DE1814776A1 - Process for the production of modified propylene polymers - Google Patents

Description

Badische Anilin- A Soda-Fabrik AG 1814776

Our reference: O.Z. 25 933 Ks / bdrm 6700 Ludwigshafen, December 12th, 1968

Process for the production of modified propylene polymers

The invention relates to a method for producing modified Polypropylene, in which hydroperoxide-containing polypropylene with tetra- or trihalogenated carbon or silicon compounds implemented.

The known molding compounds made of polypropylene are chemically inert. Very often, however, a certain reactivity of the inert polymer is desired in order to give it a deeper and more genuine color to be able to determine the affinity to fillers and the adhesive strength to inorganic or organic materials (e.g. concrete, Wood, textile fabrics).

The object of the invention was therefore to produce a polypropylene, which contains reactive, functional groups. Such polymers should, for example, have an improved affinity to fillers and have better dyeability.

The invention relates to modified propylene polymers which are obtained in the conversion of polypropylene, which is 0.01 to 5 percent by weight Has hydroperoxide groups, with compounds of the general formula

receives, in which Z can be carbon or silicon, where for the case Z = carbon the substituents R ₁ , R ₀ , R ^ and Ri ₁ chlorine, bromine or iodine and R ^, also hydrogen and for the case Z = silicon the Substituents R ₁ , R ₂ , R ^, and R ^, chlorine or bromine or R ₂ , R ^ and Ru also hydrogen, a saturated or unsaturated acy clic or cyclic aliphatic radical as well as an aromatic

^541/67 009826/1987 " ² ~

the rest of the table.

As starting materials, if. Z in the general formula Place of carbon, carbon tetrachloride, tetrabromomethane, Tetraiodomethane, trichloromethane, tribromomethane and triiodomethane used. Silicon-containing compounds that are used in the Processes according to the invention are preferably used are tetrachlorosilane, tetrabromosilane, vinyltrichlorosilane, methyldichlorosilane, Phenyltrichlorosilane and isopropenyltrichlorosilane. in the Case Z = silicon only come as saturated aliphatic residues Methyl, ethyl, propyl, butyl and cyclohexyl groups in question. Of the unsaturated organosilicon compounds, vinyl, isopropenyl and cyclohexenyltrichlorosilane are mainly used.

The production of hydroperoxide-containing polypropylenes has already been described (cf. Houben-Weyl, Methods of Organic Chemistry, G. Thieme Verlag, Stuttgart 196I, Volume 14/1, page 394). The hydroperoxide content of the polypropylene can be 0.01 to 10 percent by weight, but preferably a polypropylene is used whose hydroperoxide content is between 0.5 and 5 percent by weight. Hydroperoxide-containing polypropylene with an intrinsic viscosity pnj of 0.5 to 10 and a proportion soluble in boiling hexane of 10 to a maximum of 30 percent by weight is particularly suitable for the process of the invention.

The reaction of the hydroperoxidhaltigen polypropylene having the above-mentioned halogenated carbon or silicon compounds, if one works in absence of a solvent, at temperatures between I70 and 230 ⁰ C in mixing kneaders or screw presses. The reaction may be carried out at atmospheric pressure or elevated pressure and at temperatures of 30 to 200 ⁰ C and advantageously in solvents such as ethylbenzene, toluene, xylene, chlorobenzene and isopropylbenzene. In the reaction of the hydroperoxide-containing polypropylene with the compounds of the general formula I, hydrogen halide can be formed if at least one of the substituents is halogen. The hydroperoxide groups in the polypropylene are replaced by functional groups *, for example the trichloromethyl group, if the hydroperoxide-containing polypropylene is used

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Carbon tetrachloride is implemented. On every hydroperoxide group of the polypropylene, on average, at least one functional group is absent. 1 to 35 percent by weight of the compounds mentioned can be reacted according to the process of the invention with hydroperoxide-containing polypropylene.

If the reaction of the components coming into consideration for the process according to the invention is carried out under a carbon monoxide pressure of 1 up to 200 atmospheres, you get a modified polypropylene that contains carboxylic acid halide groups (-COX, X = halogen). The products produced in this way can, for example, if they Containing carboxyl groups are crosslinked. This increases the tear and tensile strength of molded parts made from these products are increased considerably. The modified polypropylenes made by the process of the invention also exhibit an improved solvent resistance, a better affinity for fillers and are considerably easier to dye. you will be mainly used for the production of foils, fibers, sealing plates and magnetic tapes as well as for the production of molding compounds. Table 1 gives an overview of the properties of the newly produced molding compositions. The characteristics of these? Products can can be further improved - as Tables 2 and 3 show, if the modified propylene polymers are reacted, for example, with water, alcohols and thioalkanols.

