DE2503716A1 - PROCESS FOR MANUFACTURING BITUMINOESE MASSES - Google Patents

Description

Britannic House, Moor Lane, London, EC 2Y 9BU (En gland).

Process for the production of bituminous masses

The invention relates to improved bituminous compositions consisting of bitumen and a chlorinated polyolefin.

Flexible thermoplastic masses that can be used as coating masses and membranes are known to be made from bitumen and chlorinated polymers will. For example, GB-PS -1 058 451 describes a bituminous mass made of blown or oxidized Bitumen consists of petroleum and a chlorine-containing polymer. GB-PS 1 250 756 describes a thermoplastic compound, the bitumen or pitch of mineral origin and a chlorinated polyethylene resin contains. Mixtures of bitumen with a chlorinated polyolefin have also been approved for use proposed as asphalt paving and road construction materials. The US-PS 3,050,483 describes an asphalt, in the 0.5 to 5.0 wt .- ^ of a normally solid Polyethylene that is 15 to 35 wt .- # chlorinated, are dispersed. US Pat. No. 3,316,649 describes an asphalt paving composition containing 1 to 5% by weight of a 15 to

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Solid linear polymer containing 28% by weight of chlorine of ethylene contains. ;

One of the problems with mixtures of bitumen and chlorinated polyolefins is the difficulty in ensuring that the mixtures remain homogeneous. "This problem becomes more difficult as the chlorinated polyolefin content increases. By simply mixing the ingredients at moderately elevated temperatures, for example at 110 ⁰ C, are usually obtained mixtures which are non-homogeneous at low temperatures homogeneity to ensure must be worn for a certain interaction between the bitumen and the chlorinated polyolefin _concern..;

It has now been found that homogeneous mixtures containing more than 5% by weight of chlorinated polyolefin can be produced if the mixture of bitumen and chlorinated polyolefin is heated to elevated temperatures and that the process can be accelerated by adding a dehydrochlorinating agent . ■

The method of the invention for the production of bituminous compositions is characterized in that one and heated bitumen based on the bitumen, 6 to 150 wt .- ^ preferably a chlorinated polyolefin to a temperature of 140 ° to 250 ⁰ C in the presence of a dehydrochlorinating agent .

Any compounds of which it is known that they are selected from chlorinated polyolefins at temperatures of 140 ° to 250 ⁰ C remove, can be used as a dehydrochlorinating agent HCl. Zinc oxide is preferred as the dehydrochlorination agent.

It is not intended to be bound by theory, but it is believed that by heating

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of the bitumen and the chlorinated polyolefin, first dehydrochlorination of the polyolefin and then crosslinking between unsaturated groups in bitumen and poly-; olefin ". One might expect that j simply dehydrochlorinating the polyolefin and crosslinking only the polyolefin molecules makes the mixture less would be homogeneous, but surprisingly the ■; Conversely, found a sign that the interaction between the bitumen and the polyolefin was increasing; is favored and strengthened. The greater homogeneity '

makes itself "for example in reduced exudation and leakage of the bitumen from the invention. heat mixture "noticeable.

Preferably, the mixture to a temperature of '15O ° is "heated to 200 ⁰ C. The duration of heating can be.""Depending on the temperature and on the presence or absence of a dehydrochlorinating agent;!. 5 minutes to 2 hours, respectively heating times of! at least one hour are functional in the absence of a dehydrochlorinating agent, but may ι they are reduced to 5 minutes to down in the presence of a dehydrochlorinating agent j in general, at higher temperatures, shorter heating times;! required..

Untreated mixtures of bitumen and chlorinated Polyolefins usually have a Shore Α hardness of 30 or less and are preferably treated so that the hardness rises to .35 to 80.

A natural pitch or ■ "! Is expediently used as bitumen. that commonly known as mineral pitch (asphalt). '■■■ Material or that as a by-product of the coal and Bitumen obtained from the oil industry is used. Particularly ; Either that as a residue is advantageous as bitumen material obtained from vacuum distillation of crude oil

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or the product made by blowing such
Vacuum residue with air up to a suitable one
Penetration has been obtained. The bitumen used as the starting material preferably has a penetration of 40 to 200 at 25 ^° C.

