DE2349565A1 - Light-coloured thermally stable chlorinated (co)polyolefins - by chlorination in fluidized bed in presence of carboxylic acid - Google Patents

Abstract

DT 2262535 Describes a process for the prodn. of light coloured, thermally stable chlorination prodts. of 2 and 3C alpha-olefin polymers or copolymers of ethylene with 3-6C alpha-olefins, by chlorinating the powdered polymers with a mol. wt. of 20,000-2,000,000 in fluidised bed with gaseous chloride in the presence of 0.01-3.0 wt. % carboxylic acids or their alkali(ne earth) salts (I) evenly distributed in the polymer powder. Process is improved by replacing (I) by aliphatic hydroxycarboxylic acids, or aromatic hydroxycarbocyclic acids which may be substd. in the nucleus by alkyl gps. or alkali(ne earth) metal salts of these, or anhydrides of aliphatic or aromatic mono- or di-carboxylic acids. (I) are used e.g., as plasticisers for PVC and as synthetic rubbers.

Description

Process for the production of light-colored, thermally stable C h 1 or lerun / ys products of PbIy- <x - olefins .

(Addition to P 2 262 535)

In the German Offenlegungsschrift 2 262 535 a process for the production of light-colored, thermally stable ChIox'ierungsprodukte of C ₂ and C "-C (-olefin polymers or copolymers of ethylene with aliphatic C" to Cg

- OC-olefins described by reacting the pulverulent polymers with gaseous chlorine in a fluidized or fluidized bed, which is characterized in that the chlorination is carried out in the presence of small amounts of a saturated aliphatic mono- or dicarboxylic acid with a number of carbon atoms h to J50 which is uniformly distributed in the polyolefin powder , or a mononuclear aromatic, optionally alkyl-substituted monocarboxylic acid of the carbon atom number 7 to 231 or an alkali or alkaline earth metal salt of the carboxylic acids mentioned.

It has now been found that instead of said carboxylic acids or salts with the same success oxycarboxylic acids or their salts, or also the anhydrides of aliphatic or aromatic carboxylic acids or oxycarboxylic acids "

The subject of the invention is thus the further development of the process for the production of light-colored, thermally stable chlorination products of C ₂ and G_-CA-Oiefin polymers, or copolymers of ethylene with C_ to C-ς.

- C (olefins by reacting the powdery polymers

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from a molecular weight of approx. 20,000 to 2,000,000 with gaseous chlorine in the fluidized bed or in the fluidized bed in the presence of 0.01 to. 3jO Gew .- ^ o evenly distributed in the polyolefin powder Carboxylic acids or their alkali or alkaline earth metal salts, which consists in that instead of those mentioned in the main patent Acids or salts in the presence of aliphatic oxycarboxylic acids, or aromatic, optionally ring-alkyl-substituted Oxycarboxylic acids or alkali or alkaline earth salts the aliphatic or aromatic oxyacids, or in The presence of anhydrides of aliphatic or aromatic mono- or dicarboxylic acids works.

Powdered polymers of aliphatic C "and C_-O-C olefins or copolymers of ethylene and aliphatic O ^ -olefins with 3 to 6 carbon atoms with a grain size between about kO yU- and 500Ia are suitable as starting material for the chlorination. Medium pressure or low pressure polymerization processes may have been obtained. The molecular weight can range between about 20,000 and 2,000,000. Unless Niederdruckpolyäthylene be chlorinated, are preferably those having an eta-red-value of 0.5 to 2O, preferably 1.0 to 5 »0 in question, the latter range corresponds to a molecular weight of about 3 hours from 000 to 270,000.

Aliphatic oxycarboxylic acids are straight-chain or branched oxy-monocarboxylic acids with 2 to 18, or oxy-dicar- Understood bonic acids with 4 to 10 carbon atoms in the molecule. Examples include glycolic acid, lactic acid, oxybutyric acids, Oxyvaleric acids such as oxypivalic acid, oxystearic acid, Oxysuccinic acid (malic acid), oxyadipic acid, oxysebacic acid etc. Glycolic acid, lactic acid and malic acid are particularly suitable. Have suitable aromatic oxycarboxylic acids

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7 to 11 carbon atoms and 'are derived from benzoic acid and its Alkyl substitution products. The OH group is right on bound the aromatic nucleus. Examples include oxybenzoic acids, Oxytoluic acids, oxyethyl, oxypropyl and oxybutylbenzoic acids.

Instead of the free acids, their alkali and alkaline earth salts, The barium, calcium or sodium salts are preferably used.

