CA1074937A - Bituminous mixes - Google Patents
Bituminous mixesInfo
- Publication number
- CA1074937A CA1074937A CA254,879A CA254879A CA1074937A CA 1074937 A CA1074937 A CA 1074937A CA 254879 A CA254879 A CA 254879A CA 1074937 A CA1074937 A CA 1074937A
- Authority
- CA
- Canada
- Prior art keywords
- maleinized
- bituminous binder
- aggregate
- bitumen
- bituminous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
A B S T R A C T
A process for the preparation of a mixture of a chemically modified bituminous binder with aggregate and/or filler, comprising chemically modifying, by means of a chemical modifier, at least a part of a non-emulsified bituminous binder during the mixing thereof with aggregate and/or filler. This mixture is very suitable to coat surfaces, e.g. road surfaces.
A process for the preparation of a mixture of a chemically modified bituminous binder with aggregate and/or filler, comprising chemically modifying, by means of a chemical modifier, at least a part of a non-emulsified bituminous binder during the mixing thereof with aggregate and/or filler. This mixture is very suitable to coat surfaces, e.g. road surfaces.
Description
~074937 The invention is concerned ~ith a process for the prepsration o~ a mixture Or a chemical~r modified bitumen with aggregate and/or filler and ~ith a surface coated ~ith 8 mixture so prepared.
It is knoun to coat surrace~ with mixtures of bituminous binders and aggregate ~nd/or fillers, Such mixture~ may be applied to B surrace ~such mixtures beine rererred to herein as pre-mixes) or may be prepared on the surface itself (such mixtures being referred to herein as surface-mixes); such procedures being particularly useful in spplication~ such as paring (e.g. road-mdking), hydraulic engineering, erosion control and building industry e,g. roofing, flooring, pipe-sealing etc, Both pre-mixes and surrace-mixe~ are usually prepared by mixing the components at elevated temperatures ; e.g, in the range of from 100 to 250C although lower temper~tures e,g. ambient temperature may also be used. Insofar as hot pre-mixes are concerned the components are usually pre-heated to a temperature $ in this range before they are actively or intimately mixed whereas insofar as hot surface-mixes are concerned usually only the bituminous binder is pre-heated toia temperature in this range before it } i8 mixed with the aggre8ate and/or filler on the surface. Pre-mix 2Q techniques are discussed in "Asf~lt" by Vereniging roor Bitumineuze Werken, 1973.
Various types of bituminous binder have been mixed with aggregate ~ and/or filler to form pre-mi~es or surface-mixes, but in practice ', the choice is generally limited to those types ~hich have a sufficiently low riscosity at the mixing temperature. In the case of pre-mixes, this low viscosity is necessary both for spraying or pumping the binder into the mixing zone or chamber of the mix spparatu~ and for good intimate mixing therein with the aggregate or filler.
,, ,s
It is knoun to coat surrace~ with mixtures of bituminous binders and aggregate ~nd/or fillers, Such mixture~ may be applied to B surrace ~such mixtures beine rererred to herein as pre-mixes) or may be prepared on the surface itself (such mixtures being referred to herein as surface-mixes); such procedures being particularly useful in spplication~ such as paring (e.g. road-mdking), hydraulic engineering, erosion control and building industry e,g. roofing, flooring, pipe-sealing etc, Both pre-mixes and surrace-mixe~ are usually prepared by mixing the components at elevated temperatures ; e.g, in the range of from 100 to 250C although lower temper~tures e,g. ambient temperature may also be used. Insofar as hot pre-mixes are concerned the components are usually pre-heated to a temperature $ in this range before they are actively or intimately mixed whereas insofar as hot surface-mixes are concerned usually only the bituminous binder is pre-heated toia temperature in this range before it } i8 mixed with the aggre8ate and/or filler on the surface. Pre-mix 2Q techniques are discussed in "Asf~lt" by Vereniging roor Bitumineuze Werken, 1973.
Various types of bituminous binder have been mixed with aggregate ~ and/or filler to form pre-mi~es or surface-mixes, but in practice ', the choice is generally limited to those types ~hich have a sufficiently low riscosity at the mixing temperature. In the case of pre-mixes, this low viscosity is necessary both for spraying or pumping the binder into the mixing zone or chamber of the mix spparatu~ and for good intimate mixing therein with the aggregate or filler.
,, ,s
- 2 -.i . ~ .
