# Patent

## Title
Rubber compound microwave curing method

## Abstract

A method of curing a compound having a cross-linkable, unsaturated-chain polymer base and a curing system; the method employing microwaves as a form of energy to promote curing reactions; and the curing system including compounds of general formula (I) ([R1R2R3NR5(NR4R6R7)n](n+1)+)y(n+1)Xy− (I) where: X is an atom or anionic group; R1, R2, R3, which are the same or different, are each CmH2m+1, where m is 1 to 3, or CH2CHCH2 or CHCHCH3, R4, R6, R7, which are the same or different, are each CH2CHCH2 or CHCHCH3; n is 0 or 1; y is 1 when n is 1; y is 1 or 2 when n is 0; R5 is an aliphatic group C15-C22 when n is 0; is an aliphatic group C8-C16 when n is 1; when n is 0, at least one of R1, R2, R3, R5 has a double bond.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/IB2012/053039 filed Jun. 15, 2012, claiming priority based on Italian Patent Application No. TO2011A000525 filed Jun. 15, 2011, the contents of all of which are incorporated herein by reference in their entirety.
TECHNICAL FIELD
The present invention relates to a rubber compound microwave curing method.
More specifically, the method according to the present invention applies to rubber compounds for producing tyres, to which the following description refers purely by way of a non-limiting example.
BACKGROUND ART
As is known, in traditional rubber compound curing methods, curing reactions are produced by heating the rubber compound. In tyre manufacturing, for example, the green semifinished part is inserted inside a mold, in which the rubber compound is heated.
For some time, a need has been felt within the industry for curing methods employing a form of energy other than heat.
In one such method, curing reactions are produced using microwaves, which is a highly interesting alternative form of energy in terms of easy use and low energy content.
Microwave curing tests of rubber compounds comprising conventional curing systems, however, have proved unsatisfactory in terms of the physical characteristics of the cured rubber compounds.
DISCLOSURE OF INVENTION
It is an object of the present invention to provide a method of curing rubber compounds using microwave energy, with none of the drawbacks of the known art.
The Applicant has surprisingly discovered that successful microwave curing of rubber compounds can be assured using a particular class of compounds as curing accelerants.
One object of the present invention is a method of curing a rubber compound comprising at least one cross-linkable, unsaturated-chain polymer base and a curing system; said method being characterized by comprising the use of microwaves as a form of energy to promote curing reactions; and in that said curing system comprises compounds of general formula (I)

([R1R2R3NR5(NR4R6R7)n](n+1)+)y(n+1)Xy−  (I)

where:

X is an atom or anionic group;
R1, R2, R3, which are the same or different, are each CmH2m+1, where m is 1 to 3, or CH2CHCH2 or CHCHCH3;
R4, R6, R7, which are the same or different, are each CH2CHCH2 or CHCHCH3;
n is 0 or 1;
y is 1 when n is 1; y is 1 or 2 when n is 0;
R5 is an aliphatic group C15-C22 when n is 0; is an aliphatic group C8-C16 when n is 1;
when n is 0, at least one of R1, R2, R3, R5 comprises a double bond.
The compounds of general formula (I) are preferably curing accelerants.
R1, R2, R3 are preferably CH2CHCH2.
Preferably, n is 1, and R5 is a saturated aliphatic group.
Alternatively, R5 preferably comprises a double bond, and n is 0.
The compounds of general formula (I) are preferably in the group comprising:

[(CH3)3N(CH2)8CHCH(CH2)7CH3]+X−;

[(CH2CHCH2)3N(CH2)15CH3]+X−;

[(CH3)(CH2CHCH2)2N(CH2)15CH3]+X−;

[(CH2CHCH2)(CH3)2N(CH2)15CH3]+X−; and

[(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2+2X−.

Preferably, X− is I− or Br−.
Another object of the present invention is a cured-rubber product, characterized by being made using the method according to the present invention.
Another object of the present invention is a tyre, characterized by comprising at least one rubber part made using the method according to the present invention.


BEST MODE FOR CARRYING OUT THE INVENTION
The following examples are purely indicative, and in no way limiting, for a clearer understanding of the present invention.
Examples
In the following examples, five different compounds (a, b, c, d, e) of general formula (I) were used:

    
    
        compound (a) of molecular formula [(CH3)3N(CH2)8CHCH(CH2)7CH3]+I−;
        compound (b) of molecular formula [(CH2CHCH2) (CH3)2N(CH2)15CH3]+I−;
        compound (c) of molecular formula [(CH3) (CH2CHCH2)2N(CH2)15CH3]+I−;
        compound (d) of molecular formula [(CH2CHCH2)3N(CH2)15CH3]+Br−; and
        compound (e) of molecular formula [(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2+2Br−.
    
    


Five rubber compounds (A-E) were produced, each comprising a respective compound (a)-(e).
For comparison purposes, another rubber compound F was produced comprising the curing system of the known art.
Table I shows the compositions in phr of the above rubber compounds.














