CH635854A5 - Bitumen-containing mixture, in particular for the preparation of bitumen compositions in which the bitumen is chemically bonded to polymers - Google Patents

Description

The invention accordingly relates both to the mixture defined in claim 1 and to the use of the same defined in claim 7.

The functional groups can be bound directly or indirectly to the modified bitumen and the polymer (1) or (2). “Indirect binding” is understood to mean that the functional radicals are bound to the bitumen or the polymer via an inserted divalent radical, such as an optionally substituted methylene, ethylene or phenylene group.

Suitable derivatives of the aforementioned carboxylic acid and / or carboxylic anhydride residues of bitumen and the polymer (1) are esters, lactones, acid chlorides, imides and amides. These derivatives can by separately reacting the modified bitumen and the polymer (1) and

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subsequent mixing or by reacting the mixture of the modified bitumen and the polymer (1) with the corresponding monovalent organic compound or, if it is acid chlorides, with the corresponding phosphorus or thionyl chloride. In certain cases, e.g. for the production of imide derivatives, it may be desirable to produce the bitumen and polymer (1) derivatives directly. If it is intended to use the mixture for the preparation of compositions in which the bitumen is chemically bound to a polymer, preference is given to those derivatives which are used directly with at least divalent organic compounds to give (thio) esters, amides or imides, e.g. by reaction with diepoxides, diamines and diols. In addition, those derivatives can be used which form carboxylic acid groups by hydrolysis or saponification, such as the acid halides or the esters.

Carboxylic acid anhydride and / or carboxylic acid groups are preferably attached in the modification of the bitumen and the preparation of the polymer (1).

If the mixture is to be used for the aforementioned method for connecting the bitumen to the polymer (2), functional groups of the polymer (2) which differ from the functional groups of the bitumen are those groups which correspond to the functional groups of the modified bitumen to (thio) esters, amides or imides.

The aforementioned modified bitumen is made from bituminous components, such as from naturally occurring materials, e.g. Gilsonite, but preferably made from mineral oil. Examples of suitable bitumens include: distillation or “SR” bitumens,

which is usually used in the fractional distillation of the lower boiling components of e.g. Residues obtained from petroleum and crude oils; Precipitation bitmina obtained in the solvent extraction of certain high-boiling fractions, which is usually carried out with propane; blown bitumens, which when blowing air e.g. Distillation bitumens have been obtained; and crack bitumens obtained as residues in cracking processes, such as the pitches formed as a by-product of atmospheric thermal cracking suitable distillate feedstocks such as mineral spirits or gas oils. Blends of suitable bitumens with one another and / or with solvents or diluents (“blended bitumens”) can also be used. Distillation bitumens with a penetration of 20 to 500 at 25 ° C (in Vio mm) and e.g. from 80 to 100. Also suitable are bitumens that have been blown, liquefied again and blown again (fully or double-blown bitumens).

The modified bitumen is preferably produced by reacting a bitumen with an olefinically unsaturated anhydride, although in certain cases an olefinically unsaturated acid and in particular an olefinically unsaturated dicarboxylic acid can also be used. Maleic acid is particularly suitable for this purpose, but also an imide derivative of maleic acid, such as N-phenylmaleinimide. The modified bitumens are preferably produced by means of the so-called "maleinization", i.e. by reacting with maleic anhydride, which is likely to form a bond between an a-carbon atom of the obtained succinic anhydride group and the bitumen. The maleinization can be carried out by means of the known methods, such as by heating with maleic anhydride to temperatures of 100 to 200 ° C. with stirring. The maleic anhydride is suitably used in amounts of 0.5 to 10 percent by weight, based on the weight of the bitumen. Accordingly, only a small part of the bitumen is modified. The residues are probably present in the product as anhydride residues, although a certain part can also be present as carboxylic acid residues. The amount of residues present as carboxylic acid residues can be increased by adding water to the product or by contacting with water vapor contained in the atmosphere.

The above-described polymer (1) is preferably made of an olefinically unsaturated elastomeric material with a suitable molecular weight of e.g. 100,000 to 500,000 and in particular made of a rubber, such as a natural rubber or a synthetic rubber or a rubber-like polymer or (mixed) polymer. Graft (mixed) polymers can of course also be used as the starting material. In particular, the following polymers and copolymers are mentioned as starting materials: natural rubber (NK), styrene-butadiene rubber (SBK), block copolymers, such as styrene-butadiene-styrene rubber, isoprene rubber (IK), butyl rubber (IIK), butadiene rubber (BK) Nitrile rubber (NBK), polyurethane rubber, chloroprene rubber, ethylene-propene rubber (EPDM), such as the ter-polymers with dicyclopentadiene, and mixtures of two or more (mixed) polymers. A polymer component which is particularly suitable as a starting material is SBK, a copolymer comprising styrene and butadiene in a molar ratio of approximately 1: 3 to 1: 6 and having a molecular weight of 100,000 to 500,000, such as “Cari-flex S 1712” or “Cariflex S 1500 ».

