DE2018760C3 - Thermoplastic masses - Google Patents

Description

25th

The invention relates to a thermoplastic mass made from bitumen and a thermoplastic material dissolved therein Plastic.

As is known, bituminous masses are used industrially on a large scale; so z. B. as a binder in road construction, as impregnating agent and covering compound for roofing felt, as hot glue, as hot paint and as a pipe coating agent.

There are natural limits to the bituminous masses (bitumen, tar and pitch). Upon distillation bitumen to DIN example is 1995, the plastic temperature range determined from the difference between the point of breaking (after F raass) and softening point (ring and ball), a maximum of about 7O ⁰ C. The breaking point is only at very soft bitumens satisfactory (B 300: - 2O ⁰ C), with tougher types (B 15: +3 ⁰ C) it is above 0 ⁰ C.

Therefore, the existing bitumen types according to DlN 1995 can no longer be used; in warm A considerable part of the road surface is destroyed in the summers. One used namely to winter damage to avoid on the road surface undercooled by de-icing salts, soft bitumen with deep Breaking points that can be irreversibly deformed in summer.

In high vacuum bitumen, the softening point while 130 reaches to 140 ° C, but its breaking point is far above 0 ⁰ C. These types also have a very low ductility, which limits their applicability.

Blown bitumen have plastic temperature ranges from a maximum of 120 to 130 "C. The breaking point of the highly heat-resistant types (B 115 15) is with - 10'C cheap, but still meets many requirements not. The ductility is also low, and so is the weather resistance is not sufficient for outdoor use because of the embrittlement.

The processing of bitumen requires certain viscosities, such as. B. Door asphalt wedding layers in B 300. B 200, B 80 and B 65 are available, for road surfaces in B 300 to B 45 and in mastic asphalt between B 65 and B 15. Similar production conditions

760

There are also requirements for masses for roofing felt, for the insulation of steel pipes, that Bonding paper, potting cables, for bituminous building protection compounds, for manufacturing of flooring materials and many other uses. With low viscosity are now inevitable with bitumen, low softening points and strong flowability within the range of use connected. It is therefore important to increase the softening point if the viscosity requirements are complied with increase and avoid the undesirable flow in the conditions of use.

The bitumen's ability to adhere to touching or embedded materials is not always sufficient. The resistance of bituminous compounds to chemicals such as solvents and oxidizing agents is not always satisfactory. Even with permanent heat exposure above the softening temperatures, z. B. during transport, bituminous masses are significantly changed or damaged.

It is therefore urgently desired to develop bitumen-like, thermoplastic compositions that one increased softening range and reduced cold flow, but at the same time a reduced brittle fracture range have, d. H. have an extended plastic temperature range.

The increase in viscosity due to additives during processing and transport should be as low as possible being; at the same time good weather resistance, consistent properties with long-term Effect of temperature during transport and processing and good adhesion to surfaces or embedded materials are required. The hardness requirements are different. For some uses you are looking for high softening points combined with relatively low hardness (great depth of impression according to DIN 1995), for others - e.g. road construction - a large plastic temperature range, combined with the lowest possible penetration depth. The masses to be developed should not show any signs of exudation at the use temperatures show no surface tack if possible. Some users, e.g. B. Manufacturers of tubes, prefer also the processing of bitumen granulate.

Any components to be added should be able to be manufactured economically on an industrial scale and should be easy to incorporate leave, if necessary by using powders, crumbs, handy pieces or premixes. They should have a good effect in small amounts. Production-related fluctuations Bitumen or additives should have the least possible effect on the miscibility and on the Have the quality of the finished product.

It has already been proposed to add rubber or rubber compounds.

Regenerated tire rubber are of little use, since the vulcanized mass is only embedded and does not dissolve in the heated bitumen.

Natural rubber powder does dissolve, increases the softening point and lowers the embrittlement temperature, however, heat resistance and light resistance are not sufficient. Also the rubber must contain about 40% fillers to stay in powder form. The solubility is also limited, like that that only 3 to 5% rubber is added.

Similar to synthetic rubber, its solubility it is slightly better at constant temperatures such as those used when transporting liquid bitumen from the refinery to the

Consumers or occur in road construction, degraded, which reduces the modifying effect.

The incorporation of rubber latex encounters the same limits of usability; Added to this is the difficulty of mixing in, because when the emulsion is introduced into the ^{bitumen heated to over 150 D} C, the water evaporates suddenly and causes disruptive foaming of the bituminous mass and inclusion of bubbles in the mix. Uncontrolled gelling of the rubber impairs the homogeneity of the mixtures; the cooling of the mixed material by the evaporating water reaches 5 to 1O = C.

Polychloroprene rubber - added as latex - is relatively resistant to aging, but does not achieve the necessary stability for e.g. B. road transport, which can take 1 week or more ^{at around 200 c C.}

Styrene-butadiene rubber latex is even less thermally stable; also its application is at around 3 up to 5% solid rubber, based on the bituminous binder.

Nitrile rubber dissolves more poorly than the rubbers mentioned and ages faster.

The unsatisfactory conditions are shown here on different types of rubber (bitumen, tar, asphalt, pitch, 1966, issue 9); Additional 3% each Solid. The values in brackets were measured after aging (ASTM D-1754; 5 hours - 163 ° C).

