Functionalized polymer composition

Abstract

Vulcanizable polymer compositions based on backbone-functionalized polydienes having the general formula (I): ##STR00001##

Claims

1. A vulcanizable polymer composition comprising functionalized polydienes according to the general formula (I): ##STR00013## where: x is identical or different and is an integer 1 to 8; q is identical or different and is 0 to 20; polymer is identical or different and represents polymer units of the formula (II) ##STR00014## where: n is identical or different and is 1 to 200,000, m is identical or different and is 0 to 50,000, p is identical or different and is 1 to 100,000, diene is formed by polymerization of butadiene and/or isoprene, and styrene is formed by polymerization of styrene or substituted styrene; R.sup.1 is identical or different and is selected from: a group of compounds of the formula (III)
C.sub.6(R.sup.2).sub.5(C?O)N(R.sup.3)C.sub.6(R.sup.2).sub.4(III) where R.sup.2 and R.sup.3 are identical or different and represent a hydrogen radical, a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; a radical of the formula (IV) ##STR00015## where R.sup.4 is identical or different and represents a hydrogen, a halogen, a nitro or a hydroxyl radical, a linear or branched alkyl radical having 1 to 12 C atoms, a linear or branched alkoxy radical having 1 to 12 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms, or the R.sup.4 jointly forms a radical of the formula (V) ##STR00016## where R.sup.5 is identical or different and represents a hydrogen radical, a hydroxyl radical, a linear or branched alkyl radical having 1 to 12 C atoms, a linear or branched alkoxy radical having 1 to 12 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; a radical of the formula (VI)
(R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m(VI) where: n is an integer 1 to 12; m is a number 0 to 4; R.sup.6 is identical or different and represents a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; Y represents sulphur, or a radical of the formula VIIa, VIIb, VIIc, VIId or VIIe ##STR00017## where x is an integer 1 to 8; p is an integer 1 to 12; R.sup.8 is identical or different and represents a linear or branched alkyl radical having 1 to 16 C atoms, an alkoxy radical having 1 to 16 C atoms, a phenyl radical, or a phenoxy radical; a radical of the formula (VIII)
(R.sup.9).sub.2N(C?Z)(VIII) where: Z represents sulphur or oxygen, R.sup.9 is identical or different and represents a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; or a radical of the formula (IX)
R.sup.10OC(?S)(IX) where R.sup.10 is identical or different and represents a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms.

2. The vulcanizable polymer composition according to claim 1, wherein the functionalized polydienes comprise neodymium-catalyzed polybutadienes (NdBRs) having a proportion of cis-1,4 units of >95% by wt. and a proportion of 1,2-vinyl content of <1% by wt.

3. The vulcanizable polymer composition according to claim 2, wherein the NdBR is modified with sulphur chlorides after the polymerization.

4. The vulcanizable polymer composition according to claim 1, wherein the functionalized polydienes comprise styrene-butadiene copolymers, where the copolymers are modified such that their Mooney viscosities are increased after the polymerization.

5. The vulcanizable polymer composition according to claim 1, wherein the functionalized polydienes have the following characteristics: a. a molar mass (Mw) of 1 to 10,000 kg/mol, b. a polydispersity as Mw/Mn of 1 to 5, c. a Mooney viscosity of 30 MU to 150 MU, d. a content of sulphur of 0.02 to 1% by wt. based on 100% by wt. of the functionalized polydienes, e. a content of chlorine of 0.01 to 1% by wt. based on 100% by wt. of the functionalized polydienes, and f. the number of groups R.sup.1 is 1 to 21 units per polymer unit, based on 100% by wt. of the functionalized polydienes.

6. A process for the production of the vulcanizable polymer composition according to claim 1, the process comprising: forming the functionalized polydienes by polymerizing diene and optionally styrene monomers to produce polymers, and thereafter reacting the polymers with sulphur chlorides thus increasing Mooney viscosity via sulphur bridge bonding, whereby Mooney jumped polymer is formed, and reacting the Mooney jumped polymer with a functionalization reagent mixture containing a compound having the general formula (X)
R.sup.1SSR.sup.1(X).

7. The process according to claim 6, wherein the compound of formula (X) is at least one of tetramethylthiuram disulphide and a compound of the formula (VIb)
(EtO).sub.3SiC.sub.3H.sub.6S.sub.2C.sub.3H.sub.6Si(OEt).sub.3(VIb).

