DE1595561A1 - Process for the production of chlorinated polyethylene waxes - Google Patents

Description

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Process for the production of chlorinated polyethylene waxes.

The invention relates to a process for the production of chlorinated polyethylene waxes with opposite known comparable polyethylene waxes improved physical properties.

The usefulness of the known polyethylene waxes is known because of their relatively low solubility at room temperature in the usual aromatic solvents and because of their relatively low softening points and unsatisfactory heat stability properties are severely limited. To the general usability of polyethylene waxes has therefore already been proposed, chlorinated, oxidized waxes of the telomer type from ethylene and lower alkanols

009815/1743

BATH ORIGINAL

place. Although these V / axis have improved solubility properties, however, too low softening points and thermal stability.

The present invention was therefore based on the object to create a process for the production of chlorinated polyethylene waxes which makes it possible to produce chlorinated polyethylene waxes with relatively high softening points and good thermal stability properties. The after the "process producible polyethylene waxes should be used at the same time be easily emulsifiable. Furthermore, the method should make it possible to produce specifically those V / axis that have a good surface hardness, high gloss, important flammability, good resistance to water vapor permeability, excellent adhesion to various surfaces and improved strength properties own. The waxes should also be readily soluble in aromatic hydrocarbons and with the most varied Be compatible with plastics and resins.

The invention was based on the knowledge that such

5 chlorinated polyethylene waxes having a chlorine content of Jf to 75% by weight and acid numbers can be prepared from 4 to 25, when according to the invention cp an oxidized polyethylene wax having a melt viscosity of 100 to 4,000, as measured at 125 ⁰ C and an acid number from 4 to 25 in a solution stable to chlorine

009815/1743 ~ -

Solvent dissolves and if you do so at a temperature of at least iü ° C in the presence of a chlorination catalyst introduces chlorine into the solution for a long time until the desired chlorination limit is reached.

Among oxidized polyethylene waxes that are chlorinated according to the invention weruen, the auto-oxidation substances are of lower molecular weight Understand polyethylene waxes. This '..' axis can be manufactured are caused by the thermal degradation of high molecular weight polyethylenes, possibly with the following Hydrogenation or by direct polymerization.

In detail i. For example, the following oxidized polyethylene waxes can be used to carry out the process of refining:

A '..' axis is suitable, which is obtained by autoxidation of the products, and in the case of thermal degradation of the usual or linear polyethylene hol.er l ") io: .te with molecular weights vci. R.i'rtdestenn about ": OZC Lik about ICC OüC preferably incurred IC DCC to about 3 ^ ^ 00th The softening points of such polyethylenes Lieger, preferably above about 40 ⁰ C * are referred to as oxidized degraded V / aes axis polyethylene These waxes rounder "The manufacture of such '.. Axis can in any way figs, UaE the polyethylene in a time span required for uen degradation to temperatures

009815/1743 "wheel original

from about 36ü to about '120 ⁰ C ernitzt wii'd. The molecular weight over the viscosity range can be controlled by changing the decomposition temperature and the heating time. The calibrations in the case of heat-up (- bilüenden cerirw; en .direct to products ir. With lower molecular weight unu üle / see from outside the keaklionmusse can easily be removed in a vacuum or with the help of an inert gas, such ./axes are advantageous , which are obtained with melt viscosities of about 2Gu :; about oOOO egg, pressure at 125 ° C. Liese 'axes can then be auto-oxygenated with the aid of an oxygen-containing gas

the autoxidation takes place;: with the aid of air when printing

ρ approximately atinosphere return to etv: a ji> i: r / c:;. "and i'ei / iperaturen from about 100 to about 175 C. The contact time ue :; 'Jachces'' old uer. cxyuierenuen.! euiurn nanr ^ t uabei von uer Kcv / ünccnten. 'Juurezahl of the promenade.

For judging ues /ei'fai.i'ens uer ^ ri'inuunf- si na feriiei 'solcne .. 'acnso reeicnet, uie uurch /-.ut oxy out lon von hyurierte, uurcn thermal construction;: ev.'onnenen i roau / tes-i ai-naitor, v / eraen. Also suitable sina the .. 'axis, uie ernalten v / ercen curch Autoxyaation of roiyatnyien, uie uurch ti ir ekle i'clymerisation get v; era.

Uanz generally sina selche .. 'axis {-eeignet, oie .Jchmelzvickositäten according crcoi fell from IGC to about ^ UGC op at 12 ° C ^L j be

sit and have acid numbers from 4 to 25.

The molecular weight of these waxes is preferably between about 400 and about 6000. ^ m ^ imßm * m% fkmmtgmmmmmmmmmmeettSiämBaa ^.