B 80 oline additives
3% polychloroprene

(made of latex)

5% natural rubber powder
3% natural rubber

(made of latex)
3% natural rubber
3 ", - 'ι) polyethylene-vinyl acetate
3 "/ n butyl rubber
3 "II nitrile rubber

penetration
25 C
vorlnachl
Aging

88 (55)
75 (70)

61 (57)
90 (33)

81 (65)
92 (38)
98, 85)
72 (50)

(51) Oucli- C. (3) "egg- (52) lity before! after (55) ching- (54) 4th Aging (9) piinks (52) 19th (13) before! after) (47) 55 (17) Aging (60) 10 (8th) 45 (43) 25th (17) 51 (50) 40 (20) 55 28 60 19th 50 14th 55 51 50

To improve it, the addition of a polymer mixture of polyethylene and vinyl acetate is recommended. According to German interpretation 1 301 141, however, the aging resistance of this mass is not yet sufficient out. The cold resistance is also described as inadequate.

Copolymers of ethylene and acrylic esters are too tough and do not dissolve enough. You will therefore exclusively as 50% bituminous premixes

ίο offered. The premix has a high plasticity Temperature range, good stability, and its long-term temperature resistance exceeds that of the Most of the rubber and plastic products known as bitumen additivesc. But the product does ; spite of the batching still processing difficulties due to the extremely high melt viscosity, the processing temperatures up to 220 ° C or in the casting process up to a maximum of 250 ° C may require (Kunststoffe 59 [1969], pp. 111 to 113) The production of the copolymer from several components is obviously technically complex. In addition, the 50% premix does not yet appear completely homogeneous, which results in exudation of the bitumen to the surface and a noticeable cliffiness of the manufacturing products. This According to Auslegeschrift 1 301 141, deficiencies are said to be due to homogenizing additions of polyisobutylene or Butadiene copolymers are eliminated.

Polyisobutylene leads to non-stable mixtures: they tend to flow cold. Types with relative low molecular weight are easy to incorporate, but do not increase the softening point, but rather have a plasticizer-like effect.

High molecular weight grades work better, but are extremely difficult to incorporate At temperatures above 160 ° C., segregation occurs.

Atactic polypropylene has also been added to bitumen. However, the polymer does not dissolve very well in hot bitumen, especially when added in small amounts. At high temperatures it becomes creamy, at cold temperatures the mass becomes gritty and inhomogeneous. In addition, an alkaline polypropylene with RSV 0.7 and 67% Etherexlrakl gives a primary bitumen grade of B 200, especially at low concentrations
only moderate improvement as shown in the table regardless of homogeneity

However, the addition of thermoplastic materials has also been proposed. Polyvinyl chloride must with the Mass can be heated for a long time, during which decomposition must occur. The mix is improving but low, and the solubility is limited to about 5%. At higher concentrations the mixture is no longer homogeneous. Polyethylene also results in a homogeneous mixture of up to about 5%, and the plastic also crystallizes when it cools again and shows up as a microscopic inhomogeneity. In the German translation 1 301 141 it is claimed that one can use polyolefins such as Can mix polyethylene with bitumen in any proportions. Opposed to this is the German Offenlegungsschrift I 469 971, in which it says. it is a remarkable fact that although different plastic materials, oils and other plasticizers mechanically mixed with polyethylene but only steam-cracked petroleum resins are really soluble. To the solubility

50 conc
tration
al. PP l-rwci-
ching-
Point Break
Point Prnclra
tion Oiiklility <%) V <<■ '· ι η (I 10 mm) learn) 55 0 39 - 18th 160 100 3 44 - 19th 95 40 5 45 - 19th 80 25th

i'hislischcr Temperature range

(grd)

57
63
64

The permanent heat resistance of such Mi Schungen is limited so that they are not suitable for road transport; one polymer is enough This is because phase frames: the polymer also degrades thermally. Therefore, until now, a substance which can be worked well into bitumen, only brings some improvements, while good improvements only come from substances that are difficult to incorporate.

It is true that in the French patent 1527 402 mixtures of bitumen, mineral oil and polybutene described; this is how a comparison with the company printed matter OPPANOL B *) can be seen / undoubtedly around Polyisobutylene. In the Dutch exposition 67-15 512 are asphalt mixtures with 5 to 95% Polybutcn- (l) treated: but it is not recognized that precisely mixtures that contain less than 5% Polybutene- (l) contain, are particularly valuable. Rather, one had to see the teaching of Scripture expressly restricted to the areas mentioned, assume that the edge areas are not usable are.

So there is still a need for bitumen compounds which, on the one hand, significantly improve the required Have properties, but on the other hand can be obtained technically and economically problem-free are.

This object is achieved smoothly in that the mass consists of more than 95 percent by weight Bitumen, which may contain other known plastics, rubbers and / or organic additives and less than 5 percent by weight of polybutene (l) with a molecular weight between 40,000 and 4,000,000.

Bitumen is defined as the dark brown to black, viscous, bite-hard, fusible hydrocarbon mixtures that are obtained in the processing of petroleum or that are in natural asphalt, e.g. B. from Trinidad, occur as a soluble, meltable portion. The softening points of these masses are between + 25 and + 180 ° C (DIN 1995, ring and ball), the breaking points between - 25 "C and above room temperature (DIN 1995, Fraass method) and the penetration depth between 400 and ² I ₁₀ mm (DIN 1995 Mixtures of bitumen with oils, e.g. tar oils in so-called blended bitumen, are also improved by the additives described.

Polybutene ^ I) are polymers of the Butene- (l) understood as they are in the liquid phase with or without the presence of inert solvents or are produced catalytically in the gas phase, especially by the low-pressure process. These include waxy, sticky and horn-like solid substances with molecular weights between 40,000 and 4 million with different crystallinity, which are in bulk densities between 0.85 and 0.93 and in ether extracts between 0 and 90%. The crystalline part can be in the Modifications I, I ', II and III are present. Not only the pure polymers are suitable for the addition, but also mixtures with other polymers such as polyolefins or rubbers, with bituminous ones or oily substances as well as mixtures obtained by polymerisation in oily or bituminous products.