8. The process according to claim 6, wherein the functionalization reagent mixture further comprises an activator comprising a transition metal salt, where the transition metal is selected from the group consisting of Fe, Co, Cu, Ni, Mn, and Cr.

9. The process according to claim 8, wherein the transition metal salt is an Fe salt selected from Fe phthalocyanine and Fe hemiporphyrazine.

10. The process according to claim 6, wherein the functionalization reagent mixture further comprises an activator selected from pentachlorothiophenol and its salts.

11. The process according to claim 6, wherein the functionalization reagent mixture further comprises an activator selected from organic peroxides according to the formula (XI)
R.sup.11OOR.sup.12(XI) where: R.sup.11 and R.sup.12 are identical or different and represent: a hydrogen radical, a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, a cycloalkyl radical having 5 to 8 C atoms, or a carboxyl radical R.sup.13(C?O)?, where R.sup.13 represents a linear or branched alkyl radical having 1 to 16 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms.

12. The process according to claim 6, wherein the functionalization reagent mixture additionally contains waxes and/or fillers.

13. The process according to claim 6, wherein the reacting step comprises mixing with thermal or mechanical energy input.

14. The process according to claim 13, wherein the mixing is via a mixer extruder or roller at a temperature of 70? C. to 160? C.

15. The process according to claim 6, wherein the functionalization reagent mixture comprises 5 to 100% by wt. of one or more compounds of the formula (X) based on 100% by wt. of functionalization reagent mixture.

16. The process according to claim 6, wherein the functionalization reagent mixture comprises, based on 100% by wt. of functionalization reagent mixture: a) 5 to 100% by wt. of one or more compounds of the formula (X); and at least one of: b) 0.01 to 5% by wt. of activators, proportionally to loads of the compound of formula (X); c) 0.01 to 90% by wt. of waxes, proportionally to loads of the compound of formula (X); and d) 0.01 to 90% by wt. of fillers, proportionally to loads of the compound of formula (X).

17. The process according to claim 6, wherein: the reacting step comprises mixing with thermal or mechanical energy input; the mixing is done at a temperature of 80? C.-140? C.; and the functionalization reagent mixture comprises, based on 100% by wt. of functionalization reagent mixture: a) 30 to 50% by wt. of one or more compounds of the formula (X) selected from tetramethylthiuram disulphide and a compound of the formula (VIb)
(EtO).sub.3SiC.sub.3H.sub.6S.sub.2C.sub.3H.sub.6Si(OEt).sub.3(VIb); and at least one of: b) 0.3-1% by wt. of activators, proportionally to loads of the compound of formula (X), wherein the activators are selected from the group consisting of Fe phthalocyanine, Fe hemiporphyrazine, pentachlorothiophenol, zinc salts of pentachlorothiophenol, and organic peroxides according to the formula (XI)
R.sup.11OOR.sup.12(XI) where: R.sup.11 and R.sup.12 are identical or different and represent: a hydrogen radical, a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, a cycloalkyl radical having 5 to 8 C atoms, or a carboxyl radical R.sup.13(C?O), where R.sup.13 represents a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; c) 30-50% by wt. of waxes, proportionally to loads of the compound of formula (X); and d) 10-30% by wt. of fillers, proportionally to loads of the compound of formula (X).