~07~'3~7 ]~n the case ol surface-rnixes, this low viscosity is necessary for pumping or spraying the binder onto the surface. In general, binders may be regarded as unsuitable or unhandleable if the viscosity thereof exceeds 400-500 cSt at the mixing ternperature. Potentially very useful binders are those which have been chemically modified but ~litherto such binders have not been used on a large-scale because of their high viscosities.
The Applicants have now discovered that it is possible to pre-pare mixtures of these high viscosity binders by carryir~ out at least a part of the modification thereof in-situ i.e. by modifying such binders in the presence of the aggregate and/or filler.
Accordingly, the present invention is concerned with a process for the preparation of a mixture contairL~ng a chemically modified maleinized bituminous binder having a viscosity of more than 400 cSt at a temperature of from about ambient to about 250C, which process comprises chemically modifying at least a part of a non-emulsified maleinized bituminous binder c in-situ by means of reaction with from about 28% to about 500% of the stoi-chiometric amount of a chemical modifier during the process of mixing the ~ rr leinized bituminous binder with the aggregate or filler, at a mixing :~r temperature of from about ambient temperature to about 250C, wherein the 20 chemical modifier is at least one compound chosen from the group comprising a metal compound capable of forming ionic groups with the maleinized bitum~
inous binder; an organic compound having at least two functional groups sel-ected from hydroxyl, mercapto, amino, N-hydrocarbylamino, epoxy and iso-cyanato and maleinizing compounds.
The invention is particularly useful for preparing pre-mixes, particularly hot pre-mixes i.e. pre-mixes prepared at elevated temperatures e.g. at temperatures in the range of from 100 to 250C. Insofar as pre-parir~ the mlxture at ambient temperature is concerned, the bituminous binder may be in the form of a cut-back bitumen, i.e. a bitumen which has been diluted with a volatile solvent, although such binders are not widely . .
, ~
, ' 10749~7 applied, particularly in road-construction, because of their longer curing times and the poorer physical properties of the mixture re-maining after the solvent has evaporated. ~n addition such binders, even when prepared from known chemically modified bitumens, do not always produce handleability problems; however, by applying the process of the present invention, i.e. by chemical modification in-situ, even these known chemically modified bitumens can be improved, since it bec~nes possible to use less solvent than would otherwise have been used.
Bituminous binders prepared by reacting bitumens, such as gilsonite, straight-run bitumens, propane bitumens or blown bitumens, or ':
.
i `:~
.
'''''' C
1074~ 7 mixtures thcreof with cxtcnders ag~llts and/or pol~ncrs, with say from 0.5 to 10 ~wt of olefinically unsaturated anhydrides, c.g. maleic anhydride, or olefinically unsaturated acids, e.g. maleic acids, are also known. For convenience, these types of bituminous binders are referred to herein as maleinized bituminous binders. For example, maleinized bituminous binders prepared from bitumen/polymer mixtures are described in our co-pending Application Nos. 221,269 and 221,270. Suitable polymers are olefinically unsaturated elastomeric materials of molecular weight in the range of from loo,ooo to 500,000 such as styrene-butadiene copolymers e.g. type "Cariflex"
S 1712 or type "Cariflex" S 1500 (Cariflex is a registered Trade Mark).
Suitable amounts of polymers are below 10 %wt, based on bitumen, with from 0.1 to 7.0 %wt being preferred.
` Such maleinized bituminous binders to be modified in the process suitably have acid values, determined by titration, of from 0.01 to 2.0 meq/g.
Such maleinized bituminous binders may be modified in the process by the ionic or covalent coupling thereof by the use of the approprlate chemical modifier. Suitable chemical modifiers capable of coupling malein-ized bituminous binders are also described in the aforesaid co-pending Applications as well as the coupling of emulsified maleinized bituminous binaers in the presence of aggregate and, optionally, other coupling agents.
Suitable chemical modifiers for ionically coupling maleinized bituminous binders are compounds of the metals of Group I to IV of the Periodic Table, especially those of the Sub-Groups IA to IVA, e.g. lithium, sodium, potassium, calcium, magnesium, barium, ~, ,, ~7~937 aluminium ~nd lead. ~uit~le compound~ ~re the hydroxides, alkoxides and leok acid salts o~ these metnls. Specific ex~mples include the hydroxides o~ lithium, sodiu~, potossium snd bariu~, lead II acetate, magnesium acetate, alun~nium isopropoxide ~nd aluminium sec-butoxide and mixtures thereof. Preferably the modi~ier is ; added in aqueou3 solution or i~ in the liquid state at the mixing temperature.
