DE3330356C2 - Plastic or elasto-plastic sealing compounds - Google Patents

Abstract

Plastic or elasto-plastic mass based on polymeric olefins with a composition of a) 20 to 70 percent by weight of a largely amorphous poly-α-olefin or poly-α-olefin mixture with a viscosity number J of 5 to 500 cm3 / g, this being Polyolefin can be replaced up to half by elastomers, b) 2 to 55 percent by weight of a silicone, c) to 35 percent by weight of an optionally drying oil containing hydrocarbon oil, which can be a polybutene oil, a distillation residue from cyclododecatriene production or a mixture of both, d) to 70 percent by weight of a bitumen, e) to 25 percent by weight of a flame retardant, f) to 60 percent by weight of a conventional additive. The silicone used is preferably silicone oil, silicone resin, silicone rubber or a mixture thereof.

Description

2. Plastic or elasto-plastic mass according to claim 1, characterized in that as Silicone uses a silicone oil, silicone resin, silicone rubber or a mixture thereof.

For many areas of application, such as B. in the construction sector and equipment manufacturing are plastic and elasto-plastic Masses needed. They are used in particular for sealing joints, but also for gluing and for Production of roof coverings or roof seals. Special requirements are placed on seals in acid protection structures and on seals that may come into contact with solvents. the hitherto known compositions based on polymeric olefins only partially meet these requirements. In addition their thermal resistance is not sufficient for special areas of application.

There is therefore a need for plastic and plasto-elastic to elastoplastic sealing compounds improved solvent and chemical resistance as well as improved thermal resistance. From it the task is to find masses with improved resistance.

According to the invention, this object is achieved in accordance with the details of the claims.

Surprisingly, the claimed silicones are with the polyolefin resin mixture according to the invention very well tolerated, although based on previous knowledge (Ulimann's Encyclopedia of Technical Chemie, 3rd Edition, Volume 15 (1964) page 788) methyl silicone resins are incompatible with other resins. Particularly It was surprising that the addition of silicones, even liquid low-viscosity silicones, the thermal resistance as well as the solvent and chemical resistance is improved.

As largely amorphous poly-A-olefins, which 20 make up to 70 percent by weight, preferably 40 to 60 percent by weight of the claimed melt mass, atactic poly propene, polybutene-1 are largely suitable and polyhexene-2, their copolymers with up to 20 percent by weight of ethene and / or up to 70 percent by weight Propene or up to 76 percent by weight of butene-1 5 or hexene-1 and mixtures of all kinds of these substances.

The largely atactic structure is expressed by an ether-soluble fraction of more than 60%, preferably 70 to 100%, and a heptane-soluble proportion of

ίο approx. 100%.

These polyolefins have viscosity numbers J from 5 to 500 cm ³ / g, preferably from 20 to 200 cmVg, in particular from 30 to 100 cmVg. This corresponds to molecular weights, calculated according to the solution viscosity for polybutene-1, of approx. 10,000 to 1,830,000, preferably from approx. 35,000 to 770,000, in particular approx. 60,000 to 310,000.

Such largely amorphous, plastic polyolefins are obtained by using, for example, propene, 1-butene or 1-hexene, optionally with ethene, propene, 1-butene or 1-hexene as comonomers with contacts of TiCl ₄ , TiCl ₃ or preferably TiCl ₃ . η AlCl ₃ (η = 0.2 to 0.6) on the one hand and AIR ₃ on the other hand at temperatures of 50 to 120 ⁰ C, in particular 60 to 100 ⁰ C polymerized. Aluminum alkyls with Ci- to Ce-alkyl groups, preferably aluminum triisobulyl, _{are used as AlR 3.} The molar ratio Al: Ti is preferably 2 to 3. The polymerization can be carried out continuously and batchwise, in solution or in bulk. _{C 4} or C 3 / C ₄ hydrocarbon cuts are used as solvents.

Also in the production of isotactic poly propene and polybutene-1 obtained as by-products, largely atactic poly - * - olefins are suitable. In this case, however, especially in the case of largely atactic polypropene, it is necessary that it be of crystalline, isotactic polypropene is largely free. It should be practically complete in boiling heptane be soluble.