18. A vulcanizable polymer composition of functionalized polydienes according to the general formula (I): ##STR00018## where: x is identical or different and is an integer 1 to 3; q is identical or different and is 0 to 20; polymer is identical or different and represents polymer units of the formula (II) ##STR00019## where: n is identical or different and is 1 to 200,000, m is identical or different and is 0 to 10, p is identical or different and is 1 to 100,000, diene is C.sub.4H.sub.6, and styrene is C.sub.2H.sub.3(C.sub.6H.sub.5); and R.sup.1 is identical or different and selected from: a group of compounds of the formula (III)
C.sub.6(R.sup.2).sub.5(C?O)N(R.sup.3)C.sub.6(R.sup.2).sub.4(III where R.sup.2 and R are identical or different and represent a hydrogen radical, a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; a radical of the formula (IV) ##STR00020## where R.sup.4 is identical or different and represents a hydrogen, a halogen, a nitro or a hydroxyl radical, a linear or branched alkyl radical having 1 to 8 C atoms, a linear or branched alkoxy radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms or the R.sup.4 jointly forms a radical of the formula (V) ##STR00021## where R.sup.5 is identical or different and represents a hydrogen radical, a hydroxyl radical, a linear or branched alkyl radical having 1 to 12 C atoms, a linear or branched alkoxy radical having 1 to 12 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; a radical of the formula (VI)
(R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m (R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m(VI) where: n is an integer 1 to 6; m is a number 0 to 2; R.sup.6 is identical or different and represents a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; Y represents sulphur, a radical of the formula VIIa, VIIb, VIIc, VIId, or VIIe ##STR00022## where x is an integer 2 to 6; p is an integer 1 to 6; R.sup.8 is identical or different and represents a linear or branched alkyl radical having 1 to 8 C atoms, an alkoxy radical having 1 to 8 C atoms, a phenyl radical, or a phenoxy radical; a radical of the formula (VIII)
(R.sup.9).sub.2N(C?Z)(VIII) where: Z represents sulphur or oxygen, R.sup.9 is identical or different and represents a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms; or a radical of the formula (IX)
R.sup.10OC(?S)(IX) where: R.sup.10 is identical or different and represents a linear or branched alkyl radical having 1 to 8 C atoms, a phenyl radical, or a cycloalkyl radical having 5 to 8 C atoms.

19. The vulcanizable polymer composition according to claim 18, wherein: the functionalized polydienes are neodymium-catalyzed polybutadienes (NdBRs) modified with sulphur chlorides after the polymerization; the functionalized polydienes have a proportion of cis-1,4 units of >95% by wt. and a proportion of 1,2-vinyl content of <1% by wt; and the functionalized polydienes have the following characteristics: a. a molar mass (MW) of 1 to 10,000 kg/mol, b. a polydispersity as Mw/Mn of 1.2 to 3.0, c. a Mooney viscosity of 30 MU to 150 MU, d. a content of sulphur of 0.04 to 0.5% by wt., based on 100% by wt. of the functionalized polydienes, e. a content of chlorine of 0.02 to 0.5% by wt., based on 100% by wt. of the functionalized polydienes, and f. the number of groups R.sup.1 is 2 to 15 units per polymer unit, based on 100% by wt, of the functionalized polydienes.

20. The vulcanizable polymer composition according to claim 18, wherein: the functionalized polydienes comprise styrene-butadiene copolymers modified with sulphur chlorides after the polymerization such that their Mooney viscosities are increased after the polymerization; and the functionalized polydienes have the following characteristics: g. a molar mass (Mw) of 1 to 10,000 kg mol, h. a polydispersity as Mw/Mn of 1.2 to 3.0, i. a Mooney viscosity of 30 MU to 150 MU, j. a content of sulphur of 0.04 to 0.5% by wt., based on 100% by wt. of the functionalized polydienes, k. a content of chlorine of 0.02 to 0.5% by wt., based on 100% by wt. of the functionalized polydienes, and l. the number of groups R.sup.1 is 2 to 15 units per polymer unit, based on 100% by wt. of the functionalized polydienes.

Description

EXAMPLE 1 ACCORDING TO THE INVENTION: PRODUCTION OF A BACKBONE-FUNCTIONALIZED POLYMER COMPOSITION

(1) 1a) Polymerization and Modification:

(2) A dry 20 L steel autoclave, inertized with nitrogen, was filled with 8500 g of hexane (dried over molecular sieve), 1300 g of 1,3-butadiene, 25 mmol of a 20% strength solution of diisobutylaluminium hydride in hexane, 1.44 mmol of a 10% strength solution of ethylaluminium sesquichloride in hexane, and 1.44 mmol of a 40% strength solution of neodymium versatate in hexane. It was heated with stirring to 65? C. and the mixture was polymerized with stirring for 60 min. The temperature in the reactor was kept at 70? C. The polymerization was stopped by addition of 6.5 g of lauric acid (0.5 phr) and stabilized by addition of 1.3 g of Irganox 1520.