The bitumen preferably has softening points between 25 and 90 ° C (DIN 1995, R.u.k.) and Penetration depths between 350 and IO '/ IOmm. It can both primary bitumen and blown bitumen. The bubble effect can too take place during the mixing-in process or after the addition of the polybutenes. Particularly good ones Effects are achieved with primary bitumen with softening points between 25 and 70 "C and penetration depths between 350 and 15 ', IO mm. The bitumen bond The thermoplastic mass can contain other plastics, rubbers and / or organic salting agents contained in a manner known per se.

The polybutene! 1) is preferably a polymer with molecular weights between 50,000 and 4 million, with bulk densities between 0.85 and 0.92 and ether extracts between 0.5 and 85%. The most favorable mixtures can be achieved with molecular weights between 80,000 and 3 million, bulk densities between 0.88 and 0.91 and ether extracts between 20 and 80 ¹ Vo. The greatest effect in expanding the plastic temperature range is achieved by products with molecular weights between 150,000 and 2.5 million and ether extracts between 2.5 and 60%.

In all cases still to be described, the polybutene can also be made from different polymer specifications exist, which are added at the same time or at different times. For example the dissolving process can be accelerated and the homogeneity even improved if on Instead of 4% of a high molecular weight, isotactic polybulc, only 2% of the polybutene mentioned and 2.5% of a higher atactic type are admixed. Also the addition of other plastics, which is known per se such as polyethylene, iso-atactic polypropylene, polyvinyl chloride, Polyäthylcn-Acrylsäurecster or the addition of rubbers such as styrene buladiene

Rubber, natural rubber, polychloroprene or ethylene-propylene rubber are possible and does not restrict the use of polybulene- (1). This also applies to all known additives such as Fluxölc, natural asphalt, tar oils, tar pitch. Colophonium. Linseed oil, epoxies.

Surprisingly, polybutene- (I) mixes in a very wide range of crystallinity and molecular weight easily in bituminous masses - added below 5%. Neither are inhomogeneities nor Segregation phenomena found. The origin of the bitumen within a type according to DiN 1995 and with it the content of aliphatic, naphthenic and aromatic constituents has only a minor influence on the solubility of the polybutene- (l). the Polybutenes used have the following properties:

·) OPPANOL B pamphlet of lirrrui B; idischc aniline * Soda! ahrik ACi (l% 7 |. pp. 39 and 40.

Athcrcxlnikl-
" Area
(% l 0.3 1.3 \ 2.0 RSV 3.7 4.0 Obis IO 0.7 1.0 2.3 2.5 55 10 to 20 3.8 5.4 20 to 30 1.3 4.0 30 to 40 3.5 60 40 to 50 0.8 0.9 1.4 50 to 60 0.6 1.4 1.5 60 to 70 0.6 0.0 0.9 1.7 1.2 1.3 65 70 to 80 1.4 1.0 80 to 90

The relationship / between RSV value and molecular weight is shown in the following table:

vSV Molckukii ^ euithl 0.1 14,000 0.2 35,000 0.3 61,000 0.4 90,000 0.5 122 0 (K) 0.6 156,000 0.7 192,000 0.8 230,000 0.9 269,000 1.0 310,000 j 1 394,000 1.4 482,000 1.6 574,000 1.8 669,000 2.0 766,000 2 2 866,000 2.4 968,000 2.6 1,070,000 2.8 1,176,000 3.0 I 282 000 3.2 I 390 000 3.4 I 499 000 3.6 I 609 000 3.8 1,719,000 4.0 I 830,000 4.2 1 943 1) 00 4.4 2,055,000 4.6 2,169,000 4.8 2,282,000 5.0 2,396,000 5.5 2,683,000 6.0 2,971,000 7.0 3,550,000 8.0 4,130,000 ends
biturr zn types of bitumen are:
ien R 300. B 200.

B 65, B 45, B 25,

B 15
High vacuum bitumen ... HVB 85/95,

HVB 95 105,

HVB 130 140 Blown bitumen 75/30, 8540, 105 15,

115/15. 135 10 off-cuts bitumen VB 100, VB 500

Preferred mixing ratios:

incorporated. In the case of types that dissolve quickly, Lumps of 200 to 400 g weight, with only a slight increase in the mixing times, incorporated homogeneously will.

However, these pieces are difficult to handle and practically impossible to dose. On the other hand, the dosage is of pieces up to about 100 g is still possible and is easier to achieve below 20, preferably below 10 g, even better than granules. The increased effort

ίο for the production of lumpy or powdery Material is justified at the mixing plant by the fact that the mixing times are kept short and manpower can be saved. Powder and granules are easiest to dose automatically.

One difficulty in interfering with the polybutene (l) in bitumen is that the polybutene (1) usually has sticky surfaces, so that it sticks together during transport and is difficult to handle when mixed in. Bc-

Particularly in the case of mixing plants for road construction, this makes incorporation very difficult.

The incorporation is made considerably easier if the polybutene in lumpy, crumbly or Is in powder form. This goal can be achieved by adding the polybutene- (l) during or after the Production in proportions of about 80/20 to about 40/60 parts of polybutene (1) / bitumen with bitumen mixed in the melted state and converted into lumpy form in a suitable manner when cooling, z. B.

similar to the production of plastic granules.

The amount and type of bitumen added must be selected depending on the type of polybutenes so that the goal - non-sticky polybutene concentrate Interfering with the bitumen - is achieved.