Anhydrides of aliphatic or aromatic mono- or dicarboxylic acids are understood to mean compounds obtained by intermolecular or intramolecular condensation from saturated or unsaturated carboxylic acids - optionally also oxy acids. Suitable anhydrides of aliphatic carboxylic acids with h to 50 carbon atoms are, for example, maleic anhydride, succinic anhydride, adipic anhydride, valeric anhydride, stearic anhydride, cerotic anhydride and montanic anhydride. Anhydrides of aromatic carboxylic acids with 7 to 23 carbon atoms are, for example, benzoic anhydride, phthalic anhydride, anhydrides of oxybenzoic acids, etc. Maleic anhydride, succinic anhydride and benzoic anhydride are of particular importance

The amount of carboxylic acid, salt, or anhydride is 0.01 to 3.0, preferably 0.1 to 1.0 wt .- ^, based on the amount to be chlorinated Polymers.

The mixing of the polyolefin powder with the inventive oxycarboxylic acids or salts or carboxylic acid anhydrides to be added can be done in a number of ways. For example, it can be mixed mechanically before chlorination, you can use the Blow substances into the batch before or at the start of the chlorination, you can also use the oxy acids or salts or Carboxylic anhydrides in the form of solutions in opposite to that

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Polyolefin inert, easily re-evaporable liquids such as chloroform, ether, alcohol, water on the polymers. Finally, the mixing process can also be used any preheating of the polymeriza-

tes according to the DT.OS. I72O.8OO connect.

The chlorination takes place in a known manner in a vortex or Fluidized bed carried out, with temperatures between 20 and 160 C selected depending on the nature of the polymer can be and the movement of the goods by means of the possibly inert gas-containing reaction gas and / or can also be done mechanically. Possible embodiments of the chlorination are also vortex method, as they are e.g. in the DT.-OS. 1.667.048 and I.8II.O59 are described, as well as fluidized bed chlorinations in the presence of easily evaporable liquids according to the DT.-OS. 2.I5I.I38. The use of according to the DT.-OS. I.72O.8OO thermally pretreated polyolefins is also possible, such as the chlorination of mixtures of polyolefins with solids such as talc, silica gel, barium sulfate, PVC or PVC granulate, polyfluorocarbons, glass beads, etc. The known prior art also includes chlorination in the presence of high-energy radiation or radicals supplying substances such as peroxides, azonitriles, etc. Finally, one can use both discontinuously and continuously and work without pressure or under pressure.

The properties of the chlorination products obtainable in accordance with the present process, which are further developed compared to the main patent, correspond completely to the products of the main patent and are used in the same way, namely, for example, preferably as high-molecular plasticizers in PVC compounds and as synthetic rubbers.

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The following examples illustrate the process: Example 1 ;

A vertical glass tube with a diameter of 80 mm and a height of 1000 ram served as the chlorination apparatus, in which a gas-permeable, porous plate is inserted in the lower part. Located about 100 mm above the plate inside the reaction chamber the temperature measuring point, in near them a closable nozzle through which the chlorination additives can be blown in. The apparatus is provided with a jacket for heating or cooling.

2000 g of low-pressure polyethylene (Eta ~ red- ¥ ert 1.0, grain size 40-5OO M-, heat of fusion according to differential thermal analysis (DTA) 37.8 cal / g and end of the melting range (mp.E) 13 ^ ° C) were according to the information of DT .-OS. 1,720,800 in the presence of 0.25% by weight of single- disperse silica, tempered at 122 ° C. in a stream of nitrogen. After cooling, 600 g of the product obtained were introduced into the chlorination apparatus and gassed with a mixture of 1 part by volume of chlorine and 1 hour by volume of hydrogen chloride while swirling, the temperature rising from 20 ° C. to 45 ° C. in the course of 20 minutes. At this temperature, and after reaching an internal temperature of 60, 80 and 100 ⁰ C. 0.5 g of maleic anhydride were injected through the nozzle into the reaction mixture, respectively. After a total of 3 hours of chlorination, during which the chlorination temperature was gradually increased to 137 ° C., nitrogen was used to blow out and cold. The chlorination product was a pure white powder with a chlorine content of $ 37.8.

Example 2 ;

600 g of the tempered polyethylene according to Example 1 were with

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l # 5g phthalic anhydride mixed and described in Example 1 Apparatus presented. It was then chlorinated according to the information in Example 1. The highest chlorination temperature was 136 C. The chlorination product was white and had a chlorine content of 33%.

Comparative example :

The heat-treated polyethylene from Example 1 was chlorinated as in Example 2, but without addition. The chlorination product with a chlorine content of $ 33.5 showed a yellowish color.

Example 3 ?

