DE2064170B2 - PROCESS FOR MODIFYING HYDROCARBON POLYMERS OR THEIR CHLORINATED DERIVATIVES - Google Patents

Description

20th

From US Pat. No. 2,964,517 it is already known to chlorinate oxidized polyethylene waxes. However, the process of the US patent has the disadvantage that the products obtained after the Chlorination has progressed so far that the chlorine content is approximately 30%, are completely soluble in the reaction medium and thus the isolation of the products is associated with difficulties.

In French patent 12 75 340 is a method is described, wherein the chlorinated hydrocarbon polymers, namely contact polyvinyl chloride, treated in feinverteiltcr shape with nitrogen oxides, for example, with nitrosyl halide, at temperatures between 0 j5 and 30 ⁰ C, or at higher temperatures. The nitrogen oxides act as an oxidizing agent.

The invention relates to a process for modifying hydrocarbon polymers or their chlorinated derivatives by treating the polymers in finely divided form with nitrosyl halides, which is characterized in that the treatment at -3O ⁰ C to 100 ⁰ C on 1 to 35 weight percent suspensions of polymers with Molecular weights from 1000 to 1,000,000 in aliphatic or cycloaliphatic halogenated hydrocarbons with 1 to 4 carbon atoms and 4 to 10 halogen atoms, of which at least 1 halogen atom is a fluorine atom, with nitrosyl chloride or with chlorine and nitrogen in the presence of light, heat or a free radical forming agent Initiator is carried out.

According to the invention, chloronitrosylated hydrocarbon polymers are thus produced by a process system with low viscosities which is easy to handle and provides a practically pure product, that is to say without polymer degradation, in an easily recoverable form. In addition, the chloronitrolylated hydrocarbon _{polymers which are obtained by the b} o process according to the invention give, when crosslinked, polymers with improved physical properties.

The process of the invention is a two-phase suspension process. The chlornitrosylierte polymers obtained may be crosslinked to a s _h polymers having improved physical properties by treatment with heat. The polymers produced by the process according to the invention have a chlorine content of 0.05 to 73 percent by weight and a nitrogen content of 0.1 to 5 percent by weight.

Hydrocarbon polymers that can be chloronitrosylated according to the invention have a molecular weight from 1,000 to 1,000,000, and preferably 10,000 to 150,000. The polymers cannot be fully saturated or contain residual reactive ethylenically unsaturated sites. To typical hydrocarbon polymers for the purposes of the invention include, for example, polyolefins such as polyethylene, polypropylene, Polybutylene, the higher polyalkylenes, copolymers made from mixtures of olefins such as Poly (ethylene propylene), chlorinated polyolefins such as chlorinated polyethylene, polystyrene, polymethylstyrene, polyalphamethylstyrene, Polybutadiene, polyisobutylene, chloroprene, butyl rubber, poly (styrene butadiene), and polyvinyl and polyvinylidene halides such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride and polyvinylidene fluoride.

Free radical initiators used in the preparation of the polymers according to the invention are, for example, all known and customary free radical-forming Initiators, preferably peroxides, such as hydrogen peroxide, tert-butyl peroxide, di-tert-bul.yl peroxide, benzoyl peroxide, tert-butyl hydroperoxide and dicumyl peroxide and azo compounds such as azobisisobutyronitrile. Further Peroxide initiators that can be used for the purposes of the invention are, for example

Cumene hydroperoxide, dichlorobenzoyl peroxide,

tert-butyl perbenzoate, acetylbenzoyl peroxide,

Caprylyl peroxide, lauryl peroxide,

Hydroxyheptyl peroxide, methyl ethyl ketone peroxide,

1 - Hydroxycyclohexy! Hydroperoxide ■ 1,

Di-tert-butyl perphthalate, dibenzaldiperoxide,

2,2- (tert-butylperoxy) butane,

Bis (p-bromobenzoyl) peroxide,

Bis (p-chlorobenzoyl) peroxide,

Bissuccinyl peroxide and

Bischloroacetyl peroxide.