For example, concentrates are used here as adhesive named:

Polybutene bitumen I. 99 3 97 4.8 95.2

The compositions according to the invention are produced. by appropriately putting the additives in powder form

Polybutene! I)
iithcr-

RSV

0.6
0.6
0.9
0.9
2.0
2.8
3.5
4.0

65
65

52
52
30th
60
70
30th

bitumen

Parts

50
40
50
80
80
50
75
80

Type Parts B 25 50 B 45 60 B 80 50 HVB 95.105 20th B 45 20th B 200 50 B 15 25th R 25 20th

The demand for pieces, granules or powders is of course most urgent where the Release times are the longest. While 4.5% of a polybutene (l) with 60% ether-soluble content and a molecular weight corresponding to RSV = 0.6 still in brick-sized lumps in an asphalt mixing plant distribute homogeneously under the usual conditions in about 40 seconds, one should use a polybutene- (l) with 52% ether soluble and RSV = 2 to a particle size of about 3 cm in diameter and set one of RSV = 4 to powder form. The powder is dispersed during transport and storage so strongly unlocked that it becomes slightly homogeneous when processed in the paver.

The release speed depends on various parameters as follows:

609 609/374

temperature

R. travel speed.
Bitumen type

Polybutene particle size.
Polybutene ether extract.

Polybutene RSV

Polybutene Concentration.

uonntur

deeper

less

higher

E point

large

small amount

high

higher

iiuliukoil
height

higher

higher

deliver

K point

small

high

small amount

ger.ng

The first four lines make sense. Crystallinity and molecular weight have a complicated, sometimes additive, interaction. Values for it cannot be specified in general terms, but must be specified individually depending on the other parameters to be determined. It is useful to set the temperature and stirring speed for the selected material to be coordinated with the other technical data. To give an example of the complex behavior are to be given in Fig. 1 depending on the ether extract and RSV "curves of equal dissolution times" specified (minutes). The values were determined on 4.5% solutions of polybutene! 1), in particles of about 0.1 g weight at 165 ° C. in bitumen 200. The curves indicate the times after which inhomogeneities can no longer be recognized.

The types with the short dissolution times <2 minutes dissolve within seconds as soon as they exceed their melting temperature.

The easily soluble types produce the greatest changes in the breaking point. The biggest changes in softening point, penetration and ductility, on the other hand, the types with the longest cause Release times. But that suits the areas of application, because z. B. in road construction, where the mixing times are short, the break point is crucial, but you can get through the softening point adjust the choice of bitumen. For use as a film, however, is the high softening point important, but you have more time to mix it up.

In addition to the surprisingly simple manufacturability, it can be seen that the plastic temperature range, i.e. H. the range between the softening point and the breaking point of the mixtures does not vary according to the ratio of the Components improved, but is considerably above the additive values.

A b D. 2 shows the increase in the softening points of commercially available bitumen with the addition of a polybutene (l) with 52% ether extract and RSV 0.9. It is particularly high with soft bitumen and amounts to there 3 ° C per percent additive.

Fig. 3 shows the improvement in the breakpoints, which is around 0.5% for all bitumen for this polybutene amounts to. As a result of these improvements, the plastic temperature range (A b b. 4) becomes especially there raised where it is particularly necessary: with the soft bitumen. You can already reach them in this way softest primary bitumen B 300 and B 200 plastic temperature ranges that are as large as those of the hardest primary bitumen B 25 and B 15 - but combined with even better low-temperature properties. D'C dashed lines indicate. how the values after "the proportions used were mathematically improved, if one of the properties of the polybutenes used here: softening point 100 (. '. Breaking point -30 C. The Measured improvements are 4 to 5 times better.

From b. 5 shows the penetration of the same mixtures. This means that even with small additions, the penetration rate according to DIN l ^l ) 95 decreases significantly, so the bitumen becomes stiffer against deforming forces or flow processes. The decrease in penetration is roughly the same everywhere if it is related to the values of the pure bitumen or plotted logarithmically.

Improved softening points in connection with penetration result in an improvement of the penetration index, see Fig. ft. Especially the Bitumen B 300 and B 200 are improved so that they already have the characteristics of the blown Bitumen (+ 2) come close.

A grave objection to the use / of polymers in bitumen is the increased processing viscosity or processing temperature. Lots Additives increase the viscosity of bitumen so much that the usual processing or temperature conditions must be varied noticeably. Due to higher temperatures during transport or processing but both bitumen and polymer additive are damaged.

Thus, by adding 3.75% ethylene-acrylic acid parent copolymer (that is 7.5% of the commercially available bituminous premix), the viscosity of B 200 at 150 ° C. from 100 cSt to 1000 cSt
thus increased by a factor of 10 (Fig. 7 - dashed line), and also in French patent specification 1 527 402 the putative polyisobutylene, referred to there as polybutene, is expressly added for the purpose of increasing viscosity.

Surprisingly, it was found that the viscosity of bitumen with the addition of polybutene-) 1) is hardly changed, so that during processing no measures such as temperature increase or the like have to be taken. The increase in viscosity is only slightly dependent on crystallinity and molecular weight over a wide range. Only through strong ones Increases in molecular weight and crystallinity can cause a noticeable increase in viscosity will.

Fig. 7 shows the viscosities of mixtures at 150 C. The raw materials used are commercially available Bitumen and a polybutene) 1) inil 52% Oil extract and RSV 0.9. The dotted line shows the corresponding behavior when the crystallinity is increased (Ether extract = 28%) and strong increase in molecular weight (RSV 3.8). The change in viscosity but is also low here.

