DE1770340A1 - Bitumen masses - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MIJ. N.V., Haag / NETHERLANDS

concerning:

"Bi tumenmas s s"

The invention relates to new bitumen compositions. As well as

asphaltic bitumen as were thermoplastic polymers

already for industrial purposes, e.g. as a grouting i

compounds, adhesives, protective coatings, impregnating agents and

Covering materials used. Because of their rheological

however, mechanical properties become thermoplastic Polymers highly preferred. Urn asphaltic bitumen for the

to make the mentioned purposes more suitable, was

already proposed thermoplastic in this bitumen

Incorporate polymers. Mixing asphaltic

Bitumen with thermoplastic polymers, however, often leads

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BATH ORIGINAL

to unstable products that are unsuitable for industrial applications. When stable products are obtained, it often shows that their composition is heterogeneous. This heterogeneity makes these products stable less suitable for most industrial applications.

It has now been found that, by selecting the suitable bitumen component and the suitable polymer component in the mixture, it is possible to obtain masses which are both stable and have a homogeneous structure and, because of their rheological and mechanical properties, are outstandingly suitable for industrial applications. For this purpose, the bitumen components and the polymer components must meet three conditions. The bitumen component must be a residue from the distillation of bituminous or precipitation of a n-heptane asphaltene content of less than 2 wt -.%, A penetration of less than 2000 at 25 ° C and a softening point below 80 ⁰ C.

™ owns. The polymer component must be thermoplastic

and

Polymer with a molecular weight above 10,000, a

be

Solubility parameters between 7.8 and 8.8 and a crystallinity below 60 % at 25 ° C. The amount

of polymer component in the compositions can range from 5 to ^l j0 wt -.%

are sufficient.

The new bitumen compounds according to the invention are thus characterized by a content of ^ O to 95 wt .- #

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bath

a bituminous distillation or l'ällungsrückstands with a n-heptane asphaltene content of less than 2 wt -.%, a penetration of less than 2000 at 25 ° C and a softening point below 80 ⁰ C as bitumen component and from 5 to 50 wt .- ^ of a thermoplastic polymer with a molecular weight above 10,000, a solubility parameter between 7.8 and 8.8 and a crystallinity below 00 % at 23 ^° C. as a polymer component.

The sizes of the n-heptane asphaltene content, the penetration, the softening point, the molecular weight, the solubility parameter and the crystallinity used to define the appropriate bitumen and polymer components are determined as follows:

(1) The n-heptane asphaltene content is determined in accordance with IP-IV3 certainly,

(2) the penetration is determined according to ASTM D-5 and expressed in units of 0.1 mm,

the softening point is determined by the ring and ball method according to ASTM D-J56,

(4) the average molecular weight (M) is determined viscometrically,

(j) the solubility parameter is expressed as the square root of

1 09 84 2 / 1_3.98

BATH ORIGINAL

Cohesive force density calculated, a quantity that can easily be derived from swelling tests with different polymers Solvents can be determined,

(6) the crystallinity is ntttels in the usual way X-ray diffraction determined.

As bituminous distillation and precipitation residues that are suitable for producing the compositions according to the invention, residues from crude oil are particularly suitable. The arrears of crude oil distillation can either be common distillation residues or residues of vacuum distillation. As crude oil precipitation residues residues come into question, which in the case of JSnto.- contain residues of crude oil fractions can be obtained. This deasphalting can generally be carried out that the asphaltic Residue in contact with a low molecular weight aliphatic hydrocarbon, in particular with propane, is brought «Here a bitumen is precipitated and after separation an asphalt-free oil is obtained, which is used for production of lubricating oils is suitable. If the residues from the distillation or precipitation by means of distillation or Jiitasphaltierung of crude oils or residues of crude oil fractions having been obtained with a low content of n-heptane asphaltenes, they are generally as such useful. In most cases, however, contain crude oils and residues of crude oil fractions a significant amount

n-heptane asphaltenes and those therefrom by distillation or Residues obtained from precipitation are used to produce the