To the largely amorphous poly-IV-olefins according to a) also include mixtures of the aforementioned largely amorphous plastic polyolefins Butadiene-1.S-styrene rubbers, such as those produced by radicals Polymerization can be produced with ethene-propene rubbers such as those produced by copolymerization of ethene with propene with Ziegler contacts, and with obtained by ion polymerization Butyl rubbers. These mixtures contain up to 50 percent by weight, preferably up to 25 percent by weight, these elastomer components, based on the sum of the poly-ar-olefin and these elastomer components.

Suitable silicones, which contain the masses to 2 to 55 percent by weight, preferably 5 to 30 percent by weight, in particular 10 to 25 percent by weight, are preferably silicone oils, silicone resins and silicone rubbers. Suitable silicone oils are, for example, methyl silicone oils, ethyl silicone oils, phenylmethyl and methyl hydrogen silicone oils and silicone oil copolymers, such as those used, for. B. in DE-AS 10 61 321 and DE-PS 11 01 752 are described. Suitable silicone oils generally have densities of 0.9 to 1.1 g / cm ¹ , molecular weights of 750 to 200,000 and viscosities of 5 to 200,000 mm ² · s ~ '. Suitable Si'iconharzc are, for example, methyl silicone resins, dimethyl silicone

b5 Resins and Phcnylmethylsiliconeharzc and their mixtures. They generally have viscosities from 5 to> 1,000,000 mm ² · s'. As silicone rubber z. B. Polydimcthylsiloxane, Polydiethylsiloxane, Po-

lyniethylphenylsiloxanes, polydiphenylsiloxanes and χ-ω- dihydroxypolydimethylsiloxanes and mixtures of them according to DE-PS 8 33 126, 9 59 946, 9 60 570, 9 63 276, 10 19 462 and 10 58 254. The condensation catalysts known per se can be used with the organopolysiloxanes such as amines, dibutyltin diacetate, dibutyltin laurate, dibutyltin maleate or tinh (II) octoate. Mixtures of the silicone oils with the silicone resins and / or silicone rubbers are also suitable.

Suitable hydrocarbon oils which contain 10 to 30 percent by weight of the melt masses according to the invention, in particular contain 15 to 25 percent by weight, are polybutene oils, optionally in mixtures with drying oils or distillation residues from the production of cyclododecatriene or mixtures of this.

Suitable polybutene oils are those with viscosities from 500 to 1,000,000 mPa · s / 20 ° C, in particular from 20,000 to 100,000 mPa · s / 20 ° C. They have molecular weights of 500 to 1000. They should not contain any low-boiling components that boil ^{below 100 ° C. at 15 mm Hg.}

Such polybutene oils are obtained, for example, in a manner known per se by polymerizing butene-1, 2-butene and optionally isobutene-containing Q cuts with Friedel-Crafts catalysts, preferably AICI3, at temperatures from 0 to 100 ° C.

The viscosity of the polybutene oils can be greatly increased by adding dienes and / or acetylenes (DE-PS 20 05 207). After the polymerization and optionally after a wash, e.g. B. with water, the low boilers are simply heated up by heating the polybutene oils to 100 to 150 ° C at a pressure of approx. 15 mm Hg away.

Replaces up to 30% of the polybutene oil used by a drying oil, the drying oil generally making up up to 10% of the melt mass can, so you get plastic or elasto-plastic masses that harden on the surface when exposed to air. Particularly suitable drying oils are polybutadiene oils and drying natural or synthetic ones Triglycerides, e.g. B. linseed oil or mixtures of these. Preferred polybutadiene oils are those with molecular weights from 1500 to 3000, viscosities from 750 to 3000 mPa · s / 20 ° C and iodine numbers between 400 and 500 g iodine / 100 g, as they are according to the Process of DE-PS 11 86 631 can be produced.