The behavior of the new mixtures on heat aging is also surprising. One would have here have to expect that the known strong change in the bitumen is not due to a small addition a plastic can be stopped. However, this is noticeable with the polybutene! 1) not to, the polybutene has a kind of protective effect on the bitumen even in small quantities, so that the properties of the mixtures remain astonishingly constant when exposed to permanent heat. Around To prove this effect, one can use the mixtures at the extremely high level for a bitumen with access to air Store at a permanent temperature of 200 C in an oven in open dishes for 72 hours. the

Starting and E.ndwerie u> ii bitumen and mixtures are in the table, the course isl in Λ b b. 8 and 9 again.

Softening point, C ....
Break point, c
penetration

25 C

4 C

Ductility

25 C

4 C

H Il ISuI ι 7 ^ (Sill.) Ii: oo
l> ol \ hu 40 67 oiSkI.i 17th -8th 48 170 32 - 10.5 IX 5 IK) 100 5 14th KO 0.5 60

12 (SuI. I

54
15th

54
7th

32
6th

"5

Here the values of the pure bitumen change rapidly, the softening point increases by 27 degrees. the breaking point by 9 degrees. The penetration fills up to _{s of} the initial value, the ductility sinks at 4 C to ',,, "of the initial value. The same bitumen behaves much better if only 4.5% polybutene-) I) has been added (here are mean values from two products, each 4.5% polybutene with RSV = 0.9 or 3.5 and ether extract = 52 or 75% included, used).

The softening point only increases by 6 degrees, the break point by only 3.5 degrees. The penetration changes only by half, likewise click Duklilitäl at 25 C, and at 4 C hai the Duklility still '4 of the initial value. These are surprising and in no way predictable results, which are of the highest technical importance.

The weather resistance is also improved by the addition of polybutcri- (l). In the case of primary bitumen without additives, the resistance is tested in Xenotestgcräl from Ileraeus, Hanau
with increasing hardness from level to level. H 300 and B 200 are good, B 65 and B 45 medium, and B 15 isl moderately weather-resistant, similar to blown bitumen. If, for example, 4.5% polybutene is now added to a B 80, its weather resistance wedge is improved to the level of B 3 (K), but the softening point corresponds to B 65. This results in a bitumen that is three levels better in terms of the willcrutability, which means that Area of application greatly expanded.

With the composition of the polybutene (I (the properties of the mixtures change, however within the claimed range only significant in the case of extreme shifts in molecular weight (RSV I or Athcrcxtrakt. The table gives the order of magnitude of the changes, it relates to a 4.5% addition

with .him l-.iücnsi h: if siinderiing mil / imchmciulci KSV 1'.ίμι: ηΝΐΉ; ιΓΐ I end / chmendem Athcre \ lr; ikl !end up/ per I KSV increasing increasing about 0.2 C Softening point increasing increasing el about 0.1 C Crush line ^ t falling falling times 0.98 penetration falling falling times 0.99 Ductility per Κ) ¹¹ ,,
Alhercxlr; ikl about OI C " el about 0.05 C times 0.97 times 0.98

For example, in the case of an isotactic, high molecular weight Polybutene! i) the softening point compared to a largely atactic, low molecular weight type by about 2 C and the breaking point by about 1 C higher, the penetration by the factor 1.4 and the ductility by a factor of 1.2 lower.

The solubility of bilumin-polybutene mixtures in typical solvents is similar to that of pure solvents Bitumen. If good solubility is important, the ether extract of polybutene should be high.

The chemical resistance, especially to oxidizing agents, is gradually improved. Since - analogous to the resistance to weathering - the oxidation resistance of the bitumen also increases Hardness and especially by blowing noticeably decreases, one can also here the resistance wedge by some Improve levels.

The bitumen's adhesion is slightly improved by adding polybutene ^ 1). Since the Adhesion in most cases of bitumen application from the penetration of the hot bitumen into surface structures depends, it is indirectly a problem of viscosity, and the viscosity, which increases only slightly has a very favorable effect compared to other polymer additives.

The thermoplastic compositions according to the invention are suitable because of their excellent and surprising properties Properties primarily as a binder for road construction, roofing felt, hot-melt adhesive and hot-coat inks.

For road construction, the mixture can contain 0.5 to less than 5 percent by weight of polybutene! 1) with a Density of 0.86 to 0.92, an ether-soluble fraction of 0 to 80% and a molecular weight between 80,000 and 4,000,000, as this is thermally more stable than the bitumen on which it is based, if necessary, take place during the production of the bitumen in the refinery. Either arise thus types with better overall properties, or the addition of polybutene serves to achieve the prescribed To achieve specification. Also the production of more concentrated types that are used as a premix serve and added to the final mix before use, isl possible.

The addition can also be made in the storage tank on the mixing plant. As a result of the favorable solubility wedge the need for stirring devices is minimal and usually as a stirrer or circulating pump available anyway.

It is also useful to add it to the Asphall mixing device. In the case of mixing plants for asphalt-fcinbcton, the mixture is already added to roughly fist-sized lumps homogeneous within the usual mixing times of only 30 to 60 seconds, if finer particles are added, the mixing time could in principle still be reduced. When adding

the sparingly soluble, predominantly crystalline, high molecular weight Material is the polybutene- (1) by the high shear forces are well distributed during the mixing process, but the complete solution takes place first in the first few minutes of the mandatory Transport. The usual transport temperatures for fine asphalt concrete from about 180 "C, the mixture does not represent a critical thermal load.