The aforementioned polymer (1) can be produced in the same way as the above-described bitumen. Maleic acid is suitably used in amounts of 0.5 to 10 percent by weight, based on the weight of the unmodified (mixed) polymer. Accordingly, only a small part of the aforementioned (copolymer) is modified here. In addition, other processes can be used to produce the modified polymer (1). For example, the polymerization of conjugated dienes, such as butadiene, using an alkyl lithium initiator leads to a polydiene with terminal lithium atoms, which can be converted into the corresponding dicarboxylic acids by subsequent carboxylation.Another suitable method is the copolymerization of a suitable monomer with an unsaturated carboxylic acid or an unsaturated ester, such as (meth) acrylic acid or an ester of this acid, or with an unsaturated cyclic carboxylic acid anhydride, such as maleic anhydride, which is followed, if necessary, by hydrolysis. The introduction of the carboxyl groups can also be carried out by reaction with a mercaptocarboxylic acid, such as with mercaptoacetic acid.

The aforementioned modified bitumen and the aforementioned polymer (1) can simply be mixed with one another in order to produce the mixture according to the invention. However, this mixture is preferably produced by mixing an unmodified bitumen with an unmodified olefinically unsaturated copolymer and reacting the mixture with maleic anhydride. The reaction is conveniently carried out at temperatures of 100 to 200 ° C. The maleic acid is suitably used in amounts of 0.5 to 10 percent by weight, based on the weight of the unmodified bitumen plus the unmodified (mixed) polymer.

As the aforementioned polymer (2) can be prepared from the same unmodified (mixed) polymer from which the polymer (1) was produced, but which

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Modification shows that at least two functional residues, which, however, are not carboxylic acid groups, carboxylic acid anhydride groups or derivatives of these groups, are preferably attached directly to the main chain of the (mixed) polymer. The polymer (2) contains as functional residues e.g. Hydroxyl, mercapto, amino and N-hydrocarbon amino, epoxyalkyl and isocyanate groups and preferably hydroxyl groups. These functional groups are also recommended to have a terminal position in the polymer. Favorable results are obtained with rubber materials with molecular weights of approximately 1000 to 5000.

The polymer (2) can be formally e.g. derive from a thermoplastic material and in particular from an elastomer of the group already described above, such as a butadiene rubber. Suitable modified polymers are e.g. Dihydroxypolybutadienes, which are readily obtained by polymerizing butadiene in the presence of an initiator such as alkyl lithium and then replacing the terminal lithium atoms with hydroxyl groups, e.g. by treating with ethylene oxide or formaldehyde. A particularly suitable dihydroxy polybutadiene is the commercially available «Nisso PBG 2000». Other suitable starting materials are e.g. Polyurethane rubber materials e.g. can be prepared from methylene di-phenyl diisocyanate and a polyalkylene glycol.

The proportion of carboxyl groups and / or carboxylic anhydride groups and / or the derivatives of these groups in the mixture containing the modified bitumen and the polymer (1) can vary considerably, but preferably corresponds to an acid number determined by titration of 0.01 to 2 milliequivalents per gram, in particular from 0.1 to 0.5 milliequivalents per gram and most preferably from 0.1 to 0.35 milliequivalents per gram. Mixtures having acid numbers within the abovementioned range are particularly suitable for use in the process described below for the production of bituminous compositions in which the bitumen is chemically bound to a (mixed) polymer. The mixtures can also have higher acid numbers, but are then preferably diluted with unmodified bitumen or other diluents before they are used as the starting material for the aforementioned process.

The mixtures can contain different amounts of polymer (1) and / or polymer (2), but with the proviso that the mixtures contain at most 20 percent by weight of polymer (2). These mixed materials are particularly important as bituminous mixed materials, i.e. as mixed materials, the total bitumen component (modified or unmodified) of which contains the greater part of e.g. represents more than 80 percent by weight of the mixed material. Preferably at most 10 percent by weight of polymer (1) or (2), in particular 0.1 to 7 percent by weight and most preferably 1.0 to 5 percent by weight, are used. Mixing materials with polymer contents within the abovementioned ranges are particularly suitable for use in the process described below for the production of bituminous compositions in which the bitumen is chemically bound to a polymer. It is also possible to use mixed materials with a higher polymer content, but these are diluted with unmodified and / or modified bitumen before they are used in the aforementioned processes.

As such, the mixture according to the invention can be used for special applications, in particular if it contains the polymer (1) component, in the form of a cationic emulsion in water which contains a cationic emulsifier.

agents such as "Dinoram S" or "Stabiram EM" and preferably contain mineral acids such as hydrochloric acid. Suitable aqueous emulsions contain from 100 to 300 percent by weight of the mixed material according to the invention, from 0.1 to 3.0 percent by weight and preferably from 0.5 to 2.5 percent by weight of the cationic emulsifier and from 0.05 to 2.0 percent by weight and preferably from 0 , 1 to 1.0 weight percent mineral acid, with all weight percentages based on the weight of the water in the emulsion.

An amount of bitumen is preferably used to produce the mixture according to the invention such that no subsequent dilution of the mixture with additional amounts of unmodified bitumens is required.

The mixture according to the invention has good rheological properties or, if it is present as a cationic emulsion, can be used to produce products with good theological properties. However, it has been found that the components of the mixture according to the invention can be chemically bonded to one another, whereby products with excellent theological properties are obtained, in particular if the amount of polymer (1) or (2) in the product produced in this way does not exceed 10% by weight. The products obtained have excellent properties, such as greater viscosity and hardness and in particular greater elasticity, tensile strength and elongation at break than the corresponding physical mixtures of the unmodified components or as a normal bitumen. The chemically bound products are perfectly compatible with unmodified bitumen, in which they obviously dissolve into a homogeneous system. These products also adhere very well to glass and concrete.

