AU602408B2 - Process for preparing a binder based on bitumen and polymers - Google Patents

Description

11111 11111 1.

11111 1111 II6 form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952.69 COMPLETE SPECIFICATION

(ORIGINAL)

Class I t. Class Application Numbert, Lodged; ~te Specification Lodged, 4 Accepted: Published; Pribrit' R'alated Art 6L O g J Name of Applicant: Address of Applicant: a t S 4cl aalIlInventor: Address for Service THE BRITISH PETROLEUM COMPANY P.L.C.

Britannic House, Moor Kingdom Lane, London EC2Y 9BU, United JEAN LESAGE EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: PROCESS FOR PREPARING A BINDER BASED ON BITUMEN AND

POLYMERS

The following statement is a full description of this invention, including the best method of performing it known to :*us I1.

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4 $144 4 rt 4 f I (C Process for preparing a binder based on bitumen and polymers.

The invention relates to a process for preparing compositions based on bitumen and polymers intended, in particular, for use as a road surfacing or an impermeable coating.

It is known that polybutenes such as polybutylene and polyisobutylene are compatible with polyethylenes, polyethylene waxes, polyisobutylenes such as those sold 10 under the name VISTANEX, butyl rubbers, regenerated rubbers, butadiene/styrene copolymers (GRS), and petroleum resins such as diene resins.

The Applicant has discovered that, by combining a polybutene with a copolymer of ethylene and vinyl ace- '15 tate, and by introducing this mixture, prepared beforehand, into bitumen, it was possible, surprisingly, to boost the consistency and softening properties of the bituminous binder.

The subject of the invention is hence a process 20 for preparing a bitumen/polymer mixture comprising, in a first stage, the preparation of a single additive based on polybutene and an ethylene/vinyl acetate copolymer and the addition of this additive to bitumen. This process is especially advantageous since it suffices simply to mix, for example in a static mixer, the additive with the bitumen, whereas the addition of ethylene/vinyl acetate copolymer or polybutene separately necessitates several hours' mixing using a paddle malaxator, which leads to less homogeneity in the properties of the mixture of bitumen and additive based on polybutene and the ethylene/ vinyl acetate copolymer.

Another subject of the invention consists of the additive prepared in the above manner.

The object of the invention is also the production of surfacings or scalings employing the product thereby obtained.

Other subjects of the invention will become apparent -6 2 on reading the description and the examples which fo.low.

The process according to the invention con -ess ea tia in adding to a bitumen a mixture, prepared beforehand, comprising an ethyLene/vinyL acetate copolymer and a polyisobutylene having a moLecular weight of between 400 and 1,000.

The composition comprising the mixture of the ethylene/vinyL acetate copoLymer and poLyisobutyLene constitutes another subject of the invention. It is preferably prepared by the gradual addition of granules of ethyLene/vinyL acetate copolymer to a Liquid polyisobutylene at a temperature slightly above the -empyr ture nf rlii nlit-i n of the ethylene/vinyl acetate copolymer, by mixing in a slow paddle maLaxator or injection by pump and stirring.

The ethylene/vinyL ac-'tate copoLymer is preferably a copolymer containing 5 to 45% by weight of vinyl acetate units, and preferably a proportion smaller than and a melt flow index of between 0.1 and 600, and i-.cr preferably between 100 and 200. The polyisobutylene preferably has a molecular weight of Less than 1,000 and greater than 400. The mixing of polymers is performed in ratios of polyisobutylene to ethyLene/vinyL acetate of between 90:10 and 50:50, and preferably of the order of 80:20.

The bitumen is preferably a blown or direct road bitumen, which is well known in the prior art.

The composition based on the mixture of polymers is added to this bitumen, preferably in proportions of 1 to 35% with respect to the total ight of the composition, and preferably in proportions from 5 to The Applicant has found that it was possible to prepare a bituminous binder directly on site, by mixing the composition based on polymers, as defined above, and bitumen in times of Less than 1/4 hour, with, for example, a paddle malaxator, or almost immediately with a static m xe mixer.

3-- The Applicant has found that the addition of the composition containing the mixture of polymers, as defined above, enables a synergistic effect to be obtained as a result of an increase in the softening point and a parallel Lowering of the low-temperature breaking point.

