DE1594796C3 - Roofing compound based on bitumen containing polymers - Google Patents

Description

3 4

from 350 to 450, preferably from 370 to 430 Saybolt- increase toughness, tensile strength and hardness; Alles

Seconds at 99 ° C (SSF, measured in the Saybolt-Furol - these characteristics were unpredictable. The increase

Viscometer). the hardness due to the presence of the chlorinated poly-

Instead of or in addition to the soft, direct phenyl resins in the compositions according to the invention

bar in the oil refining resulting bitumen 5 z. B. in direct contrast to their effect

Varieties can be used to build the neoprene according to the invention (polychloroprene), in which the polyphenyl

In bulk, a limited range of blown resins also act as plasticizers.

Use bitumen, namely those whose er- The present in the compositions according to the invention

softening point is between 43 and 85 ° C. It is characterized by chlorinated polyphenyl resins it was found that when using stronger io a very good solubility in benzene and toluene and

blown bitumen, d. H. of those with higher solubility in acetone or methanol.

Softening points, the breaking length of the finished mass The one polymer component of the invention

decreases significantly. block copolymers representing masses

The use of blown bitumens has increased the general configuration A-B-A, in which the hardness and tensile strength of the resulting 15 A each are essentially a polymer block of a vinyl-substituted composition. Most suitable blown aromatic hydrocarbon is, namely vorBitumen having a softening point between 46 preferably styrene, but homologs and and 8O ⁰ C. A rule for determining the vis- analogs of styrene such. B. the alkylated in the ring viscosity of such bitumen is found in the American styrenes, such as vinyl toluene or alphamethyl styrene, single-channel standard ASTMD-2170-63T; the definition 20 are related; the middle block B is a polymer block and the softening point can be determined from that of a conjugated diene. Particularly suitable con-ASTM regulation D-36-62T can be found, and the above-jugated dienes have 4 to 5 carbon atoms in the said Saybolt viscosity is determined according to ASTM D 88-44 molecule, although polymers of conjugated ones are also determined. Serving higher molecular weight in place of or

The present benützten to build up the masses 25 according to the invention together with those of C ₄ _ ₅ dienes chlorinated Polyphenylharze can be lend. The preferred dienes are therefore primarily the important butadiene and isoprene in the end product, but methyl property can also be used to increase the fire resistance, but isoprene.

Surprisingly, also the hardness and tensile strength The terminal blocks A have a medium MoIe-

of the product. The extent to which a gross weight is between 8,000 and 45,000, during the

set of chlorinated polyphenyl resins on the physi- central block B a molecular weight between

kaiischen properties of the masses is supposed to have from 40,000 and 125,000. The best combination

can be seen in the examples. nation of physical properties is achieved,

In order to have the maximum effect in terms of fire when the terminal plastic blocks, e.g. B. the

resistance and physical properties 35 polystyrene blocks, 23 to 40 percent by weight of the material

to obtain, one uses the resins in amounts of complete block copolymers,

between 15 and 35 percent by weight, preferably the most effective and therefore preferred class

between 20 and 30 percent by weight, based on that in which the polystyrene end blocks are

three essential components, namely bitumen, average molecular weight from 9000 to 20,000

Block copolymer and chlorinated polyphenyl 40 have and 25 to 28 percent by weight of the total

resin. Another defining characteristic of the resins make up block copolymers, during the

is that they have an average molecular weight of 30 to 65, preferably 35 to 55, weight central diene block

contain percent chlorine and preferably has an Er between 45,000 and 100,000,

softening point between 50 and 200 ° C, in particular

those between 150 and 195 ° C (determined according to the 45 suitable block copolymers are the following:

ASTM method E 28-51 T) have pollen. Polystyrene-polyisoprene-polystyrene and

In most cases the resins do not need clear polystyrene-polybutadiene-polystyrene.
being; they can be colored because due to the

The presence of bitumen plays a role in the color of the resin. The block copolymers described above

generally does not matter. · 5 ° can be used as such or im up to any

It should also be noted that the presence of degrees of hydrated state can be used. your chlorinated resins within the known and common resistance to oxidation and ozone Borrowed rubbers based on kon- is significantly improved by the hydrogenation of the jugierte dienes leads to adhesives, in particular entire block copolymers up to one when an aromatic solvent is present. 55 degrees, which is at least 50% of the original un-dies is even more true as adhesive is on rubber saturation. The hydrogenation does not affect it or rubber base, usually rubber types, only in the sense of an improvement in the oxidation properties, which has not yet vulcanized and therefore in stability, but also increases the tackiness when softening The state of both the aroma point of the polymer.

table solvent as well as the added 60. The molecular weight values are due to the chlorinated resin is promoted. However, since in the he ratio between basic molecular weight and mass according to the invention, the block copolymers of osmotic molecular weight (intrinsic and osdie Properties of a vulcanized rubber (motic molecular weight) determined, the viscosi having and there is no volatile aromatic solubility measurements after the formation of each one If medium is present, it has been shown that the presence of polymer blocks has been made. These values The name of the chlorinated polyphenyl resins is precisely the one in which they agree with the tritium counts, which an reverse effect on the masses, d. that is, they under blocks and block copolymers with end pressures the stickiness, increase the modulus and permanent tritium were made.