The products having a chemical bond between their components are also advantageous from an economic point of view. The chemical bond can in most cases be considered formally as the result of the reactions of carboxylic acid residues.

The new chemically bound products can be conveniently divided into types A, B and C. A bitumen mass usually consists only of a small proportion of the chemically bound product. As explained above, the chemically bound product is preferably prepared from mixtures which contain the carboxyl and / or acid anhydride groups and / or their derivatives in an amount which corresponds to an acid number of 0.01 to 2 milliequivalents per gram. Accordingly, the finished product contains, in addition to the chemically bound product, a larger proportion of unmodified bitumen. However, it may be desirable to produce a chemically bound product from a mixture with a very high acid number, resulting in a product in which virtually all of the bitumen and all of the polymer are chemically bound to one another. Such completely chemically bound products can be added to unmodified bitumen. The coupling reaction between the bitumen and the polymer can also be carried out in solvents, such as a hydrocarbon or a chlorinated hydrocarbon solvent, such as dichloromethane.

Preferred chemically bound products have the type A ionic structure. They can be described in a simple manner as derivatives produced on the one hand from a bitumen with attached carboxyl groups and on the other hand from a polymer also containing carboxyl groups, which are chemically linked to one another via metal ions originating from a suitable metal compound

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have been bound. The mixture to which the metal compound is added either already has the carboxyl groups or the carboxyl groups are e.g. formed by hydrolysis of an anhydride or acid chloride group or by saponification of mixtures containing ester groups derived from carboxyl groups. The chemical compound may form ionic aggregates or cluster ions comparable to the ionic mycelles found in certain metal soaps dispersed in non-polar media.

Another preferred group of chemically bonded products (type B) differs from the aforementioned group in that the chemical bond is not produced via metal ions, but via an at least divalent organic radical, which can be imagined from an organic compound, which has two or more functional radicals which form ester, thioester, amide or imide bonds with carboxyl and / or carboxylic anhydride groups and / or their derivatives.

In a third preferred group of chemically bound products (type C), the connection between the modified bitumen and the polymer is not established via a bridge made of a metal or an organic residue, rather the polymer (2) as such contains functional groups which are associated with form the functional groups of the bitumen (thio) ester, amide or imide bonds.

The chemically bound products of type A can contain a large variety of metals as metal ions. Metals suitable as metal ions are iron, chromium, manganese and metals from groups I to IV of the Periodic Table of the Elements and in particular the metals from subgroups Ia to IVa, such as lithium, sodium, potassium, calcium, magnesium, barium, aluminum and lead. These products preferably contain lithium, sodium, potassium, calcium, magnesium, barium, aluminum, iron, chromium and manganese ions. The valency of the metal ions in question generally affects the thermoplastic properties of the materials produced. Thus, when using metal ions with a higher valency, products are obtained whose elasticity only disappears at higher temperatures than when producing products using metal ions with a lower valence. This temperature is e.g. 130 ° C and can be higher than 175 ° C when using aluminum ions. When it cools down again, the original elasticity is restored. The thermal reversibility of the elasticity of the products chemically bonded via ionic bonds is a valuable property for many applications.

If the chemically bound products are made from non-emulsified mixtures, a simple metal compound is used. Suitable metal compounds in this case are the oxides, hydroxides, alkoxides or the salts of relatively weak acids, generally those with a pK value above about 4.2 at 25 ° C., such as acetates, of the aforementioned metals. Suitable coupling agents are e.g. the hydroxides of lithium, sodium, potassium and barium, lead (II) acetate, magnesium acetate, aluminum isopropoxide and aluminum sec-butoxide. Mixtures of two or more coupling agents can also be used if desired. The coupling agents are preferably used in aqueous solution or in the liquid state prevailing under reaction conditions, such as aluminum isopropoxide or sec-butoxide.

The coupling reaction leading to type A products is generally carried out by heating a mixture of the starting material with the coupling agent to temperatures from 100 to 200 ° C and preferably from 160 to 190 ° C until the by-products such as water, alcohol or acetic acid are virtually completely removed , carried out by evaporation. As the reaction progresses, the reaction mixture becomes increasingly viscous and rubber-like. It is therefore generally advisable to adjust the temperature to the viscosity by e.g. assumes a temperature of about 120 ° C and this temperature increases to about 175 ° C in the course of the reaction. The coupling agent is usually added in an amount of 25 to 500 percent by weight of the amount stoichiometrically required for the neutralization reaction. Preferably 50 to 300 percent by weight and in particular 75 to 200 percent by weight of the stoichiometrically required amount of coupling agent is used.

In the manufacture of type A chemically bound bitumen polymer products and mixtures containing these products, it is often convenient to use the starting material, i.e. to use the mixture according to the invention of a modified bitumen and a polymer (1) in the form of the above-described cationic emulsion in water. In such emulsions, the coupling reaction can be carried out by means of metal ions present in metal complex compounds, such as mineral aggregates and / or mineral fillers.