(3) A conversion sample was taken. The butadiene conversion after the polymerization was 95%. The polymer composition solution has the following intermediate parameters:

(4) Starting Mooney viscosity (ML 1+4 at 100? C.): 29.8 MU;

(5) Microstructure: 97.3% by wt. 1,4-cis; 1.8% by wt. 1,4-trans; 0.8% by wt. 1,2-vinyl

(6) 720 g of the polymer composition solution were transferred to a 2 L reactor. At 65? C., a solution of 0.187 g of disulphur dichloride (0.2 phr) in 10 mL of hexane was added for modification. The solution was stirred at 65? C. for a further 30 min. The polymer composition was precipitated by introducing into 5 kg of ethanol, stabilized with further Irganox 1520 (0.1 phr) and dried in vacuo at 70? C.

(7) The polymer composition, the Mooney viscosity of which was increased (Mooney-jumped), has the following parameters:

(8) Mooney viscosity (ML 1+4 at 100? C.): 45.1 MU,

(9) Gel content <0.3 by wt.-%

(10) 1b) Functionalization of the Mooney-Jumped Polymer Composition:

(11) As a functionalization reagent mixture, a functionalization reagent mixture (Variant 1) of 4 g of DBD was mixed with 6 g of talc and 0.08 g of iron phthalocyanine in a mortar.

(12) 70 g of the polymer composition from 1a) were treated at 120? C. with 0.44 g of the pre-mixture on the laboratory roll. The roll gap was 0.4 mm, the roll diameter 10 cm. The roll time was 15 min.

(13) Mooney viscosity (ML 1+4 at 100? C.): 29.4 MU

(14) The Mooney-jumped polymer composition from 1a) was used as a comparison example for the production of the vulcanizates (P1) and (P1*), as the Mooney viscosity of this polymer composition corresponds to that of the backbone-functionalized polymer composition according to the invention according to 2b).

(15) The backbone-functionalized polymer composition according to the invention from 1b) was not used for the vulcanizate test because of the low Mooney viscosity.

EXAMPLE 2 ACCORDING TO THE INVENTION: PRODUCTION OF A BACKBONE-FUNCTIONALIZED POLYMER COMPOSITION ACCORDING TO THE INVENTION

(16) 2a) Polymerization and Modification:

(17) A dry 20 L steel autoclave, inertized with nitrogen, was filled with 8500 g of hexane (dried over molecular sieve), 1300 g of 1,3-butadiene, 21 mmol of a 20% strength solution of diisobutylaluminium hydride in hexane, 1.44 mmol of a 10% strength solution of ethylaluminium sesquichloride in hexane, and 1.44 mmol of a 40% strength solution of neodymium versatate in hexane. It was heated to 73? C. with stirring and polymerized for 60 min with stirring. The temperature in the reactor increased to 90? C. The polymerization was stopped by addition of 6.5 g of stearic acid (0.5 phr).

(18) A conversion sample was taken. The butadiene conversion was 98.7% after the polymerization.

(19) The polymer composition solution has the following intermediate parameters before the modification:

(20) Starting Mooney viscosity (ML 1+4 at 100? C.): 40 MU;

(21) Mooney stress relaxation (MSR at 100? C.): 0.65

(22) Microstructure: 97.5% by wt. 1,4-cis; 2.0% by wt. 1,4-trans; 0.5% by wt. 1,2-vinyl

(23) 3.33 g of disulphur dichloride (0.3 phr), less the amount for the determination of the butadiene conversion and for the determination of the intermediate parameters, were added to the polymer composition solution at 95? C. for modification. The solution was stirred at 95? C. for a further 10 min. The polymer composition was precipitated by introducing into 5 kg of ethanol, stabilized with Irganox 1520 (0.2 phr) and dried at 70? C. in vacuo.

(24) The now modified or Mooney-jumped polymer composition has the following parameters:

(25) Mooney viscosity (ML 1+4 at 100? C.): 62.7 MU, Mooney stress relaxation (MSR at 100? C.): 0.46; gel content <0.3% by wt.

(26) Microstructure: 97.4% by wt. 1,4-cis; 2.0% by wt. 1,4-trans; 0.6% by wt. 1,2-vinyl

(27) Molar mass: Mn=212 kg/mol, Mw=462 kg/mol, Mz=1150 kg/mol; polydispersity (Mw/Mn)=2.17

(28) Solution viscosity: 288 mPas

(29) 2b) Functionalization of the Mooney-Jumped Polymer Composition:

(30) 230 g of rubber were mixed for 5 min in the internal mixer of the Brabender type at a speed of rotation of 20 rpm and heated to 130? C. 1.44 g of the functionalization reagent mixture (Variant 1) were added to this and mixed for 1 min under the same conditions as from Example 1b). This procedure was carried out a total of 4 times. The rubber was combined.

