Clear binder that is solid when cold

Abstract

A clear binder, in divided form, that is solid when cold, and to the different ways in which it is formed. Also, the method for transporting and/or storing and/or handling the binder, as well as to the uses of the binder for road and/or industrial applications.

Claims

1. A clear binder that is solid under cold conditions and in divided form, comprising: at least one clear binder base and from 0.1% to 5% by weight, relative to a total weight of said clear binder base, of at least one chemical additive selected from the group consisting of: (i) a compound of general formula (I)
Ar1-R-Ar2  (I), in which: Ar1 and Ar2 represent, independently of one another, a benzene nucleus or a system of condensed aromatic nuclei of 6 to 20 carbon atoms that are substituted by at least one hydroxyl group and R represents an optionally substituted divalent radical, a main chain of which comprises from 6 to 20 carbon atoms and at least one group selected from the group consisting of amide, ester, hydrazide, urea, carbamate, and anhydride functions, (ii) a compound of general formula (V):
R″—(COOH).sub.z  (V), in which R″ represents a linear or branched and saturated or unsaturated chain comprising from 4 to 68 carbon atoms and z is an integer from 2 to 4, (iii) a polyphosphoric acid, and (iv) mixtures thereof.

2. The clear binder as claimed in claim 1, comprising from 0.5% to 4% by weight of said chemical additive relative to the total weight of said clear binder base.

3. The clear binder as claimed in claim 2, comprising from 0.5% to 2.8% by weight of said chemical additive relative to the total weight of said clear binder base.

4. The clear binder as claimed in claim 3, comprising from 0.5% to 2.5% by weight of said chemical additive relative to the total weight of said clear binder base.

5. The clear binder as claimed in claim 1, wherein the chemical additive is an organic compound which has a weight-average molar mass of less than or equal to 2000 gmol.sup.−1.

6. The clear binder as claimed in claim 1, further comprising at least one plasticizer, at least one structuring agent, and at least one copolymer.

7. The clear binder as claimed in claim 1, in the form of blocks or pellets.

8. A kit comprising at least: one clear binder that is solid under cold conditions and in divided form as claimed in claim 1, one capsule comprising a compound chosen from at least one copolymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, for example based on butadiene units and styrene units, at least one adhesion dopant, at least one coloring agent and a mixture thereof.

9. The kit as claimed in claim 8, wherein the clear binder that is solid under cold conditions and in divided form is in the form of blocks.

10. The kit as claimed in claim 8, wherein the clear binder that is solid under cold conditions and in divided form comprises, on one of its faces, a cavity for housing all or part of the capsule.

11. The kit as claimed in claim 10, wherein the capsule is removably housed entirely or partially in said cavity.

12. A process for preparing a clear binder as claimed in claim 1, comprising: mixing the at least one clear binder base and the at least one chemical additive, to form an additivated clear binder, and shaping the additivated clear binder in the form of a block or pellets.

Description

EXAMPLES

Materials and Methods

(1) The clear binder bases according to the invention are prepared according to the following general process:

(2) (i) the oil is heated, for example to 170° C.;

(3) (ii) the resin is added, and mixing is carried out, for example, for 1 h to 2 h at 170° C. with a stirring speed of 300 rpm;

(4) (iii) the powdered copolymer is added, and mixing is carried out, for example, for 2 h at 170° C. with a stirring speed of 300 rpm;

(5) (iv) where appropriate, the adhesion dopant is added in liquid form and then mixing is carried out, for example, for 15 minutes at 170° C.

(6) The rheological and mechanical characteristics of the clear binder bases according to the invention to which reference is made in these examples are measured in the way shown in table 1.

(7) TABLE-US-00001 TABLE 1 Abbre- Measurement Property viation Unit standard Needle penetrability at 25° C. P.sub.25 1/10 mm NF EN 1426 Ring-and-ball softening RBT ° C. NF EN 1427 temperature

(8) The variation in the ring-and-ball softening temperature (RBT) is measured according to the NF EN 1427 standard from said composition between the sample extracted from the top part of the sample tube and the sample extracted from the bottom part of the sample tube.