A detailed description of known free radical initiators that are necessary for the invention Purposes can be found in Radical Polymerization by J. C. Bevington, (Academic Press, 1961), pp. 5-28.

Fluorocarbons which are necessary for the present invention Purposes that can be used are aliphatic or cycloaliphatic halogen hydrocarbons having 1 to 4 carbon atoms and 4 to 10 halogen atoms, provided that there is at least one halogen atom is a fluorine atom. Such fluorocarbons are, for example

Tetrafluoromethane, bromotrifluoromethane,

Chlorotrifluoromethane, dibromodifluoromethane,

Dichlorodifluoromethane,

Trichlorofluoromethane, hexafluoroethane,

1,2,2-trichloro-1,1,2-trifluoroethane,

1,1,2,2-tetrachloro-1,2-difluoroethane,

1,2-dibromo-1,2,2-tetrafluoroethane,

1,2,2-tribromo-1,1,2-trifluoroethane,

Octafluoropropane, decafluorobutane,

Hexafluorocyclopropane,

1,2,3-trichloro-1 ^, S-trifluorocyclopropane,

Octafluorocyclobutane.

1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane and

1,2,3,4-tetrachloro-1,2,3,4- (etral'luorocyclobutane.
The amount of fluorocarbon used in the present invention depends on the particular one used

Fluorocarbon and the molecular weight of the hydrocarbon polymer. Generally amounts to however, the concentration of polymers in the fluorocarbon is 1 to 35 weight percent solids and preferably 5 to 15 weight percent solids.

The inventive reaction is carried out at a temperature between -30 degrees C and 100 degrees C, preferably between -30 degrees C and 80 degrees C, carried out. The temperature used in the individual case depends on the diluent used Fluorocarbon, the hydrocarbon polymers, the initiator and other reaction conditions, z. B. reaction time and reaction pressure. Preferably the reaction is under reflux conditions performed. The reaction can be carried out at atmospheric pressure, elevated pressure or reduced pressure will. The reaction time depends on the reactants used and on the reaction temperature away. Generally, however, from one hour to 60 hours, and preferably from one hour to 24 hours sufficient to ensure that the reaction has taken place.

After the chloronitrosylation has ended, the process according to the invention can be used easily isolate produced products by simple filtration methods.

The chloronitrosylated polymer can then be heated to a temperature of 80 to 225 degrees C. hardened. The curing of the polymers can take place under pressure. In general, the hardening in the presence of a filler, e.g. B. of carbon black and magnesium oxide or other basic oxides, e.g. B. Zinc, lead or calcium oxides. The hardened polymers have increased tensile strength, decreased elongation and insolubility in organic solvents.

The invention is illustrated in more detail by the following examples. All parts refer to that Weight, unless otherwise stated. In the following examples, the chlorine content was given as a percentage according to Molir's chlorine determination method and the nitrogen content in percent using the nitrogen determination method determined by Dumas. The physical properties of the cured polymer were determined according to ASTM standard test regulations.

example 1

A glass reaction vessel, which is equipped with a thermometer, a stirrer, a reflux condenser and inlet and heat exchange devices, is with 3130 parts of U ^ -Trichlor-U ^ -trifluoroethane and 200 parts of polyethylene with a molecular weight of about 60,000, a melt index of 20 and a density of 0.915. The polyethylene has a large surface area, which is achieved by dissolving 1000 parts of the polyethylene in 950 parts of hot carbon tetrachloride and then precipitating it by slowly adding the solution to approximately 8900 parts of intensely stirred isopropanol. The fine crumb is at 8O ⁰ C and 0.2 mm Hg to constant weight ho dried.

The feed is heated to 48 ° C in a nitrogen atmosphere, at which temperature reflux occurs. While the feed is held at this temperature, i, j Hours through the reaction vessel under irradiation with a 500 watt lamp 40 parts of nitrosyl chloride eguided. After the 2 hours in which the nitrosyl chloride is fed into the reactor, the The reaction mixture is cooled to room temperature and the product is isolated by filtration and taking Ambient conditions dried to constant weight. An analysis of the fine white free flowing Product gives 4.2% chlorine and 0.51% nitrogen.