Suitable chemic~l modifiers which co-valently couple maleinized bituminous binders are those which form (~hio)ester, amide or imide groups. Such group6 are formed when organic compounds having at least two runctional groups capable of reacting with the groups f attached to the msleini~ed bituminous binder are used as chemical modiriers. Suitable functional groups include: hydroxyl, mercapto, amino and N-hydrocarbylamino, epoxy e.B. epoxyalkyl, snd isocyanato groups. Thus examples Or Yuitable coupling agents are: ethylene glycol; diethylene glycol; 1,4-butsnediol; glycerol; trimethylolpropane;
: the diglycidyl ester Or bisphenol A; methylenediphenyl-4,4'-di-isocyanate;
tolylene-di-isocyanates; triethylenetriamine; tetraethylene pentamine and diethsnolamine.
,~ 20 The amount Or chemical modifier used to couple the maleinized ~ituminous binders is from 28 to 500 %w Or that needed stoichiometricslly to react with, e.g. to neutralize, the binder. Amounts ranging ~ro~ 50 to to 300 %w, particulsrly from 75 to 200 %w Or the theoretical a~ount are prererred however. m e ~aleinized bituminous binder msy be blended with extenders and/or polymers before they are modified in the proce3s.
As stated above, the present invention i~ particular~Y suitable ., ; 6 ~749~7 for preparing mlxtures of chemically moclified n~leinized bituminous binders with aggregate and/or filler. The reason for this is that although maleinized bitum~lous blnders, especial~y those prepared with less than 10% w maleic anhydride, have vlscosities of below 400-500 cSt at the usual mixing temperatures and therefore are handleable, the chemically dified maleinized bituminous binders have viscosities well in excess of 400-500 cSt, usually in excess of 1000 cSt, at the usual mixing I temperatures and therefore are not handleable and are difficult to mix.
However, the present invention is not restricted to the preparation of mixtures of chemically modified bituminous binders of the above types. For example, it n~y be used to prepare maleinized bituminous binders having a high acid content. As stated hereinbefore maleinized bituminous binders prepared from below 10% w of maleic anhydride may have viscosities below 500 cSt at the mixing temperature but if the amount of maleic anhydride is increased say to about 20% w then the resultant binder ma~ have a viscosity which is too high to be handleable. Hence the present invention may be used to maleinize a bitumen such as a straight-run bitumen or to further maleinize an already maleinized bituminous binder.
The aggregate and/or filler to be used in the process may be any conventional aggregate of filler. Examples of suitable aggregates include gravel, bauxite, granite, gritstones, basalt, porphyry, dolomite, slags and limestone whereas limestone, sand, asbestos and glass fibre are examples of suitable fillers. In general, aggregates may be described as particles which do not ., , - 7 -:, A ~
.~ ' "
pQss through a 75 micron ~ieve wherea~ fillers sre psrticleu which do pas~ through a 75 micron sieve, In general the ~mount of aggregate in the mixture i~ ~rom 10% to 5,000 %w based on weight Or homogeneous bituminous binder.
In the case of preparing pre-mixes, the three components used in the process i.e. the bituminou~ binder, the aBeregate and/or filler and the chemical modifier may be fed as separate streams to the mixing zone but it is also possible to prior mix the aggregate and/or filler with the chemical modifier or binder.
It is desirable to add, the chemical modifier to the mixing zone srter some mixing of bitu~inous binder and sggregate and/or filler ~, has already taken pl~ce.
m e in~ention will now be illustrated with reference to the , following Examples. In the Examples the ~iscosities were determined by the capillary ~iscosimeter (ASTM D-2170). The penetrations are the ASTM-D5 penetrations (25C, 0,1 mm) and the ~oftening '- points the Rin8 and B~ll softening points (C). m e Marshall test was carried out according to ASTM D-1559, after compaction at 160 C.
~, EXAMPLE I
:~: Preparation of a maleinized bituminous binder ., _ _______ ___________ _______ ___ ________ A Kuwait fully blown bitumen (penetration 40; sortening point 85 C; 1000 g) was extended with 200 8 Or an aromatic oil extract ~, (Dutrex 729 HP), The mixture was then heated to 175C, maleic J anhydride added (24g, 2 %w) and the mixture maintained at 170-180C
for 2 hours with continual ~tirrinB. m e ~isco~ity Or the homogeneous '' 25 product w~s about 175 cSt at 190C and the product h~d an ~cid ~ol~e Or 0.23 ~eq/g, -- 8 _ , . .