(9) Examples of C.sub.1 to C.sub.7 clear binder bases according to the invention are prepared according to the process described above with the constituents and in the proportions (in percentage by weight relative to the total weight of clear binder) indicated in the following table 2:

(10) TABLE-US-00002 TABLE 2 Compositions of clear binder bases C1 C2 C3 C4 C5 C6 C7 RAE .sup.1 oil 61.8% 62.0% — — — — — DAO oil .sup.5 — — 63.8% 63.8% 63.8% 61.6% 54.3% Resin .sup.2 33.0% 32.8% 31.0% 31.0% 31.0% 33.2% 40.0% SBS copolymer .sup.3 5.0% — — 5.0% 5.0% 5.5% EVA polymer — 2.0% — — — — — EPDM polymer — — — 5.0% — — — thermoplastic 3.0% 5.0% — — — — copolymer .sup.4 Dopant 0.2% 0.2% 0.2% 0.2% 0.2% 0.2% 0.2% Penetration 62 59 72 92 68 64.4 27.9 (1/10 mm) RBT (° C.) 51 53.4 90.4 61 76.5 82.0 84 .sup.1 RAE means “Residual Aromatic Extracts” and refers to the residues of aromatic extracts of petroleum products. The RAE oil used in examples C1 to C4 has the following composition: 31% of paraffinic compounds, 49% of naphthenic compounds, and 20% of aromatic compounds, by weight of component relative to the total weight of the oil .sup.2 Hydrocarbon resin obtained by polymerization of C.sub.9-C.sub.10 unsaturated aromatic hydrocarbons. Its melting point is between 135 and 145° C. according to ASTM D 3461. .sup.3 70/30 Styrene/butadiene/styrene linear block copolymer comprising a content by weight of 1,2-butadiene of 28.5% based on the total weight of the monomers and a weight-average molecular weight of about 140 000 daltons polystyrene (PS) equivalent. .sup.4 Solution-polymerized butadiene/styrene thermoplastic copolymer of radial structure, comprising a weight content of 1,2-butadiene of 7.1% and a weight-average molecular weight of about 330 000 daltons polystyrene (PS) equivalent. .sup.5 DAO oil is a propane deasphalted oil characterized by a content of 67% of paraffinic compounds, 19% of naphthenic compounds, and 14% of aromatic compounds as plasticizer, by weight of component relative to the total weight of the oil.

1. Preparation of the Additivated Clear Binder Bases

(11) The additivated clear binder base compositions B.sub.1, B.sub.2, B.sub.3, B.sub.4, B.sub.5 and B.sub.6 are prepared from compositions C1 and C5 prepared previously and from the following additives: 2′,3-bis[(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl)]propionohydrazide, denoted Additive A1, N,N-ethylene-bis-stearamide, denoted Additive A2, and 1,10-decanedioic acid, denoted Additive A3.

(12) The amounts as weight percentage used for each additivated clear binder base are shown in table 3 below:

(13) TABLE-US-00003 TABLE 3 Additivated clear binder base B.sub.1 B.sub.2 B.sub.3 B.sub.4 B.sub.5 B.sub.6 Composition C1 99.15% 96.5% 97.2% — — — Composition C5 — — — 99.15% 98.5%  96% Additive A1  0.85% — 0.85%  0.85% — — Additive A2 —  3.5% 1.95% — — 2.5% Additive A3 — — — —  1.5% 1.5%

(14) The additivated clear binder bases are prepared in the following manner.

(15) The clear binder base C1 or C5 is heated at 160° C. for two hours in an oven and then the chemical additive(s) is (are) added. The whole mixture is homogenized for 1 hour at a temperature between 160° C. and 180° C. and with stirring at 300 rpm.

2. Storage Stability

Load Resistance Test for Compositions B.SUB.1., B.SUB.2., B.SUB.3 .and B.SUB.4

(16) This test is carried out in order to evaluate the load resistance of the additivated clear binder compositions B1, B2, B3 and B4 prepared previously at a temperature of 50° C. under a compressive load. This test makes it possible to predict the behavior of clear binder pellets obtained from the same additivated clear binder compositions B1, B2, B3 and B4 during their transportation and/or their storage in bulk in 10 to 30 kg bags or in 500 to 1000 kg Big Bags or in 200 kg drums. This test makes it possible in particular to predict the behavior of the pellets in terms of agglomeration.

(17) The load resistance test is carried out using a texture analyzer marketed under the name LF Plus by the company Lloyd Instruments and equipped with a thermal enclosure.