Examples of mineral aggregates suitable for this purpose are gravel, granite, coarse sand, basalt, porphyry, dolomite, slags, calcined bauxite and limestone, which is also a particularly suitable filling material. In general, mineral aggregates can be described as particles that do not pass through a 75 micron mesh screen, while fillers are materials with a particle size through a 75 micron mesh screen. All aggregates and fillers can be used, from which sufficient amounts of metal ions are leached out when they come into contact with the abovementioned emulsions to form ionic structures. Which metal ions are leached depends on the chemical structure of the aggregate and / or the filler, but practically all metal ions and in particular potassium, sodium, calcium, magnesium *, iron, chromium and manganese ions are suitable. In general, all aggregates and / or fillers, which are added when e.g. 100 g demineralized water to e.g. 10 to 150 g aggregate or filler lead to a pH of at least 7 and preferably at least 8 or 9. These further metal compounds can be used as the only metal compounds providing the metal ions or together with one or more of the simple metal compounds described above. However, they are also suitable for sole use.

The aforementioned cationic aqueous emulsions are e.g. after application of a surface layer of mineral aggregate sprayed onto a road surface or, in certain circumstances, are previously mixed into the aggregate and the mixture obtained is applied to the road surface. In general, the aqueous emulsion and filler are mixed together before use.

The chemically bound products of type B contain difunctional or higher functional units with an ester, thioester, amide or imide structure, such as -CO-X-R'-X-OC-, in which the CO groups are attached to the bitumen or the polymer is bonded, X represents oxygen, sulfur or nitrogen atoms and in which the radical R 'generally contains at most 25 carbon atoms. The carbon atoms can e.g. in s

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an optionally branched and / or substituted chain, which may contain heteroatoms and / or cyclic structures. The free valences of the nitrogen atom (if X = N-) can e.g. combine with hydrogen or a hydrocarbon residue or with another CO group (e.g. that of a succinimide structure).

Such structures are obtained from organic compounds with at least two functional residues which react with the functional residues attached to the modified bitumen and the polymer (1) to form ester, thioester, amide or imide bonds. Suitable functional radicals are the hydroxides, mercapto, amino and N-hydrocarbonamino, the epoxy, such as an epoxyalkyl, and the isocyanate groups. Although the compounds in question generally contain the same functional groups, they can, if desired, have two or more different functional groups. In general, the compounds in question contain at most 25 carbon atoms in the molecule. The carbon atoms are e.g. in an optionally branched and / or substituted chain, which may contain heteroatoms and / or cyclic structures.

Examples of suitable coupling agents are accordingly e.g. Ethylene glycol, diethylene glycol, 1,4-butanediol, glycerol, 1,1,1-tris (hydroxymethyl) propane, diglycidyl ether of bisphenol A, methylene diphenyl 4,4'-diisocyanate, tolylene diisocyanate, diethylene triamine, tetraethylene pentamine and diethanolamine.

The coupling reaction is usually carried out according to the generally known methods for the production of e.g. (Thio) esters, amides and imides are carried out from compounds with suitable functional groups. Accordingly, diethylenetriamine is conveniently reacted in a practically stoichiometric amount at about 160 to 180 ° C.

According to a further embodiment of the present invention, chemically bound products of type C are produced. In this case, the polymer (2) itself carries the functional residues - at least two residues per polymer - which are necessary for binding to the corresponding functional residue of the modified bitumen. In this case, no special coupling agent is required in these reactions, which form (thio) ester, amide or imide structures. The components are preferably connected to one another via ester bonds.

The coupling reaction is usually carried out in the manner described above for the preparation of the type B product, e.g. by heating the polymer (2) with a practically stoichiometric amount of modified bitumen in the presence of a basic catalyst, preferably a tertiary nitrogen base, such as tri-n-butylamine, to temperatures of 120 to 160 ° C.

The chemically bound products can expediently be in the form of an anionic emulsion. Such emulsions are formed when the mixtures containing the modified bitumen and the polymer (1) are mixed with water containing anionic emulsifiers, such as metal salts of weak acids and metal hydroxides. Anionic emulsifiers which can be mentioned are, for example, the alkali metal salts of weak acids, such as the sodium salts of oleic and lauric acid, and the alkali metal hydroxides, such as sodium hydroxide. A mixture of a weak acid salt and a metal hydroxide is suitably used. Since the aforementioned metal compounds bring about the coupling reaction for producing the chemically bound products according to the invention, a product containing chemically bound products is obtained, and it has surprisingly been found that the aforementioned aqueous anionic emulsions are stable.

The bitumen compositions containing the chemically bound bitumen polymer product (types A, B and C) and this product, if necessary with the usual auxiliaries such as fillers, sand and stones (which can play a role in the coupling reaction), are extremely suitable for a large number of applications . The aforementioned products are particularly suitable for the production of load-bearing ceilings, e.g. in road construction, for hydraulic engineering and erosion control, for buildings and for industrial applications, e.g. for the production of roofs, floor coverings, briquettes, mastrix materials and for the protection of conduits against corrosion.

The examples illustrate the invention.

The penetration values given in the examples relate to penetration at 25 ° C (0.1 mm) according to ASTM D5, the softening point to the ring and ball softening point in ° C according to ASTM D36 and the viscosity to the viscosity at 150 ° C in Poise.

