Determination of the degree of branching

Patent metadata

Field	Value
Publication number	US-2016231305-A1
Application number	US-201415028550-A
Country	US
Kind code	A1
Filing date	Oct 9, 2014
Priority date	Oct 16, 2013
Publication date	Aug 11, 2016
Grant date	—

Abstract

The invention relates to a process for determining the degree of branching of modified polymers wherein the polymers are modified in the sense that their degree of branching after polymerization was increased once more, wherein the modified polymers are treated with a polar transformation mixture comprising a compound of general formula (I)
R 1 —S—S—R 1    (I)

wherein the Mooney viscosity (ML 1+4 at 100° C.) of the polymers is determined before and after the treatment with the polar transformation mixture and the degree of branching is determined.

First claim

1 . A process for determining the degree of branching of modified diene polymers wherein the degree of crosslinking/branching of the modified diene polymers has been increased, the process comprising:
determining the Mooney viscosity (ML 1+4 at 100° C.) of the modified diene polymers, treating the modified diene polymers with a transformation mixture, thereby forming further modified diene polymers, wherein the transformation mixture comprises a compound of general formula (I)
R 1 —S—S—R 1   (I)

where
R 1 in either occurrence is the same or different and is selected from a group of
moieties of formula (II)
C 6 (R 2 ) 5 —(C═O)—N(R 3 )—C 6 (R 2 ) 4 —  (II)

 where R 2 and R 3 in each occurrence is the same or different and they each represent a hydrogen radical, a linear or branched alkyl radical of 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, a phenyl radical, a cycloalkyl radical of 5 to 8 carbon atoms;
moieties of formula (III)

 where R 4 in either occurrence is the same or different and represents a hydrogen, halogen, nitro or hydroxyl radical, a linear or branched alkyl radical of 1 to 12 carbon atoms, a linear or branched alkoxy radical of 1 to 12 carbon atoms, a phenyl radical, a cycloalkyl radical of 5 to 8 carbon atoms or the R 4 's combine to form the moiety of formula (IV);

 where R 5 in each occurrence is the same or different and represents a hydrogen or hydroxyl radical, a linear or branched alkyl radical of 1 to 12 carbon atoms, a linear or branched alkoxy radical of 1 to 12 carbon atoms, a phenyl radical, or a cycloalkyl radical of 5 to 8 carbon atoms;
moieties of formula (V)
(R 6 O) 3 Si—(CH 2 ) n —(Y) m —  (V)

 where
 n is an integer from 1 to 12;
 m is from 0 to 4;
 R 6 in each occurrence is the same or different and represents a linear or branched alkyl radical of 1 to 16 carbon atoms, a phenyl radical or a cycloalkyl radical of 5 to 8 carbon atoms;
 Y represents sulphur, a moiety of formula VIa, VIb, VIc, VId or VIe

 where
 x is an integer from 1 to 8;
 p is an integer from 1 to 12;
R 8 in each occurrence is the same or different and represents a linear or branched alkyl radical of 1 to 16 carbon atoms, an alkoxy radical of 1 to 16 carbon atoms, a phenyl radical or a phenoxy radical;
moieties of formula (VII)
(R 9 ) 2 N—(C═Z)—  (VII)

 where
 Z represents sulphur or oxygen,
 R 9 in either occurrence is the same or different and represents a linear or branched alkyl radical of 1 to 16 carbon atoms, a phenyl radical or a cycloalkyl radical of 5 to 8 carbon atoms;
a moiety of formula (VIII)
R 10 —O—C(═S  (VIII)

 where
 R 10 is the same or different and represents a linear or branched alkyl radical of 1 to 16 carbon atoms, a phenyl radical or a cycloalkyl radical of 5 to 8 carbon atoms,

determining the Mooney viscosity (ML 1+4 at 100° C.) of the further modified diene polymers, and
determining the degree of branching of the further modified diene polymers according to equation (I):
degree of branching in %=( K−L )/ L* 100
where
K is the Mooney viscosity (ML 1+4 at 100° C.) of the modified diene polymers before treating with the transformation mixture, and
L is the Mooney viscosity (ML 1+4 at 100° C.) of the further modified diene polymers after treatment with the transformation mixture.