The chlorination of the oxidized polyethylene waxes takes place in a solvent. is consistent with the major by-product of the reaction. Carbon tetrachloride has proven to be particularly advantageous. The solvent used should also be possible have such a low boiling point that it is easily removed from the Reaction product can be separated.

The concentration of the oxidized wax in the solvent can vary widely. Expedient but it has been proven to concentrations of no more than 25 percent - to use%.. The use of 5 to about 20 percent by weight solutions has proven to be advantageous. The production of solutions which contain more than 25% by weight of wax is somewhat difficult because it results in highly viscous solutions which cannot easily be chlorinated with the desired uniformity.

009815/1743

The reaction temperature during the chlorination can also be very different. Chlorination temperatures of about 1 to about 16 ° C. have proven to be expedient. Below 10 ° C. the reaction rate may be too slow, while above 160 ° C. the wax may degrade. Temperatures from JO to 80 ^° C. have proven to be particularly advantageous. It may be advantageous to carry out the reaction under the pressure of the chlorine fed in, in order to increase the solubility of the chlorine in the liquid phase. It has proven advantageous to carry out the chlorination with vigorous stirring of the axis solution.

The course of the chlorination reaction can be in different ./eise be monitored. It has proven to be useful to periodically take samples from the reaction mass and determine the density to determine these samples. Since the density of the / axis of the Depending on its chlorine content, the chlorine content can easily be determined by density measurements. On the other hand, it's natural also possible to determine the course of the reaction ^ by viscosity measurements, by measuring the amount of evolved hydrogen chloride and the like.

Once a product with the desired chlorine content is present, the chlorinated wax can be isolated from the reaction mass. The isolation can be done in different ways.

009815/1743

it ;; o for example, has proved advantageous in the case V / axes with high chlorine content, ie // axes having a chlorine content in excess of about ^ O% a oprühtrocknunp; To be used in the production of axes with a medium chlorine content, for example a chlorine content of about 20 to about ^ U % , it may be more advantageous to remove the solvent from the external reaction product in a vacuum. Anceror side: it is also possible to drive off the solvent by aspirating distillation. Finally, it is also spatially possible to fill in and filter out aas chlorinated .. 'axrf with the help of an alcohol lower.'. ClOKUlai -.-.- , to w: iscnei; ui.i to dry.

The chlorination reaction can be jure :, uitraviolet light or one of the more common ones. Chlerierur.rskat al.vL'atcreti, in particular fi'eie VerLinaun-er., Such as Peroxy de, carried out, throw · AIr. free I-: a _v ikaie iiefernae üatalycatoreii

are for example: Liicoproi ylj ei'cxydicarboi.at, Az ^ - bisisobutyronitril, Laurcylieroxya, ^ er.zoyir-eroxyd,.-let i.y läthy Ir. ketonperoxya, Uecanoylrex'cxya una

The following table shows the properties from after Process of Epfinuun .-- producible !: chlorinated; en? O ^ .yathylenr grow corpses "

BATH ORIGINAL

The molecular weights were determined by raising the boiling point in benzene using benzil as a known compound. The method used is described, for example, in the book Interscience Publishers Industries, H. Y., UoA, 1958 »pages 59 to 109. Line device for determining molecular weights is also described, for example, in Analytical
Chemistry, iiand 33, 1961, Jeite '477.

Chlorine content: Density:

Acid number:
; Molecular weight: Softening points:

Colour:

Flar.irr.en resistance; Solubility:

Solution viscosity: 5-75% by weight

0.97 - 1.6b (generally uni so bigger, the higher the Chlorine content is)

4 - 25
6CO - bOOO

üic to 200 C for highly chlorinated products. With medium chlorine contents (30 - ¹ JO % Cl) some products are calibrated at ambient temperature;

Gardner · color value <1 for 33 % solutions in toluene;

^ ei about ^ u / i chlorine;

^ oi chlorine content over 30 % soluble in liquid aromatic substances, ketones and chlorinated lower aliphatic hydrocarbons;

.. 'less than 150 cp at 30 bic ' iO% "l; ~ en solutions in the anrt-.reber.er/Lösungsr.ltteln.

00981571743

If the chlorine content rises, chlorination products are quickly produced with medium chlorine levels a minimum softening point, whereupon the hardness and softening point rapidly with the The chlorine content increases.

The chlorinated ones which can be prepared by the process of the invention Polyethylene waxes can be divided into three groups according to their chlorine content, namely into emulsifiable polishing waxes, adhesive waxes and coating waxes.