10 9842/1398

BAO ORIGINAL

fImmediate masses are not suitable without further measures. In order to produce suitable bitumen components from these asphaltene-rich base materials, a jin asphaltene operation other than distillation or precipitation should be carried out. This enfasphaltenisation can generally take place in that the asphaltene-containing residue is brought into contact with a low molecular weight aliphatic hydrocarbon, in particular with pentane. It then becomes M

an n-heptane-asphaltene-rich phase is precipitated and after the Separation, an oil phase with a low concentration of ri-heptane asphaltene can be obtained. To separate the Precipitated asphaltenes are preferred to use one or more Hydroeyclones. By applying the right ones Treatment temperature and the correct weight ratio Pentane with regard to the residue to be aspirated can products with a content of ri-heptane asphaltenes below 0.1 wt .- ^ obtained in a simple manner will. If the production of the residues with low asphaltene concentration is by distillation or precipitation is carried out together with an iin-fiberization, The order in which these procedures are performed may vary. iis can thus e.g. asphaltenize the Jin ^ be carried out on a residue of the distillation or precipitation, the distillation or precipitation of a Crude oil or a crude oil residue fraction

1 0 9 8 A 2/1 3 9 8

is. The desired residues can also be obtained by making a de-asphaltene residue a crude oil fraction is distilled or precipitated. In the preparation of the ßitumerir masses according to the invention by degasifying the residue of a crude oil fraction and subsequent distillation, care should be taken to ensure that the distillation temperature is above about 400 ° C, since n-heptane asphaltenes can be formed again at a higher temperature.

Very favorable results have been obtained by using the following still bottoms as Bitumen components in the production of the invention Masses:

(1) Residues from the distillation of a crude oil with a low n-heptane asphaltene content,

(2) Residues from the de-asphalteneization of residues from crude oil distillation,

(3) Residues from the distillation of deasasphaltenes Residues of crude oil fractions.

Although Ditumenkornponenten with a n-heptane asphaltene content of less than 2 wt -.% In general for the preparation of

1098O / 1398

Bitumen compositions according to the invention are suitable, bituminous distillation and precipitation residues are preferred to have a content of n-heptane asphaltenes under 0.1 - possess.%.

With regard to the penetration values and the softening point of the bitumen components, those components are preferred which have a penetration below 500 at 25 ° C

and a softening point between 25 and 6O ⁰ C be g

sit.

The thermoplastic polymers which are suitable for the production of the bitumen compositions according to the invention,

preferably have molecular weights greater than 50,000.

With regard to the crystallinity, it has already been stated that

that this should be less than 60> j at 25 ° C.

However, polymers are preferred which have a considerable amount have lower crystallinity, especially amorphous

Polymers. f

Ks got good results by using thermoplastic Achieved polymer made by polymerizing olefinically unsaturated monomers are. These polymers can be either homopolymers or copolymers. Depending on the choice of monomer these can be divided into the following two groups:

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(1) Polymers made from monomers that are exclusively carbon and contain hydrogen. Examples of such polymers are polyisobutylene, polyisoprene, polybutadiene, Ethylene-propylene copolymers and styrene-butadiene copolymers. Good results have been obtained using polyisobutylene and ethylene-propylene copolymers achieved as a polymer component in the production of the bitumen compositions according to the invention.

(2) Polymers made from monomers which, in addition to carbon and hydrogen, at least partially have 1 or more others Contain elements such as oxygen. Examples of such polymers are ethylene-vinyl acetate copolymers, Ethylene-ethyl acrylate copolymers and ethylene-n-butyl acrylate copolymers. Favorable results have been obtained using copolymers of ethylene with vinyl acetate or obtained with n-butyl acrylate in the production of the bitumen compositions according to the invention.

