DE1720551A1 - Bitumen mixture - Google Patents

Description

The present invention relates to and processes for their production «It is known Bitwinen.dwrah Addition of Polymerisatea su improve and such a thing Achieving bitumen build-up suitable for road surfaces in particular. Bitumen mixtures known to date have ever been used a lack of homogeneity iuid are unstable »

The present invention has set itself the task, Bitumen mowings of better quality with better physics to propose technical characteristics that look in particular ", lent their brittleness, flexibility, elasticity, adhesiveness, Aging resistance and also in economic terms are superior to the previously known varieties ^

Bitumen slurries are proposed to solve this problem, which are obtained by dividing monomers. wise-polymerized or micro-polymerized and thin the

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Polymerization or interpolymerization in molten Bitumen, in a liquid hydrocarbon or in a single melted or dissolved resinous solid product continues, the products of the liquid hydrocarbon and the melted or dissolved resinous pessraese are added to the melted bitumen »if the polymerization is completed in a liquid, a petroleum distillate or extract is preferably used,

which can also be used as a flux or blending agent for the

Bitumen acts * When the polymerization in a molten or dissolved resinous solid is completed »a petroleum resin is preferably used *

The starting monomers for the preparation of the polymer are preferably two or more of the following products: vinyl acetate and an ester of a ethylene or diethylene acid, preferably methyl methacrylate, butyimethacrylate, lauryl methacrylate, Cg _-1 Q fumarate, Cg ^ ^ q acrylate or Cg ^ ₁ Q methacrylate Other monomers that can be used are vinylpyrrolidone, oleooldimethacrylate and DläthylaMnotttbylnethacryläto

Any bitumen can be used as bitumen, including plasticized or oxidized or blown Bitumeneorteno V

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The first partial polymerization of the monomers is known to have occurred Way in which the monomer is heated, and although, for example, to a temperature of 80 to llö ^ C in the presence of a Polynierisierungsanr-sgera, "" B * Azodiiscbutyronitril or a tertiary butyl perhenzoate »where the polymerization is carried out up to a certain viscosity, which depends on the desired end product The viscosity is most expediently adjusted in that through the flow rate of the partially polymerized product observed a pipe between two brands of tents. For example, you can set the flow time in seconds between two markings measure that at a distance of 50 mm in a calibrated Tube of 5 mm in diameter takes place.

When the polymerisation in the molten bitumen itself is brought to an end, the molten bitumen is added in one or more stages to the not yet completely polymerised product and then the polymerisation takes place for a further period of 30 minutes Minutes to 2 hours completed "The polymerization is ended by adding, for example, an antioxidant such as a ditertiary butyl-p-cresol and / or by lowering the temperature, excess and unreacted monomers can be removed, for example by stripping with nitrogen"

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The products produced by the process according to the invention can contain 1 to 95 and preferably 3 to 20% by weight of the polymer based on the total weight of the mixture of polymer and bitumen . Bitumen mixtures can be applied in a known manner, for example by painting on in the hot state or as an emulsion. which contain petroleum resins are particularly suitable as adhesives, for example to stick elastomers such as butyl rubber to substrates

In a modified method according to the invention, the incompletely polymerized product is used instead of the melted product Bitumen a flux medium or a liquid for blending, ZoBo a petroleum distillate or an extract, added with stirring in one or more stages and the polymerization in this blending liquid, z »Bo in After 50 minutes to 2 hours, the polymerization is terminated as described above, excess monomer is removed, for example, by stripping with nitrogen under vacuum and molten bitumen is turned added with stirring in one or more stages “This last process step can be independent of the previous one

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Steps are carried out so that one has a previously prepared Distillate or an extract can use »which that contains polymeric resin as bitumen blending compound.

The concentration of the polymer in the extract or distillate can be 30 to 80 and preferably Λ0 to 60 wt. #, Based on the total weight of polymers) and carrier liquid ο The types of bitumen containing this product can contain 1 to 95 and preferably 2 to 20 wt. # of polymers! "Based on the total weight of the mixture" included.