The following examples, which explain the invention in more detail, show in particular the functions of the individual Components and the advantages that can be achieved thereby.

The roofing compound can contain fillers in proportions of 10 to 250 parts by weight> per 100 parts which have three basic components. The. Fountain pens can serve a variety of functions; she can e.g. B. a reduction in stickiness, an increase in hardness or a reduction in production costs cause. You can use the usual fillers, such as whipped chalk, asbestos, pigments, ground Shale or crushed rock can be used.

example 1

The function of the chlorinated polyphenyl resin to increase the hardness, the modulus (voltage value) and tensile strength are shown in the following comparative examples. That for these purposes The bitumen used was a flowable mass with the following properties:

Flash point 313 ° C

Soluble in CCl ₄ 99.8 percent by weight

»Oliensis test« *) negative

"Spot test", heptane-xylene

Equivalent **) 20 to 25

Viscosity up to 99 ° C 410 SSF

♦) “Oliensis test”: see ASTM method no. D 1370-58 (ASTM standards on Petroleum Products and Lubricants, Vol. IH, 39th edition [1962] pp. 473/474).
· *) "Spot test", heptane-xylene equ. see “American Assoc. of State Highway Officials ", method T102 / 42.

From the values given it can be seen that the bitumen is too soft in the unmodified state, to have an appreciable tensile strength at room temperature. The one used for comparison Block copolymer was a polystyrene-polybutadiene-polystyrene with an average block molecular weight of about 12,000-59,000-12,000. The chlorinated ones Polyphenyl resins had the chlorine contents and softening points given in Table I. Be it ίο emphasizes that every single one of the chlorinated polyphenyl resins the physical properties required of good quality roofing materials, significantly improved (see Table I).

Example2

The influence of fillers on the physical properties of the three basic components The composite roofing material can be seen from the values given in Table II. As a filler whiting and asbestos were used to modify the composition of sample B. would. For comparison purposes, samples A and B from Table I are listed again in Table II. It should be noted that the addition of

asbestos and whiting chalk both the hardness and the Tensile strength of the masses improved (cf. Table II).

Example 3

Table III shows the influence of the various proportions of bitumen in relation to the other components on the physical properties of the resulting masses. For comparison purposes Table III shows the composition and physical properties of the Sample A repeated.

Table I.

composition Weight Weight Weight Chlorinated polyphenyl E.-P. ¹ ) properties Weight
share - Chlorinated polyphenyl E.-P. ¹ ) 10 Weight _ 300% Fracture- Tear length % properties 300% breakage Softening Tear in sample share share share block Shore - 41 share - module *) elongation in in 1500 Shore point in Module ¹ ) elongation length ¹ % bitumen bitumen polymer % C1 134 ° hardness 150 _ 26th _ 280 kg / cm ¹ 900 hardness ⁰ C in 400 100 85 ° 150 % Cl 134 ° 23 150 26th 8.45 900 111 kg / cm ¹ 1500 A. 400 100 39 95 ° 150 134 ° 39 150 92 13.4 900 132 900 B. 400 400 100 51 204 ° + 150 _ 34 74 13.1 800 140 26 8.45 387 C. 400 400 100 55 204 ° + 150 39 43 7.35 800 10 146 92 13.4 D. 400 400 100 54 39 82 16.9 41 - - 19.3 E. 400 100 - 94 17.6 78 - F. 'TT chalk table composition sample Weight share block asbestos polymer A. 100 _ B. 100 - G ' 100 100

^l ) E.-P. = Softening point.

*) Stress value at 300% elongation.

table 400
233
233 Weight
share block
polymer Chlorinated polyphenyl
% Cl E.-P. ¹ ) weight
share chalk asbestos properties
Shore- 300%
Hardness module ² ) 26th
390 fracture
strain
in
kg / cm ¹ Tear
length
in απ 100
100
100 39 134 ° 150 333
333 67
67 10
44
51 8.5
25.0
29.3 1500
275
394 composition
Sample weight
share
bitumen A.
H
J

^x ) E.-P. = Softening point.

^s ) Stress value at 300% elongation.