If the polymer produced above is cured by heating it to 149 ° C. for one hour, so have foils produced therefrom have the following physical properties:

Tensile strength, kg / cm ² 124.0 300% modulus 93.7 100% modulus 85.3 Elogation,% 365

The above-described procedure is repeated except that reaction (a) 24 Hours at 80 ° C in the presence of benzoyl peroxide and (b) 12 hours at 75 ° C in the presence of Azobisisobutyronitri! is carried out. In any case, practically the same product as before is obtained.

Example 2

A glass reaction vessel fitted with a thermometer, stirrer, reflux condenser, and inlet and outlet Heat exchange equipment is equipped with 3130 parts of l, l, 2-trichloro-l, 2,2-trifluoräth8n and 200 Parts of polyethylene with a melt index of 20 and a density of 0.915 are charged. The polyethylene has a large surface area, which is achieved in that 1000 parts of the polyethylene in 950 parts hot Dissolved carbon tetrachloride and then intensively by slowly adding the solution to about 8900 parts stirred isopropanol are precipitated. The fine crumbs are constant at 80 ° C and 0.2 mm Hg Weight dried.

The feed is heated to 48 ° C in a nitrogen atmosphere, at which temperature reflux occurs. While the feed is held at this temperature, are added to the reaction vessel under Irradiation with a 500 watt quartz lamp initiated 84 parts of nitrosyl chloride over a period of 4 hours. After the 4 hours in which the nitrosyl chloride is fed to the reactor, the reaction mixture cooled to room temperature and the product isolated by filtration and stored under ambient conditions dried to constant weight. An analysis of the fine white free flowing product gives 1.30% chlorine and 0.51% nitrogen.

If the polymer produced above is cured by heating it to 149 ° C. for one hour, so have foils produced therefrom have the following physical properties:

Tensile strength, kg / cm ² 131.6 300% modulus 103.4 100% modulus 93.9 Elongation,% 378

Example 3

A glass reaction vessel fitted with a thermometer, stirrer, reflux condenser, and inlet and outlet Heat exchange equipment is equipped with 3130 parts l, l, 2-trichloro-l, 2,2-trifluoroethane and 200 Parts of polyethylene with a melt index of 20 and a density of 0.915 are charged. The polyethylene has a large surface area, which is achieved by heating 100 parts of the polyethylene in 950 parts

Dissolved carbon tetrachloride and then intensively by slowly adding the solution to about 8900 parts stirred isopropanol are precipitated. The fine crumbs are constant at 80 ° C and 0.2 mm Hg Weight dried.

The feed is heated in Stidcstoffatmosphäre at 48 ⁰ C, at which temperature reflux occurs. While maintaining the charge at this temperature, 179 parts of nitrosyl chloride are passed through the reaction vessel under irradiation with a 500 watt quartz lamp over a period of 9 hours. At the end of the 9 hours that the nitrosyl chloride was added to the reactor, the reaction mixture is cooled to room temperature and the product is isolated by filtration and dried to constant weight under ambient conditions. Analysis of the fine white free flowing product found 1.84% chlorine and 0.70% nitrogen.

If the polymer prepared above gjhärtet hour by heating to 149 ⁰ C, so it slides have generated the following physical properties:

Tensile strength, kg / cm ²
100% modulus
Elongation,%
Stretch limit

106.1
88.0

291
82.5

Example 4

Tensile strength, kg / cm ² 168.7 300% modulus 47.3 100% modulus 25.3 Elongation,% 645

Films made from the untreated chlorinated polyethylene have the following physical properties Features on:

Tensile strength, kg / cm ² 68.2 300% modulus 25.8 100% modulus 15.9 Elogation,% 707

Example 5

A glass reaction vessel equipped with a thermometer, stirrer, reflux condenser, and inlet and heat exchange devices is filled with 1565 parts of 1,1,2-trichloro-1,2,2-trifluoroethane and 200 parts of chlorinated polyethylene having a molecular weight of about 20,000 , a chlorine content of 36% and a bulk density of 0.45 g / cm ³ .