(18) A 25 mm diameter metal container containing the additivated clear binder composition B1, B2, B3 or B4 is placed inside the thermal enclosure set at a temperature of 50° C. for 3 hours. The piston of the texture analyzer consists of a cylinder with a diameter of 20 mm and a height of 60 mm. The cylindrical piston is initially placed in contact with the upper layer of the additivated clear binder composition B1, B2, B3 or B4. Then, the piston is depressed vertically downwards, at a constant speed of 1 mm/min over a calibrated distance of 10 mm so as to exert a compressive force on the composition B1, B2, B3 or B4 placed in the container. Software makes it possible to record the resulting force as a function of the vertical movement of the piston and to determine the resulting maximum force recorded. The results are given in table 4 below.

(19) TABLE-US-00004 TABLE 4 Composition B.sub.1 B.sub.2 B.sub.3 B.sub.4 Max force 82.4 1.3 97.7 174 (in N)

(20) The clear binder compositions B1 and B4, obtained by the addition, to a clear binder base, of a hydrazide chemical compound (Additive A1), have a high hardness.

(21) The clear binder composition B2, obtained by the addition, to a clear binder base, of an amide chemical compound (Additive A2), has a low hardness. However, the composition B3, obtained by the addition, to a clear binder base, of an amide chemical compound (Additive A2) and a hydrazide chemical additive (Additive A1), has a high hardness.

(22) In particular, the hardness of the composition B3 is greater than the hardness of the composition B1 and than the hardness of the composition B2. The increase in the hardness of the composition B3 thus illustrates a synergy between the two chemical additives.

(23) Because of their high hardness, the clear binder compositions B1, B3 and B4 make it possible to obtain clear binder pellets which will be stable during storage and transportation thereof in bulk in 10 to 30 kg bags or in 500 to 1000 kg Big Bags or in 200 kg drums.

3. Preparation of Cores of Pellets of Clear Binder Composition

(24) The cores of pellets of clear binder composition G1, G2, G3, G4, G5 and G6 are prepared respectively from the additivated clear binder compositions B1, B2, B3, B4, B5 or B6 according to one of the following protocols.

3.1 General Method for Preparing Cores of Additivated Clear Binder Composition of the Pellets

(25) The additivated clear binder composition B1, B2, B3, B4, B5 or B6 is heated at a temperature between 150 and 180° C. for two hours in an oven before being poured into a silicone mold having different holes of spherical shape so as to form the cores of pellets. After having observed the solidification of the additivated clear binder composition in the mold, the surplus is levelled off with a blade heated with a Bunsen burner. After 30 minutes, the solid additivated clear binder composition in the form of uncoated pellets is demolded and stored in a tray coated with silicone paper.

3.2 General Method for Preparing the Cores of Additivated Clear Binder Composition of the Pellets with an Industrial Process

(26) For the implementation of this method, use may be made of a device and of a process as described in great detail in patent U.S. Pat. No. 4,279,579. Various models of this device are commercially available from the company Sandvik under the trade name Rotoform.

(27) Pellets of additivated clear binder composition may also be obtained from the additivated clear binder composition B1, B2, B3, B4, B5 or B6 poured into the reservoir of such a device and maintained at a temperature of between 130 and 270° C.

(28) An injection nozzle or several injection nozzles make(s) possible the transfer of the additivated clear binder composition B1, B2, B3, B4, B5 or B6 into the double pelletizing drum comprising an external rotating drum, the two drums being equipped with slots, nozzles and orifices making possible the pelletizing of drops of clear binder composition through the first fixed drum and orifices having a diameter of between 2 and 10 mm of the external rotating drum. The drops of additivated clear binder composition B.sub.1, B.sub.2, B.sub.3, B.sub.4, B.sub.5 or B.sub.6 are deposited on the upper face of a tread, horizontal, driven by rollers.

4. General Method for Preparing Pellets of Solid Additivated Clear Binder Composition Comprising a Coating Layer Composed of at Least One Anti-Caking Compound

(29) The clear binder pellets obtained according to methods 3.1 and 3.2 are left at ambient temperature for 10 to 15 minutes. The pellets thus formed are covered on their surface with an anti-caking compound and then sieved to remove excess anti-caking compound.

(30) The pellets G1′, G2′, G3′, G4′, G5′ and G6′ are prepared respectively from the pellets G1, G2, G3, G4, G5 and G6 prepared previously and according to the method described above using as anti-caking compound pyrogenic silica, commercially available under the reference Aerosil®200.

(31) The weight percentage of the coating for the pellets G1′, G2′, G3′, G4′, G5′ and G6′ is approximately 1% by weight relative to the total weight of the clear binder of the pellets.

(32) It is noted that the pellets obtained have the advantage of being easily transportable and have good storage resistance.