Examples 1-6

In these examples, the rubber used is either (1) an oil-extended styrene-butadiene rubber with a molecular weight of 400,000, which contains 23 percent by weight of bonded styrene and 37.5 parts by weight (100 parts by weight) of oil (“Carifiex S 1712”), or (2) a styrene-butadiene rubber with a molecular weight of 200,000 and containing 23 percent by weight of bound styrene (“Cariflex S 1500”) is used as a 13.5 percent by weight solution in toluene.

In the examples below, the bitumen used is (1) Lagunillas bitumen (ASTM penetration 80 to 100), or (2) Kuwait bitumen (ASTM penetration 200) or (3) semi-blown Kuwait bitumen (ASTM penetration) 80 to 100) is used. Bitumens (1) and (2) represent distillation bitumens.

The rubber (1) or the rubber solution (2) cut into pieces of approximately 0.5 to 1.0 gram are mixed all at once while stirring with the bitumen having a temperature of approximately 160 ° C. in a wide-necked round bottom flask. The dispersion of the rubber is brought about by continuous stirring at this temperature over the course of about 2 hours.

The bitumen-rubber mixture obtained or a part of this mixture is then heated to 175 ° C., then maleic anhydride (MA) is added and the mixture is kept at 170 to 180 ° C. for 2 hours with continuous stirring and the opening of the reaction flask is closed with an aluminum foil .

The acid numbers of the product produced are determined by titration. The types of the starting material, the amounts used and the acid numbers determined are summarized in Table I.

Some properties of some products are summarized in Table III at the end of Example 13. For reasons of comparison, two mixtures of bitumen (2) and rubber (1) are produced.

The first mixture contains 100 parts by weight of bitumen (2) and 2.7 parts by weight of rubber (1); the mixture has a penetration of 66 and a softening point of 55. The second mixture contains 100 parts by weight of bitumen (2) and 5.4 parts by weight of rubber (1); the mixture has a penetration of 71 and a softening point of 54.

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Table I

635 854

Example] Rubber Quantity of rubber g

bitumen

Amount of bitumen

Gew.-® / «rubber, based on the weight d. Bitumen

Maleic acid wt. C

amount of anhydride g

Maleic anhydride based on weight of

Rubber + bitumen

Acid number of the product, mequ / g

1

1

13.5

1

490

2.7

2.56

2.0

0.14

2nd

2nd

52.5

1

354

2.0

7.2

2.0

0.14

3rd

1

13.5

1

490

2.7

3.84

3.0

0.24

4th

1

13.5

2nd

490

2.7

3.84

3.0

0.15

5

1

26.7

2nd

660

4.0

19.8

3.0

0.25

6

2nd

52.5

3rd

354

2.0

5.4

1.5

0.17

Examples 7 to 12

(a) Kneading 2.5 kg of "Cariflex S 1500" (see Examples 1 to 6) in a Z-blade kneader and then adding 5 kg of bitumen (1) (see Examples 1 to 6) and continuous kneading with cooling until a homogeneous mass is produced, a bitumen-rubber base mixture is produced.

(b) Part of the base mixture produced is cut into pieces of approximately 5 g and dissolved in one of the bitumens mentioned below with stirring for two hours with a paddle mixer at 160 to 180 ° C.

(4) Kuwait bitumen (ASTM penetration 200)

(5) Kuwait bitumen (ASTM penetration 300)

(6) Fully Blown Kuwait Bitumen (ASTM Penetration 25, ASTM Softening Point 85)

(7) Bitumen obtained by mixing 5 parts by weight 20 parts of heavy Iranian vacuum residue (ASTM penetration 500 to 600) with 1 part by weight of light Iranian propane bitumen (ASTM penetration of 300).

(c) The solution obtained under (b) is then reacted with maleic anhydride with stirring at 175 ° C. 2s The product from Example 9 is liquefied with 50% by weight of a Brightstock furfural extract.

The acid numbers of the products produced are determined by titration.

The bitumen types, the amounts of starting material used and the acid numbers are summarized in Table II.

Some properties of some maleated products are shown at the end of Example 13 in Table III.

Table II

Example of basic bitumen mixed amount, mixed amount, g added g bitumen type

% By weight maleic acid acid-in product b, hydride-based on quantity. Weight g d. Bitumen

% By weight

Maleic acid

anhydride,

related to

weight of

Rubber plus

bitumen

Acid number of the product, mequ / g

7

60

4th

960

2nd

20.4

2nd

0.18

8th

60

5

960

2nd

10.2

1

0.14

9

35

6

530

2nd

5.6

1

0.12

10th

150

7

850

5

30th

3rd

0.31

11

60

5

960

2nd

20.4

2nd

0.21

12

120

7

920

4th

20.8

2nd

0.20

Example 13

(a) A mixture containing an equal amount of “Cariflex S 1500” (cf. Examples 1 to 6) and lagunillas bitumen (ASTM penetration 80 to 100) is obtained by kneading the rubber in a water-cooled two-roll mill, slowly adding the bitumen and kneading until a homogeneous mass is formed.

(b) 400 g of this mixture is cut into 5 g pieces and in 10.2 kg Kuwait bitumen (ASTM penetration 300) by stirring for four hours in a high shear Silberson mixer at 160 ° C

dissolved and thereby produced a solution containing 2% by weight of rubber in the bitumen. This solution is reacted with 200 g of maleic anhydride (2 percent by weight, based on the weight of rubber plus bitumen) for 2 hours at 175 ° C. with stirring using a paddle mixer.