., 1t)7~937 EXAMPLE 2 (Comparati~e) The maleinized bituminous binder (1200 e) prepared according to Example 1 wa8 heated to 160-180C and ~0~ (15 e) added with stirring. The temperature was maintained at 160-180C for from 0,5 to 2.0 hour~. The viscosity of the product wss too high to determine and it was not possible to use the product in ~tandard hot-mix apparatus.
Maleinized bituminous binder (66g) prepsred according to Example 1 ~as pumped at 175-180C into the mixing zone of a laboratory hot-mix apparatus simultan~ously with the separate addition of '; 10 1200e of normal road building aggregate (55 %w stone (0.2-l,ôcm),:
35% sand (2mm) and 10% filler (~64~)) at 175-180C. KOH (1.0 g) was added as an aqueous ~olution to the mixture and ~ixing continued for 1 minute. The pre-mix of chemically coupled bituminous binder and aggregate had excellent properties including good compactability.
The Marshall test data for the product are given in Table 1, Preparation of a maleinized bituminous binder .` ___ _________________________________________ Example 1 was repeated using Kuwait semi-blown bitumen (penetration 80-100; for Marshall test data, see Table 1) and 48g of maleic anhydride (4 %w), The homogeneou~ product had a viscosity of about j 109 cSt at 190C and an acid value Or about 0.40 meq/g.
EXAMPLE 5 (comparative) ; 20 Ex~mple 2 ~as repeated using the maleinized bitu~inous binder (1200 g) prepared according to Example 4 and 34g of the diglycidyl ether of bisphenol A. The viscosity of the product ~as lôOO cSt at 190C and it was not possible to use the product in 6tandard S hot-mix appsratus, _ g _ . .
.~
1074~3'7 ~XAMPLE 6 Exa~ple 3 wa~ repeated using the maleinized bituminous binder (66 g) prepared according to ~x~mple 4 and 1.9 g of the di~lycidyl ether of bisphenol A. ~,le hot-mix of chemically coupled bituminous binder and aggregate had excellent properties including good compactability.
The Marshall test d~ta for the product are given in Table 1. Similar results were obtained using KOH instead of the diglycidyl ether of bisphenol A.
Preparation of a maleini~ed bitu3inous binder Ex~mple 1 was repeated using a bitumen (penetration 80-100) prepared by fluxing (565g) an Irsnian propane bitumen with 635g Or an Iranian short residue, to which was added 4 %w Or a ~tyrene-bu-t6diene rubber ("Cariflex" S 1500). The amount of msleic anhydride used ~as 24g (2 %w). The visco~ity Or the homogeneous product wa~ about 200 cSt at 190O' and it had an acid value Or 0.17 meq/g.
EXAMPLES 8 snd 9 (Comparative) Example 2 was repeated using the maleinized bituminou~ binder (1200 g) prepared according to Example 7 and 26,9 g of ~OH (Example 8) or 39,3 g of aluminium sec-butoxide (Example 93. The viscositie~
of the products were too high to determine and it wa8 not po-~sible to use the products in standard hot-mix appars,tus.
EXAMPLES 10 snd _11 Example 3 was repeated using the maleinized bituminous binder (66 g) prepared according to Example 7 and 1.5g o~ ~OH (Example 10) and 2.2g of aluminium sec-butoxide (Example 11). Thc pre-mixes of chemically coupled bitu~inous binder and ag~regate h~d excellent properties including good compactabili'y. The Marshell test dsta , .
:"
/
:
. .
., ~ 0749371 for the products are glven in Table 1.
Table 1 Example 1* 2*
PM(kN) FM(~) QM(PM/FM) .
Kuwait 80/100 3* 6.7 4.8 1.4
~07~'3~7 ]~n the case ol surface-rnixes, this low viscosity is necessary for pumping or spraying the binder onto the surface. In general, binders may be regarded as unsuitable or unhandleable if the viscosity thereof exceeds 400-500 cSt at the mixing ternperature. Potentially very useful binders are those which have been chemically modified but ~litherto such binders have not been used on a large-scale because of their high viscosities.