(31) Mooney viscosity (ML 1+4 at 100? C.): 41.0 MU, Mooney stress relaxation (MSR at 100? C.): 0.42; gel content <0.3% by wt.

(32) The now backbone-functionalized polymer composition according to the invention is used for the production of vulcanizates.

EXAMPLE 3: FUNCTIONALIZATION OF THE MOONEY-JUMPED POLYMER COMPOSITION USING A FUNCTIONALIZATION REAGENT MIXTURE (VARIANT 2)

(33) 230 g of the polymer composition from Example 2a) were mixed for 5 min in the internal mixer of the Brabender type at a speed of rotation of 20 rpm and heated to 130? C. A functionalization reagent mixture consisting of 0.58 g of (EtO).sub.3SiC.sub.3H.sub.6S.sub.4C.sub.3H.sub.6Si(OEt).sub.3 and 0.1 g of iron phthalocyanine (Variant 2) was added and mixed under identical conditions for a further minute.

(34) Polymer composition before the functionalization: Mooney viscosity (ML 1+4 at 100? C.): 62.7 MU

(35) Polymer composition after the functionalization: Mooney viscosity (ML 1+4 at 100? C.): 45.1 MU

EXAMPLE 4: FUNCTIONALIZATION OF THE MOONEY-JUMPED POLYMER COMPOSITION USING A FUNCTIONALIZATION REAGENT MIXTURE (VARIANT 3)

(36) 230 g of the polymer composition from Example 2a) were mixed for 5 min in the internal mixer of the Brabender type having a speed of rotation of 20 rpm and heated to 150? C. Only 1.1 g DBD were added to this as a functionalization reagent (Variant 3). It was mixed under the same conditions, for another 5 min.

(37) Polymer composition before the functionalization: Mooney viscosity (ML 1+4 at 100? C.) 62.7 MU

(38) Polymer composition after the functionalization: Mooney viscosity (ML 1+4 at 100? C.): 42.2 MU

(39) Tests:

(40) A: Determination of the gel content of polybutadiene in styrene as a gravimetric procedure analogously to the method BAYELAS MO AQ 259A LAB:

(41) 25.0 g of polymer are weighed accurately to 0.1 g on the laboratory balance. The edges are cut off beforehand and discarded. The polymer is cut into small pieces. 850 ml of filtered styrene are introduced into a 1 l wide-necked flask and the polymer is dissolved on the shaker for about 4 hours.

(42) The wire mesh annealed beforehand consisting of a wire gauze having a mesh width 0.036 mm, ? 50 mm is added for cooling to a dry glass beaker in the desiccator. After cooling, the wire mesh is taken out of the dry glass beaker and weighed accurately to 0.1 mg on the analytical balance. The weight A results. In each case, 100 ml of filtered styrene are prepared in three glass beakers. The wire mesh having a diameter of 50 mm is inserted in the Gelman metal filtration system (seal/filter/seal) and the funnel attachment is screwed on.

(43) The polymer solution is then poured through the filter. The first of the three glass beakers coated with styrene is used for rinsing the wide-necked flask and this solution is likewise added through the filter. The filter is subsequently rinsed with the two further portions of styrene.

(44) The filter is now carefully removed with forceps and placed on clean cellulose. The edge of the filter is carefully pressed with the forceps. The evaporating styrene is observed using a magnifying glass. The damp wire filter, still wetted with styrene, becomes visibly lighter with decreasing amount of styrene. If all meshes of the filter are styrene-free, it is immediately re-weighed on the balance. The weight B results. After re-weighing of the filter, it is dried in the drying cabinet for 15 minutes at 100? C. (?5? C.) for determination of the dry gel content. The filter here is situated in an open dry glass beaker. After drying, the glass beaker together with filter is added to the desiccator for cooling for approximately 10 minutes and subsequently weighed again. The weight C results.