In particular, those with chlorine contents of 5 to 25 % have proven to be emulsifiable polishing waxes. With such chlorine levels, the reaction products consist of moderately harsh hates. In the ilaße in which the chlorine content rises from 5% to 25 % , the Piing and Ball softening point drops from about 95 ° C to about 35 ° C. The chlorinated v / axis can be described by the following characteristics:

Chlorine content: 5 - 25 %

Softening point (Ring & Ball): 95 - 35 ° C Density: 0.97 - 1.15

Molecular weight: 600-6000

Acid number: 4-25

The chlorination products with 5 to 25 wt. Chlorine can emulsify more easily in water than the more highly chlorinated products. Emulsions of this chlorinated axis can be used to

009815/1743

BATH

Create layers and coatings that are hard and wear-resistant are una aie to be able to be polished to high gloss coatings.

The following table lists the properties of two horpholin oleate emulsions described using a chlorinated polyethylene according to egg invention and a non-chlorinated Polyethylene were made. The table also specifies the properties of coatings that consist of the two Emulsions were created on vinyl asbestos floor tiles.

Chlorinated, by by thermal

thermal degradation degradation got

preserved and oxidized po-

oxidized polyethylene ethylene

Molecular weight IiIOO 1250 Chlorine content 18 % 0 Acid number 12th 15th % Solids in the emulsion 20th 20th ⁺ Permeability of the emulsion 65 % 70 % Urookfield viscosity at 25 ° C 15 cp 15 cp Gardner color value of the emulsion 6th 7th III
60 ° Gardner gloss, originally 39 37 60o Gardner gloss, polished 53 48 Water resistance excellent very good

Transmittance of an emulsion containing 1% solids at a wavelength of 525 my.

For coatings on vinyl asbestos floor tiles.

009815/1743

They have special features as adhesives or adhesives the following have proven to be suitable:

With chlorine contents of 25 to 50%, the chlorinated polyethylene waxes pass through a softening point at a chlorine content of about 30 to 35 % chlorine. Thereafter, the softening points increase with chlorine contents of about 50% to about 6 ° . to 70 ⁰ C. Depending on uem .lolekulargewicht of AusganpsMaterialn that provide chlorinated Proaukte beii: i lirweichun-üpunkt-.iinii.-iun (chlorine content 30 to 3b; ί) very soft and sticky hate (at Verwenuun; * a Aue · transfer of the material nieuerei :; "oleicular ^ eWicht) to tough and elastomeric compositions (Lei use of a Ausgan ^r:.... snaterials high Molekulargewicj.L) represents Jle Chlorlerungsi roaukte obtained by thermal degradation of oxidized polyethylenes having a chlorine content from J'j to 5 ^ ^ ^ chlorine can be characterized by the following properties:

Softening point: \ au2.; Ter..j erature up to 70 C

Density:. 1.15-1.35

•• iolekulargevficijt: oC'G - uCOO

Acid number; ^ - 25

Solubility: soluble in liquid flavor

table hydrocarbons, oysters, ketones and chlorinated lower aliphatic

.-hydrocarbon very open

009815/1743

These products can be produced in an excellent way use of xleb masses. In the fol'-enue table sinu the adhesion characteristics of different './axis reproduced, on a Kraft paper of 18.1 kg and on a

Metallne / foil applied and at 121 ⁰ C at a pressure of 2.10

kg / cm were sealed for half an hour. The suitability results from the restrained results this ./axis as adhesives.

Chlorinated, chlorinated, through thermal through thermal mixing Mixing Dismantling preserving construction preserving construction preserving oxidizing

nes
tes
len r
C. oxidizing
Polyethy- nes poly
ethylene tes polyethy
len Chlorine content: 47 % 47 % 0 Softening point: 65 ° C 64 ° C 102 ° C Molecular weight 2300 1300 Adhesion to
Paper (g / 2.5 ^ cm) Ö17 520 103 Adhesion to
a metal foil 640 342 To (g / 2.54 cm)

As ueschichtungswachse, in particular so-called. Barrier resins (carrier Coatings Resins) can be especially t chlorination with a chlorine content of about 50 to about 75%

u
use. These products are hard, high-melting waters that can be characterized by the following key data:

0098 15/1 74 3

Vicat softening point:

Molecular weight:

Density:

Flame resistance:

Acid number:

Solubilityί

up to 200 ° C 600 - 6000 1.35 - 1.68 excellent 5-25

Easily soluble in liquid aromatic hydrocarbons, esters, ketones and chlorinated lower aliphatic hydrocarbons

These chlorination products provide excellent water vapor barriers and gas barriers. The effectiveness of these products as a water vapor barrier results from the following

Measured values:

A chlorinated, thermally degraded, oxidized polyethylene with a chlorine content of 66.1 % was dissolved in toluene. From this solution, layers 0.00254 mm thick were applied to high, medium and low density polyethylene films 0.0254 mm thick. At a temperature of 37.8 ⁰ C and a humidity of 90% the following water vapor permeability were · "

measured values:

Water vapor permeability (g / 645 cm2 / 24 hours / 0.0254 mm)