The Applicants have now discovered that it is possible to pre-pare mixtures of these high viscosity binders by carryir~ out at least a part of the modification thereof in-situ i.e. by modifying such binders in the presence of the aggregate and/or filler.
Accordingly, the present invention is concerned with a process for the preparation of a mixture contairL~ng a chemically modified maleinized bituminous binder having a viscosity of more than 400 cSt at a temperature of from about ambient to about 250C, which process comprises chemically modifying at least a part of a non-emulsified maleinized bituminous binder c in-situ by means of reaction with from about 28% to about 500% of the stoi-chiometric amount of a chemical modifier during the process of mixing the ~ rr leinized bituminous binder with the aggregate or filler, at a mixing :~r temperature of from about ambient temperature to about 250C, wherein the 20 chemical modifier is at least one compound chosen from the group comprising a metal compound capable of forming ionic groups with the maleinized bitum~
inous binder; an organic compound having at least two functional groups sel-ected from hydroxyl, mercapto, amino, N-hydrocarbylamino, epoxy and iso-cyanato and maleinizing compounds.
The invention is particularly useful for preparing pre-mixes, particularly hot pre-mixes i.e. pre-mixes prepared at elevated temperatures e.g. at temperatures in the range of from 100 to 250C. Insofar as pre-parir~ the mlxture at ambient temperature is concerned, the bituminous binder may be in the form of a cut-back bitumen, i.e. a bitumen which has been diluted with a volatile solvent, although such binders are not widely . .
, ~
, ' 10749~7 applied, particularly in road-construction, because of their longer curing times and the poorer physical properties of the mixture re-maining after the solvent has evaporated. ~n addition such binders, even when prepared from known chemically modified bitumens, do not always produce handleability problems; however, by applying the process of the present invention, i.e. by chemical modification in-situ, even these known chemically modified bitumens can be improved, since it bec~nes possible to use less solvent than would otherwise have been used.
Bituminous binders prepared by reacting bitumens, such as gilsonite, straight-run bitumens, propane bitumens or blown bitumens, or ':
.
i `:~
.
'''''' C
1074~ 7 mixtures thcreof with cxtcnders ag~llts and/or pol~ncrs, with say from 0.5 to 10 ~wt of olefinically unsaturated anhydrides, c.g. maleic anhydride, or olefinically unsaturated acids, e.g. maleic acids, are also known. For convenience, these types of bituminous binders are referred to herein as maleinized bituminous binders. For example, maleinized bituminous binders prepared from bitumen/polymer mixtures are described in our co-pending Application Nos. 221,269 and 221,270. Suitable polymers are olefinically unsaturated elastomeric materials of molecular weight in the range of from loo,ooo to 500,000 such as styrene-butadiene copolymers e.g. type "Cariflex"
S 1712 or type "Cariflex" S 1500 (Cariflex is a registered Trade Mark).
Suitable amounts of polymers are below 10 %wt, based on bitumen, with from 0.1 to 7.0 %wt being preferred.
` Such maleinized bituminous binders to be modified in the process suitably have acid values, determined by titration, of from 0.01 to 2.0 meq/g.
Such maleinized bituminous binders may be modified in the process by the ionic or covalent coupling thereof by the use of the approprlate chemical modifier. Suitable chemical modifiers capable of coupling malein-ized bituminous binders are also described in the aforesaid co-pending Applications as well as the coupling of emulsified maleinized bituminous binaers in the presence of aggregate and, optionally, other coupling agents.
Suitable chemical modifiers for ionically coupling maleinized bituminous binders are compounds of the metals of Group I to IV of the Periodic Table, especially those of the Sub-Groups IA to IVA, e.g. lithium, sodium, potassium, calcium, magnesium, barium, ~, ,, ~7~937 aluminium ~nd lead. ~uit~le compound~ ~re the hydroxides, alkoxides and leok acid salts o~ these metnls. Specific ex~mples include the hydroxides o~ lithium, sodiu~, potossium snd bariu~, lead II acetate, magnesium acetate, alun~nium isopropoxide ~nd aluminium sec-butoxide and mixtures thereof. Preferably the modi~ier is ; added in aqueou3 solution or i~ in the liquid state at the mixing temperature.