The acid number of the maleinized product obtained by titration is 0.28 milliequivalents per gram.

Some properties of the maleated product are shown in Table III below.

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Table III

example

penetration

Softening point

Viscosity at 150 ° C,

No.

poise

1

59

57

6.6

3rd

50

62

8.0

6

52.5 '

59

-

7

120

46

3.2

9

98

55

-

11

201

40

2.4

13

203

41.5

-

Example 14

A cationic emulsion of the maleinized product prepared according to Example 8 is prepared by mixing 650 g of this product, 2.6 g of "Dinoram-S" emulsifier (an N-alkylpropylenediamine) and 0.9 g of hydrochloric acid with 350 g of water.

Example 15

A cationic emulsion of the maleinized product prepared according to Example 8 is prepared by mixing 650 g of the aforementioned product, 2.6 g of "Stabiram EM" emulsifier and 1.75 g of hydrochloric acid with 350 g of water.

Example 16

A cationic emulsion of the maleinized product prepared according to Example 8 is prepared by mixing 600 g of the aforementioned product, 3.0 g of "Stabiram-EM" emulsifier and 3.0 g of hydrochloric acid with 400 g of water.

Examples 17 to 25

Coupling reaction using alkali metal hydroxides Various maleinized products prepared in the previous examples are heated to 120 ° C and the stoichiometric amounts of alkali metal hydroxides dissolved in water (e.g. 3 ml) are added with vigorous stirring. Within about a minute, the viscosities of the 15 mixtures increase and the temperature is then raised to 160 to 180 ° C, held at this level for half an hour to 2 hours to remove the water by evaporation, and stirring is continued at a slower rate. After cooling to room temperature, 20 chemically bound products with rubber-elastic properties, such as a large elongation at break, are obtained. The rubber-elastic properties decrease when heated e.g. to temperatures above 130 ° C and obviously disappear completely in the product produced according to Example 17. In all cases, the rubber-elastic properties return on cooling.

The type of alkali metal hydroxide used, its amount and some properties of the chemically bound products are shown in Table IV.

Table IV

Example of maleated product used (example no.)

Coupling- coupling agent medium amount, parts by weight per part of product

Penetration softening viscosity point, ° C at 150 ° C, poise

17th

1

NaOH

0.55

40

72

15

18th

2nd

NaOH

0.55

-

-

-

19th

3rd

NaOH

0.9

47

72

22

20th

9

NaOH

0.55

-

108

-

21st

6

NaOH

0.55

-

86

22

3rd

LiOH

0.8

43

75

25th

23

3rd

KOH

1.8

40

87

21st

24th

6

KOH

1.8

-

88

-

25th

9

KOH

1.8

-

116

-

Examples 26 to 28

These examples illustrate the coupling reactions with alkali metal compounds and the preparation of the chemically bound products in the form of anionic aqueous emulsions.

Anionic aqueous emulsions of the chemically bound products are prepared from the maleinized products of Examples 11 and 12. The following amounts of components are used:

(a) 600 g of the maleinized product from Example 11 and 400 g of water containing 0.2% by weight sodium laurate and 0.5% by weight sodium hydroxide (Example 26);

(b) 550 g of the maleinized product from Example 11 and 450 g of water containing 0.5 percent by weight sodium laurate and 0.3 percent by weight sodium hydroxide (Example 27);

(c) 500 g of the maleinized product from Example 12 and 500 g of water containing 0.5 percent by weight sodium oleate and 0.5 percent by weight sodium hydroxide (Example 28).

In all examples, a stable emulsion of the chemically bound products is obtained, which has a high viscosity in Examples 26 and 27. The fact that these are chemically bound products is shown by separating a sample of the product from Example 28 by 55 evaporation. The product has a high strength, exceptional rubber elasticity and practically the same properties as the chemically bound products produced in the preceding examples.

60

Examples 29 to 34 coupling reaction using Ba (OH) 2 • 8H2O

The coupling reaction is carried out in the manner described in Example 17 65 and the stoichiometrically required amount of Ba (OH) 2 • 8H2O is dispersed in 200 g of the maleinized product at 120 ° C. with vigorous stirring and the stirring for a further 2 hours at 175 ° C.

635 854

continued. It is not necessary to dissolve the barium hydroxide in water.

In Example 33, the chemically bound product is transferred to a Z-blade mixer after heating for two hours at 175 ° C. and kneaded at 175 ° C. for 3 hours.

The chemically bound product has the same rubber-elastic properties as the chemically bound product of Example 17, but has a considerably greater tensile strength. The rubber-elastic properties partially disappear when heated to 175 ° C, but are retained again after cooling. The rubber-elastic properties of the chemically bound product from Example 33 at 175 ° C. exceed those of the other chemically bound products.

The amounts of coupling agent used and some properties of the chemically bound products are summarized in Table V.

Table V

Example used maleinized product (example)

Amount of coupling agent, parts by weight per 100 parts by weight of product

penetration

Softening point, ° C

Viscosity at 150 ° C, poise

29

30th

31

32

33

34

1

3rd

4th

5

6 9

2.2 3.4 2.2 4.2 2.2 2.2

37 36 165 118

90 104 46 67 97 117

30 44 6.5

Example 35

Coupling reaction with aluminum sec-butoxide

The coupling reaction is carried out in the manner described in Example 17 and the stoichiometric amount, namely 20 g (1.1 parts by weight) of Al- (0-sec.-C4H9) 3, is introduced into the maleinized product at 175 ° C. Stirring is then continued at 175 ° C for one hour.