Foil made from poly foil made from foil

ethylene high polyethylene polyethylene

Density middle lower

Dense density

Uncoated film Coated film

0.8 0.12

1.4

0.2

The effectiveness of the described coating compound as a gas barrier layer results from the following measurement results:

009815/1743

BATH ORIGINAL

Gas permeability in cia ^ / 645 cm / 24 hours / O _a O254 mm, measured at 21 ° C and 1 AT

nitrogen

Oxygen carbon dioxide

Low density polyethylene film

Coated film made of low density polyethylene

Medium density polyethylene film

Coated film made of medium density polyethylene

High density polyethylene film

Coated film made of high density polyethylene

550

120

2900

75 280 990 16 62 150 50 125 580 11 33 90

The waxes that can be prepared by the process of the invention are excellent as barrier layers and top layers on a wide variety of fabrics, especially polymeric fabrics, Wood and natural and synthetic threads and the like.

The waxes which can be prepared by the process of the invention also have excellent heat stabilities in comparison to comparable known polyethylene waxes. For example, it has been found that according to the method of the invention Manufactured chlorinated polyethylene waxes with a chlorine content of 42 to 75 J, for example at 175 ° C, three times more stable are as chlorinated polyethylene waxes with the same chlorine content, which were produced by chlorination of oxidized

009815/1743

Ethylene alkanol telomer waxes.

Chlorinated polyethylene waxes produced by the process of the invention with a chlorine content of greater than 25 % are also characterized by excellent solubility in aromatic hydrocarbons such as benzene, toluene and xylene, in ketones such as methyl ethyl ketone, in esters and chlorinated lower aliphatic hydrocarbons , such as carbon tetrachloride, at room temperature. With chlorine contents between about 50 and about 75 ί, solutions, coatings and coatings can be produced that are highly water-repellent. For example, they can be applied to masonry and bricks. They form hard, tightly adhering flexible films when applied to metal, paper and other surfaces. Furthermore, the highly chlorinated waxes soften at temperatures significantly above 10 ° C., so that they are not attacked by boiling water.

The following describes the preparation of some oxidized polyethylene waxes suitable for carrying out the process of refining described in more detail w

A) Approximately 900 grams of plain high pressure polyethylene with a melt index of £ and a density of C, 32 were put into a 2 liter plastic flask equipped with an anchor stirrer. The flask was not a loud one to heat up and a

009815/1743

thermometer housed in a case, which was immersed in the polymer melt. The flask was purged with nitrogen before heating, and a nitrogen atmosphere was maintained in the flask even during the heating. The flask placed on the polyethylene was heated for about half an hour to 39O ^Ü C, ^ au eye polymer was then cooled to about 250 ° C, to which low-boiling components by vacuum were subtracted. iJachderri had cooled the wax under nitrogen, it was applied on; removed from the flask and granulated. La bestano from a white, brittle and hard hat with an uck.ielz viscosity, measured according to urookfield of 1000 c \, at 12 °

300 g of this wax were then placed in a 1 1/2 ml three-necked flask which was equipped with a blade-shaped stirrer made of Teflon, an inlet tube that reached down to the bottom of the flask, and an outlet for exhaust gases. The flask wurue placed in a eriiitztes to l ^c jG ülbac ° C. After the '..' axis had been melted and set in motion by the Hührer. introduced into the piston. Waxes were taken from the flask and acidic numbers were determined. As a result, the course of the xyaatic process could be determined, the '...' axis had a total of 15 hours, after which the oxidation process was stopped. Zihz obtained wax tesaL a melt viscosity according to xircokfielo of 988 cp

009815/1743

B) The procedure described under Λ) was repeated, with the exception, however, that the polyethylene for 2 1/2 hours to a Schraelzviskcosity of 200 cp, measured at 125 ° C, degraded and then up to an acid number of 16 and one Melt viscosity of 250 cp, eaten at 125 ° C was oxidized.

C) The procedure described under A) was repeated. However, this time a polyethylene with a melt index of 1.7 and a density of 0.93 was used. The polyethylene was poured for 3½ hours up to a melt viscosity of 290 cp at 125 ° C, broken down and up to an acid number of and a melt viscosity of 360 cp, as measured at 125 ⁰ C, oxidized.

D) A sample of a linear high density polyethylene with a melt index of 8.0 and a density of 0.98, produced by polymerizing ethylene in the presence of a chromium oxide-aluminum oxide catalyst at an ethylene pressure of about 352 kg at a temperature of about l60 ° C was degraded for the specified under A) A method by which it was heated to 400 ⁰ C for 2 hours. It had a melt viscosity of 360 cp, measured at 150 ° C. Subsequently, the polymer was degraded cp up to an acid number of 17 and a .Schmelzviskosität of 480, measured at 150 ⁰ C, oxidized.

