Melt index 1 gr/10 min density 0.857 g/cm.sup.3 Eltex P HF 100 thermopl. phase (b) 22.50 DHBP (d1) 0.05 Vinyltrimethoxysilane (d1) 1.45 Maleic Anhydride anhydride (c) 1.00

(11) The total amount of ingredients will be 50 gr by weighted according the example 1.1. Exact 8842 and Eltex P HF 100 are introduced in the mixing chamber and mixed until homogenisation. Vinyltrimethoxysilane/DHBP mixture are injected in the mixing chamber, after 5 minutes grafting/compounding time the Brabender Torque reached a value from 6 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 minutes. The Brabender Torque value increased to 13 Nm after 6 minutes and dropped at 6 Nm, which indicated that, the cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 Bars, having the following characteristics:

(12) TABLE-US-00006 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [MPa] 8.5 at break Elongation at break ISO 37 .sup.1) [%] 810 Melt Index ISO 1872-1, [g/10 min] 0.8 (190 C./5 kg) No 18T Shore hardness A ISO 868 75 Gel content ISO 6427 [%] 32 .sup.1) Pulling speed 50 mm/min

(13) The above data show, that this specimen shows characteristics of a TPV. Further, the specimen is transparent and odourless.

EXAMPLE 1.4

(14) TABLE-US-00007 Ingredient component % Vistalon 1703P rubber phase (a) 75.00 EPDM ex ExxonMobil: Mooney Viscosity ML (1 + 4) @125 C. = 25 Eltex P HF 100 thermopl. phase (b) 22.50 DHBP (d1) 0.05 Vinyltrimethoxysilane (d1) 1.45 Maleic Anhydride anhydride (c) 1.00

(15) The total amount of ingredients will be 50 gr by weighted according the example 1.1. Vistalon 1703P ethylene propylene diene terpolymer (EPDM) and Eltex P HF 100 are introduced in the mixing chamber and mixed until homogenisation. Vinyltrimethoxysilane/DHBP mixture are injected in the mixing chamber, after 5 minutes grafting/compounding time the Brabender Torque reached a value from 5 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 minutes. The Brabender Torque value increased to 11 Nm after 6 minutes and dropped at 5 Nm which indicated that the cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 Bars, having the following characteristics:

(16) TABLE-US-00008 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [ ]MPa 8.5 at break Elongation at break ISO 37 .sup.1) [%] 380 Melt Index ISO 1872-1, [g/10 min] 1.0 (190 C./5 kg) No 18T Shore hardness A ISO 868 82 Gel content ISO 6427 [%] 35 .sup.1) Pulling speed 50 mm/min

(17) The above data show, that this specimen shows characteristics of a TPV. Further, the specimen is transparent and odourless.

EXAMPLE 2

Silane Thermoplastic Vulcanised Elastomers, Sulphur Curable

(18) The experiments were carried out on a Brabender Plasticorder having a mixing chamber from 50 CC and equipped with Sigma mixing knives. The setting temperature was 190 C. and mixing speed used was 120 RPM.

EXAMPLE 2.1

(19) TABLE-US-00009 Ingredient component % NBR: Perbunan 3430F ex Lanxess rubber phase (a) 75.00 Mooney Viscosity UML (1 + 4) at 100 C. = 32; Bound Acronitrile = 34 Eltex P HF 100 .sup.2) thermopl. phase (b) 22.65 Si 69: Bis(triethoxysilylpropyl) (d2) 1.95 polysulfide ex Degussa Maleic Anhydride anhydride (c) 0.40

(20) The total amount of ingredients will be 50 gr by weighted according the example 1.1. Perbunan 3430F butadiene-acrylonitrile copolymer (NBR) and Eltex P HF 100 are introduced in the mixing chamber and mixed until homogenisation. Bis(triethoxysilylpropyl)polysulfide is injected in the mixing chamber, after 5 minutes grafting/compounding time the Brabender Torque reached a value from 7 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 min. The Brabender Torque value increased to 15 Nm after 7 minutes and dropped at 7 Nm after 10 minutes, which indicated that, the cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 bars, having the following characteristics:

(21) TABLE-US-00010 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [MPa] 32 at break Elongation at break ISO 37 .sup.1) [%] 650 Melt Index ISO 1872-1, [g/10 min] 0.4 (190 C./5 kg) No 18T Shore hardness A ISO 868 88 Gel content ISO 6427 [%] 33 .sup.1) 50 mm/min pulling speed

(22) The above data show, that this specimen shows characteristics of a TPV. Further, the specimen is oil resistant.

EXAMPLE 2.2

Comparison

(23) TABLE-US-00011 Ingredient component % NBR: as ex. 2.1 rubber phase (a) 75.00 Eltex P HF 100 thermopl. phase (b) 22.65 Si 69 Maleic Anhydride anhydride (c) 0.40

(24) The total amount of ingredients will be 50 gr by weighted according the example 2.1. Perbunan 3430F and Eltex P HF 100 are introduced in the mixing chamber and mixed until homogenisation. After 5 minutes grafting/compounding time the Brabender Torque reached a value from 7 Nm. Maleic Anhydride is added in the mixing chamber, compounding time 10 minutes. The Brabender Torque value increased to 7 Nm after 6 minutes and remains at 7 Nm, which indicated that, no cross-linking reaction has taken place. A moulded specimen, 1.5 mm thickness, is pressed at 210 C./20 bars, having the following characteristics:

(25) TABLE-US-00012 Physical Property Method Unit Value Tensile strength ISO 37 .sup.1) [MPa] 6 at break Elongation at break ISO 37 .sup.1) [%] 450 Melt Index ISO 1872-1, [g/10 min] 7 (190 C./5 kg) No 18T Shore hardness A ISO 868 78 Gel content ISO 6427 [%] 0 .sup.1) 50 mm/min pulling speed

(26) The above data show that this specimen shows NOT the characteristics of a TPV.