DE1947924A1 - Vinyl chloride polymers and process for their preparation - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-ING. GERHARD COLDEWEY

Patent attorneys Λ Q Λ "7 Q 7 A

8 MÖNCHEN 23 ■ CLEMENSSTRASSE 30 · TELEFON 34 50 67. TELEGRAM ADDRESS: INVENT / MÜNCHEN ■ TELEX 5-29

Sep 22, 1969

U ₀ Z ₀ : E 677 (Vo / kä)

DIAMOND SHAMROCK CORPORATIOIi '
Cleveland, Ohio, V ₀ St ₀ A ₀

"Vinyl chloride polymers and processes for their production" Priority: September 23, 1968, V.St.A. », No. ₀ 761 840

The invention relates to new vinyl chloride homo- and copolymers

height

te that have unexpected / thermal stability »It concerns in particular vinyl chloride polymers which differ in their structure from the known vinyl chloride polymers. The invention also relates to a process for the preparation of the new vinyl chloride polymers by polymerization in aqueous suspension,

Vinyl chloride homopolymers and their copolymers with other ethylenically unsaturated monomers have been known for a long time and are currently used in a wide range of applications by the synthetics industry. You can by various methods, oo which are described in detail in numerous patents and technical Veröffentli-ω RELATIONS, are produced "This ~ * procedures are generally as mass or Blockpolymeri-J _0, organization of a monomer or monomer mixture or solution , Emulsion or suspension polymerization in aqueous

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Medium is called “In all processes, the polymerization primarily by contacting the monomer or mixture of monomers with suitable free radical generating polymerization catalysts accelerated ο Since, however, generally higher yields of polymer are more economical and convenient through the Emulsion or suspension processes that can be achieved in an aqueous medium are used in practice for the production of vinyl chloride polymers mainly these types of proceedings are preferred.

In the aqueous suspension polymerization process used to date, "the vinyl chloride monomer or a mixture with one or more copolymerizable monomers is brought into contact with a polymerization catalyst which generates free radicals, a suspension that is stable in an aqueous medium being maintained using a suspending or dispersing agent" , which the volume after the reactor usually fills up to 80 #, kept under an established pressure and for different periods of time at different temperatures reaction temperature is usually between 20 ° and 100 ° C, preferably between 20 and 8O ⁰ C, the reaction time is up to 24 hours or even longer

The vinyl chloride graft copolymers have become known recently These products usually have properties that are somewhat similar to those of vinyl chloride homopolymers or their random copolymers differentiate between »graft copolymers are mainly produced by converting an aqueous suspension

^. 3 -

pension located polymer with vinyl chloride or a mixture of this compound with another, monoethylene unsaturated monomers produced. In the Hegel this reaction takes place in the presence of a free radical generating compound carried out.

This method is described, for example in the USA. Patentsciiriften-3,305,606 and 3,332,858 and British Patents 1,021,324, 1,075,642 and 1,075,643 ₀ in numerous patents. The catalysts used are the same as those which were used for the production of previously known vinyl chloride homo- and copolymers. In the same way, the conditions for carrying out the graft polymerization are essentially the same as for the preparation of the. other polymers, ie the graft polymerization is generally carried out at temperatures between 20 and 100 ° C., preferably between 20 and 80 ° C., for a period of around 20 or more hours

It has now been found that in the production of vinyl chloride polymers in aqueous suspension using polymerization temperatures of 90-165 ° C., as described above, valuable polymers are obtained which have a special structure and unexpected further processing properties

Accordingly, the invention relates to an easily practicable method for the production of vinyl chloride polymers by polymerization in aqueous suspension in the presence of catalysts which form free radicals, at which polymerization temperatures of

009813/1709

90 to 165 C instead of the usual much lower temperatures will «, conditions are preferred in which the The reactor is essentially full of liquid.

The available, highly branched polymers are structurally verscnieden of the known vinyl chloride polymers, as the analysis shows that the percentage of chloromethyl groups is much higher at the ends of the branches than in the products by conventional methods polymers which have an equivalent molecular weight ₀ These products The conventional polymers hitherto used for this purpose are valuable for a large area of application the Vinylchioridpoly ™ merisate at such high polymerization temperatures is impracticable because they require extremely high pressures and in particular because each resulting polymer would be thermally degraded in the reactor _e

As has already been stated above , the polymers produced according to the invention can be used for many different plastics • turns. The vinyl chloride may in Hoinopolymerlsate 2 ₀ B _e as adhesives, as flame retardants and as a processing aid. used in the production of other polymers. They can also be used as a plastic component in vinyl puss flooring material as well as in the production of solid vinyl foam.

0098 13/1709

Random copolymers are currently used as process modifiers and as a plastic component in vinyl flooring material and in records. The graft polymers are particularly valuable for the production of coatings and for various articles that are manufactured by compression molding or injection molding »·

The expressions used in the description and the claims, such as vinyl polymers and vinyl chloride polymers, "relate to vinyl chloride homopolymers and random copolymers with one or more monoethylenically unsaturated compounds." Special comonomers which are suitable for use are olefins with 2 to 4 carbon atoms, ie, ₀ ethylene, propylene or butene-1, monoolefinically unsaturated carboxylic acids having 3 to 4 carbon atoms, such as acrylic or methacrylic acid, lower alkyl esters of acrylic and methacrylic acid and their hydroxy- and aiainosubstitüierte derivatives Vinylester of unbranched or branched monocarboxylic acids with 2 to 12 carbon atoms, maleic anhydride and the diesters of maleic and fumaric acid with aliphatic alcohols which contain up to 18 carbon atoms. for example “p-chlorostyrene or p-terto-butylstyrene can be obtained., The He The producibility of these special copolymers is completely unexpected in view of the fact that it has not previously been easy to produce these polymers by aqueous suspension polymerization, which is attributable to the enormous difference between the reactivity of the two monomers in the polymerization system.