The rubber-elastic properties of the chemically bound product obtained at room temperature practically correspond to those of the product from Example 29, but they do not completely disappear at 175 ° C. The chemically bound product has a penetration of 35, a softening point of 73 and a viscosity of 11 poise at 150 ° C.

Examples 36 to 38 below illustrate the use of mineral aggregates for the chemical bonding of maleinized products.

Example 36

(a) 13 g samples of the cationic emulsion prepared according to Example 14 are poured into bowls with a diameter of 14 cm and covered with 100 g of gravel with the following properties: particle size 2.0 to

3.4 mm, pH 9.3 (100 g gravel per 100 g water).

The contents of the dishes are washed at intervals of one hour with an aqueous solution containing 0.5% by weight of «Dinoram-S» and the mineral aggregate is turned over with a spatula to reveal any undamaged emulsion underneath the stones. The material is washed further until a clear wash water is obtained. The contents of the dishes are finally washed with distilled water and then with acetone and then dried to constant weight. The percentage of bitumen deposited is then determined based on the weight of the bitumen contained in the emulsion. It was found that the bitumen is 100 percent separated from the emulsion after only 2 hours and that the bitumen obtained has good elastic properties.

(b) The experiment is repeated using a conventional cationic bitumen emulsion with the same continuous phase as in the above emulsion. It was found that after 2 hours, only less than 15 percent by weight of what was present in this emulsion

25 existing bitumen are deposited and that the deposited bitumen has poor elastic properties.

Example 37

(a) Example 35 is repeated using 13 g samples 30 of the cationic emulsion prepared according to Example 15 and an aqueous solution containing 0.5% by weight of “Stabiram-EM” as washing liquid. After 5 hours, a 65 weight percent deposition of a bitumen with good elastic properties is obtained. 35 (b) A conventional cationic emulsion containing the same continuous phase as the above emulsion results in less than 10 weight percent deposition of the bitumen with poor elastic properties after 5 hours.

40

Example 38

A 100 g sample of the emulsion prepared according to Example 16 is mixed with 25 g of limestone filling material with a pH in demineralized water (100 g limestone filling material per 100 g of water) from 8 to 9 and from time to time Stir time by hand until stirring becomes impossible after approximately 30 minutes due to breakage of the emulsion. After an hour, the precipitated material is washed with water. It is then dried by dissolving it in toluene and distilling off the water azeotropically. After all the water has been removed, the toluene is distilled off in vacuo. The properties of the material obtained are listed in Table VI under (A). For reasons of comparison, the properties of the maleated ss bitumen-rubber mixture before the emulsification are given under (B). Also for reasons of comparison, a 60 g sample of the maleinized bitumen-rubber mixture is mixed with 25 g dry limestone filling material at 90 ° C. The softening point of this mixture is given in the table below under (C). A comparison of these values shows that mixing the emulsion with limestone filler leads to a product with a softening point (A) higher than that caused by the purely physical presence of the filler (C). This shows that in the first case a coupling reaction has taken place, which does not take place when dry limestone filling material is mixed with the non-emulsified maleated bitumen-rubber mixture.

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Table VI

example

Penetration at 25 ° C (0.1 mm)

Softening point, ring and

No.

Sphere, ° C

A

129

49.5

B

180

41.5

C.

-

45

Examples 39 to 46 illustrate the use of organic compounds for chemical bonding of the maleinized products.

Example 39

Carrying out the coupling reaction with diethylenetriamine

In the manner described in Example 17, 0.35 ml (0.5 part by weight) of diethylenetriamine is added to 73 g of the maleinized product with vigorous stirring at 170.degree. The reaction proceeds with the formation of water, the reaction mixture becomes more viscous in the course of the reaction and changes into a product with rubber-elastic properties. Stirring is continued at 175 ° C for one hour.

The tensile strength of the chemically bound product obtained at room temperature is slightly below the tensile strength of the chemically bound products from Examples 19, 30 and 35. The rubber elasticity at 175 ° C., on the other hand, is considerably lower. The chemically bound product has a penetration of 43, a softening point of 62 ° C and a viscosity at 150 ° C of 8 poise.

Examples 40 to 46 The maleinized product obtained according to Example 10 is chemically bound using the coupling agents described in Table VII. The coupling reaction is carried out at 140 ° C using the stoichiometric amounts of coupling agent. The progressive reaction is assessed by stirring by hand and the time until a noticeable increase in viscosity (gelation time) occurs.

The chemically bonded products have good strength and rubber-elastic properties after cooling to room temperature. «Epicote 828» has a stronger effect than the other coupling agents. The gel time of the chemically bound products is shown in Table VII.

Table VII

Example No.

Coupling agent

Gel time, min.