This modification according to the invention is particularly suitable for the treatment of bitumen types with penetration values of 20/30 (near ABTSH / 100g / 5s / 25 ° C), which are ^{softened so that penetration values at 25 0} O are obtained, which are the values of road asphalt of 180/220 or 80/100 or other desired penetration values »These types of bitumen can be" applied "like the bitumen types known so far" for example "by hot coating or emulsion coating be used"

According to a further modification according to the invention can to the incompletely polymerize a melted product

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or dissolved resin, especially petroleum resin, added and the polymerization will be completed while the resins are molten or in solution, whereupon the obtained product mixed with molten bitumen or mixed with resin and bitumen. These mixtures have good setting properties, excellent flow resistance and good adhesive properties, especially with respect to natural or synthetic elastomers to apply them to a wide variety of substrates, e.g. wood, minerals, as.B to glue cement, concrete, asbestos, metal and glass.

The following products are used as starting monomers in the the following compositions are preferred:

Cg _-1 Q fumarate / vinyl acetate in a quantitative ratio

from 68: 32 weight pounds; Cg _-1 Q pumarate / vinyl acetate / vinyl pyrrolidone / butyl fumarate

in weight * of 63.3 / 17.0 / 5.3 / lM;

^c 8-l8 ^^ & x ^ t / butyl monomaleate ainylacetate / butyl fumarate in weight * of 74.5 / 1.7 / 18.3 / 5 * 5.

As petroleum resins, thermoplastic resins can be used which are obtained by polymerization in the presence of Friedel-Crafts catalysts from steam-cracked petroleum distillates have been obtained that boil in the range of 30 to 80 ° C,

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or fractions of such distillates have the same boiling range, the polymerization preferably being carried out at temperatures of from 70 and in particular from 10 to 55.degree. Optionally, these resins can also be obtained from steam cracking distillates at high temperature, ZoB. from 250 to 320 and preferably 290 to 3K) O ⁰ C, at pressures of up to 2 (MO- * and preferably 15.10- * to 25 "10-> _e Pascal and distillation of the polymer to separate the Harass at temperatures of 220 to 350 and preferably from 260 to 290 ⁰ C can be obtained.

Instead of Dampfcraekerdöldesti.liate the rlslerende to polyme "Charge for the production of petroleum Hans it consist of ainesi mixture of olefins and diolefins ^, can the latter being present in an appropriate amount to provide a resin and not afforded an oil or a rubber-like elastomer" These resins are polydiene resins and have a softening point between 50 and 180 ° C.

You can also use resins, which are liquid Do not dissolve hydrocarbons, such as butadiene / styrene copolymers, Butadiene / acrylonitrile copolymerization, styrene / acrylonitrile copolymers, thermoplastic styrene polymers,

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Acrylic and methacrylic resins, thermoplastic vinyl polymers and mixed polymers, e.g. polyvinyl chloride and polyvinyl & cofcatj, Condensation polymerizates such as Glycerojphthalsäurelmrzej, Polyurethanes, polyureas, polyesters and mixtures thereof.

The mixtures of polymer and resin can be 5 to 95 and preferably 50 wt. # polymer, based on the total «· "weight of the mixture.

The mixtures of polymer and petroleum resin were heated and preferably to a temperature of 100 to 150 ⁰ and then mixed with the molten resin and then with the bitumen, heated to the same temperature, the temperature being increased, for example, by 20 ° C and the mixture Stirred for half an hour to 2 hours. Any common bitumen can be used, such as straight bitumen, softened bitumen (plus bitumen), oxidized bitumen and blown bitumen.

The mixtures can contain 5 to 40 and preferably 10 to 20 oevr. Polymer, 10 to 40 and preferably 15 to JO Gow <, # petroleum resin and 20 to 85 and preferably 20 to 70 wt% bitumen contain.

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These mixtures are particularly useful as adhesives for elastomers in particular on mineral substrates »such as Concrete, suitable.