Thus, as a result of the combination, it is possible to improve the plastic range and the penetration index.

This is especially surprising in the light of the properties of the separate polymers.

Another advantage of the invention is that the IF composition based on the mixture of polymers, designed to be added to bitumen, may be stored without any problem S for a long period without degradation and with retention ,q S of the initial viscosity.

The road surfacings thus produced behave particularly well in strong heat;, the Applicant has, in effect, found that the binder retains sufficient consistency and viscosity to prevent any irreversible deformation due to S flow of the surfacing, in particular under the action of heavy traffic.

Moreover, in cold weather, the binder thus applied displays resistance to cracking in the cold, which enables the surfacing to withstand winter stresses such as the use of spiked tyres. The bituminous binders prepared in this manner possess, moreover, exceptional properties of elasticity, tenacity and adhesiveness to the aggregates.

The examples which follow are designed to illustrate the invention without, however, being limiting in nature.

EXAMPLE 1 23 parts of an ethylene/vinyl acetate copolymer, having a vinyl acetate content of 18% and a melt flow index of 140, and 77 parts of a polyisobutylene having a molecular mass of 900 are mixed at a temperature of 1400C in a paddle malaxator, the ethylene/vinyl acetate copolymer being introduced in the form of granules. With 3 kg L U~I ~CLII 4of polymers at 300 rpm, fusion of the echylene/vinyl acetate granules in the polyisobutylene is obtained in Less than 1/4 hour.

Keeping this polymer mixture for 15 days at a temperature of 135 0 C shows that the mixture is completely stable and retains its initial viscosity. No settling is observed.

This mixture is added to road bitumen (40/50) in proportions of 30% of the poLymer mixture with respect to the total weight of the composition. The polymer/ bitumen rixture is produced in Less than 1/4 hour by means of a paddle malaxator.

EXAMPLE 2 (comparative) 2% of ethylene/vinyl acetate copolymer containing 15 18% of vinyl acetate and having a melt flow index of 140 is added. to a grade 40/50 bit.umen (penetrability 41, softening point 56, Fraass point -90C, penetration index The softening point is brought to 60.50C and the penetration index to 0.85 without the Fraass point being modified. The plastic range has risen from 65 to 69.5 0

C.

S* t The addition of 5% of polyisobutyLene of molecuar mass 900 to the same bitumen does not modify the softening point, Lowers the Fraass point to -160C and brings the penetration index to +0.5 and the pLastic range to The addition to the same bitumen of a composition as defined in Example 1, based on ethyLene/vinyL acetate copolymer and polyisobutylene and containing 28% of ethyLene/vinyL acetate copolymer and 72% of polyisobuty- Lene, this composition being added in the proportion of 7% to the bitumen composition, brings the softening point to 580C, the Fraass point to 1 7 0C, the penetration index to +1.2 and the plastic range to 750C.

The addition of the composition hence makes it possible to improve the bituminous binder in respect of all these properties, without increasing its service stresses.

i EXAMPLE 3 A formulation is prepared containing 10 parts of polyisobutylene having a molecular mass of 900 and 3 parts of ethylene/vinyl acetate copolymer having a vinyl acetate content of 18% and a melt flow index of 140, and this is introduced into 87 parts of 40/50 bitumen as defined above.

The following viscosities are observed: at 1400C: 722 mPa.s; at 1600C: 297 mPa.s; at 1800C: 142 mPa.s; whereas the base bitumen has the fot- Lowing viscosities: I "I at 1400C: 600 mPa.s; at 1600C: 263 mPa.s; at 1800C: 142 mPa.s.

It is found that the combination according to the' S 15 invention enables the viscosity when hot to be increased slightly, and also improves t.he ease of handling of the mix. This is observed in the Laboratoire des Ponts de Chaussees rotary shearing press test, on a discontinuous 0/14 mix of formula: S 20 10/14 porphyry: 26% 6/10 porphyry: 31% 0/2 porphyry: 39% calcareous fines: 4% binder content: 7.7 pph (parts by weight per hundred parts of aggregates).