The better heat aging of the bitumen mixtures with polybutene (1) makes these mixtures whole particularly suitable to withstand the thermal conditions on mastic asphalt. When processing Mastic asphalt, the bituminous mass is usually kept at temperatures of 180 to 240 C for hours. The usual polymer additives cannot withstand these temperatures. Polybutene- (1), however, will not noticeably damaged and has a beneficial effect on the stability of the bitumen.

The addition of polybutene (l) is particularly beneficial for mastic asphalt, because it is often bitumen types with high softening points such as B 45, B 25 and B 15 are used, which are relative in the breaking point are high. By adding 2 to less than 5% polybutene- (l) to the binder, a softer Bitumen are used. Its favorable breaking point is further improved, the softening point is set to the desired height by the addition, the penetration is also set to the desired type.

For asphalt mastic, the compound must be homogeneous and thin for processing at temperatures of 160 up to 200 C. The low viscosity state can be reduced due to the only slight increase in viscosity Achieve the addition of polybutene ^ 1) particularly well, so that the plastic temperature range also with asphalt mastic can be expanded by adding polymer, which is by no means the case with all polymer additives is the case (see Fig. 7).

For roofing felt cardboard, glass fleece or fabric or jutcgcwcbc with bitumen B 200, Impregnated with B 80 or B 65, practically all blown bitumen is used as a covering material. the Ready-made products are sprinkled with various minerals.

If, instead of the primary bitumen, one is used that is reinforced with polybutene ^ I), a lower breaking point is obtained with the same hardness set. Normally 2 to less than 5% of a polybutene- (l) with RSV = 0.5 to ? and 0 to 70% ether extract can be used. In the case of higher requirements, it is advisable to reduce the ether-soluble fraction and / or to increase the length of the core. It is also advantageous to add different types at the same time, e.g. B. 2% polybutene with 0 to 10% ether extract and RSV = 3 to 5 and 2.5% polybutene- (l) with ether extract = 40 to 70% and RSV 0.5 to 1.5.

The blown bitumen can be temperature-dependent Properties are largely replaced by the addition of polybutene ^ I) and then has much better weather conditions.

This makes it possible to produce roofing felt that can withstand the weather without a mineral coating can be exposed.

I ^- Ur AuIk liver, a content of I is to less than 5 weight percent of a Polybutcn- (l) having a molecular weight of KK) (KK) to 2 (KK) (XK) and IO "> is 70" / ,, iiiherlöslichem Portion.

They are then suitable as "floating glue" between the various materials and plastics, z. B. between metals and polyolefins or dumber plastics and polyolefins. You can therefore used to cover steel tubes with foils made of polyethylene (hard or soft) or isotaktiüchem Polybutene-II) to be coated in a manner known per se or tubes made of fiberglass polycersler with the required liner made of said polyolefins to undress.

In the same way, containers with foils can vein Panels made of polyethylene, polypropylene or polybutene-il) are lined. Let these plastics do not stick with the usual adhesives.

To steel so z. B. to protect against abrasion (e.g. for slides, bunkers and self-contained railway wagons), one must use unusual tricks and usually drill through the plastic plates, locally screwed or clamped, the abrasion at the connection point has a point of attack at which the wear begins . The plastic panels to be applied can be delivered - coated with the connecting layer - and are then connected to the substrate by sintering the composite panel or by gluing with hot bitumen.

As a highlight, the mixtures also prove useful for attaching plastic road markings, preferably on bituminous road surfaces.

Since the adhesive adheres well to the asphalt and polyethylene, it has a wide plastic temperature range and must have good shear strength, here is also a mixture of bitumen and Polybutene {1} appropriate. The required conditions are from primary bitumen B 200 to B 45 or blown bitumen B 70/30 - both with? until 4.5% polybutene! 1) addition - to achieve.

Paint, preferably based on primary bitumen expediently have a content of 1 to less than 5 percent by weight of polybutylene- (l) a molecular weight between 100,000 and 2,000,000 and 0 to 75% ether-soluble content. The mixtures described are therefore suitable for outdoor use and / or wherever as a result Steepness of the painted surfaces the bitumen could run off.

For layering transport and storage containers Bitumen mixtures of this type are also suitable, especially where there is a high degree of plasticity Temperature range must be combined with good chemical resistance. There is an interest Chemicals that are still hot during production can also be filled while hot. Bitumen hold that are sufficiently cold-resistant, not always off.

The required plastic temperature range can, however, be improved with polybutylene- (1). This works by a content of 1 to less than 5 weight percent polybutylene (1) mil molecular weights between 1000000 and 3000 (KK) and 0 to 80% ether-soluble content.

Bitumen with high softening points, especially B 45 to 15, can be used for the coating of pipes. High vacuum bitumen B 85.95 to 95 105 and blown bitumen B 75.30 to about 115 15 are used are with a content of 2 to less than 5 weight percent Polybutcn- (l) with a molecular weight / between 100 0 (M) and 3 (KK) 000 and 0 until SO ", 1 ether-soluble portion. The mixture of liochniole-

tular, isotactic polybutene !!) with atactic Polybutene ^ 1) can bring additional advantages here. Me mixing in bitumen, the additional Containing polymer components can be advantageous if these polymer additives meet the requirements. When coating tubes, the conditions are this industry has to take into account the relatively small amounts of bitumen for a long time Withstands temperatures of around 200 "C. The coatings must then be used during assembly and transport Can withstand impacts and low temperatures and are as weatherproof as possible being. For installation, they have to be re-insulated using simple means at the welds and damaged areas can be. When installed, the insulation layer must still be resistant to the pressing through of hard objects such as stones, etc. These requirements become - as from the description the properties emerge - favored by the addition of polybutene (])

example 1

Bitumen B 200 is made with polybutene-f 1) - RSV = 0.9; 52% ether extract - in pieces of about 0.1 g weight in a thick-walled beaker (»chlorination pot«) heated to 170 ° C. within about 10 minutes. The mass is further with a paddle stirrer Stir for 5 minutes. The total amount of the mixtures is 400 g each, the concentration of polybutene-f 1) 0.5, 1, 2, 3, 4 and 4.8%. The property values of the mixtures according to DIN 1995 are given in A b b. 2 to 6 reproduced.