009815/174 3 bad owe., «:

- l8 -

Hydrogenation products obtained from ciurcu thermal degradation Polyethylenes can be brought into contact in a known manner of the decomposition products with hydrogen at pressures of about 0 to 422 kg / cm at temperatures of 100 to 400 C. The hydrogenation can be carried out by what is known as a slurry or fixed bed process with or without a diluent and in the presence of suitable hydrogenation catalysts, such as, for example, Raney nickel or nickel deposited on Kieseiguhr.

In the following, the hydrogenation of waxes is under E, F and G and under H the autoxidation of such hydrogenation products is described.

H) 900 g of a normal low density polyethylene with a melt index of 7 »ö and a density of 0.9191 were placed in a 2 liter synthetic resin flask equipped with an anchor stirrer. The flask was heated by means of an electric heating mantle. The temperature could be measured by means of a thermometer, which was immersed in a shell in the polymer melt. The flask was flushed with nitrogen before heating. During the decomposition, a nitrogen atmosphere was maintained in the flask, the polymer was then heated ^{to a temperature of 390 ° C. for 20 minutes with stirring.} The polymer was then cooled to a temperature of approximately 30O ⁰ C, whereupon the low-boiling components were removed in vacuo.

009815/1743

ter nitrogen had been cooled, it wurue removed from the flask una granulated. The wax obtained consisted of a white, very hard mass with the following properties:

Viscosity (125 ⁰ C) = 1950 cps

Softening point (K & ß) = HG ⁰ C

Penetration = l, ^c _>

(Jesam unsaturation = Ü, Ö2 % C = C

F) In a 1 liter autoclave were added 3 ^ 0 f- uurch of thermal degradation wax obtained genai: ^) brought, as well as 2 £ a catalyst bestenenu from nieuergeschlagenem on Kleselgunr winding. The autoclave was heated to 18 ° C., before

Hydrogen was injected up to a pressure of 13.0 kft / cn. The autoclave was circulated during the hydrogenation. The time of oyuration was' »hours. The polymer was then removed from the autoclave and the catalyst was removed by filtration. The harvested white, narte l ^: ci.v:; ier beraf. the following properties;

Viscosity ν * - '; - ^C C)' = dlJ ~ cps

Expansion point = ill C

Durcharinrunf: = 1, ^

5 Gesan; tungesätti .: theit = <s. , 03

G) The process described under F) was repeated, this time only 0.1 were applied Jeooch i des.Katalysators. Furthermore,

0 0 9 8 1 b / 1 7 4 3 ■ - w,. . ' __ ^

8AD ORIGINAL

= 2150 CpS = 111 ° C = 1 . * » = 0 , on

ue hydrogenated at a temperature of 300 ^{° C.} The hyuration product obtained had the following properties after filtration:

Viscosity (125 ° C) softening point penetration % total unsaturation

H) In a [300 ml three-necked round-bottom flask equipped with a stirrer, an inlet tube, aas reached down to the ooaen ues flask and an outlet for aogas, 250 g (- »es according to F) produced ./axes with a viscosity of 2100 cps,

e ο

measured at 125 C and a percentage unsaturation of 0.03 brought. Jer Aeolians were then placed in an oil bath, which was on 150 ° C heated what was brought. After the wax melted was, the I-.ührer was switched on. The stirring speed corresponded to 700 revolutions per minute. Through the inlaiirChrchen Then add oxygen at a rate of approximately Introduced 1 liter per minute. Samples were taken periodically and examined for their number. Cobald the I acid number had reached a value from I ^ to l6, aie 0 ^ - uation interrupted and the .. 'ax poured into a bowl, in eggs it cooled down. After an oxyation time of 5 hours it had . ■ / axis has the following properties:

00981 b / 1 7 Λ 3

bath

Viscosity (125 ° C) = 910 cps

Acid number = 14.6

Semolina - 1 - d (excellent)

Emulsion = excellent

Softening point = 106.7

Penetration = 2.1

Density = 0.9449

Color = 1-

The melt viscosity and parstability of the wax result from the following measurement results:

Days at 125 ° C

0
°

Viscosity (125 ° C) 910 1160 I960 3300 Color 1- 2 4 5

After heating for 3 days, the material had an acid number of 12.4 and made excellent emulsions.

Used to carry out the method of the invention are polyethylene waxes used, which are produced by autoxidation of polyethylenes, i.e. polyethylenes that are produced before autoxidation are not thermally degraded, they can be produced in the following way. Through direct polymerization Polyethylenes of low molecular weight are produced from ethylene. For example, they can be obtained by

009815/1743

ÖAD ORiGINM.

polymerization of ethylene at temperatures from 200 to 300 ⁰ C and pressures from 300 to 800 atmospheres. Catalysts which produce free radicals can be used for their preparation, such as, for example, benzoyl peroxide, di.tert.-butyl peroxide, lauroyl peroxide, cumene hydroperoxide and t.-butyl perbenzoate and the like. It has proven to be particularly advantageous at pressures of 500 to 700 atmospheres and temperatures to work from 250 to 29O ⁰ C and to use di-tert-butyl peroxide as a catalyst. The method may in the usual devices i <t> for the high pressure polymerization of ethylene can be carried out either by a one-stage or multistage process. It is possible to work in an alutoclave or in a tubular reactor.