The chlorinated polyolefins used are preferably polyolefins obtained from Cp-C monoolefins. For example, high or low density polyethylenes are suitable, but chlorinated polyethylene can also be used Polypropylene can be used. The chlorine content of the polyolefin can be 15 to 45 wt .- ^ of the chlorinated Polyolefins.

Products which are manufactured according to the invention with 6 to 150 wt .- ^ chlorinated polyolefin, based on the bitumen, form flexible thermoplastic
Compounds which are suitable as coating compounds and membranes. It is to be regarded as particularly surprising that mixtures containing these relatively high amounts of chlorinated polyolefin are made homogeneous with the aid of the method according to the invention
can be. Preferably, 50 to 120% chlorinated polyolefin based on the weight of the bitumen is used.

The bitumen and the chlorinated polyolefin can be used in
mixed and heated in any suitable container, preferably with constant mixing or stirring.

As already mentioned / it may be necessary to change the
Hardness recognizable crosslinking by simple heating
preferably be achieved in the presence of a dehydrochlorinating agent. However, if necessary
crosslinking through compounds that are known in the field of rubber and polymer technology as crosslinking agents and accelerators, e.g. sulfur ________

benzothiazyl disulfide, cadmium diethyldithiocarbamate,
Ethylene thiourea and suitable oil-soluble phenol-formaldehyde resins, e.g. the product "Bakelite"
CKR 14634 "(BXI Limited), accelerated * This
Compounds should be added during the later stages or towards the end of the heating.

If the mixture of bitumen and chlorinated polyolefin is processed into coatings or other products, it is to be expected that it will be reheated to melt, so that there is a possibility that further dehydrochlorination will result in further changes in hardness instead of- ^: -

finds. After heating the mixture according to the He-; finding it can therefore be useful to find a stable! -; add sator to further dehydrochlorination and ^!

Prevent networking. Stabilizers of this type j are in the field of rubber and polymer techno- ■; logy known. For example, lead or lead are suitable Calcium stearate or phthalates, organotin compounds, Epoxy resins and epoxidized soybean oil.

The amount of dehydrochlorinating agent and dispensing! wetting agent and accelerator as well as any stabilizer used depend on the ί desired degree of crosslinking, but are expediently 0.5 to 5 wt .- $ in the case of dehydrochloride! agent, 0.5 to 10 wt .- ^ in the case of Vernet! Zungsmittel or accelerator and 1 to 10 Gew .- $ -i in the case of the stabilizer, based in each case on the
chlorinated polyolefin.

Depending on the use of those produced according to the invention Masses can contain these fillers, e.g. limestone powder, ground fuel, soot, ion, silicon dioxide or asbestos.

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The invention is further illustrated by the following examples. In the experiments described there the following basic components were used

Bitumen: Kuwait bitumen with penetration 80/100

25 ° 0:

Chlorinated polyethylene: product "CPE 3614" (manufacturer Dow Chemical Co.), chlorine content 36 wt .- ^.

j Dehydrochlorinating agent: zinc oxide |

Stabilizers: lead stearate ^:

"Epon 828" (manufacturer Shell Chemicals) Accelerator: phenol-formaldehyde resin "Bakelite CKR 14634 ", (manufacturer BXL Limited). I

The ingredients were mixed in a Brabender mixer [ with a mixing head for rubber compounds. After mixing, the product was pressed and cut into test specimens of suitable size for determining the physical properties. !

Stabilizers, if used, were added towards the end of the mixing process. An accelerator, if used, was added after mixing and after cooling the mixture to 60 ^° C., but before pressing. Samples of the pressed product were tested for hardness, tensile strength, elongation at break, tear resistance, and exudation or strike-through. In the last-mentioned test, strips were placed on paper and ^{kept at 65 °} C. for 16 hours. The discoloration of the paper was visually rated (a rating of 10 corresponds to a discoloration or staining of $ 100, while a rating of 0 means that no staining has occurred).

The ingredients used, the mixing temperature and Mixing time, the ambient temperature and time and the Test results are given in the following tables.