The distillation residue that can be used from cyclododecal production has an average molecular weight of 400 to 600, a density of about 0.93 g / cm ³ and a viscosity of 400 to 250O mPa.s / 20 ° C. It consists of 5 to 10% cyclododecatriene. About 35 to 38% of the residue can be distilled, of which approx. 11% are Ci2 hydrocarbons, approx. 12% Ci6 hydrocarbons, approx. 10% C20 hydrocarbons and approx. 5% C24 to Cj2 hydrocarbons. The double bonds of the Cydododecatiienrückstandes are predominantly, over 80%, trans double bonds and about 10 to 15% cis double bonds. The distillation residue is obtained during the distillative purification of the cyclododecatriene produced from butadiene-1.3 with titanium contacts and organoaluminum compounds. This residue from the cyclododecatriene distillation is also used up to 35 percent, preferably 10 to 30 percent, in particular 15 to 25 percent by weight. Like drying oils, it has the property of hardening on the surface when exposed to air.

To accelerate the hardening one can use the

add siccatives to drying oils, preferably cobalt octoate and cobalt naphthenate in amounts up to 0.5%, in particular 0.02 to 0.2%, based on the drying oil.

Suitable bitumens, which make up 70, preferably 30 to 60, in particular 40 to 50 percent by weight of the molten mass claimed, are primary bitumen, blown bitumen and natural asphalt. The softening points of these compositions are preferably between + 25 and -I-120 ° C, in particular between +25 and + 75 ° C (to DIN 1995, ring and ball), the refractive points between -2O ⁰ C to above room temperature, preferably between -20 ° C and +3 ⁰ C (DIN 1995, Fraass) and the penetration depth between 400 and 2 1/10 mm, in particular between 300 and 10 1/10 mm (DIN 1995); Cuttings, tar and pitch, e.g. B. Bitumen B 500 with a lower pour point.

Chlorinated paraffins are suitable as flame retardants, which can be added in amounts of up to 25 percent by weight, which contain up to 75%, preferably 50 to 70%, in particular 52 to 55% chlorine and aromatic Bromine compounds. Brominated amines according to DE-PS are suitable as aromatic bromine compounds

11 27 582 or tribromaniline according to DE-PS 11 03 020, Brominated aromatic or aromatic aliphatic ethers such as penta- or decabromodiphenyl ethers according to DE-PS 11 23 823 and 11 35 654, bromine compounds of Ci2 ring such as hexabromocyclododecane according to DE-AS 1128 975, brominated diaromatics according to DE-PS 1135 653, all of which if desired according to DE-PS

12 30 209 can be used together with chlorinated paraffins, but preferably bromine compounds like 2,4,6-tribromophenyl- / i ', ^ - dibromopropyl ether or the 2,2- to -4 - (/?, / - dibromopropoxy) -3,5-dibromophenyl propane according to DE-AS 16 69 811. The bromine compounds are used in amounts of up to 15 percent by weight, preferably from 1 to 5, in particular from 1.5 to 2.5 percent by weight. One can use these bromine compounds also use in a mixture with chlorinated paraffins, which contain 45 to 60% chlorine, in a ratio of 95: 5 to 30:70.

Such mixtures are used in amounts of up to 15 percent by weight, preferably 1 to 10, in particular 2 up to 5 percent by weight. These halogen compounds make the masses flame retardant, in particular after adding 0.5 to 10, preferably 1 to 5 percent by weight of an additive such as tin dioxide, antimony trioxide or modified clays, e.g. B. Dimethyl dioctadecyl ammonium montmorrillonite.

Customary fillers that can be added to the compositions according to the invention up to 60 percent by weight are Fillers such as talc, barite and silica. If necessary, one sets the masses stabilizers such as z. B. 4.4-thio-bis (6-tert-butyl-3-methylphenol).

Surprisingly, the plastic and plastoelastic to elastoplastic masses, even without the addition of stabilizers, is already an excellent one Stability.

example 1

50 parts by weight of a largely amorphous copolymer of propylene with 30 mole percent butene-1 and 3 mole percent ethylene with a viscosity number J of 55 cm Vg, an ether-soluble fraction of 94% and a melt viscosity of 25,000 mPa.s / 190 ^c C and

33.5 parts by weight of a dimethyl silicone resin with 5% ethoxy groups and a molecular weight of 1,300 are in 16.5 parts by weight of a polybutene oil with a viscosity of 20,000 mPa-s20 ° C at a Dissolved temperature of 180 ° C. A casting compound is obtained with improved benzene resistance.