In the following, the production of such polyethylenes will be described in more detail:

I) polyethylene having a purity of 99.3% was fed into a polymerization reactor and polymerized at a pressure of 600 10 atmospheres and a temperature from 257 to 283 ^0C. The polyethylene obtained was discharged from the autoclave through a series of vessels, the pressure being reduced first to 250 atmospheres and then to 0.28 kg / cm. The melted polyethylene was then processed into strips that were chopped into chips. The degree of conversion was 17 to 20 % and the yield was around

009815/1743

272 kg of polyethylene per 0.4 ^ 3 kg of di-tert.-outylperoxyα. The received Polyethylene had the following properties:

Viscosity according to ^ rco,

measured at 12 ° C ^c j = 920 cps;

Density, less than 0.09;

flexural strength = 211 kg / cm ² ;

Noise point according to Ring ßall = 90, C ⁰ C;

Tensile strength = 42 kg / cm ² ; Total unsaturation, less than 0.2 %.

J) The procedure described under I was repeated, however, it was polymerized at a pressure of ₁ of bOJ atmospheres, and the resulting rolyatnylschnitzel uesai-en feigenae properties:

iicniaelzvisivosity, i-enesseii uei

1 ^ i) ⁰ C = 17 ¹ IO ct-s;

Lichte, less than = ^, "J; üiegefest ^ koit = 337 kjVcn ^ - The conversion>, r ία uetru: I ^ to ? A ,. ^: U: ia the yield about 3ü2 k _f ~ Polyatnylen t-ro 0 , ^ ¹ Jj ', -. ■ - inserted di-tert.uutylperoxyu.

i \) The method described under I wruue wiederiiolt, jeaoch wurae this:;:. :: il cei a pressure VCN ¹ ^ GL polymerized Atnxospliären. . Jas obtained polymer tesa · a Ücinaelzviskositat, genessen Lei 125 ⁰ C vcn ICO cps UNU a density of v; ei.ifter than G, ->".

009815 / 17A3

L) The procedure described under I) was repeated, but this time the polymerization was carried out at a pressure of 775 atmospheres. The polyethylene obtained had a melt viscosity measured at 125 ° C from 3775 cps, a flexural strength

speed of 605 kß / cm and a density of 0.9000. The degree of conversion was 21 to 23 % and the yield Iac was about
453 kg per 0.453 kg of dietary jutyl peroxide used.

K) The procedure described under I) was repeated, but this time the polymerization was carried out at a pressure of 725 atmospheres. The polyethylene obtained had a melt viscosity of 23 * 40 cps, measured at 125 ° C, a density of
0, "iy5t) and a flexural strength of ¹ HO kti / cm. The degree of conversion was around 20 to 24% and the yield was around 317 kg per 0.4.53 kg of di.tert-jutylperoxyu used.

The following examples are given as a method of the invention
illustrate naner:

example 1

400 g of an oxidized, extremely thermal degradation obtained
Polyethylene wax was dissolved in 3500 ml of high-purity carbon tetrachloride at chewing temperature. The v / axle was obtained by thermal degradation of conventional polyethylene at a

00981 5/1743

ner temperature of 39O ° C up to a viscosity of 1000 ep, measured at 125 ° C and auto-oxygenation of the degraded polyethylene at 150 ⁰ C in the presence of air. The oxidized wax had a melt viscosity of 988 cp, measured at 125 ° C., and an acid number of 15. The wax solution was placed in a 5 liter -ilals flask which was equipped with a stirrer, chlorine inlet tube, thermometer sleeve and a reflux condenser with a Trap was connected, in which unreacted Cülor and formed hydrogen chloride could be absorbed. To the flask was added an additional 5 ml of a 20 üew.-Ä solution of üiisopropylperoxydicarbonat in heptane, and the solution was heated at 7 ^ ⁰ C with stirring. The solution was saturated with chlorine with stirring and 700 ml samples were taken every half hour for a period of 3 and a half hours. The solvent was removed from the samples taken in vacuo. In the course of Chlorierungsprozesses ¹ J samples were taken, the waxes having a chlorine content from 12 to 60.6%.

In a comparative experiment, an oxidized ethylene-isopropanol teromer wax with an acid number of 15 and a melt viscosity of 330 cp, measured at 125 ° C., was chlorinated in the same way. The samples taken had chlorine contents of 11.5 to 59.8 %.