TABLE I







A
B
C
D
E
F




















NR
100




N660
30



ZnO
2



S
2















comp. (a)
2
—
—
—
—
—



comp. (b)
—
2
—
—
—
—



comp. (c)
—
—
2
—
—
—



comp. (d)
—
—
—
2
—
—



comp. (e)
—
—
—
—
2
—



TBBS
—
—
—
—
—
2



Stearic acid
—
—
—
—
—
1










As shown in the Table I compositions, in each of rubber compounds A-E, a compound of general formula (I) was substituted for the TBBS (N-terbutylbenzothiazolesulphenamide) accelerant.
Also, only rubber compound F contains stearic acid.
Rubber compounds A-E were cured using microwave energy.
This was done using a Microwave System CEM laboratory oven, model MDS-2100, which has PID temperature control for testing at constant temperature.
More specifically, the main characteristics of the oven used are:

    
    
        0-1000±50 watt power range with programmable 1% increments;
        fibre optic sensor temperature control (maximum operating temperature 185° C.). PID temperature control is performed by the internal processor on the oven.
    
    


The tests below were conducted using 100 W microwave power for 50 minutes.
To obtain a significant comparison, the control rubber compound F was cured using microwave energy as described above, as well as the conventional curing method by heating to 150° C. for 15 minutes.
The physical properties (TB, 100%, 300%, EB) of the cured rubber compounds were tested as per ASTM Standard D412C, and hardness (HD) as per ISO48.
Table II shows the physical properties expressed in MPa, and Shore A hardness.















TABLE II







A
B
C
D
E
FMW
FT























TB
12.1
12.5
12.8
13.5
28.5
11.3
29.0


100%
1.02
1.05
1.03
1.07
1.12
0.80
1.21


300%
3.98
4.02
4.23
4.32
5.80
1.30
6.59


EB
563
542
538
523
512
434
603


HD
38
39
40
40
43
30
45









The results in Table II clearly show how substituting the compounds of general formula (I) for the TBBS accelerant provides for more effectively microwave curing the rubber compound, and more specifically how microwave curing rubber compounds A-E provides for obtaining rubber products of acceptable physical properties, unlike those obtained by microwave curing control rubber compound F.
As will be obvious to anyone skilled in the art, the physical property results may be improved by adding appropriate ingredients.
Comparison with the Table II results relative to the heat-cured rubber compound F (FT) also shows how microwave curing may be substituted for heat curing without completely compromising the physical properties of the end product, which, as stated, may be further improved by adding appropriate ingredients.
Curing rubber compounds using the method according to the present invention improves energy consumption, and enables rubber compounds to be cured in conjunction with already-cured rubber with no risk to the latter.
Unlike conventional curing methods, which may result in deterioration of the already-cured rubber compound.
One example of such a situation is rubber compounds used to repair parts of cured tyres. In which case, it is important that the repair rubber compound, once applied to the repair area, be cured without subjecting the cured rubber of the tyre to prolonged thermal stress.
In this connection, another important point to note is the ease with which microwave energy can be targeted, and which is a particularly important advantage when applying curing conditions to one rubber compound forming part of a more complex rubber product, such as a tyre.

## Claims

1. A method of curing a compound comprising a cross-linkable, unsaturated-chain polymer base and a curing system; said method being characterized by comprising a curing step wherein the compound is cured by using microwaves as a form of energy to promote curing reactions; and in that said curing system comprises compounds of general formula (I)


([R1R2R3NR5(NR4R6R7)n](n+1)+)y(n+1)Xy−  (I)

where:
X is an atom or anionic group;
R1, R2, R3, which are the same or different, are each CmH2m+1, where m is 1 to 3, or CH2CHCH2 or CHCHCH3;
R4, R6, R7, which are the same or different, are each CH2CHCH2 or CHCHCH3;
n is 0 or 1;
y is 1 when n is 1; y is 1 or 2 when n is 0;
R5 is an aliphatic group C15-C22 when n is 0; is an aliphatic group C8-C16 when n is 1;
when n is 0, at least one of R1, R2, R3, R5 comprises a double bond.

2. A rubber compound curing method as claimed in claim 1, characterized in that said compounds of general formula (I) are curing accelerants.

3. A rubber compound curing method as claimed in claim 1, characterized in that R1, R2, R3 are CH2CHCH2.

4. A rubber compound curing method as claimed in claim 3, characterized in that n is 1, and R5 is a saturated aliphatic group.

5. A rubber compound curing method as claimed in claim 1, characterized in that R5 comprises a double bond, and n is 0.

6. A rubber compound curing method as claimed in claim 1, characterized in that the compounds of general formula (I) are in the group comprising:


[(CH3)3N(CH2)8CHCH(CH2)7CH3]+X−;



[(CH2CHCH2)3N(CH2)15CH3]+X−;



[(CH3)(CH2CHCH2)2N(CH2)15CH3]+X−;



[(CH2CHCH2)(CH3)2N(CH2)15CH3]+X−; and



[(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2+2X−.

7. A rubber compound curing method as claimed in claim 1, characterized in that X− is I− or Br−.