Example 2

Under the conditions of Example 1, B 300, B 80, B 65, B 45, B 25 and 3 15 mixtures with 1, 2, 3 and 4.8% polybutene are produced. In the case of B 25 and B 15, the temperature is increased to 180.degree. The property values are shown in Figures 2 to 6. ". 11th
^{& for} example 3

In order to determine the time and temperature required for homogeneous dissolution, the experiments from Examples I and 2 repeated and supplemented with other bitumen. This is done by hand stirred with the thermometer in order to be able to constantly observe the melt. The search mechanisms amount to 100 g each. The bitumen is poured into an enamelled steel container within 5 to 10 minutes Heated temperature given in the table. The polybutene! I) is in pieces of about 0.1 g [Type 952 *)] or .0.5 g [Type 665 *)] in one portion

♦) Type 952 bedculcl RSV = 0.9. Ether extrakl = 52 ",,
**) Type 665 means RSV ^ 0.6. Ether extract = 65 ",,

Type
B 200

B 300

B 80

bitumen

crowd

93
91

75

additive

Art

PE soft
PP iiiiiktisch

Ethylene-acrylic ester for bitumen

crowd

4.5

20th

I- ■

added and stirred by hand. The necessary for homogeneous dissolution within 2 to 5 minutes Temperatures are given as ranges; the amount is between 1 and 4.8% in all cases.

Bitumen type

Poly butene! 11- type "

Temperature (Cl

ίο B 300 to B 15 952 160

B 75.30; 105.15; 115.15 .... 952 170

B135 / 10 952 180

HVB 85 95; 95 105 665 160

HVB 130.140 665 180

Example 4

In order to determine the dependency of the dissolution speed on the To determine the molecular weight and of the ether extract, the experimental setup of Example 3, but constant at 160 ° C., attempts to dissolve each with 95 g of B 200 and 5 g of polybutene- (l), about 30 different ones Types carried out. The results are shown as "curves of equal dissolution times" in A b b. 1 reproduced.

Example 5

95 g of bitumen B 300 each are heated to 180 ° C. in the test order of Example 3, 5 g each Polybutene! 1) added to the composition given in the table below and until homogeneous touched. The values of the mixtures according to DIN 1995 are shown in the table.

B 3 (X)

95
95
95

Polybutene! 11th
isotic

Polybutcn-l I)
Type 665

4.5
3.5

2.5

trwei- Breeh Pene ching-
Point pimkl tration (C) I C) ('. in mm 35 -18 260 48 -20 150 50 -10 130

Example 6

In the test order of Example 3, vcr schicdcnc plastic or rubber products untei the cell temperature specified in the following table and quantity conditions are added Amounts and types of polybutene (1) given and stirred for 10 minutes. The properties are in the following Table compiled.

Temp (C)

Polybutene! 1) crowd Expansion
chungs Break Ig) Point Point ^ ohr / eit Tvm (mini ■ »Ρ (C) (C) 15th isotact. 4.5 54 - IS (39) (-17) 30th 952 5 S3 -21 (34) (-IH) 40 665 100 _ ti (46) (-12)

penetration

('mi mm)

80

(160)

IK)

(260)

15th

(901

continuation

bitumen crowd On Zusai / Temp. Ruhr / eit Pül) bulen- (l) crowd
ig! T> P 91 NK powder crowd 180 20th T> P 4th B 80 92 SBR chew
chuk
(as latex) 5 100-170 30th 952 4th B 200 4th 3570

Expansion Break chungs Point Point ι / ·. ί Cl -14 64 -16 66

penetration

40

45

The values of the initial bitumen are given in brackets under the property information.

Example 7

A 4.5% mixture of polybutene-) 1) is produced in the following way. 2.5 kg Poiybuten- (l), type 3570 (RSV = 3.5; "'7O% ether extract), are in a 5-1 kneader with 2.5 kg B 80 at 18O ⁰ C kneader temperature within 20 minutes (Kneader and bitumen preheated). 4.5 kg of this mass are added to about 45 kg of bitumen B 80 in a bitumen cooker and stirred homogeneously for about 10 minutes at about 180 ° C. These masses have a softening point of 63 ° C., a Breaking point of - 14 C and a penetration of 35 ¹ Z ₁₀ mm.

Application example 1 - ₀

In a continuous mixing plant, 10 t of fine asphalt concrete are produced from 630 kg of binding agent each and 9,370 kg of mineral compound each. The mixing temperatures are around 200 ^r C, the mixing times are 40 seconds when adding pure bitumen and 80 seconds when adding bitumen and polybutene ^ 1). Polybutene with RSV = 0.9 and 52% ether extract is added in fist-sized lumps and is distributed homogeneously within the mixing time. The three 10 t batches are transported to the construction site, as is customary in road construction, and remain at over 160 ^° C. for up to 5 hours until they are installed.