Suitable chemic~l modifiers which co-valently couple maleinized bituminous binders are those which form (~hio)ester, amide or imide groups. Such group6 are formed when organic compounds having at least two runctional groups capable of reacting with the groups f attached to the msleini~ed bituminous binder are used as chemical modiriers. Suitable functional groups include: hydroxyl, mercapto, amino and N-hydrocarbylamino, epoxy e.B. epoxyalkyl, snd isocyanato groups. Thus examples Or Yuitable coupling agents are: ethylene glycol; diethylene glycol; 1,4-butsnediol; glycerol; trimethylolpropane;
: the diglycidyl ester Or bisphenol A; methylenediphenyl-4,4'-di-isocyanate;
tolylene-di-isocyanates; triethylenetriamine; tetraethylene pentamine and diethsnolamine.
,~ 20 The amount Or chemical modifier used to couple the maleinized ~ituminous binders is from 28 to 500 %w Or that needed stoichiometricslly to react with, e.g. to neutralize, the binder. Amounts ranging ~ro~ 50 to to 300 %w, particulsrly from 75 to 200 %w Or the theoretical a~ount are prererred however. m e ~aleinized bituminous binder msy be blended with extenders and/or polymers before they are modified in the proce3s.
As stated above, the present invention i~ particular~Y suitable ., ; 6 ~749~7 for preparing mlxtures of chemically moclified n~leinized bituminous binders with aggregate and/or filler. The reason for this is that although maleinized bitum~lous blnders, especial~y those prepared with less than 10% w maleic anhydride, have vlscosities of below 400-500 cSt at the usual mixing temperatures and therefore are handleable, the chemically dified maleinized bituminous binders have viscosities well in excess of 400-500 cSt, usually in excess of 1000 cSt, at the usual mixing I temperatures and therefore are not handleable and are difficult to mix.
However, the present invention is not restricted to the preparation of mixtures of chemically modified bituminous binders of the above types. For example, it n~y be used to prepare maleinized bituminous binders having a high acid content. As stated hereinbefore maleinized bituminous binders prepared from below 10% w of maleic anhydride may have viscosities below 500 cSt at the mixing temperature but if the amount of maleic anhydride is increased say to about 20% w then the resultant binder ma~ have a viscosity which is too high to be handleable. Hence the present invention may be used to maleinize a bitumen such as a straight-run bitumen or to further maleinize an already maleinized bituminous binder.
The aggregate and/or filler to be used in the process may be any conventional aggregate of filler. Examples of suitable aggregates include gravel, bauxite, granite, gritstones, basalt, porphyry, dolomite, slags and limestone whereas limestone, sand, asbestos and glass fibre are examples of suitable fillers. In general, aggregates may be described as particles which do not ., , - 7 -:, A ~
.~ ' "
pQss through a 75 micron ~ieve wherea~ fillers sre psrticleu which do pas~ through a 75 micron sieve, In general the ~mount of aggregate in the mixture i~ ~rom 10% to 5,000 %w based on weight Or homogeneous bituminous binder.
In the case of preparing pre-mixes, the three components used in the process i.e. the bituminou~ binder, the aBeregate and/or filler and the chemical modifier may be fed as separate streams to the mixing zone but it is also possible to prior mix the aggregate and/or filler with the chemical modifier or binder.
It is desirable to add, the chemical modifier to the mixing zone srter some mixing of bitu~inous binder and sggregate and/or filler ~, has already taken pl~ce.
m e in~ention will now be illustrated with reference to the , following Examples. In the Examples the ~iscosities were determined by the capillary ~iscosimeter (ASTM D-2170). The penetrations are the ASTM-D5 penetrations (25C, 0,1 mm) and the ~oftening '- points the Rin8 and B~ll softening points (C). m e Marshall test was carried out according to ASTM D-1559, after compaction at 160 C.
~, EXAMPLE I
:~: Preparation of a maleinized bituminous binder ., _ _______ ___________ _______ ___ ________ A Kuwait fully blown bitumen (penetration 40; sortening point 85 C; 1000 g) was extended with 200 8 Or an aromatic oil extract ~, (Dutrex 729 HP), The mixture was then heated to 175C, maleic J anhydride added (24g, 2 %w) and the mixture maintained at 170-180C
for 2 hours with continual ~tirrinB. m e ~isco~ity Or the homogeneous '' 25 product w~s about 175 cSt at 190C and the product h~d an ~cid ~ol~e Or 0.23 ~eq/g, -- 8 _ , . .