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Table 1A example

Chlorinated

Polyethylene

GPE 3b14

Bitumen Kuwait bitumen 80/100,

Dehydrochlorinating agent zinc oxide, g

stabilizer

Epon 828
G

Bleis te ar at ,
S.

accelerator

Phenol-formaldehyde resin CKR 14634, g

cn ο cc oo

1 2 3 4 5 6

35 35 35 35 35 35 35

35 35 35 35 35 35 35

1.0

0.5 0.5 0.5 1.0

0.6
0.6

1.5
1.5

3.6

cn o to

Facts 1B

With mixed mixed temperature duration, temperature, min. ⁰ C

Tremendous
"exercise
Time,
Min. Molding
temperature,
⁰ C Shore A
hardness VJl . 150 31 VJl 150 32 VJl 150 30th VJl 150 34 5 150 42 60 l6o 56 5 150 50

Tensile strength - breakage - tear, elongation, strength - MN / m ² . i » keit,

N / mm

Exuding after hours at 65 ^ 3

O CO GO CO

30 30 60 20 45 45 5

90 140 160 160 160 160 160

3.3 900 3.0 670 5.0 1000 4.8 740 7.8 400 1.8 110

11 10

20 26 29

18th

7 2 2 1 1 0 0

cn

Example 1 shown in Table 1 is a 7-"example which was not carried out in accordance with the invention. It shows that a relatively soft material with a pronounced tendency to exudate and bleed through is obtained when the bitumen and the chlorinated polyolefin are added low temperature are mixed. in Examples 2 to 7 is according to the invention carried out experiments show that by mixing at higher temperatures, sometimes in the presence of zinc oxide exudation and strike through is reduced. in the '■'. for Examples 2 and 3, the other characteristics are not greatly affected, but in the case of Examples 4 to 6, where it was mixed at 16O ⁰ C in the presence of zinc oxide to detect a sharp increase in hardness and tear strength. in the case 'of example 4, this improvement has been the Hardness and tear strength achieved without deterioration in elongation at break ie ^! Amount of zinc oxide at the temperature used to be too high, since too strong dehydrochlorination results and a weak, porous structure j is obtained.

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Claims (13)

9 R Π ^ 7 1 R Claims ζουο / io characterized in that bitumen and, based on the weight of the bitumen, 6 to I50 wt -% of a chlorinated polyolefin, optionally in the presence of a dehydrochlorinating agent to a temperature of.: Heated 140 ° to 25O ⁰ C. ; - ι 2. The method according to claim 1, characterized in that zinc oxide is used as the dehydrochlorinating agent. ; 3. The method of claim 1 or 2, characterized in that heating the bitumen and the chlorinated polyolefin to a temperature of 150 ° to 200 ⁰ C. j 4. The method according to claim 1 to 3, characterized in that that the treatment is carried out in such a way that the hardness increases 35 to 80 Shore A increases. 5. The method according to claim 1 to 4, characterized in that chlorinated produced from Cp-C ^ monoolefins Polyolefins used. 6. The method according to claim 1 to 5, characterized in that there is chlorinated polyolefins with a chlorine content from 15 to 45 wt. # used. 7. The method according to claim 1 to 6, characterized in that that the chlorinated polyolefin in an amount of 50 to 120 wt -.% Of the bitumen used. 8. The method according to claim 1 to 7, characterized in that the preferably added dehydrochlorinating agent in an amount of 0.5 to 5 wt. % Of the • uses chlorinated polyolefins. 509832/0919 9. The method according to claim 1 to 8, characterized in that that one has a crosslinking agent or an accelerator during the later stages or towards the end of the Heating clogs. 10. The method according to claim 1 to 9, characterized in that the crosslinking agent or the accelerator in an amount of 0.5 to 10 wt -% of the chlorinated polyolefin is added.. 11. The method according to claim 1 to 10, characterized in that at the end of the heating, a stabilizer added to prevent further dehydrochlorination. 12. The method according to claim 1 to 11, characterized in that the stabilizer in an amount of 1 to 10 wt .- # of the chlorinated polyolefin added. 13. According to claim 1 to 12 prepared mixtures from Bitumen and chlorinated polyolefin. 509832/091 «