Although it is possible to obtain stable homogeneous mixtures with interesting rheological and mechanical properties by using these polymers as a blending component for bitumen with a low asphalt content, however, it is preferred to use a particular group of block copolymers for this purpose. This are block copolymers of the general formula A-B-A, wherein both groups Λ similar or dissimilar polymer

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blocks of a monovinyl-substituted aromatic

Are hydrocarbon and B is a polymer block of one conjugated diene is. These block copolymers possess at room temperature the properties of a vulcanized

Rubber. The disappears at a higher temperature

vulcanized character, which makes these block copolymers excellent dispersible in molten bitumen materials.

can be yawed. When these mixtures cool down,

the vulcanized character of the block copolymers M reverses

back and it will be very elastic rubbery

Obtain products with excellent processability.

Both the polymer blocks A and the polymer block B can

fully or partially hydrogenated.

The polymer blocks A preferably have an average molecular weight in the range from 7,500 to 100,000, in particular from 10,000 to 50,000. The polymer block B preferably has an average molecular weight in the range from 25,000 to 1,000,000, in particular from 35,000 to 150,000. The amount of polymer clocks A in the block copolymers ranges preferably from 10 to 70% by weight, in particular from 20 to 50% by weight. Examples of monovinyl aromatic compounds which are suitable in the preparation of the polymer blocks are styrene and methyl styrene. Suitable conjugated dienes in the production of the polymer blocks B are preferably dienes with k üis 8 carbon atoms per molecule, in particular iJuta-

10 9 8 A 2 / Ί % 9 "8 _BAD

177034G 10

diene and isoprene.

Examples of suitable block copolymers are polystyrene-polyisoprene-polystyrene and polystyrene-polybutadiene-polystyrene. Preferably a block copolymer Styrene-butadiene-styrene as a polymer component in the Production of the bitumen compositions used according to the invention.

The masses can be prepared in a simple manner by stirring in the polymeric component as finely divided Solid or in the form of a solution in, for example, benzene or toluene in the molten bitumen component take place. The solvent can then be evaporated.

The bitumen compositions according to the invention are suitable for a large number suitable for industrial uses, e.g. as grouting compounds, Adhesives, protective composition, impregnating agents and covering materials. The masses can also be used in the t3au by J bream.

Depending on the intended application, it is possible to also incorporate other substances into the masses, in addition to the bitumen component and the polymer component. This includes essentially all materials, which are generally mixtures of bitumen and polymers be added. Examples of such substances are glass fibers,

109842/1398

- ¹⁰ - ^BATH

As best fas era, - talc, sand and soot. These substances can in different mixing ratios in combination be used with the bitumen compositions according to the invention. The ratio of the bitumen component to the polymer component in such masses, however, should be so., that the masses 5 to 50 parts by weight of the polymer component, calculated on 100 parts by weight of the mixture of bitumen and polymer. ^

When used as an adhesive, those compositions are preferably selected which contain 5 to 25 parts by weight of the polymer component, based on 100 parts by weight of the mixture of bitumen and polymer.

When used as a jointing compound, compounds that are preferably 25 to 50 parts by weight are selected the polymer component, calculated on 100 parts by weight of the mixture. made of bitumen and polymer.

The invention is illustrated by the following examples explained in more detail.

A number of bituminous compounds were made by mixing the the following bitumen components and polymer components are produced: ~

- 11 -109842/1388 _BAD ORISINAU

177034G

Polymer 1: styrene-butadiene-styrene block copolymer

M _v = 100,000, solubility parameter 8.50, crystallinity 0 %,

Polymer 2; Styrene-butadiene-styrene block copolymer,

M _v = 92,000, solubility parameter 8.6O, crystallinity 0 %,

Polymer 3: ethylene-vinyl acetate copolymer, M 50,000, melt index (according to ASTM D-1238) 45 to 65, solubility parameter 8.6O, crystallinity 5 %.

Polymer 4: ethylene-vinyl acetate copolymer, M 50,000, melt index 22 to 28, solubility parameter 8.40, crystallinity 18 %.

Polymer 5; Ethylene-vinyl acetate copolymer, M 50,000, melt index 12 to 18, solubility parameter 8.35, crystallinity 22 %.

Polymer 6; Ethylene-vinyl acetate copolymer, M _v 50,000, melt index 5 to 7, solubility parameter 8.35, crystallinity 22 %.