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Table 1

Implementation product according to the example

Peroxide content wt.%

[77] Tear strength
kp / cm

Tensile strength kp / cm *

Removable

nung kelt in

% Toluene

Colorability

liability
on metal or

1 a - 2.1 296 517 730 + + + 1 b ■ - 3.5 290 525 620 - + + 2 - 2.2 298 520 725 + + + 3 - 1.8 2 95 325 736 + + + 4th - 2.1 271 315 550 + + + 5 - 1.7 280 340 675 + + + 6th Starting poly- 1,2 2.9 305 390 550 - + + propylene 1.9 260 305 535 +

α> ο ο f

The parts given in the examples are parts by weight.

example 1

a) In a stirred flask, parts heated 100 polypropylene having an intrinsic viscosity / "^ 7 = 1 * 9 and a hydroperoxide content of 1.2 percent by weight, 10 parts of carbon tetrachloride and 500 parts of toluene to 100 ⁰ C. at After the reaction mixture 5 hours 100 ⁰ C is stirred, allowed to cool and then the solvent is distilled off in vacuo. the residue remains a powdery modified polypropylene is dried in a vacuum oven at 5O ⁰ C. it has a λ intrinsic viscosity / 77i ~ 2.1, and a trichloromethyl group content of 2.9 percent by weight.

b) In 100 parts of the ^ oh Example 1, a modified polypropylene produced are kneaded homogeneously distributed in a commercial Mlschkneter 5 parts of pulverized magnesium acetate at a temperature of 200 ⁰ C. Moldings are produced from this mass in the injection molding process, whose intrinsic viscosity ^ J = 3 * 5 * their tear strength is 290 kp / cm, their tensile strength is 325 kp / cm and their elongation is 620 % .

Example 2

In a stirred flask, 100 parts of polypropylene having an intrinsic viscosity FRSS = 1.9 and a hydroperoxide content of 1.2 percent by weight, 10 parts of carbon tetrabromide and 500 parts of ethylbenzene heated to 10O ⁰ C. The mixture is ^{stirred at 100 °} C. for 5 hours. After cooling, the solvent is distilled off in vacuo and a modified polypropylene is obtained as residue, the tribromomethyl group content of which J> weight percent Mz ^ j £ \ χύ has an intrinsic viscosity of /> ^] = 2.2.

Example J5

100 parts of polypropylene with an intrinsic viscosity π? 7 = 1.9 and

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a hydroperoxide content of 1.2 percent by weight * 20 parts of tribromomethane and 500 parts of toluene are mixed thoroughly in a pressure vessel for J> hours at a temperature of 115.degree. The reaction mixture is then allowed to cool with continued stirring and the toluene is then distilled off under reduced pressure. The pulverulent residue is dried at 50 ^° C. in a vacuum drying cabinet. It contains 6.2 percent by weight of dibromomethyl groups, its intrinsic viscosity is [r ^] = 1.8.

Example 4

In a pressure vessel equipped with a mechanical stirrer, 100 parts of polypropylene having an intrinsic viscosity \ j ~ ll = 1.9 and a hydroperoxide content of 1.2 percent by weight, heated for 10 parts of carbon tetrachloride and 500 parts of toluene to 100 ⁰ C. . The components are thoroughly mixed, carbon monoxide is injected and the reaction is carried out under a carbon monoxide pressure of 5 atmospheres and a temperature of 100.degree. The reaction is over after 10 hours. After cooling and after releasing the pressure from the pressure vessel, the solvent is distilled off in vacuo. 100 parts of water are added to the reaction product and the mixture is stirred at 50 ° C. for two hours. The insoluble polymer is filtered off, washed with water and dried at 60 ° C. in a vacuum drying cabinet. A modified polypropylene is obtained which has 1.2 percent by weight of carboxyl groups and an intrinsic viscosity / ^ 7 = 2.1. It can be dyed very well and fast with disperse dyes, reactive dyes and also 1: 2 metal complex dyes.

Example 5

100 parts of polypropylene with an intrinsic viscosity Wn- 1 * 9

a hydroperoxide content of 1.2 percent by weight / with 20 parts of 'trichlorosilane in 500 parts of ethylbenzene is implemented at 150 C within one hour. The reaction mixture is worked up according to the method described in Example 1. The modified polypropylene contains about \ k percent by weight dichlorosilyl groups. The intrinsic viscosity is [r ^ J = 1.7.