(45) Calculations:

(46) $\mathrm{Wet}\mathrm{gel}=\frac{\left(B-A\right)*{10}^6}{25}\left[\mathrm{ppm}\right]$$\mathrm{Dry}\mathrm{gel}=\frac{\left(C-A\right)*{10}^6}{25}\left[\mathrm{ppm}\right]$$\mathrm{Swelling}\mathrm{index}=\frac{\mathrm{wet}\mathrm{gel}}{\mathrm{dry}\mathrm{gel}}\left[\mathrm{without}\mathrm{dimension}\right]$
B: Mooney viscosity and Mooney stress relaxation according to ASTM D1646-00
C: Solution viscosity according to ISO 3105:

(47) 5.43% polymer solution in toluene is measured at room temperature using a Brookfield DV-I type rotational viscometer.

(48) D: GPC was carried out by Currenta.

(49) E: Microstructure determination

(50) Currenta, ELA 101: A solution of the polymer in toluene is added to a KBr window, the solvent is evaporated and the polymer film is measured between 2 KBr windows by means of FTIR spectroscopy.

(51) Irganox 1520: 4,6-Bis(octylthiomethyl)-o-cresol from BASF.

(52) Preparation of Rubber Mixtures and Vulcanizates

(53) Rubber mixtures were prepared which contain the Mooney-jumped polymer composition from Example 1a) as a comparison example (P1) and the backbone-functionalized polymer composition according to the invention from Example 2b) (P2). Both polymer compositions have a comparable Mooney viscosity of 45 MU and 42 MU respectively.

(54) In the case of the rubber mixtures P1* and P2*, in each case 50 phr of the above-mentioned polymer composition were treated with in each case 50 phr of natural rubber.

(55) The backbone-functionalized polymer composition from Example 1b) was not employed for the rubber mixture because of the low Mooney viscosity of <30 MU.

(56) The rubber mixtures were firstly prepared without sulphur and accelerator in a 1.5 L kneader.

(57) The substances sulphur and accelerator were then admixed on a roller at 40? C.

(58) Table 2 lists the recipes and test results of the vulcanizates.

(59) The following substances were employed for the mixing studies:

(60) TABLE-US-00001 TABLE 1 Trade name Manufacturer CORAX N 326 as carbon black Evonic Degussa GmbH VIVATEC 500 as oil Hansen und Rosenthal KG ZINKWEI? ROTSIEGEL as zinc oxide Grillo Zinkoxid GmbH EDENOR C 18 98-100 as stearic acid Caldic Deutschland GmbH VULKANOX 4020/LG as stabilizer Lanxess Deutschland GmbH VULKANOX HS/LG as stabilizer Lanxess Deutschland GmbH VULKACIT? CZ/EGC as accelerator Lanxess Deutschland GmbH RHENOGRAN IS 60-75 as sulphur RheinChemie Rheinau GmbH TSR/RSS 3 DEFO 700 Natural rubber of the type Defo 700

(61) TABLE-US-00002 TABLE 2 P1 P2 P1* P2* Mooney-jumped polymer composition 100 50 from Example 1a Example 2b according to the invention 100 50 TSR/RSS 3 DEFO 1000 50 50 STATEX N 330 50 50 50 50 VIVATEC 500 4 4 4 4 EDENOR C 18 98-100 2 2 2 2 VULKANOX 4020/LG 2 2 2 2 VULKANOX HS/LG 3 3 3 3 ZINKWEISS ROTSIEGEL 3 3 3 3 MAHLSCHWEFEL 90/95 CHANCEL 2.36 2.36 2.36 2.36 VULKACIT CZ/EGC 1.4 1.4 1.4 1.4 Monsanto - MDR: 160? C., 30 min Minimum torque [dNm] 2.52 2.52 2.02 1.89 Maximum torque [dNm] 26.4 24.2 22.4 21.4 Rise time TS1 s 141 124 133 121 Rise time TS2 s 163 139 151 136 10% turnover time s 167 140 151 135 50% turnover time s 210 175 188 169 95% turnover time s 371 319 326 299 Mooney viscosity ML1 + 4/100 ML 1 + 4 ME 68.7 72.5 56.1 54.7 Tensile test rod S2 RT S10 MPa 0.7 0.6 0.7 0.6 S100 MPa 2.7 2.7 3.1 3.2 S300 MPa 12.5 13.7 14.4 15.7 D Median % 367 354 419 440 F Median MPa 16.8 17.3 22.0 24.3 Hardness at 60? C. Shore A 63.5 63.5 62.0 62.0 Rebound elasticity at 60? C. % 65.6 66.5 65.6 68.1 MTS amplitude sweep @ 60? C., 1 Hz G* (0.5%) MPa 2.42 2.06 2.24 2.1 G* (15%) MPa 1.49 1.41 1.28 1.26 G* (0.5%) ? G* (15%) MPa 0.93 0.65 0.96 0.84 tan d (max.) 0.108 0.097 0.122 0.114 Dynamic damping DIN 53513; Ares strip, 10 Hz, 1 K/min E(0? C.) MPa 12.01 9.22 15.62 11.7 tan d (0? C.) 0.068 0.068 0.089 0.085 E (23? C.) MPa 10.9 8.44 13.32 10.14 tan d (23? C.) 0.058 0.057 0.073 0.064 E (60? C.) MPa 9.89 7.77 11.02 8.71 tan d (60? C.) 0.048 0.046 0.058 0.050 Abrasion DIN 53516 mm.sup.3 13 12 49 45