Example 2

50 parts by weight of a largely amorphous copolymer 6es propylene with 28 mol percent 1-butene and 2 mol percent ethylene with a viscosity number] of 60 cmVg, an ether-soluble fraction of 92% and a melt viscosity of 20,000 mPa.s / 190 ° C. are stirred at 28O ⁰ C melted.

50 parts by weight of the silicone resin used in Example 1 are stirred in at this temperature. The temperature drops in this case to 230 ⁰ C. The potting compound obtained can be processed at this temperature. After cooling, a sealing material with elastoplastic properties is obtained, which is suitable for sealing structural joints. The joints filled with this material can be walked on and driven over.

Comparative example A.

50 parts by weight used in Example 2 substantially amorphous copolymers of propylene are melted with stirring at 28O ⁰ C. 50 parts by weight of a polybutene oil with a viscosity of 20,000 mPa.s / 20 ° C. are then stirred in. The temperature drops to 210 ° C during this process. The mass obtained is very fluid at this temperature. After cooling, it is very soft, therefore not accessible and plastic, without elastic properties.

Example 3

33.3 parts by weight of a largely amorphous polypropylene with a viscosity number j of 50 cm ³ / g, an ether-soluble content of 88% and a melt viscosity of 20,000 mPas / 190 ° C. are melted at 260 ° C. 33.3 parts by weight of a distillation residue from the production of cyclododecatriene (CDT residue) with a density of 0.93 g / cm ³ , a viscosity of 1400 mPa.s / 25 ° C. and a molecular weight of 500 are then stirred in. The temperature drops to 140 ° C during this process. 33.4 parts by weight of the silicone resin used in Example 1 are added with stirring. The temperature drops to 100 ° C. For subsequent processing, the mass is heated to 190 ° C. After cooling, an elastoplastic product is obtained which is comparable to the material according to Example 2.

Example 4

50 parts by weight of a largely amorphous polybutene-1 with a viscosity number J of 40 cmVg, an ether-soluble fraction of 96% and a melt viscosity of 1200 mPa · s / 170 ° C are melted at 285 ° C. Then 16.5 parts by weight of the distillation residue used in Example 3 from the production of cyclododccatriene is stirred in. The temperature drops to 235 ° C. 33.5 parts by weight of a phenylmethyl silicone oil with a viscosity of 500 mm ² · s' (cSt) are then added. The temperature drops to 190 ⁰ C. At this temperature, the mass is thin. After cooling, the mass is elastoplastic. It is suitable for joint seals that can be walked on or driven over.

Example 5

33.5 parts by weight of a largely amorphous propene-butene-1-ethene copolymer with a butene content of 22% and an ethene content of 8%. a viscosity number] of 40 cmVg and an ether-soluble content of 85% are melted at 28O ⁰ C. 16.5 parts by weight of a distillation residue from the production of cyclododecatriene with a density of 0.93 g / cm ³ , a viscosity of 1000 mPas / 25 ° C. and a molecular weight of 450 are added to the melt . Then 50 parts by weight of a silicone rubber based on dimethylpolysiloxane are added. A joint material with excellent elastic properties is obtained.

Example 6

30.8 parts by weight of the largely amorphous propene-butene-1-etene copolymer used in Example 5 are at 170 ° C in 15 parts by weight of a polybutene oil with a viscosity of 20,000 mPa · s / 20 ° C and a molecular weight of 750 dissolved.

At this temperature, 15.8 parts by weight of the silicone resin used in Example 1 are added and 38.4 parts by weight Parts by weight of talc.

An elastoplastic compound is obtained for sealing structural joints with the following properties:

Density: 1.19 g / cm Softening point after ring and ball: 155 ° C Penetration at 25 ° C: 54 '/ 1 ο mm Breaking point according to Fraass: -40 ° C Ductility: 2.5 cm Flash point: 248 ° C

Example 7

28 parts by weight of the substantially amorphous propylene-butene-1-ethylene copolymer used in Example 5 is dissolved at 180 ⁰ C in 14 parts by weight of Polybutenöles used in Example 6. Fig. Then 14 parts by weight of the silicone resin used in Example I, 9 parts by weight of an unsaturated ethylene-propylene rubber with a Mooney viscosity ML-1.4 of 85, measured according to DIN 53 523, and a double bond content of 8 DB / 1000 C in Crumb form and 35 parts by weight of talc.