., 1t)7~937 EXAMPLE 2 (Comparati~e) The maleinized bituminous binder (1200 e) prepared according to Example 1 wa8 heated to 160-180C and ~0~ (15 e) added with stirring. The temperature was maintained at 160-180C for from 0,5 to 2.0 hour~. The viscosity of the product wss too high to determine and it was not possible to use the product in ~tandard hot-mix apparatus.
Maleinized bituminous binder (66g) prepsred according to Example 1 ~as pumped at 175-180C into the mixing zone of a laboratory hot-mix apparatus simultan~ously with the separate addition of '; 10 1200e of normal road building aggregate (55 %w stone (0.2-l,ôcm),:
35% sand (2mm) and 10% filler (~64~)) at 175-180C. KOH (1.0 g) was added as an aqueous ~olution to the mixture and ~ixing continued for 1 minute. The pre-mix of chemically coupled bituminous binder and aggregate had excellent properties including good compactability.
The Marshall test data for the product are given in Table 1, Preparation of a maleinized bituminous binder .` ___ _________________________________________ Example 1 was repeated using Kuwait semi-blown bitumen (penetration 80-100; for Marshall test data, see Table 1) and 48g of maleic anhydride (4 %w), The homogeneou~ product had a viscosity of about j 109 cSt at 190C and an acid value Or about 0.40 meq/g.
EXAMPLE 5 (comparative) ; 20 Ex~mple 2 ~as repeated using the maleinized bitu~inous binder (1200 g) prepared according to Example 4 and 34g of the diglycidyl ether of bisphenol A. The viscosity of the product ~as lôOO cSt at 190C and it was not possible to use the product in 6tandard S hot-mix appsratus, _ g _ . .
.~
1074~3'7 ~XAMPLE 6 Exa~ple 3 wa~ repeated using the maleinized bituminous binder (66 g) prepared according to ~x~mple 4 and 1.9 g of the di~lycidyl ether of bisphenol A. ~,le hot-mix of chemically coupled bituminous binder and aggregate had excellent properties including good compactability.
The Marshall test d~ta for the product are given in Table 1. Similar results were obtained using KOH instead of the diglycidyl ether of bisphenol A.
Preparation of a maleini~ed bitu3inous binder Ex~mple 1 was repeated using a bitumen (penetration 80-100) prepared by fluxing (565g) an Irsnian propane bitumen with 635g Or an Iranian short residue, to which was added 4 %w Or a ~tyrene-bu-t6diene rubber ("Cariflex" S 1500). The amount of msleic anhydride used ~as 24g (2 %w). The visco~ity Or the homogeneous product wa~ about 200 cSt at 190O' and it had an acid value Or 0.17 meq/g.
EXAMPLES 8 snd 9 (Comparative) Example 2 was repeated using the maleinized bituminou~ binder (1200 g) prepared according to Example 7 and 26,9 g of ~OH (Example 8) or 39,3 g of aluminium sec-butoxide (Example 93. The viscositie~
of the products were too high to determine and it wa8 not po-~sible to use the products in standard hot-mix appars,tus.
EXAMPLES 10 snd _11 Example 3 was repeated using the maleinized bituminous binder (66 g) prepared according to Example 7 and 1.5g o~ ~OH (Example 10) and 2.2g of aluminium sec-butoxide (Example 11). Thc pre-mixes of chemically coupled bitu~inous binder and ag~regate h~d excellent properties including good compactabili'y. The Marshell test dsta , .
:"
/
:
. .
., ~ 0749371 for the products are glven in Table 1.
Table 1 Example 1* 2*
PM(kN) FM(~) QM(PM/FM) .
Kuwait 80/100 3* 6.7 4.8 1.4
3. 11.3 2.1 6.3 6. 14.2 4.1 3.5 ' 10. 11.5 3.9 3.
11. 12.2 3.3 3-7 l* stability 2* flow value 3~ see E~:mple 4 : ' :
., '.
.~ .
., .
Gl ~ . ,
11. 12.2 3.3 3-7 l* stability 2* flow value 3~ see E~:mple 4 : ' :
., '.
.~ .
., .