2 . The process according to claim 1 , wherein the transformation mixture comprises 2,2′-dibenzamidodiphenyl disulphide (DBD).

3 . The process according to claim 1 , wherein the transformation mixture comprises the compound of formula (IXa)
(EtO) 3 Si—C 3 H 6 —S 4 —C 3 H 6 —Si(OEt) 3   (IXa).

4 . The process according to claim 1 , wherein the transformation mixture comprises the compound of formula (IXb)
(EtO) 3 Si—C 3 H 6 —S 2 —C 3 H 6 —Si(OEt) 3   (IXb).

5 . The process according to claim 1 , wherein the transformation mixture comprises tetramethylthiuram disulphide.

6 . The process according to claim 1 , wherein the transformation mixture comprises transition metal salts, by way of activator, selected from the group of Fe, Co, Cu, Ni, Mn, and Cr.

7 . The process according to claim 6 , wherein the Fe salts comprise Fe phthalocyanine or Fe hematoporphyrin.

8 . The process according to claim 1 , wherein the transformation mixture comprises, by way of activator, pentachlorothiophenol and salts thereof.

9 . The process according to claim 1 , wherein the transformation mixture further comprises a organic peroxide activator of formula (VIII)
R 11 —O—O—R 12 ,  (VIII)
where
R 11 and R 12 are the same or different and each represent a hydrogen radical,
a linear or branched alkyl radical of 1 to 16 carbon atoms, a phenyl radical or a cycloalkyl radical of 5 to 8 carbon atoms,
a carboxyl radical R 13 —(C═O)—, where R 13 represents a linear or branched alkyl radical of 1 to 16 carbon atoms, a phenyl radical or a cycloalkyl radical of 5 to 8 carbon atoms.

10 . The process according to claim 1 , wherein the transformation mixture further comprises waxes and/or fillers.

11 . The process according to claim 1 , wherein the treating step comprises mixing the modified diene polymer with the transformation mixture under thermal or mechanical input of energy.

12 . The process according to claim 1 , wherein the treating step comprises mixing the modified diene polymer with the transformation mixture in a mixer, in an extruder or on a roll at a temperature of 70° C. to 160° C.

13 . The process according to claim 1 , wherein the transformation mixture is present in amounts of 0.01 to 2 wt %, based on 100 wt % of modified polymer used.

14 . The process according to claim 2 , wherein the transformation mixture comprises:
a) 5 to 100 wt % of one or more compounds of formula (X), b) optionally 0.01 to 5 wt % of activators, at the quantitative expense of compound of formula (X), c) optionally 0.01 to 90 wt % of waxes, at the quantitative expense of compound of formula (X), d) optionally 0.01 to 90 wt % of fillers, at the quantitative expense of compound of formula (X), based on 100 wt % of transformation mixture.

15 . The process according to claim 1 , wherein the modified diene polymers are in the form of a solid material.

16 . The process according to claim 1 , wherein R 1 in either occurrence is the same or different and is selected from the group of:
moieties of formula (II)
C 6 (R 2 ) 5 —(C═O)—N(R 3 )—C 6 (R 2 ) 4 —  (II)

where R 2 and R 3 in each occurrence is the same or different and they each represent a hydrogen radical, a linear or branched alkyl radical of 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, a phenyl radical, a cycloalkyl radical of 5 to 8 carbon atoms;
moieties of formula (III)

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Kloppenburg Heike
• Le-Sattler Alicia

Classifications

• G01N33/442 Primary

  Resins; Plastics · CPC title

• C08C19/25

  Incorporating silicon atoms into the molecule · CPC title

• G01N11/162

  Oscillations being torsional, e.g. produced by rotating bodies · CPC title

• C08F2/60

  Polymerisation by the diene synthesis · CPC title

• C08C19/20 Primary

  Incorporating sulfur atoms into the molecule · CPC title