All chlorinated products were on one for 20 hours C under a

009815/17

Heated to a temperature of 175 ° C under a nitrogen atmosphere,

BATH ORIGINAL

using a device in which the leg) thermal degradation generated hydrogen chloride could be captured.

It was found that, in particular with chlorine contents of over 40%, the chlorinated polyethylene waxes produced by the process of the invention were significantly more thermally stable than the chlorinated waxes obtained by chlorinating oxidized ethylene isopropanol teromer waxes.

Example 2

200 g of a polyethylene wax obtained by oxidation of a polyethylene obtained by thermal degradation with an acid number of 16 and a Sehmel viscosity, measured according to Brookfield, at a temperature of 125 ° C. of 250 cp were dissolved in 3500 ml of a high-purity carbon tetrachloride at room temperature. The solution was placed in a 5 liter, k neck flask equipped with a stirrer, chlorine inlet tube, a thermometer sleeve and a reflux condenser. The reflux condenser was connected to a trap! in which unreacted chlorine and hydrogen chloride formed could be absorbed. % Ml of a 20% strength by weight solution of diisopropyl peroxydicarbonate in heptane were added to the solution, whereupon the solution was heated to a temperature of 74 ° C. with stirring. While stirring, the solution was with; Chlorine

009815/1743

saturated, whereupon several 150 "ml samples were taken within 6 hours. During the 6-hour chlorination period, two further 1 ml portions of the 20-hour solution of diisopropyl peroxydicarbonate in heptane were added at 2 hour intervals. After a total reaction time of 8 hours The introduction of chlorine and heating were interrupted. The reaction solution was then flushed with nitrogen to remove the hydrogen chloride and unreacted chlorine. The reaction mixture was then poured into cold methanol, in which the chlorinated wax precipitated. It was separated off and washed three times with fresh, cold methanol A total of 415 g of dry, powdery white polymer with a chlorine content of 66.3 % and a molecular weight of 3440, determined by increasing the boiling point, were obtained. The samples taken during the chlorination process were precipitated in ethanol in the same way and worked up. In the table below are the response the duration, the chlorine content and the densities of the samples taken and the end product are given:

Total response time density % Chlorine la poly 55.6 in hours g / CEl3 mer 59.3 2.25 1,4ö5 63.2 3 1.526 65.4 I, 5c6 66.0 5 1,591 66.4 6th 1,595 8th 1.621

009815/17 * 3

BAD ORJGiNAl

3b 1 p 39 , 2 39 ,8th

Example 3

The procedure described in Example 2 was repeated, with four different chlorinated axles with chlorine contents of 56.3 to 60.3% by weight of chlorine were produced. These chlorination products when they were dissolved in toluene to give 33% solutions, colorless solutions of low viscosity, vfe results from the results given in the following table results in:

Chlorine content 33 5-strength solutions of the polymers in toluene

in Ζ üaruner color value viscosity ep, 26 ^Ü C

56.3 1-

57.2 1-

59.2 1

60.3 1+

90 g of a mixed chlorinated polyethylene wax with a chlorine content of oC, 3 » and 15 ₍ . Dibutylj.hthalat were in 72 g of a solvent made from aromatic hydrocarbons (oolvesso 10C) ._, <- loL" t in one 1 Healing device with 150 g of water contained; oC g of an acrylic sizing agent (b Uew .- ^ acrylic resin) as well as 12 g of a surface-active Vercinuun = - mixed. The emulsion obtained was then deposited on vinyl asbestos tiles .Let to dry. Ls was a hard, atrieLresi:; tenter ^ oerzur: eriialten, polished too high a gloss, could, .vurue the ijoerzu ;; Ir ^ used a flame, so he veivionlte, burned jeaoen riicht.

009815/1743

1 YYYYU

Example k

The process described in Example 2 was repeated, but this time 200 g of an oxidized wax were used, which was also obtained by oxidation of a polyethylene wax obtained by thermal degradation and had a Lrooicfield melt viscosity, measured at 125 ° C. of 360 cp and an acid number of Io owned. 425 g of a dry, powdery, white product with a chlorine content of 66.6 % were obtained. This chlorination process could easily be dissolved in 33% solutions in toluene, xylene, methyl acetyl ketone, ethyl acetate and tetrachloroethane.