(62) Compared with the comparison examples P1 and P2, the tests P1* and P2* according to the invention show a decrease in the vulcanization time needed in Monsanto MDR, marked improvement of the indicators for the low rolling resistance, such as a high rebound elasticity at 60? C., a low tangent delta maximum in the MTS test at 60? C. and a low tangent delta at 60? C. in the Eplexor test, better results in the tensile strain test, apparently from a higher quotient of S300/S10 and lower values in the abrasion test.

(63) Vulcanizate Tests

(64) The following characteristics of the vulcanizates were determined according to the standards mentioned:

(65) DIN 53505: Shore A hardness at 60? C.

(66) DIN 53512: Rebound elasticity at 60? C.

(67) DIN 53504: Tension values at 10%, 100%, and 300% elongation (?.sub.10, ?.sub.100, and ?.sub.300), tensile strength and elongation at break

(68) DIN 53516: Abrasion

(69) For the determination of the dynamic characteristics (temperature dependence of the storage modulus E in the temperature range ?60? C. to 0? C. and tan ? at 60? C.), an Eplexor apparatus (Eplexor 500 N) of the company Gabo-Testanlagen GmbH, Ahlden, Germany was employed. The measurements were determined according to DIN53513 at 10 Hz on Ares strips in the temperature range ?100? C. to +100? C. with a heating rate of 1K/min.

(70) Using the method the following measured variables were obtained, which are designated according to ASTM 5992-96:

(71) E (60? C.): Storage modulus at 60? C.

(72) E (23? C.): Storage modulus at 23? C.

(73) E (00? C.): Storage modulus at 0? C.

(74) and

(75) tan ? (60? C.): Loss factor (E/E) at 60? C.

(76) tan ? (23? C.): Loss factor (E/E) at 23? C.

(77) tan ? (00? C.): Loss factor (E/E) at 0? C.

(78) E yields an index for the grip of the winter tyre tread on ice and snow. The lower E, the better the grip.

(79) Tan ? (60? C.) is a measure of the hysteresis loss during rolling of the tyre. The lower tan ? (60? C.), the lower the rolling resistance of the tyre.

(80) DIN53513-1990: Elastic characteristicsFor the determination of the elastic characteristics, an MTS elastomer test system (MTS Flex Test) of the company MTS was employed. The measurements were determined according to DIN53513-1990 on cylinder samples (2 samples, each of 20?6 mm) with overall 2 mm compression at a temperature of 60? C. and a measurement frequency of 1 Hz in the region of the amplitude sweep from 0.1 to 40%.

(81) Using the method, the following measured variables were obtained, which are designated according to ASTM 5992-96:

(82) G* (0.5%): Dynamic modulus with 0.5% amplitude sweep

(83) G* (15%): Dynamic modulus with 15% amplitude sweep

(84) G* (0.5%)?(15%): Difference in the dynamic modulus with 0.5% to 15% amplitude sweep

(85) and

(86) tan ? (max): maximal loss factor (G/G) of the entire measuring range at 60? C.

(87) G* (0.5%)?(15%) yields an index for the Payne effect of the mixing, where a low value indicates a good filler distribution and thus a low rolling resistance.

(88) Tan ? (max) is a measure of the hysteresis loss during rolling of the tyre. The lower tan ? (max), the lower the rolling resistance of the tyre.