Gl ~ . ,
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a mixture containing a chemically modified maleinized bituminous binder having a viscosity of more than 400 cSt at a temperature of from about ambient to about 250°C, which process comprises chemically modifying at least a part of a non-emulsified maleinized bituminous binder in-situ by means of reaction with from about 28% to about 500% of the stoichiometric amount of a chemical modifier during the process of mixing the maleinized bituminous binder with the aggregate or filler, at a mixing temper-ature of from about ambient temperature to about 250°C, wherein the chemical modifier is at least one compound chosen from the group comprising a metal compound capable of forming ionic groups with the maleinized bituminous binder;
an organic compound having at least two functional groups selected from hydroxyl, mercapto, amino, N-hydrocarbylamino, epoxy and isocyanato and maleinizing compounds.
an organic compound having at least two functional groups selected from hydroxyl, mercapto, amino, N-hydrocarbylamino, epoxy and isocyanato and maleinizing compounds.
2. Process according to claim 1 wherein the maleinized bitumen is a material obtained by reacting a bitumen with an olefinically unsaturated acid or olefinically unsaturated acid anhydride.
3. Process according to claim 1 wherein the maleinized bitumen con-tains up to 10% by weight of a polymer.
4. Process according to claim 2 wherein the olefinically unsaturated acid or acid anhydride is maleic acid or maleic anhydride.
5. A process as claimed in claim 1, wherein the mixture is formed before it is applied to a surface.
6. A process as claimed in claim 1, wherein the mixture is formed at a temperature in the range of from 100 to 250°C.
7. A process as claimed in claim 1, wherein the amount of chemical modifier is from 75 to 200% wt of the theoretical amount required to react with the non-emulsified bituminous binder.
8. A process as claimed in claim 1, wherein the metal compound is a simple compound of a metal of sub-groups IA to IVA of the Periodic Table.
9. A process as claimed in claim 8, wherein the metal compound is an oxide, hydroxide, alkoxide, or a salt of a weak acid.
10. A process as claimed in claim 1, wherein the amount of aggregate and/or filler is from 10% to 5,000% wt based on weight of non-emulsified bituminous binder.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB29611/75A GB1515945A (en) | 1975-07-15 | 1975-07-15 | Bituminous mixes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074937A true CA1074937A (en) | 1980-04-01 |
Family
ID=10294301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA254,879A Expired CA1074937A (en) | 1975-07-15 | 1976-06-15 | Bituminous mixes |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5212228A (en) |
| BE (1) | BE843858A (en) |
| CA (1) | CA1074937A (en) |
| CH (1) | CH622025A5 (en) |
| DE (1) | DE2631468A1 (en) |
| FR (1) | FR2318217A1 (en) |
| GB (1) | GB1515945A (en) |
| NL (1) | NL7607725A (en) |
| SE (1) | SE425916B (en) |
| ZA (1) | ZA764135B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4921539A (en) * | 1987-10-30 | 1990-05-01 | Shell Oil Company | Modified pitch specially adapted to bind coal particles |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1381248A (en) * | 1962-04-05 | 1964-12-14 | Exxon Research Engineering Co | Improved compositions comprising solids and asphalt and method of manufacture thereof |
| GB1393732A (en) * | 1973-05-21 | 1975-05-14 | Wiggins & Co Ltd Berry | Screed materials |
-
1975
- 1975-07-15 GB GB29611/75A patent/GB1515945A/en not_active Expired
-
1976
- 1976-06-15 CA CA254,879A patent/CA1074937A/en not_active Expired
- 1976-07-07 BE BE1007491A patent/BE843858A/en unknown
- 1976-07-13 FR FR7621413A patent/FR2318217A1/en active Granted
- 1976-07-13 JP JP51082611A patent/JPS5212228A/en active Pending
- 1976-07-13 DE DE19762631468 patent/DE2631468A1/en not_active Withdrawn
- 1976-07-13 ZA ZA764135A patent/ZA764135B/en unknown
- 1976-07-13 SE SE7607982A patent/SE425916B/en unknown
- 1976-07-13 NL NL7607725A patent/NL7607725A/en not_active Application Discontinuation
- 1976-07-13 CH CH896076A patent/CH622025A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2318217B1 (en) | 1979-05-18 |
| BE843858A (en) | 1977-01-07 |
| NL7607725A (en) | 1977-01-18 |
| SE7607982L (en) | 1977-01-16 |
| CH622025A5 (en) | 1981-03-13 |
| ZA764135B (en) | 1977-06-29 |
| FR2318217A1 (en) | 1977-02-11 |
| SE425916B (en) | 1982-11-22 |
| GB1515945A (en) | 1978-06-28 |
| DE2631468A1 (en) | 1977-02-03 |
| JPS5212228A (en) | 1977-01-29 |
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