Claims (3)

1 2 consists of three components, namely 1.) from 45 to claims: 75 percent by weight of a bitumen directly from the refining nation with a viscosity 1. Roofing compound based on poly between 350 and 450 Saybolt seconds at 99 ° C bitumen containing mers, characterized by a 5 or blown bitumen with a softening mark, that they essentially consist of a point between 43 and 85 ° C or a mixture consists of three components, namely 1.) from 45 to from both types of bitumen; 2.) from 15 to 35 weight-75 Weight percent of one immediately from the percent of a chlorinated polyphenyl resin with a Refining bitumen with a Vis chlorine content of 30 to 65 percent by weight and 3.) viscosity between 350 and 450 Saybolt seconds from 10 to 30 percent by weight of a block copolymer 99 ° C or a blown bitumen with merisates of the general constitution A — B — A, a softening point between 43 and 85 ° C where A is each for a polymer block of a vinyl or a mixture of both types of bitumen; substituted aromatic hydrocarbon and 2.) from 15 to 35 percent by weight of a chlorinated B for a polymer block of a conjugated diene Polyphenyl resin with a chlorine content of 30 15, and the average molecular weight of A. up to 65 percent by weight and 3.) from 10 to 30 Ge between 8000 and 45000 and the average molecular weight percent of a block copolymer the weight of B is between 40,000 and 125,000 and . general constitution A-B-A, in which A is the total content of the block copolymer because for a polymer block of a vinylsubsti- polymer blocks A 23 to 40 percent by weight tuierten aromatic hydrocarbon and B 20 carries, and / or a hydrogenated derivative of a sol- for a polymer block of a conjugated diene block copolymer, stands, and the average molecular weight of A The unexpected properties of the invention between 8000 and 45000 and the mean molar mass show up in a surprising Weight of B between 40,000 and 125,000 Improvement of the physical properties, in particular and the total content of the block mixed poly- 25 special the breaking length, elongation at break, des merisates of polymer blocks A 23 to 40 Ge modulus (tension value) and the hardness, however, is is by weight, and / or a hydrogenated one is also remarkable that these highly skilled Derivatives of such a block copolymer. Roofing fabrics have excellent weather resistance 2. Roofing compound according to claim 1, characterized speed and toughness is inherent. In addition, the chlorinated polyphenyl resin surprisingly has a largely fire-resistant resin with a softening point between 50 and 200, which is particularly remarkable.
preferably between 150 and 195 ° C. The above-mentioned block copolymers, the 3. Roofing compound according to claim 1 or 2, an essential part of the invention characterized in that they form a filler in moderate proportions, are a special class of in an amount of 10 to 250 parts by weight, being an elastomer which improves the properties of a vulcanized material to 100 parts of the three basic ingredients, canised rubber, but without containing vulcanized rubber. to be canized. Their use within the meaning of the invention means a technical and economic advantage over the use of similar 40 borrowed known elastomers based on conjugated Serve that a vulcanization treatment Require bitumen from oil refining if the masses prepared with them (formerly also called asphalt bitumen) is known to have really good physical properties tes material for the production of roofing parts. and coatings that are used as asphalt paints, solution 45 In addition, it has been shown that the above Medium-cut, single-layer membranes, shingle block copolymers extremely compatible or brick-like panels can be used. are with the bitumen of the type in which the The material, which is very useful in many respects, is limited in its discovery. However, with regard to some physical properties, the bitumen types as the basis for the defective in accordance with the invention, and it appears desirable that these 50 equivalents are limited to a ratio of properties to improve. You have a moderately small selection. If bitumen is used Efforts to improve by adding varieties that have the properties described above do not know rubber types on the basis of conjugate, so is especially the resistance jugate Like neoprene, they are used by resins or by filling capacity against sagging masses mean and hoped that this would make the physical properties worse. If bitumen is used, their Erschaft of the bituminous binder is at least partially higher than the softening point described above, so to be able to improve. This purpose was admittedly noticeable in the breaking length of the resulting mixtures one or another property of the borrowed back. Bitumen, but certain deficiencies could be found. The chlorinated polyphenyl resins mentioned above Do not eliminate aHein with additives. So the 60 will serve to reduce the stickiness of the mass of bitumen known masses, even if some of them reduce one and block copolymer and are equally awarded Weather resistance and good sealing to increase their hardness and stiffness so much that have management and binding properties, yet easily they are suitable for roofing purposes and not so Sticky in the heat, and also other physical soft and limp that the coatings at Properties often leave a lot to be desired. 65 are no longer accessible in hot weather. The roofing compound according to the invention on the The types of bitumen required for the inventive The basis of bitumen containing polymers is used masses are proportionate characterized in that it consists essentially of soft; their viscosity is within a range