The charge is heated to 48 ° C. in a nitrogen atmosphere, at which temperature reflux occurs. While maintaining the charge at this temperature, 109 parts of nitrosyl chloride are passed through the reaction vessel under irradiation with a 500 watt quartz lamp over a period of 6 hours. After the 6 hours in which nitrosyl chloride is added to the reactor, the reaction mixture is cooled to room temperature and the product is isolated by filtration and dried to constant weight under ambient conditions. Analysis of the fine white free flowing product found 36.7% chlorine and 0.92% nitrogen.

If the polymer produced above is cured by heating it to 149 ° C. for one hour, so have foils produced therefrom have the following physical properties:

A glass reaction vessel equipped with a thermometer, stirrer, reflux condenser, and inlet and heat exchange devices is filled with 1565 parts of 1,1,2-trichloro-1,2,2-trifluoroethane and 200 parts of chlorinated polyethylene having a molecular weight of about 20,000, a chlorine content of 36% and a bulk density of 0.45 g / cm ³ .

The feed is heated to 48 ° C in nitrogen atmosphere, at which temperature reflux occurs. While the feed is held at this temperature, are added to the reaction vessel under Irradiation with a 500 watt quartz lamp initiated 53 parts of nitrosyl chloride over a period of 2 hours. After the 2 hours in which the nitrosyl chloride is fed to the reactor, the reaction mixture cooled to room temperature and the product isolated by filtration and stored under ambient conditions dried to constant weight. An analysis of the fine white free flowing product gives 36.3% chlorine and 0.81% nitrogen.

If the polymer prepared above is cured by heating at 149 ° C for one hour, then prove foils produced therefrom have the following physical properties:

Tensile strength, kg / cm ²
300% modulus
100% modulus
Elongation,%

91.1
68.9
26.2
379

Example 6

Following the procedure described in Example 1, various tests are carried out with 120 parts of the in Example 1 described polyethylene carried out. The polyethylene is made by passing nitrosyl chloride through it by a two-phase suspension system using various fluorocarbons chloronitrosylated for a period of 2 hours under reflux conditions. The used Fluorocarbons, their amounts and reaction temperatures are given below:

(A) Trichlorofluoromethane, 2950 parts, 24 ° C

(B) Trichlorofluoromethane, 1475 parts, 24 ° C

(C) 1,1,2,2-tetrachloro-1,2-difluoroethane,
3268 parts, 93 ° C

(D) U-dichloro-IU ^ -tetrafluoroethane,
2284 parts, 4 ° C,

(E) 1,2-dibromo-1,2,2-tetrafluoroethane,
2500 parts, 47 ° C

(F) dichlorodifluoromethane, 2292 parts, -3O ⁰ C.

Practically the same product as in Example 1 is obtained in each experiment.

Example 7

A reaction vessel equipped as described in Example 1 is filled with 1565 parts of 1,1,2-trichloro-1,2,2-

W) trifluoroethane and 120 parts of polypropylene powder with a melt flow index of 12 g / 10 minutes and one Filled density of 0.904. The feed is heated to 48 ° C in nitrogen atmosphere, at which Temperature reflux occurs. While the batch is being held at this temperature through the reaction vessel under irradiation with a 500 watt quartz lamp in a time of 3 hours 60 Parts of nitrosyl chloride passed. After the 3rd

For hours the reaction mixture is cooled to room temperature and the product is filtered off isolated and dried to constant weight under ambient conditions. An analysis of the fine white free flowing product gives the presence of both chlorine and nitrogen.

Claims (1)

Claim: A method for modifying hydrocarbon polymers or their chlorinated derivatives by treating the polymers in a finely divided form with nitrosyl halides, characterized in that the treatment at - 30 ° C to 100 ⁰ C at 1 to 35 weight percent suspensions of polymers having molecular weights from 1000 to 1,000,000 in aliphatic or cycloaliphatic !! Halogenated hydrocarbons having 1 to 4 carbon atoms and 4 to 10 halogen atoms, of which at least 1 halogen atom is a fluorine atom, is carried out with nitrosyl chloride or with chlorine and nitrogen in the presence of light, heat or a free radical initiator.