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Example 6

100 parts of polypropylene with an intrinsic viscosity [i ^ J = 1.9 and a hydroperoxide content of 1.2 percent by weight, 20 parts of vinyltrichlorosilane and 500 parts of ethylbenzene are mixed thoroughly and heated to 80.degree. After a reaction time of 5 hours at 80 ⁰ C the mixture with stirring is allowed to cool, then distilled ethylbenzene under reduced pressure and dried, the remaining powder, 2.3 weight percent silicon and 8.7 percent by weight of chlorine, in a vacuum drying cabinet at 60 ° C. The product obtained in this way is sensitive to moisture and has an intrinsic viscosity f ^ J- 2.9 · After adding water, a product is formed which is completely insoluble in organic solvents.

To 10 parts of the solvent-free, modified polypropylene, 90 parts of a cement mixture (cement: sand: water like 1: 4: 2) given. After the cement has hardened, it is a homogeneous mass with excellent mechanical properties. Against are Molded parts made from mixtures of unmodified polypropylene and cement are inhomogeneous and also have insufficient breaking strength.

Example 7

100 parts of polypropylene with an intrinsic viscosity [η] = 1.9 and a hydroperoxide content of 1.2 percent by weight, 20 parts of trichlorosilane and 500 parts of benzene are reacted ^{at 70 ° C. in a pressure vessel equipped with a mechanical stirrer.} The reaction time is 10 hours. The solvent is then distilled off ^{at 30 ° C. in vacuo.} 1/5 of the remaining powder will be

a) with 30 parts of water,

b) with 30 parts of ethanol,

c) with 30 parts of ethylene glycol,

d) with 10 parts of mercaptoethanol,

e) with 10 parts of vinylthioethanol

implemented and then dried to vacuum drying cabinet. The properties of the test specimens produced from these molding compounds

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summarized in the following table 2:

peroxide
salary
in % ■ Table 2 Si
salary
in % Tear
stig
ability 2
kp / cm Zugfe
stig
ability 2
kp / cm Deh
tion
* Sol
lich
speed
in To
luene Example product
7th 1.2 you 2.9 260 305 535 ♦ Starting poly
propylene
modified
Polypropylene - 1.9 3.1 270 295 480 - a - 2.7 3.0 265 305 390 - b - 2.5 2.9 320 352 38O - C. - 3.2 2.9 360 375 355 - d - 3.9 2.7 315 340 362 - e 2.9

The implementation products according to Example 7a and 7e are insoluble in organic solvents such as pentane, hexane, toluene, styrene, benzene, xylene, p-diisopropylbenzene or dimethylformamide and, in contrast to the starting polypropylene, are not swollen by such substances. The product according to Example 7 e is curable at temperatures above 100 ⁰ C and results, for example after extrusion or pressing at 170-230 ⁰ C cross-linked, no longer deformable, solvent-resistant moldings.

* Example 8

100 parts of polypropylene, the hydroperoxide content is 1.2 weight percent, with 20 parts of HSiCl ₂ CH, during 60 minutes at 150 ⁰ C - as described in Example 5 - implemented. The modified polypropylene obtained thereafter has a content of SICl ₂ CH, groups of 10.5 percent by weight. Each 1/5 of this material will be

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a) with 30 parts of water,

b) with 30 parts of ethanol,

c) with 30 parts of ethylene glycol,

d) with 10 parts of mercaptoethanol,

e) with 10 parts of vinylthioethanol

implemented and then dried in a vacuum drying cabinet.
The properties of the test specimens produced from these molding compositions are summarized in the table below;

Tabel Example 8

Si %

Tensile strength tensile strength

2 ο speed kp / cm kp / cm % in toluene

modified
Polypropylene - 2.5 2, 5 y t SiCl ₂ GH ₃ - - - ♦ a 2.6 1, 1 263 285 495 b 3.3 2, 9 270 300 415 G 3.7 1, O 295 315 427 d 2.7 8th 315 360 390 e 7th 290 320 405

Here, too, the reaction products according to Example 8 a to 8 e are not soluble in the solvents listed in Example 7 "

or swellable.

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Claims (1)

-10- Patent claim 1 81 A 7 7 D Process for the production of modified propylene polymers, characterized in that polypropylene which contains 0.01 to 5 percent by weight of hydroperoxide groups is mixed with compounds of the general formula R ₁ -? - converts, in which Z can be carbon or silicon, where for the case Z = carbon the substituents R «, R ₀ , R., and R ₂ , chlorine, bromine or iodine and R ₁ , also hydrogen and for the case Z = Silicon the substituents R., Rp, R ^. and Rj, chlorine or bromine or Rp, R., and R ₂ , also denote hydrogen, a saturated or unsaturated acyclic or cyclic aliphatic radical and an aromatic radical. Badische Anilin- & Soda-Fabrik AG 009828/1987