The invention is to be explained in more detail below with the aid of examples?

example 1

There was a Cq _-1 D fumarate having a molecular weight of 480, a density at 5O ⁰ C of 0.883, a freezing point according to ASTM of 50 ⁰ C, a flash point (open vessel) of 176 ⁰ C and a saponification number of 254 »This fumarate was obtained by esterification of a natural 29-5-Cg ^^ g alcohol with a Hydroxylsahl of 290 or a synthetic Cg ^ ₁ Q alcohol with a Hydroxylz & hl of ·. 165 g of this product was added with 135 g of vinyl acetate and 0.4 g Azodilsohutyronltril in a 1 liter reaction flask and heated to 78 to 8O ⁰ C. * The Ausmas the polymerization was carried Hesse the flow time between two 50 mm distant from each other brands of a calibrated tube with a diameter of 5 mm. When the flow time between these marks was 40 seconds, a standard bitumen 180/220 (SfcraSenasphalt biturnen) was added, the properties of which are given in Table I below.

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This road asphalt was first heated to 80 ° C, after which 320 g of this product in the polymerization mixture was poured in three portions with stirring. After additions of all the bitumen was stirred further to complete the polymerization and homogeneity of the mass. Excess vinyl acetate was removed by wiping with a stick. fabric removed «The copolymer consisted of $ 68 Furaarat and from 32 # vinyl acetate,

Finally, a mixture of Copplymerisat and bitumen was obtained these two components of equal parts by weight, whereupon two mixtures were prepared by the addition of further bitumen quantities, of which the mixture a) 5 wt. # Copolymer and the mixture b) 10 wt _o $ copolymer containing . The properties of these blends are listed in Table I.

Example 2

In a 500 ml flask were the following ingredients

given:

Lauryl methacrylate 71 * 4 g Methyl methacrylate 14.3 g Butyl methacrylate 11.4 g glycol dimethacrylate 2.9 g tertiary butyl perbenzoate 0.5 g.

This mixture was heated to 105 to 107 ⁰ C and n eh Erreiohen a flow time of 20 seconds were 100 g

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Stir bitumen of 100 ° C in three portions down into the Reaction genius given «Then there was another Stirred for an hour «whereupon traces of not urcge» settled monomers were removed by nitrogen stripping became. The mixture obtained contained equal amounts of copolymer and bitumen and was then added by adding further bitumen adjusted to a mixture which contained 5 wt. # copolymer. The characteristics of this Product are given in Table I,

Example 5

The following substances were placed in a 500 ml reaction vessel

give:

Cg-jg methacrylate 71 »^ g

Methyl methacrylate iy g

Diethylaminoethyl methacrylate ll, 3 g

tertiary butyl perbonzoate 0.5 g

The Cg _- jg methacrylate can be obtained from natural or synthetic ^G 8-18 ^Alkotto1 by transesterification with methyl methacrylate.

The polymerization was carried out according to Example 2, and bitumen was again added in the same way, to get equal amounts of copolymer and asphalt » Again, adding more bitumen became a final one Gemlsoh obtained with 5 wt. £ copolymer. the

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Di · properties are also shown in Table Z, in the penetration according to ASTM D5 (100g, 5 sec.) At 25 and 35 ⁰ C, the ductility according to ASTM DL13 at 25 ⁰ C in cm, the viscosity at l40 ° C in cps and the softening point according to Ring and Ball in ⁰ C and the breaking point in ⁰ C according to Ι · Ρ. 80/53 are specified

-13-

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Table I.

default example 1 b) 10Sg Example 2 Example 3 penetration
at 25 ^° C
penetration
_; at 55 C 192
> 40Ö a) 5% 151 172
> 36O Ductility 120 141
> 33Ö > 200 > 200 185
> 360 Viscosity at 14 0 ⁰ C 155 > 200 , 700 320 ? 200 Softening point
in ^Q C 35 285 49.2 39
I'INI Il I Breeh point in ⁰ C »19 47.2 -29. 38 ^ 27 -3 ©

Example 4

In a 1 liter flask were

I65 g of C fumarate according to Example X,

8-18
135 g vinyl acetate,

o, 4-g azodiisobutyronitrile

and optionally up to 8O ⁰ C "heated to 78 Upon reaching a flow time of 40 seconds was of Central once petroleum extract and the other a heavy Tiajuana added extract having the following characteristics in small quantities:

Density at 15 ^° C
Flash point in ⁰ C

Viscosity at 98.9 ⁰ C in centistokes

Acid number

Aniline point

Solidification point in ⁰ C

Middle east
extract severe Tia ° Juana
extract 0.990 1.020 254 204 25.2 0.05 4.5 59 20th 50 0

This extract was added with constant stirring, followed to complete the polymerization and to achieve stirring was continued for a better homogeneity. Above" Excess vinyl acetate was added to nitrogen with stirring

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removed. As Copolymerleat a product of 68 wt.% Was used Cq ^ ₁ Q fumarate and 32 wt.% Vinyl acetate. Ee materials were obtained which contained equal amounts of the Middle East extract and polymer (mixture I) or of heavy Tia »Juana extract and milk polymer (mixture II).

The bitumen used was a straight-run bitumen 20/30, namely a road bitumen 20/30 and a deasphalt bitumen 5/15. The former had a softening point of 55 ° E and a penetration of 30, while the other one he · welehungspunkt of 65 ⁰ C and had a penetration of 12th

These ingredients were heated to HO ⁰ C and then. Two mixtures A and B processes which # Tia Juana-extract containing both 7 ^ i5 Gßw · road bitumen 20/30, 5 Gew.ji Deasphaltierblturnen 5/15, 1.5 Oev.% lightweight extract and lh wt. '. " Mixture A differed from mixture B in that in the former, 10 wt A comparison of the properties of these mixtures A and B with a straight-run bitumen 180/220 is shown in the following table

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Table II

180/220

Penetration according to ASTM D5 (100 g, 5 sec.)

at ~ 15 ° C

0 ⁰ C

10 ⁰ G

15 ° C 25 ° C

Ductility according to ASTM DIlJ at 25 ° C in cm

Softening point in ° C according to ring and ball

Breaking point according to Praas in ⁰ C (IP, 80/55)

2.5
17th
42
73

ISO

55

• 19th

4-

13 59 62

195

> 530> .33O

200> 200

Example 5

The mixture I geroM.8 Example 4 was used as a flux Production of a road bitumen 80/100 from an S. bitumen 20/50 used, the following Mi. D # E and F produced at 110 ° C vmr

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mixture

E P

Bitumen 20/30 85 83 * 3 82 Tla ~ Juana, extract 15 11 * 5 8 Mixture IO 3 10

The mixture D corresponds to a 'usual. Bitumen 80/100 road * while the mixture E .2.5 percent "$ copolymer the mixture P trad 5 percent _o ^ ^ e ^ Copoi isat - contained" bites Mischungenbasitsen the properties shown in the following "Table"

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Table III P. Ξ -27 0 F. 82 82 79 Penetration ASTM (100g / 5 sec / 25 ° C) 180 200 200 Ductile! Did ASTM 113-44 at 25 ⁰ C 1 5 5 ASTM 113-44 ductility at O ⁰ C 2, 6 3.5 4.8 Viscosity at 140 ° C in poise -47 . 48.5 51 * 5 Softening point in ⁰ C.
ASTM D36-26 (ring and ball) «18 »27 -28 Breaking point in ⁰ C according to Praas
I.Po 80/53 0, 625 0.035 0.045 Weight loss in % (Hölßluft-
Sample according to ASTM 1754 -60T
163 ° C - 5 hours) 65 66 69 Residual penetration at 25 ° C 71 81 87 Initial penetration in # 50 50 51.5 Softening point in ⁰ C (ring and
Ball) 3 1.5 0 Deviation in ⁰ C (ring and ball) -12 -28 Break point in ⁰ C 6th 0 Deviation of the breaking point in ⁰ C Example 6

In a 500 ml reaction vessel were

125 g of lauryl methacrylate, 50 g of methyl methacrylate and 0.4 g of tertiary butyl perbenzoafc

given and the mixture heated to 105 bits 107 ° C. at

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When a Durohflusszeit of kO seconds was reached, Tia-Juana extract, heated to 80 ° C., was added to the polymerization mixture in two portions, as in Example 5, with stirring. Then another. Hour, whereupon unreacted monomers were removed with nitrogen. The mixture obtained from the copolymer! Sat and Tia-Juana extract in equal parts was referred to as mixture III. This mixture III was processed at 110 ° C with blown asphalt and with Tia-Juana extract to two mixtures 0 and H with the following composition:

0 mixture 86 H blown asphalt
90/40 by weight £ I * 85 Tia Juana Extract O 10 Mix III 10

These two mixtures 0 and H had the following properties:

G H

ASTM penetration

100g / 5 sec / 25 ^ C 78 76

Ductile! Tat according to ASTM D133

(25 ⁰ C) in cm 10;

Penetration point in ⁰ C

(Ring and Ball) 64 77

Breaking point in ⁰ C (Fraas)

I «P. 80/53 126

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The above results show that there is a significant improvement ductility and focal point achieved when blown plasticized asphalt according to the invention is treated *

Example 7

A 1000 liter jar came with

165 g of Cg ^ jg fumarate according to Example 1 with;

135 g vinyl acetate and

0.4 g asodiisobutyronitrile

charged and heated to 8O ⁰ C and as previously polymerized "After reaching a Durchflußselt of MQ seconds were J510 g of molten Erdölhars added This" petroleum resin obtained by reacting at 40 ° C and in the presence of Vf> aluminum chloride resulting from the steam cracking of a The fractions obtained from petroleum distillates are polymerized, the petroleum resin exhibiting the following properties:

Molecular weight IhQQ

Softening point (ring and ball) 96 ⁰ C

Gardner color in 50 # toluene solution 10 «,

After addition of the petroleum resin, the temperature was maintained for one hour at 8O ⁰ C with stirring and Excess "vinyl acetate removed" The mixture IV obtained contained equal weights of Copolymerinat and Erdölhars? "

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This mixture was heated to 120 to 13O ⁰ C was added with further quantities of petroleum resin. Then two types of asphalt from a Tia-Juana crude oil with penetration values of 20/50 and 130 were added «. Mixtures L, M, N and O with the following composition were produced from the mixture XV obtained:

L. Mixing N 0 24 M. 24 24 Mix IV 13th 24 13th 13th Petroleum resin 63 13th 40 25th Tia-Juana bitumen 130 - 23 32 Tia-Juana bitumen 20/30 63

The adhesive and flow properties of this product were rated as follows · A butyl rubber sheet of 50x40 mm size was glued to an asbestos cement plate " after which the force required to pull it off with a Zwick dynamometer was measured. The pulling speed was 60 mm / min. On an area of 15 x20 mm about 1 g of adhesive applied »

The hot-flow liquid was measured with a 5x5 cm Butyl chewing sheet examined, which was glued to an asbestos cement board and placed in a drying oven

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Temperatures of 60, 70, 80, 85 and 9O ⁰ C warv suspended The KaltfließfHhigkelt was untereuoht with a 50x50 nan large Butylkautsohukbogen "was glued cement plate on an asbestos". which was kept at room temperature and gradually loaded with wedges from 400 to ISOO g. The results of these investigations are given in Table 3V below.

Table IV

Adhesion in kg after 9 hours

Hot flowability 8 days at 6O ⁰ C for 8 days at 7O ⁰ C for 8 days at 80 ° c for 8 days at 85 ⁰ C for 8 days at 90 ⁰ C.

Cold fill capacity 2 days for 400 g 2 days for 500 g 2 days for 600 g 2 days for 800 g 2 days for 1000 g 2 days for 1200 g

Mixtures
MN O

7.35 5.5 17.3

5.5

no no no no

no no no no

something none a little none

does not flow does not flow

flows - flows

no no no no

no no no no

something no no no

flows none none none

none none none

something no something

The above values show that the registers according to the invention exhibited good adhesion and excellent resistance to hot and cold fluidity.