An elastoplastic mass with improved elasticity is obtained.

Density: 1.22g / crn Softening point (Ring and ball): 158 ° C Penetration at 25 ° C: 51 '/ io mm Breaking point according to Fraass: -50 ° C Ductility: 4.0 cm Flash point: 2 50 "C

It is used instead of the unsaturated ethylene-propylene rubber a saturated ethylene-propylene rubber, an elastoplastic mass is obtained

se with the following properties:

Density:

Softening point
(Ring and ball):
Penetration at 25 ° C:
Breaking point according to Fraass:
Ductility:
Flash point:

1.18 g / cm ³

152 ° C
53 Vio mm
below -50 ⁰ C 2.0 cm
240 ° C

dissolved in 37.9 parts by weight of Polybutenöles used in Example 1 at 18O ⁰ C. At this temperature, 16 parts by weight of the silicone resin used in Example 1 and 4.2 parts by weight of antimony trioxide are added and, after cooling to 150 ^° C., 4 parts by weight of a chlorinated paraffin with a chlorine content of 70%. The mass can be processed at this temperature. It is flame retardant and has the following properties:

10

15th

If the phenylmethyl silicone oil used in Example 4 is added instead of the silicone resin, the result is Masses with comparable properties.

Example 8

19.5 Gewichlsieiie that used in Example 1 largely amorphous copolymers of propylene are in a mixture of 5 parts by weight of the in Example 6 Polybutene oil used and 4.7 parts by weight of the distillation residue used in Example 3 of the Cyclododecatriene production dissolved at 170 ° C.

Then 9.8 parts by weight of the silicone rubber used in Example 5, 23.2 parts by weight of talc and 31.6 parts by weight of quartz sand of the grain size are added 0.1 to 0.3 mm and 6.2 parts by weight of the unsaturated ethylene-propylene rubber used in Example 7 to. An elastoplastic mass is obtained, which inter alia. is suitable for embedding floor panels, with the following properties:

30th

35

It is used instead of the unsaturated ethylene-propylene rubber a saturated ethylene-propylene rubber, the break point is lowered below -50'C.

Density: 1.49g / cm ^J Softening point (Ring and ball): 160 ⁰ C Penetration at 25 ⁼ C: 54 /] Q mm Breaking point according to Fraass: -45 ° C Ductility: 2.0 cm Flash point: 250 ⁰ C

Example 9

45

25.2 parts by weight of the largely amorphous propylene copolymer used in Example 2 with 8.4 parts by weight of the distillation residue used in Example 3 from the production of cyclododecatriene and 50.4 parts by weight of a bitumen B 200 melted at 180 ° C. with stirring. At this temperature 16 parts by weight of the silicone resin used in Example 1 are added. The crowd can with this Temperature to be processed.

After cooling, a sealing compound with plasto-elastic properties is obtained, which is used for sealing of building joints is suitable. The joints filled with this Maieriai can be walked on and driven on. The mass has the following properties:

60

Softening point
after ring and ball:
Flash point:

133 ^C
260 ^:

Example 10

65

37.9 parts by weight of the largely amorphous copolymer of propylene used in Example 2 become the softening point
after ring and ball:
Flash point:

139 ⁰ C
239 * C

Claims (1)

Patent claims: 1. Plastic or elasto-plastic mass based on polymeric olefins, characterized by a composition a) 20 to 70 percent by weight of a largely amorphous poly-a-olefin or Pcly-ar-olefin mixture with a viscosity number J of 5 to 500 cm ³ / g, this polyolefin being up to half of butadiene-1,3-styrene rubbers, Ethene-propene rubbers and butyl rubbers can be replaced, b) 2 to 55 percent by weight of a silicone, c) 10 to 30 percent by weight of an optionally drying oil containing hydrocarbon oil, which can be a polybutene oil, a distillation residue from the production of cyclododecatriene, or a mixture of both, d) up to 70 percent by weight of a bitumen, e) up to 25 percent by weight of a flame retardant, f) up to 60 percent by weight of a conventional filler, g) optionally stabilizers.