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Polymer 7: ethylene-vinyl acetate copolymer M 50,000, melt index 335 to 465, solubility parameter 8.3o, crystallinity 28 %.

Polymer 8: ethylene-vinyl acetate copolymer M 50,000, melt index 16 to 22, solubility parameter 8.30, crystallinity 28 %.

Polymer 9: ethylene-vinyl acetate copolymer M _v 50,000, melt index 2.1 to 2.9, solubility parameter 8.25, crystallinity 38 %.

Polymer 10; Ethylene propylene copolymer M = 150,000,

Solubility parameter 7.95, crystallinity 0 %.

Polymer 11; Polyisobutylene, M _y = 100,000, solubility parameter 7.95, crystallinity 0 %,

ability parameter 7.95, crystallinity 0 %,

Polymer 12; Polyisobutylene, M _y = 420,000, solubility

Polymer 13; Polyisobutylene, M _y = 1,200,000, solubility parameter 7.95, crystallinity Ό %.

Polymer 14; Ethylene-n-butyl acrylate copolymer, M ": - 50,000,

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177034G

Solubility parameter 8.10, crystallinity 50 *.

Polymer 15: polyethylene, M _v 50,000, solubility parameter 8.00, crystallinity 65 %.

Polymer 16:

Polypropylene, M. 50,000, solubility parameter 7.95, crystallinity 95 %.

Polymer 17:

Polystyrene, M = 200,000, solubility parameter 9.10, crystallinity 0 %.

Polymer 18:

Polyvinyl chloride, M - - 50,000, solubility parameter 9.60, crystallinity - 60 %.

Bitumen 1:

Bitumen a penetration 1800-2000 at 25 ⁰ C, softening point 25 ° C, PI = -1.9,-heptane asphaltene content of 0.1 wt n? from the de-asphalteneization of a normal distillation residue of a crude oil from the Middle East with pentane.

Bitumen 2:

! Bitumen penetration 8C0 üei 2 3 ⁰ C, 26 ⁰ C iirweichungspunkt, PI = -0.5 and n-heptane asphaltene content -. 0.1 -fo from the ErA asphaltenisierung a residue of vacuum distillation of a crude oil from the

middle east with pentane. - 14 -

109842/1398

Bi gymnastics j ?: bitumen penetration yy at 25 ⁰ C, softening point of 44 ⁰ C, PI = -1.1 and n-heptane asphaltene content - '.0.1 wt -.% As .Rückstand the vacuum distillation of a by normal distillation obtained residue of a crude oil from the Middle East, which is dasphaltenized with pentane.

Bitumen 4: bitumen of penetration 54 at 25 ° C, softening point of 44 ⁰ C, PI = -2.3 and a n-heptane asphaltene content of 1.1 weight - from ° Ό as a residue of vacuum distillation of a crude oil. the far east.

Bitumen ^: bitumen of a penetration 12 at 25 ⁰ C, softening point 54.5 ° Ci PI = -2.7 and an n-heptane-asphaltene content of 1.8 wt .- ^ as a residue of the vacuum distillation of a crude oil from the distant East. ■ ■ "

Bitumen 6: bitumen of a penetration 88 at 25 ⁰ C,

Softening point 45 ° C, PI = -12 and n-heptane-asphaltene content HjO% by weight as vacuum residue during the distillation of a crude oil from South America.

Bitumen '(ι bitumen a penetration 94 at 25 ⁰ C,

109842 / tlÄ

Softening point 46.5 ° C, PI = 0.5 and a n-heptane asphaltene content of 14.0 wt -. ° / o of the part bubbles of a residue of the vacuum distillation of a crude oil from the Middle East ·

Bitumen 8: bitumen with a penetration 21 at 25 ° C., softening point 89.5 ° C., PI = 3 * 5 and n-heptane P · asphaltene content 25.0% by weight, obtained by

Blowing a residue from vacuum distillation of a Middle Eastern crude oil.