The 0/14 mix with the polymer binder according to the invention achieves 89.5 compactness at 10 rotations 92.0 compactness at 20 rotations 95.0 compactness at 50 rotations.

The binder prepared in this manner possesses, moreover, properties of resistance in the fatigue test and of resistance to stripping by water or adhesiveness which are also improved.

A fatigue test is performed, according to the LCPC (Laboratoire Central des Fonts et Chaussees) method in sinusoidal bending to constant deformation of trapezoid 6 test pieces, the test being performed using plates of mixes manufactured and compacted according to the Laboratoire des Ponts et Chausses procedures, on the mixes of the foLLowing formula: 6/10 La Noubleau 33% 2/6.3 La NoubLeau 24% 0/2 La NoubLeau 40.7% calcareous filler: 2.3% binder 5.75 pph.

The following figures are obtained at a frequency of 25 hertz and at 100C: at 106 cycles, the relative deformation is: 1.40 x 10 for the reference mix (40/50 binder), -4 but 2.20 x 10 for the mix with the bitumen/polymer binder defined above.

5 at 10 cycles, the relative deformation is: 2 x 10 for the reference mix; and 4 3 x 10 for the mix with the bitumen/polymer Sbinder.

It is hence observed that there is a Larger per- 1 missible deformation for the same fatigue test time for Sthe mix containing the polymer binder according to the invention. In the water stripping test, this property is demonstrated by the ratio of the resistances at 180C in 25 the DURIEZ (or LCPC) unconfined compression test, with t

C

retention on immersion in water for 7 days with respect S to the concentration in the dry state also for 7 days.

Taking the following mix formula: 10/14 La NoubLeau 69% 0/2 La Noubleau 27.5% calcereous filler: binder content 5.5 pph the ratio of the resistances is 0.88 for the 40/50 reference mix, compared with 0.96 for the mix with the bitumen/polymer binder as defined above.

Claims (10)

1. Process for preparing a bituminous binder which comprises mixing with a bitumen 1 to 35% by weight based on the total weight of the mixture of a composition of an ethylene/vinyl acetate copolymer and a polyisobutylene having a molecular weight of 400 to 1,000, wherein the ratio of polyisobutylene to ethylene/vinyl acetate is from 90:10 to 50:50.

2. Process according to claim 1 in which the ethylene/vinyl acetate copolymer is a copolymer containing to 45% by weight of vinyl acetate units and having a melt e flow index of 0.1 to 600.

3. Process according to claim 1 or 2 which is carried out at the site of use, the mixing time not exceeding 1/4 hour. o d

4. Process according to claim 3 in which, after mixing is complete, the resulting mixture is applied as a road surfacing.

Process for preparing a composition of an ethylene/ Svinyl acetate copolymer and a polyisobutylene having a ti rr, molecular weight of 400 to 1,000, wherein the ratio of tit polyisobutylene to ethylene vinyl acetate is from 90:10 to 50:50 which comprises gradually adding granules of the s ethylene/vinyl acetate copolymer to the polyisobutylene at a temperature slightly above the melting point of the ethylene/vinyl acetate copolymer in the liquid polyisobutylene and mixing. k j 4-) 1

6. hereir Il ii I~i-ii_~i~~ 8 Process according to claim 5 substantially as Ibefore described. 00 t* 0 o 0 o 00 0 0 00 00 0 0 0 0

7. A composition whenever prepared by a process as claimed in claim

8. Process according to claim 1 or 2 which comprises mixing with a bitumen 1 to 35% by weight based on the total weight of the mixture of a composition according to claim 7.

9. Process according to claim 1 substantially as described in Example 1 or 3.

10. A bituminous binder whenever prepared by a process as claimed in any one of claims 1 to 4, 8 and 9. DATED this 4th day of July, 1990. I: I 11 vI 0 90 0 0 0009 009 o e f0 0 49 99«« THE BRITISH PETROLEUM COMPANY Plc WATERMARK, PATENT TRADEMARK ATTORNEYS, 290 BURWOOD ROAD, HAWTHORN, VIC. 3122. AUSTRALIA. DBM:LPS:JZ (11.4) o~ 'U ii i: i~ z YS.a~ Pt::~ -e