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Claims (1)

Are Verfahrsn for preparing bitumen compositions, where, mere partially polymerized or tniGchpolymerisiert, dadur ch gekennz eichnet "that the polymerization or copolymerization is completed in a melted bitumen or in a liquid hydrocarbon or in a molten or dissolved solid resin, wherein the products dss liquid Kohlenwassei Substance and dee 'molten or dissolved solid resin are added to the molten bitumen o Method according to claim 1 "characterized in that the polymerization of the partially polymerized monomers or mixed monomers in a molten road asphalt or blown bitumen ■ 2- 109827/1614 BAD 3 »Process according to claim 1, characterized in that the partially polymerized monomers or Minchm <M \ are added to a molten or dissolved petroleum resin, the polymerization in the petroleum resin is completed and the product obtained is added in a molten state to the molten bitumen, or a Made of petroleum resin and bitumen » 4 "The method according to claim 1, characterized in that which partially polymerize monomers or mixed monomers are added to the petroleum distillate or extract »the polymerization is completed and that Product is added to molten bitumen in a liquid state 5 ο Process according to Claims 1 to 4, characterized in that at least two of the following compounds are used as monomers: vinyl acetate, esters of ethylenic or diethylenic acids « 6 "Process according to claim 5, characterized in that the ester of an ethylenic acid is a Co, g fumarate, a Cg ^ ₁ Q acrylate, a <'g 13 methacrylate lauryl methacrylate, butyl methacrylate or methyl meth. rylai used 1 O 9 8 2 7/1 G U BAD OPIiGfNAL 7o method according to claim 5 and 6? thereby g It is not possible to use a polymerizable mixture of monomers used, which vinyl pyrrolidone, G ^ aldimethacyylat and / or diethylamlnoäthylraethacrylat contains Method according to claims 1 to 7 *, characterized in that the bitumen is straight bitumen, sin flurtes Bitumen »used an oxidized bitumen or blown bitumen Β 9 «The method of claim 1 to 8 * geksnnselchnet in that it contains a Bitufflen / Polyraerisatfnisehung verwen- \ _f DEFC which Ί to 95% polymer Gsw _e 10 «, method according to claim 8, characterized in that raan used a Bituraen / Polymerisatrrdsühung »which 5 to 30 wt. # Polyj ^ risat contains » 11, process according to claim 1 to ICf, characterized in that the petroleum haree used is thermoplastic Harjsö, which by polymerization in the presence of Friedel Oraft catalysts & us steam-cracked petroleum distillates in a boiling range of 30 to 28Q ⁰ C or fractions of such distillates with same boiling range are obtained » 109827/161 A. β The method of claim 1 to 9 "dadwrc g's net that one egg as petroleum resin: .i Polydlüiihar which has a ErweichungspyTikt between $ 0 \ mu LSO ° C and by polymerization of a Geraisclies from 01υ:? ~ η ιη and diolefins. 13 »The method according to claim 11 or 12 _g aiiuxwch characterized _p ciaö the resin / polymeris & t ^ GefflisBh & uf 100 Mk 150 ⁰ C, exposed molten bitumen, the temperature increases and the mixture 30 minutes to 2 foreheads stirs. 14 _g mixtures which are produced by addressed IO * characterized in that sis contain 5 to hQ wt »# PoIjmeres, 10 to 40 wt _o $ Eraölharz and 20 to 85 Gcw. $ Bitumen. 15 "A mixture according to claim 14, characterized gekennzelchnöt, ^ that, 15 to JO weight" $ petroleum resin and 20 to 70 wt.% Of bitumen containing 10 to 20 wt * $> * polymer. 16. The method according to claim 1 to 13 »characterized in that that one to the partially polymerized monomers. or ComoBomere with stirring a petroleum distillate or Adding the extract in one or more stages, completing the polymerization in the distillate or extract, 109827 / 16U BATHROOM OWGINAL unreacted monomer removed and melted Bitumen added in one or more stages " 17 «Method according to claim 16, characterized in that that the concentration of the polymer in the distillate or extract * based on the total weight of the solution to 50 to 80 wt. £ adjusts. 18. The method according to claim 17, characterized in that that one has a concentration of dte polymers from 40 to " 60 Gew.Ji sets. ' 19 · Mixture produced by the method according to claims 16 to 18, characterized in that it 1 to 95% by weight of polymer * based on the total weight of polymers and fluxed bitumen. 20. Mixture according to claim 19f, characterized in that dafi it contains 2 to 20 percent by weight of the polymer, based on the total ₍ weight of polymer and fluxed bitumen). Ue: mU 10982771614-