62 bitumen compounds were produced by mixing one of the R & ymer components 1 or 14 with one of the bitumen components 1 to 5. B ¹ The penetration at 25 ^° C., the softening point and the penetration index were determined for each mass. The penetration temperature curve between 0 and 60 ^° C. was used to determine the penetration index. The mixing ratios and properties of the mass are given in Table I.

TABLE I:

- 16 109842 Π 398

OXONONUIVJI Ul VJl VJl VJl VJl VJl VJl Ul 4 = -4 = -4r-4 = -4 ^ 4 = -4 = -4 = "4 = r 4 = -V> l V) IV) IVJlV) IV) IVjIViIV) IViIrUrOrOrOrUrOrUrOrOrOHHHHHHH MHH IV> M OVD CO-Q ONVJl 4 = -VjJ ΓΟ H OVD CO— 3 ONVJl 4 ^ VjI ΓΟ HOVO CO — 3 ON VJl 4 = rVjlfOHOVOCO — 1 CJlUl 3 JrVJVOI-ItjlUl JrVjI

ovoco — 3

JVjI ΓΟ μ μ ΓΟ VjI ΓΟ H VjI ΓΟΗ UlVjirOHtOHVjIVjirOHH VjirOHH 4 = · Vj) ΓΟ HH ') O OVJl QVJiÖQÖQVJlQQQVJlQQQQQQUlQQQVJlQUlQQUIOUlQQQUlQQUlQ

_l ro H H VjI VjJ ΓΟ H H

U) -Q-QW-QVS <3 .Q A »Ui ο Ui

VJl VjJ ro I- · -5 VJl

ö'ö'ö'ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo

MMMMH ¹ MMMV- ¹ MMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMI- ¹ MMMMMMMMMMMMMMMMMMM

Previous year

-3-3 COCOV

VQ

CO— 3 COV

ro

COV

ι ΓΟ H H η H O O VO CO CO CO CO CO -3-3-3-3-3 ONVJl VJIUIUIUI 4 ^ 4 = -4 ^ -l

1 VD Ul -O GDVO CO CO ~ J —3 COCOVO VO - J COCOVDVD ON — 3 CO COVO VO-3 CO COVO VO —3

ι COVOVD -3-3 CO COVD VD -3 COVJl-J COVD VD VO

öiöJtDöJttCdtiJöWttMö H- Η · H "H- Η · Η · Η · H- Η · Ρ · Η · Μ ·

OJrjJtebJrjJtDCdötjJüJ

H- Η · H- Η · Η · Η · Η · Η · Η · H- Η · H- Η · Η · Ρ · Η · Ι- ¹ · Η · H- Η · Η · Η · Η · Η · H- H- H- H- H- H- H- H- ti) H- Η · H- H- H- H- H- H- Η · H- H- H- H- H- > +

<- ^ c + c ^ (Γ ^ cl · cH- <Γ ^ c + d-c ^ ctΓ ^ d · c ^ cl · cl · c + cl · ctctc ^ ctc + c + c + rf

Vj) Ci-

rororororororororororovjivjivjj Vjj vjjvji vjj Vjj ν »VjJ Vjj Vji v» Vjj v> i vji Vjj Vjj v> j vji v> i Vji vjj vjj Vjj vjj \ jivjjvji4 = r4 ^ j = -4 = r4 ^ j = -4

fei ρΓ 4 W

• M

0 B)

ro g

?! ■

1 ti

M.
ro cj \ Oncoct \ -j ι

ONCOVJlVjIVjJ 4 = "

_. _ \ Vjl ^ -J -3Ul 4 ^ ONH H VjJ H rO4 = -4 = -VJ14 ^ V> JVjl 4t-U1-OnhVjI 4 ^ 4 = -VJl ONrO4 ^ UlVJl- <14 ^ Vjl ON- ~ q CO 4 = · 4 = " ^{- 3 OVjI H4 ^ VJ1VjI 1} OOOVJlOOOOOrOO I VjlVDUlOCOVjlVjlHCOVOVDONUlOrOON - 3 COVD ΓΟ ΓΟ - SONhVjJhUI - JUIVO - 3 00N4 ^ V> irOO

Ui ui '· .