The paving is carried out with a paver type »Vögele, Super 150«, between the individual mixes no difference found in the installation. When solidifying with the roller, the faster one shows up good compression the more polybutene ^ 1) is added. During installation, samples are taken that show the result in the following values:

PoKhulcn-dl-

crowd
in the binder

0 3 4.5

softening

punkl
(R 11. k- C)

50

59

Maivh.illprtifiiim

stability
Iki ·)

610
670
710

(',, mm 1

38
46
52

55

60

For road construction, compounds with 0.5 to less than 5 percent by weight of polybutene ( I), which has a bulk density of 0.86 to 0.92. a jither soluble fraction of 0 to 80 "" and a molecular weight between M) (K) O and 4000000.

Application example 2

1 liter of mastic asphalt is produced in a continuous mixing plant, as indicated in the table and laid in a test area. The mixing temperatures are around 220 C. The mixture is initially Prepared as usual in 40 seconds, then the isotactic polybutene is made as a powder and the atactic polybutene was added in fist-sized pieces and mixed for another 60 seconds. The installation takes place after about 3 hours of transport and storage. The initial volume is B 45.

"1
I l'oUbiiicn-l

Pumice

men isolak- T> P lish 357 » lkgl (kg 1 Ikul 75 72.5 I. 1.5 71.5 1.5 -)

Eruei-

cluings

punki

iR.u.k .. (Ί

60
67
71

Vcrformuiii! (mm) at

Roll the dice.

at

KKK) kp
load

2.7 1.9

Pris-mcn.

KX) kp cnr load

4.1 3.6 2.9

Application example 3

Roofing felt a) with primary bitumen and blown bitumen, b) and c) with different Primary bitumen with the addition of polybutene! 1) manufactured. Strips of 0.333 kg raw felt board 50 cm long and 10 cm wide are placed in impregnating bitumen at 200 C soaked and squeezed between two rollers preheated in the oven. The so The raw felt cardboard obtained is dipped into the top layer bitumen, which is also at a temperature of 200 C, and how pinched off at the top. Composition and properties are given in the table. The atactic one Polybutene-) 1) has RSV = 3.5 and 70% ether extract. The covering weights also contain 1 kg of slate powder each.

The samples are tested in accordance with DIN 52 123. Resistance to cold is tested with the bending plate 25. Deviating from the norm, the temperatures are varied upwards and downwards in such a way that they run off or breakage occurred. The resistance to whitings is tested in the Xenotestgeräl 450 from Hcraeus, Hanau. It corresponds to the covering weights used.

bad = blown bitumen.
good = ^{great 1} , bitumen.

Polybutenes suitable for roofing felt are preferred! Molecular weights between 100,000 and 3,000,000.

Request for input

BiuiiiK-n

T> P

lul

B 200 j 2 (X) O
B 3iio j 1900
B 300 19 (X)

PnKbulen-ih

lül

! 0

95

55 deck muw
Bilumen 'I'uKbrlen-

I. T) P (gl

B 75 30 2000

B25 j 1900 j

B26 1900 40

cliché Wfirmc-
beslfin-
diukeil K-eldc-
besli-
diukeil Wiilerunus-
hcMUiniliii-
wedge (Ul I C) (Cl I Ci 73 -14 bad 95 72 - 8th Well 55 74 - 7th Well

Application example 4

üiii sandblasted steel pipe with an outer diameter of about 2 (X) mm is preheated to 80 C in a heating cabinet, a mixture of 95.5 parts bitumen B 65 and 4.5 parts polybutene! 1) (RSV = 4 / j; 35% ether extract! Is applied to the pipe with a hand broom in an approximately 1.5 mm thick layer at 130 ° C. Immediately afterwards, a strip of film 12 cm wide and 0.7 mm thick is pulled gently wound onto the bituminous layer so that the film overlaps about 3 cm . The area of overlap is additionally coated with the bitumen mixture. The wound pipe is then stored for 30 minutes at 100 ° C. so that the coated areas do not lie on top.

Application example 5

Air-dry bricks ("clinker") are made with about 1 mm thick layers of different compositions painted and, after cooling, exposed to temperatures increasing from 5 to 5 C for 2 hours. In the table, in addition to the composition, the temperature is given at which the first significant Deformation is observed.

'5 B 300
B 200
B SO
B 45

B 300
B 200
B SO
B 45
B.

25th

45
B 25

men Polxhulcn-II Parts utuklisch Parts " ^T > JL - Parts - KX) - 100 - 100 2 3 100 3570 4th 95 2 665 3 96 2 95 5 98 3570 3 95 952 97

I let begin

35 40 45 55 50 50 60 60 65 75

35

Hot paints expediently have a Ciehah of I to less than 5 percent by weight of polybutene! I. with a molecular weight between 100,000 and 2,000,000 and an ether-soluble fraction of 0 bb 75 "»: for tubes, mixtures containing 2 to less than 5 percent by weight are particularly suitable Polybulene (l) with a molecular weight of 100 * 0,000 and 3 (X) OOOO and an ether soluble Own share of 0 to 80%.

In addition 9 sheets of drawings

Claims (3)

Claims: 2018 1.Thermoplastic mass made of bitumen and a thermoplastic material that has been dissolved in it, characterized in that they are made from more than 95 percent by weight of bitumen possibly contains other known plastics, rubbers and / or organic additives, and less than 5 percent by weight poly- ίο butene (l) with a molecular weight between 40,000 and 4,000,000. 2. A method for producing the thermoplastic mass according to claim 1, characterized in that characterized in that the polybutene (l) is in the form of a concentrate of 40 to 80 parts by weight of polybutene (l) and 60 to 20 parts by weight Bitumen is used. 3. Thermoplastic mass according to claims 1 and 2 as a binder for road construction, Roofing felt, hot glue and hot paint.