As described in Example 1, 1500 g of low-pressure polyethylene from Eta-red- ¥ ert 1.2 with a grain size of 40 to 800 It and the heat of fusion 42.0 cal / g (melting point 135 ° C) in the presence of 0, 1 $ finely dispersed silica tempered. 6OO g of this annealed polyethylene powder were mixed with 1.5 g of ^t BernsteinsäureK uncropped mixed 5 g silica and in the apparatus described in Example 1 was chlorinated (4 parts by volume of HCl and 1 Vol.Teil chlorine). The chlorination temperature was increased from approx. 60 ° C. to 137 ° C. over the course of 21/4 hours. The chlorination was then continued for about 5 minutes at this temperature, after which it was cold-blown and blown out with nitrogen. The chlorination product was white and had a chlorine content of $ 32.4.

A comparison test without an additive produced a yellow discolored one Chlorination product with a chlorine content of 32.9 / »«

Example 4 ;

As in Example 1, 1500 g of Niederdx ^ uckpolyäthylen from Etared- ¥ ert 1 »2 _S grain size 40 to 500 Uu and the heat of fusion 44.0 cal / g (mp, E 136 ⁰ G) annealed without the addition of silica.

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600 g of this annealed polyethylene were mixed with 1.5 U of glycolic acid and 2.0 g of finely dispersed silicic acid and in the apparatus described in Example 1 was chlorinated (HCl: Chlorine = 4 parts by volume of Si). The chlorination temperature was increased from .60 to 145 ° C. in the course of 21/2 hours, followed by chlorination at this temperature for a further 5 minutes. The chlorination product with a chlorine content of $ 34.7 showed a pure white color.

Comparative example ;

Example 4 was repeated without the addition according to the invention. The chlorination product had a chlorine content of $ 35 and was colored dark yellow.

Example 5 ? ·

Vie in Example 1 were 1500 g of low-pressure polyethylene from the Etared value 4.2, the grain size 40 to 500 and the heat of fusion 45.2 cal / g (melting point 140 ° C) annealed with 0.2 $ finely divided silica.

A solution of 1.5 g was added to 600 g of the tempered product Malic acid in 20 ml dist. Spray water evenly. That The product was chlorinated as described in Example 4. The final chlorination temperature was 143 C.

The pure white chlorination product had a chlorine content of $ 39.3.

Comparative example :

The polyethylene used in the example 5 was, however, according to _f Angäben of Example 4 without the addition erfindtingsgemäßen

The chlorination product had a chlorine content of $ 38.3 and was

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colored dark yellow.

The table below shows the essential properties of the chlorination products. The color * was assessed visually on the one hand and measured spectrophotometrically in accordance with DIN 5033 on a 1 mm thick alzfell made from a stabilized mixture of 30 g chloropolyolefin and 180 g suspension polyvinyl chloride. The thermal stability was determined by rolling a mixture of ho g chloropolyolefin, 160 g suspension polyvinyl chloride and 2 g stabilizer (Ba-Cd-laurate) until black decomposition streaks appeared.

Finally, the starting material was also used by infrared spectroscopy examined for double bonds.

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E.g".
No. Source material ■ Double bin
dung 2)
ABC Chlorination product colour photo— "*
metric ' ThermoSta
mobility
(Min.) chlorine 1
2
Ver
same Type ¹ \ ο bc
whether c
ο bc visually 6th
1
.18 36
38.
34 37.8
33.0
33.5 3
Ver
same HHH ο bc
ο bc - White
White
yellowish 3 43
40 32.4
33.0 4th
Ver
same II
II O 3 C
ο bc White
yellow 5
> 28 40
31 34.7
35.0 5
-
same II
II ABC
ABC White
dark/
yellow 1 37
23 cn cn
ON 00
cn cn III
III White
dark/
yellow

1) I = ND polyethylene Eta-red. 1.0 II = ND polyethylene Eta-red. 1.2

III = ND polyethylene Eta-red. 4.2

2) The double bonds present are:

a = transvinylene groups

b = vinyl groups

c = vinylidene groups

ο = none

3) according to value numbers, where

1 = white, 20 = yellowish.

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Claims (1)

"* ¹⁰ ~ HOE 73 / P 812 (Ge. Claim. : Further development of the process for the production of light-colored, thermally stable chlorination products of C "and C" - oC olefin polymers, or copolymers of ethylene with C "to C, - (A -olefins by reacting the palver-shaped polymers with a molecular weight of approx until
2,000,000 with gaseous chlorine in the fluidized bed or
in the fluidized bed in the presence of 0.01 to 3 »0 wt .- ^ of in
the polyolefin powder evenly distributed carboxylic acids or their alkali or alkaline earth salts according to patent « characterized in that, instead of the acids or salts mentioned in the main patent, in the presence of aliphatic Oxycarboxylic acids, or aromatic, optionally ring-alkyl-substituted ones Oxycarboxylic acids, or alkali or alkaline earth metal salts of the aliphatic or aromatic oxy acids, or works in the presence of anhydrides of aliphatic or aromatic mono- or dicarboxylic acids. 509817/0937