40

«Epicote 828» *

10th

41

Diethanolamine

10th

42

Triethanolamine

10th

43

1,1,1 -T ris- (hydroxy-

20th

methyl) propane

44

Glycol

35

45

Ethylene glycol

40

46

Diethylene glycol

40

* Diglycidyl ether of bisphenol-A

Example 4 7

Preparation of a mixture of a maleinized bitumen and a polymer with terminal hydroxyl groups:

(a) A maleinized bitumen is prepared by adding 4 g of maleic anhydride to 200 g of Lagunillas bitumen (ASTM penetration 80 to 100) at 175 ° C. and then stirring for three hours at the aforementioned temperature.

(b) 10 g of a dihydroxypolybutadiene with terminal hydroxyl groups (“Nisso PBBR2000”) are then mixed in with stirring at 140 ° C.

Example 48

After 15 minutes, 0.5 mol of tributylamine is added to the mixture obtained in Example 47 with stirring. Stirring is continued at 140 ° C for one hour to obtain a chemically bound product. A comparison of the penetration and the softening point before and after the addition of the catalyst shows that a coupling reaction has taken place:

Penetration before catalyst addition: 67 Penetration after catalyst addition: 55 Softening point before catalyst addition: 47 Softening point after catalyst addition: 56

10th

5

10th

15

20th

25th

30th

35

40

45

ß

Claims (14)

635854 1. Mixture containing bitumen, of which at least a part of chemically modified bitumen is modified with functional groups from the class carboxyl and acid derivatives of carboxyl, and a) a polymer (1), of which at least part also functional groups from the class carboxyl and Has acid derivatives of carboxyl, and / or b) a polymer (2) which has at least two functional groups, which groups do not belong to the carboxyl and acid derivatives of carboxyl class and which have ester, thioester, amide and functional groups of the modified bitumen or can form imide bonds, the proportion of polymer (2) being at most 20 percent by weight, based on the total weight of bitumen, polymer (2) and, if present, polymer (1). 2. Mixture according to claim 1, characterized in that it contains a polymer (1) in admixture with the bitumen component and that these two components together have an acid number of 0.01 to 2.0 milliequivalents per gram. 2nd PATENT CLAIMS 3. Mixture according to claim 1, characterized in that it contains a chemically modified styrene-butadiene rubber as a polymer (1). 4. Mixture according to claim 1, characterized in that it contains a dihydroxypolybutadiene as the polymer (2). 5. Mixture according to claim 1, characterized in that it is in the form of an aqueous cationic emulsion. 6. A method for producing a mixture according to claim 1, containing the polymer (1), characterized in that a mixture of a bitumen and an olefinically unsaturated polymer is maleinized. 7. Use of the mixture according to claim 1 for the production of bitumen compositions in which the polymer (s) is (are) chemically bound to the modified bitumen, the modified bitumen and the polymer (1), if present, by reaction with a metal compound which forms ionic groups with the said functional groups of the modified bitumen and the polymer (1) and / or an organic compound with at least two functional groups which with the said functional groups of the modified bitumen and the polymer (1) reacted to form ester, thioester, amide or imide bonds, and wherein the modified bitumen and the polymer (2), if present, are linked to form ester, thioester, amide or imide bonds. 8. Use according to claim 7, characterized in that a compound of metal from one of subgroups Ia to IVa of the periodic system of the elements is used as the metal compound for forming ionic groups. 9. Use according to claim 7, characterized in that the bitumen and the polymer (1) are used in the form of an aqueous cationic emulsion and the metal compound in the form of a mineral aggregate or a mineral filler. 10. Use according to claim 7, characterized in that a compound having at least two hydroxyl, epoxy or primary amine groups is used as the organic compound having at least two functional groups. 11. Use according to claim 7, characterized in that the metal compound or the organic compound is used in an amount of 75 to 200 percent by weight of the amount theoretically required for the chemical bonding of the components of the mixture. 12. Use according to claim 7, characterized in that a bitumen and a polymer (1) are reacted, to which carboxyl and / or carboxylic anhydride groups are bound as functional groups. 13. Use according to claim 7, characterized in that a bitumen with carboxyl and / or carboxylic anhydride groups and a polymer (2) with hydroxyl groups are reacted as functional groups. 14. Use according to claim 7, characterized in that the bitumen is reacted with the polymer (2) by means of heating in the presence of a basic catalyst. In order to reduce the cost of certain polymer products and / or to combine the valuable properties of the components in the manufactured product, various mixtures of a bitumen and a polymer material are produced. In this way it is often possible to produce modified materials with improved properties for the desired application. Accordingly, bitumen is added to certain polymers or copolymers, such as a styrene-butadiene rubber, on the one hand, thereby replacing part of the relatively expensive materials, which also gives the latter materials favorable hysteresis properties. On the other hand, small amounts of polymers and copolymers are mixed into bitumen in order, inter alia, to improve the rheological properties of the bitumen, which are of particular importance when the bitumen is used as a binder in road construction and in various industrial applications. In areas that have very high temperatures in summer and very low temperatures in winter, bitumen used in road construction must have both a sufficiently high resistance to plastic deformation at high temperatures and sufficient plasticity at low temperatures, which can be achieved by adding suitable additives can. Although the above-described physical mixtures of bitumens and (mixed) polymers lead to improved properties of the material for various purposes, it has now been found that this advantageous effect is generally considerably increased and, in addition, other desirable properties of the material can be achieved if the Components of a bitumen / polymer mixed material - at least in part - are both chemically modified and chemically bound to one another either directly or indirectly, in the latter case by adding a coupling agent.