HH M ir
VD M CO 4 ^ C
O CO 4 = - OO

O ON ΓΟ M -3 Ul l4 = -OON4 = -OC04 = rVjlON4 = -VjlVjl ΓΟ CO-J η 4 ^ ON COCOON ΓΟ Ul VjJ ON 4 = -VjJ-J OO ΓΟ

O CO-3 ON ON ONUl -3 ON ONUl Ul CO- <1 ONONVJlUl ONONUlUlUl ON Ul VJl 4 ^ 4 ^^ COON ONVJl 4 = "4 ^ ΓΟ ONh O CO CO -J Ul CO 4 = -VO ONVjI -J O Ul H COUl Ul O Ul ΓΟ VD ONUl O COUl H VJl -J 4 ^ -q 4 = - OOVO -) ro W OMÜ O \ H 0 \ 0 ChO Jr

Ui vji

VJl Ul Ul Ul

Ul

Ul ul. Ul

Ul UlUl

Ui Ui

Ul ul

VJl

& cd

CD ti H-CS

Γ0 4 Ul P Oc + O HO 3

2 part

R- (D

c + H-

- O

P 3

ir ir ¹

I ONVjJ Γ0ΟΗ | C04 ^ H I -3 VjI O I VJlVjirOH ι ONI ONUlVjJOOIOHHOO l - <! VJ14 = -VjjHVjirO.MHOHOOOH'ONrOVD — JVjlOVOVOUlVjirOCOONVjl

O ^ ^ U Ό Ό

ι ONI ONUlVJOOIO

ON O Ol ^ -3 VQ ^ 3VJlUl Ό Ό CO OVjirOPO OH VjI O 4 = "Ul 4 ^ -3 VjI CO

+ + + + II + H + + + I +
OHOOOH'ONrOVD — JVjlOVO

CO COUl VjI VJl -pr VjJ CO O Γ0 VJl ON 4 = · 0OVjJ Γ0 H 4 = "ΓΟ VJl PO VJl O OO O COVD O * C0

Meissen 1 to 62 were all stable and also homogeneous. Regarding the terms "staoil" and "homogeneous" apply the following characteristics:

. A stable mass is characterized by the fact that the components do not separate after melting. When the components separated, the mass was considered to be instaoil ρ.

A stable mass can be described as homogeneous if it does not separate when it is spread out in a thin layer Components can be recognized. When discernible separate components appear, the mass is said to be heterogeneous.

If one compares the penetration values, the softening points

^ and the penetration indices of the masses according to Table I P of

with those with bitumen components having low n-heptane asphaltene content of the bituminous component itself so the following is apparent:

(1) Ethylene-propylene copolymers and polyisobutylenes cause the softening point to rise to a considerable extent, while the PI value increases only moderately,

(2) Styrene-butadiene-styrene block copolymers cause a 1 09 8 42/1398

_ 18 - ^{AD 0} WGtNAL

Considerable increase in PI values with only a moderate increase in softening point. This is related with the workability of the masses an advantage,

(>) Ethylene-vinyl acetate copolymers and ethylene-n-butyl acrylate copolymers have only a small influence on the softening point and the PI values.

For comparison purposes, 16 bitumen compounds were also used either by mixing one of the polymer components 1 to 14 with one of the bitumen components 6 to 8 or through Mixing one of the polymer components 15 to 18 with one of the bitumen components 1 to 5 or by mixing one of the polymer components 15 to 18 with one of the bitumen components 6 to 8. The mixing ratios and the stabilities of the blends are given in Table II.

