DE2041513A1 - Bitumen composition and process for their production - Google Patents

Description

W. R. Grace & Co. (priority 22 August 19Ö9 -

^u - ^s -

62, Whittemore Avenue

Cambridge, Mass. / V.St.A. _Hamburgj ". _{Auguet mo}

Bitumen composition and process too their manufacture

The invention relates to bitumen compositions with a λ high proportion of rubber; The compositions can easily be prepared in simple devices by mixing a molten bitumen or a bitumen made liquid by the addition of an extender oil with a liquid polybutadiene having terminal halogen atoms and then adding an organic amine as a catalyst for chain extension and crosslinking at a suitable time.

With the invention, rubber-containing bitumen compositions are thus obtained which can be produced quickly at relatively low temperatures and with particularly simple devices; the mixing of the rubber with the bitumen can be carried out at any point. The compositions contain rubber and bitumen in proportions that were previously in

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were not available in practice; in addition, they have an adjustable viscosity. The compositions can be used as a road surface without the high temperatures required, as they normally are must be used when processing such compositions.

It has been found, surprisingly, that compositions of this type can be obtained if one first has a liquefied bitumen mixed with a liquid polybutadiene with terminal halogen atoms and then an organic amine is added, which catalyzes the vulcanization of the polybutadiene to a rubbery consistency. The catalyst-containing mixture can be cured without any further steps, or it can be applied to a substrate first apply and cure on the same.

The bitumen compositions according to the invention contain in addition to a bitumen, a liquid polybutadiene with terminal halogen atoms and an organic amine as Hardener or a reaction product of the polybutadiene and the organic amine.

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The advantages attributable to the use of these particular types of liquid rubbers are striking. First of all, mixing the ingredients can be easy and take place quickly, without the need for time-consuming and energy-wasting mastication and dispersion, such as they are traditionally required when adding rubber to bitumen * until the amine catalyst has taken effect (which can be fully controlled), If the compositions according to the invention have a relatively low viscosity, so that, for example, when foaming and gelling no special Difficulties arise. The mixing process can be further simplified by using the bitumen diluted with a non-volatile hydrocarbon oil so that the use of lower temperatures is sufficient. Control of the viscosity of the mixture can be achieved by stopping the addition of the catalyst partially or completely delayed until curing did- |

should actually take place. A further control with regard to the desired pot life can thereby be achieved achieve that nan selects a specific amine catalyst.

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2OA 1.51

The compositions can be used for various purposes, which heretofore for rubber-containing Bitumen compositions were out of the question. That this at all possible is due to the surprising tolerability recycle the liquid halogen-terminated polybutadiene with the bitumen; the compatibility is so good that the further polymerization of the low molecular weight rubber itself or for example as a complex with asphalt is not disturbed.

Suitable types of bitumen are native asphalt, pyrogenic asphalt and pitch of various origins, for example Trinidad asphalt, petroleum asphalt, coal tar pitch and resins from the cracking of naphtha for the production of ethylene compounds. Such non-oxidized bitumen products suitable for road construction, sewer pipe lining, roofing, and the like are preferred. The bitumen can be diluted with a hydrocarbon oil before the rubber is mixed ; this can be beneficial for various reasons, for example to facilitate the subsequent mixing process and to enable lower mixing temperatures. Suitable oils are non-volatile petroleum fractions, and similar liquid hydrocarbons having an initial boiling point of not less than 119 ⁰ C.

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Organic liquids compatible with bitumen with lower boiling points are also useful, provided that their in situ volatilization does not cause difficulties leads »In general, 20 to 50 parts of oil and 50 to 80 parts of bitumen are used.

The polybutadiene advantageously has an average molecular weight of less than 10,000, preferably of about 5,000; it consists of relatively short chains g of butadiene units with a terminal calogen atom which is bonded directly to a terminal group which can be an allyl or vinyl radical or a primary or secondary carbon atom. Conveniently, 1 to 15 parts of liquid rubber are used per 100 parts of the bitumen phase, although the mixing process according to the invention certainly enables the effective incorporation of much larger amounts of liquid rubber. In a compatible system, these low molecular weight polymers can be polymerized or crosslinked by chain extension, with the aid of the amine via ionic bonds. Any amine including ammonia, preferably "in aliphatic" tertiary * polyanine is suitable for this. Tertiary monoamines break the chain, diamines, on the other hand, lengthen the chain

BATH ORIGINAL

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and crosslinking amines of higher functionality. Suitable polyamines include methylated triethylenetetramine, methylated hexamethylenediamine, triethylenetetramine, Tridimethylaminophenol, hexamethylenetetramine, 1,3-Di-Cl'-pyridyl) -propane, l ^ -Di-Cl'piperidyD-propane, Di- (4-picolyl) -arain, tris- / "1- (2-methyl) -aziridinyl-7-phosphine oxide (MAPO) and bis- £ 1- (2-methyl) aziridinyl 7-phenylphosphine oxide.