Example 5

The procedure described in Example 2 was repeated, but this time 400 g were used instead of 200 g Ausgarig3i.iaterLal. The total reaction time was also limited to 1 hour. Samples were taken every 15 minutes. The chlorinated axis, which were obtained from the samples taken, were emulsified by adding λ g of the samples η with 2 ml of oleic acid

were heated at 125 ° C., 2 ml of aminoethyipropanol being added each time. The melt was then in ICO: cast nl sieaendea vaster under lalhren, i.acn IL-ac em Verfanren were Jiiioi * L: runssprodukte 7 »^ 3 * 13 * 7;" and 18.2 eraulgiart Ί chlorine, uej GhLorierungssprdukt;: iit a

0 0 ^f ) 8 1 ^r ) / 1 7 U "} ■

BATH ORIGINAL

Chlorine content of 18.2 % was melted together with paraffin in a beaker. A melt with a chlorination product content of 40% was produced. For comparison purposes, a melt was prepared in the same way from 40% by weight of an ethylene-vinyl acetate copolymer (27 to 29 % vinyl acetate) and paraffin. These V / Axis mixtures were applied in the molten state to stainless steel plates using a coating knife (Gardner knife). Films 0.254 µm thick and 1.270 mm thick were made. The tensile strengths and elongations of the films obtained were measured. The resulting gaps are shown in the following table:

Material (40 % Ln tensile strength in k ^ / cm ^ elongation in % paraffin wax

O,
pi 25 4
Ir. ππ- 3 i
F. , 270 im-
1 in ü, 254 mm
FiIm 1,270 mm
FiIm 69 7th 50.4 50 90 56, 39.9 30th 50

Chlorinated wacho

Sthylen-Vinylacet at-Mis chpolymer1-sat

The mixtures obtained were also applied in a layer thickness of approximately 0.0254 mra to a bleached Kraft paper with a thickness of 18.1 kg. Aen papers were said to have resistance to FdUu, uer gloss and the "asseruanprdurehlo.ssigkei.t-Ljstimc"; got! I.rijebniose are in the following table vriecier-.:-.· ,; eoen:

0 0 ¹ J η I- ^r . /! 7AI

Material (40 % Resilient shine Water vapor through in paraffin wax) speed versus ₊ % in % nonchalance Fat in seconds from simple folded Papie'r tem paper Chlorinated wax 240 50 0.072 0.102 Ethylene-Vlnylace- tat mixed polymer 72 33 0.155 0.244 s at

+) The time it took for a dye to stand in turpentine oil was measured was dissolved, needed to penetrate the material when a drop of the colored turpentine oil was on the test piece Material was brought and the latter was placed on a sheet of filter paper

Example 6

400 g of an oxidized polyethylene wax obtained by oxidation of a polyethylene wax obtained by thermal degradation of polyethylene were produced by thermal degradation of a high density polyethylene with a melt index of 8 and a density of 0.98 by heating to 400 ^° C. for 2 hours thermal degradation, a wax with a melt viscosity of 360 cp at 150 ^° C. was obtained. The wax was then subsequently cp by heating at 150 ⁰ C in the presence of oxygen up to an acid number of 17 and a melt viscosity of 480, measured at 15O ⁰ C, autoxydiert. A solution in 3500 ml of highly purified carbon tetrachloride was prepared from the wax, which was placed in a 5 liter 4-necked flask equipped with a stirrer, chlorine inlet tube, thermometer sleeve and a reflux condenser, which was connected to a trap to remove unreacted chlorine and absorb hydrogen chloride. The solution was then added 2 ml of a 20 weight Jigen solution of diisopropyl peroxydicarbonate in heptane was added, and the solution was heated with stirring to 74 ⁰ C. The solution

009815/1743

was saturated with stirring, chlorine being passed in for a total of 8 hours. During this time, 2 ml portions of the 20% strength by weight solution of diisopropyl peroxydicarbonate in heptane were added three times at intervals of 2 hours. The reaction mass was then flushed with nitrogen for 15 hours in order to remove unreacted chlorine and hydrogen chloride formed. The reaction mass was then poured into cold methanol, whereupon the chlorination product precipitated. It was separated off and washed 3 times with fresh cold methanol. The dried, snow-white, powdery reaction product had a chlorine content of 66.1 %. The yield was 890 g. The chlorination product could easily be dissolved in 33% solutions in toluene, xylene, methyl ethyl ketone, ethyl acetate and tetrachloroethane.

00981B / 17A3

Claims (3)

. Claims 1. Process for the production of chlorinated polyethylene waxes with a chlorine content of 5 to 75 percent by weight and one Acid number from 4 to 25, characterized in that an oxidized polyethylene wax with a melt viscosity of 100 to 4000 cp, measured at 125 ° C. and an acid number of 4 to 25, dissolves in a solvent that is stable to chlorine and that at a temperature of at least 1O ° C in the presence a chlorination catalyst introduced chlorine into the solution until the desired degree of chlorination is reached is. 2. The method according to claim 1, characterized in that the chlorination is carried out at a temperature of 40 to 80 ° C. 3. Process according to Claims 1 and 2, characterized in that a polyethylene wax obtained by autoxidation of a thermally degraded polyethylene is chlorinated a melt viscosity of 200 to 8000 cp, measured at 125 ° C. 009815/1741