TABLE II:

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TABLE II

Dimensions
No. 15 ί composition
Weight % 85: 6th stable, heterogeneous 63 10 5 % Pol. 2 + 90 ί 7th dto. 64 15 y * Pol. 2 + 85 ί 7th dto. 65 20 5 % Pol. 2 + 80 y 7th dto. 66 10 p % Pol. 2 + 90 ί 8th unstable 67 10 ^c , ί pin 11 + 90 5 8th stable, heterogeneous 68 10 ) ί pin 13 + 90 5 2 dto. 69 20 5 ί pin 15 + 80 5 2 dto. 70 30 5 S pin 15 + 70 p 2 unstable 71 10 5 ί pin 15 + 90 y 2 dto. 72 20 y 2 pin 16 + 80 "j 2 dto. 73 30 p 5 pin 16 + 70 5 2 dto. 74 10 y ¹ o pin 16 + 90 5 2 dto. 75 10 y 5 pin 17 + 90 y 4th dto. 76 1.0 Jl 5 pin 17 + 90 y 2 dto. 77 5 y 5 pin 18 + 95 y 8th dto. 78 5 pin 17 + £ bit. g bit. 2 bits. S bit. % Bit. C bit. g bit. ί bit. S bit .. S bit. S bit. 5 bits. t bit. ί bit. {Bit. 5 bits.

Most of the masses 6j5 to γ8 were unstable or heterogeneous to such an extent that no reproducible penetration or softening points could be measured.

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Tests for tensile properties were carried out on 6 compositions according to the invention using the method according to ASTM D-412 (B'ormkopf C). For comparison purposes, the same tests were carried out with a commercially available composition A consisting of 50% by weight of a copolymer of ethylene and n-butyl acrylate and of 50% by weight of an asphalt bitumen with an n-heptane-asphaltene content greater the mass was 10%. with 3 according to the invention and with the commercial product a, the loading tests were repeated after the compositions were stored with an oil absorbent substrate 5 weeks at 25 ⁰ C inBerührung.

The results of the loading tests are shown in Table III specified (the! foung module was calculated from the voltage curves found).

TABLE Uli

- 21 -

10984 2/1398

TABEL

III

Mass no.

30th

41

Weeks at 25 C on an oil-absorbing substrate

30th

62

Load limit ο

kg / cm

Tensile stress

2 kg / cm

Module 300 _%%

ο kg / cm

8.5

35

36

14th

9.9

9.9 13

46

2.5

17th

7.4

module

ρ kg / cm

2.0

Elongation at break yy 2000

Breaking load %

Young's modulus according to kg / cm Young hardness © Shore A

1600 20 5.5 38

3.3 21st 1260 780 - 460 - 16 57

9.3 15

840

3.4

23

8.5

510 970 141O 760 1100 310 660 18th 450 670 16 44 9.0 - 15th 39 72 mm

130

177034C

IS

The jirge onis se of the load tests result in the following:

(1) When comparing the tensile stress of the commercial product A with a content of 50 wt .- ^ o polymers! With the tensile stresses of the compositions according to the invention with a lower polymer content, it can be seen that the latter compositions, despite their lower polymer content, still have tensile stresses of the same order of magnitude. Λ

(2) Compositions of a bitumen component with a low n-heptane-asphaltene content and a styrene-butadiene-styrene block copolymer In addition to a fairly low modulus, they also have a very high elongation at break, Der low modulus is beneficial when making preparations should be used as jointing material and as adhesives, as these properties are effective Show relaxation on stress, creating stress concentrations be avoided at the bonding surfaces. .

The masses, the styrene-butadiene-styrene block polyesters contain practically no permanent deformation

(4) The compositions of the present invention are excellent Storage stability.

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_BATH

6 compositions according to the invention were investigated as adhesives for rubber sheets for masking purposes. This experimental set-up also produced 8 products examined with, however, not within the scope of the invention fall. These were initially the already mentioned dimensions 6j, 64, 65 and 66 and the bit urn component 8 and also 3 commercially available adhesives with the following composition:

Mass B: A solution of 35 % of a non-vulcanized rubber in a benzene fraction of the boiling range 58 to 121 ⁰ G.

Mass C: A mixture of unvulcanized rubber and an asphalt bitumen with an η-heptane-asphalt content of 1 ^ 10 %.

Compound D: A mixture of 25 wt .- ^ of Compound C and 75% by weight bitumen 8.