An interesting aspect of the process according to the invention is that the bitumen / polymer mixture can be vulcanized at a speed that is favorable for the intended application, for example by 1) delaying the addition of the amine catalyst, 2) the amine catalyst according to its vulcanization time (which is between minutes and Weeks) selects, 3) increases or decreases the vulcanization temperature, ¹ I) uses a combination of chain-extending and crosslinking amines and adds these to the mixture either together or in succession and 5) the liquid polymer according to the relative reactivity of the terminal halogen atoms and of the Bndgruppen of the chains, the reactivity with the amines for the halogens in the order iodine, bread and chlorine decreases and for the terminal groups in the

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BATH ORIGINAL

Order of allyl residue, primary carbon atom, secondary carbon atom and vinyl residue decreases. These different Measures to control the vulcanization rate can optionally also be combined be combined.

It is clear that the compositions for the most diverse Applications are suitable, including where previously conventional rubber-containing Bitumen compounds were used »For example, they can be used advantageously for roofing, for sealing against water, in the street and for repair work insert·

The following examples are intended to provide a more detailed explanation of the invention, in which all information is given in parts and Prosents are always based on weight

example 1

60 parts of a molten petroleum asphalt (ring and Kugelerweichungepunkt 82 ° C) and 40 parts of a mineral oil (Erdölkohlenwaseerstoff fraction with an initial boiling point of lli9 ° C) were stirred together at about 57 ⁰ C, was obtained until a solution. The stirring and heating

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was continued while 10 parts of a liquid allylbroinide-terminated polybutadiene (middle Molecular weight about 5,000, specific gravity 0.95, Brookfield viscosity 650 cP at 25 ° C and 50 cP at 80 ° C) and then 0.4 part of a methylated Trietylenetetramine (MTETA) was added. After at most 30 minutes was made using an appropriate usual Mixing device for liquids containing rubber Obtained a composition of great utility which can be applied to various substrates and at 12 ° C within a few minutes or at room temperature can be vulcanized within several days with reproducible properties.

Example 2

200 parts of coal tar (Koppers Company, Englsx viscosity 26 till 40 at 50 ° C) were mixed together with 16 parts of Polybutadiene according to Example I with stirring at 54 ⁰ C heated. 3.2 parts of an amine catalyst (Versamid 140, a polyamide resin from General Mills, with an Air.in value of 350 to 400, a viscosity of 125 to 175 cP at 25 ° C. and a specific gravity of 0.97) were then added and stirring was continued until the mixture was homogeneous. The composition obtained

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for example, could be heated for a rapid curing at higher temperature * doors, about 20 minutes is long cooled to 104 ⁰ C, or could to room temperature, resulting in a slower vulcanization.

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Claims (1)

Claims before 1. Bitumen composition, characterized in that they in addition to a bitumen, preferably an asphalt, a liquid polybutadiene with terminal halogen atoms and an organic amine, preferably a aliphatic tertiary polyamine, as a vulcanizing agent, or a reaction product of the organic amine with the polybutadiene. 2. Composition according to claim 1, characterized in that the polybutadiene with terminal halogen atoms is a polybutadiene that has been reacted with allyl bromide. 3. Composition according to claims 1 or 2, characterized in that the polybutadiene with terminal Halogen atoms have an average molecular weight of less than 10,000, preferably about 5,000 . 109809/2035 4 · Composition according to claims 1 to 3 »thereby characterized in that they contain about 1 to 15 parts of the polybutadiene with terminal halogen atoms per 100 parts the remaining components. 5. Composition according to claims 1 to 4, characterized characterized in that the bitumen with a hydrocarbon oil, preferably with 20 to 50 parts of Ul 50 to 80 parts bitumen, is diluted. { 6. Composition according to claims 1 to 5 »thereby characterized in that it is in vulcanized form. 7. Process for the preparation of a composition according to claims 1 to 6, characterized in that the bitumen in liquid form with the liquid Polybutadiene mixed with terminal halogen atoms and then the mixture the Vulkanisiermitfcel inflicts. 8. The method according to claim 7, characterized in that the vulcanizing agent is used immediately Composition adds. 109809/2035 9. The method according to claims 7 or 8, characterized in that a smaller amount of vulcanizing agent is added than for complete vulcanization of the liquid polybutadiene with terminal halogen atoms is required. 10. The method according to claims 7 to 9, characterized in that the Oemisoh is heated in order to accelerate the vulcanization by the vulcanizing agent. coll: wy 109809/2035