These compositions were tested as adhesives in the following manner. There were rubber strips of 2 mm Thick, 20 cm long and 1 cm wide on top of each other

glued on an area of 10 cm. Adhesion tests were carried out with these glued strips leads parallel to the binding surface and perpendicular to the binding surface. In the adhesion tests, that was

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BATH ORIGINAL

Uriverklete end of 2 strips over the whole 1 cm wide and pulled apart at a constant pulling speed of 5 cm per minute, either parallel or perpendicular to the binding surface. The results of the adhesion tests are in Table IV ".

TABLE IV:

109842/1398

TABEL

IV

Adhesion tests parallel to the bonding surface Adhesion tests perpendicular to the Binding surface

κ '■ O Dimensions Shear Elongation at break CO No. strength % OO kg / cm _k CaJ CO
OO 7th 1.46 230 9 1.14 220 10 1.48 360 11 2.10 380 12th • 1.77 360 13th 1.40 280 63 1.02 170 64 1.15 170 65 0.83 100 66 0.85 100 Bit. 8 0.62 55 B. 0.30 12th C. 0.32 25th D. 0.51 60

Peel Strength, kg

4.55

2.8

4.4

6.0

6.5

5.5

1.83

2.07

1.03

0.73

0.3

1.0

0.35 0.3

177034G

The result of the adhesion tests shows that that the compositions according to the invention have the highest penetration strength values and peel strength values and also have the highest elongation at break.

The blown bitumen and the three products available on the market should take into account their properties compared to the compositions according to the invention viewed as of inferior quality for this purpose will.

PATENT CLAIMS;

109 842/1398

Claims (12)

8 MÜNCHEN 90 SCHWEIGERSTHASSE 2 22 06 01 TELEQRAMMADnKSSIi: PHOTECTPATENT MUHCHKH IA-34 515 PATENT CLAIMS: 1) bitumen compositions having a polymer content, characterized by a content of 50 to 95 wt -.% Of a bituminous residue of the distillation or precipitation with a n-heptane asphaltene content of less than 2 wt .- ^, a penetration of less than 2000 at 25 ⁰ C and a softening point below 8O ⁰ C as a bitumen component ^ and 5 to 5 ° wt .- ^ of a thermoplastic polymer with a molecular weight above 10,000, a solubility parameter between 7.8 and 8.8 and a crystallinity at 25 ° C below 60 % as Polymer component. 2) bitumen compositions according to claim 1, characterized by an n-heptane-asphaltene content of the bitumen component below $ 0.1 - 1 - 109842/1398 3) bitumen compositions according to claim 1 or 2, characterized by a penetration of the bitumen component below 500 at 25 ° C. 4) bitumen compounds according to claim 1 to 3, characterized by a softening point of the bitumen compound between 25 and 60 ° C. 5) bitumen compound according to claim 1 to 4, characterized by a molecular weight of the polymer component over 50,000. 6) bitumen compound according to claim 1 to 5 * characterized by an amorphous polymer component. 7) bitumen compound according to claim 1 to 6, characterized characterized in that the polymer component is obtained by polymerizing olefinically unsaturated monomers has been. 8) bitumen compound according to claim J _3, characterized in that the polymer component is a polyisobutylene, an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer or an ethylene-n-butyl acrylate copolymer. 109842/1398 so ^177cmo 9) bitumen compound according to claim ^r (, characterized in that the polymer component is a block copolymer of the general formula A - B - .A is where both A are the same or different polymer blocks of a monovinyl substituted aromatic hydrocarbon and 3 is a conjugated diene polymer block. 10) bitumen compound according to claim 9, characterized in that the polymer blocks A an average Molecular weight in the range from 7,500 to 100,000, in particular 10,000 to 50,000 and the polymer block B. average molecular weight in the range of 25,000 to 1,000,000, in particular 55,000 to 150,000 own. 11) Bitumen compound according to claim 9 or 10, characterized in that the amount of the polymer blocks A is in the range from 10 to 70% by weight , in particular 20 to 50% by weight, based on the weight of the block copolymer. 12) bitumen compound according to claim 9 to 11, characterized in that the polymer component is a styrene-butadiene-styrene block copolymer is. 1098A2 / T3 "9B