^ 009813/1709

In general, the random copolymers according to the invention contain about 50 to 99.5 percent by _e - #, preferably about 65 to 99 Gewo-jS of polymerized vinyl chloride and 0.5 to 50 wt _o - #, preferably 1 to 35 Gewo- ^ of the polymerizing comonomer. The currently preferred polymers are those which contain vinyl chloride which is copolymerized with olefins, in particular with propylene, since these products can best be adapted to a wide range of applications.

The expression vinyl polymers and vinyl chloride polymer is also intended to refer to copolymers which contain polymerized vinyl chloride which is grafted onto another polymer, which can be a homopolymer or a copolymer. Currently preferred polymers for grafting according to the process of the invention are polyolefins such as polyethylene or polypropylene, their chlorinated derivatives and copolymers of the olefins mentioned, homopolymers of vinyl esters of monocarboxylic acids with 1 to 8 carbon atoms, Z ₀ B, vinyl acetate, vinyl propionate or vinyl butyrate, and their copolymers with C «j olefins, the copolymers mentioned containing a varying percentage by weight of polymerized vinyl ester, homopolymers of acrylic and methacrylic acids and their lower alkyl esters, homopolymers of acrylamides, methacrylamides and acrylonitrile and the copolymers of these monomers »

The preparation of the copolymers, which in combination with the grafted polyvinyl chloride the grafted polymers of others Containing ethylenically unsaturated monomers, of course, are within the scope of the subject matter of the invention, although presently only the grafted polyvinyl chloride is preferred * Off f-; ί 0098 137 1709

for this reason, particular reference is made below to vinyl chloride graft polymers. Such a description does not imply any restriction of the Brfindungegegenetande · but is only intended to serve as an explanation · Of the polymers which can be grafted accordingly, the copolymers of ethylene and vinyl esters, especially vinyl acetate, are currently preferred.

The grafted copolymers according to the invention generally contain 60 Ms 95% by weight of polymerized vinyl chloride, the total weight of the polymer containing 5 to 4 % by weight of polymer substrate. The z. Zt ₀ preferred Pfropfpolymerisa te contain 7ϊ> Ms 85 percent, -j6 polymerisierte.s vinyl chloride and 3 5 2 bia?> Wt .-? '· Ethylene copolymer Vinylaoetat. The copolymers contain 10 to 40 parts by weight, preferably 18 to 30 parts by weight, of polymerized vinyl acetate *

As described above, the vinyl differ chloridpolymerisate the invention in terms of structure of oen in known Wej.se polymers produced, the structural differences are out looking mainly in the higher Versweigungsgrad, as the type of the ramifications beenüentien groups, which in the comparison of the products geuiäes of the invention over the previously known, conventional polymers emerges openly.

In order to distribute the structural differences firmly, both the products according to the invention, as well as representative examples o ^; Vinyl chloride polymers produced as usual with different molecular weights on methyl end groups

0 0 9 8 13/1709. ", ...

BAt) ORfOINAL

. (.- CH *) rait uses infrared spectroscopy (IR) to examine “These Samples were examined in detail before and after they were reduced by the standard known method of hydrogenation with lithium aluminum hydride (LiAlH ^) Methods of investigation are discussed later in a specific example reproduced o

The investigations into the iactität in the molecule by means of IR showed, that conventional PVC is a little more syndio-tactical than that

*. Polymers of this invention are built up. The test results show that in the branches of conventional PVC the CH4 end groups adjacent to the monomer units predominantly have a head-to-head configuration. This can be seen that for both the polymers before and after the reduction, the almost same values for are the number of CH ~ -Grüppen per 1,000 CEP groups found ,, üe wur- As specified, conventional Vinylchloridpolymerisabe are those which at polymerization from. 0 to 90 ° C _T, preferably from 20 to 80 C, can be obtained. The average content of CH, -

ψ End groups in these, unreduced polymers is about 9 to 10 ■ CHjj groups to 100 CH ₂ groups ₀ Analysis of the polymers after reduction gives values of about 10 Ms 13 GHj groups to 1000 CH ₂ groups _o Da , in the reduction chlorine is replaced by hydrogen, it must be concluded that the difference found in CHy groups of the unreduced polymer compared to those of the reduced, ie 1 to 3 CH, groups per 1000 CH ₂ groups, the chloromethyl groups at the ends of the branching chains of the non-reduced "polymer, are attributed-kaiui-o .-" During., the reduction-of-the.-polymer will be . :: -. r \; U <i *.: - r # v> - 0 0 981 3/1 7 0 9 - "- ¹ -

^ v «- ^ ■ '*'■" .-- : - ■ BAD

the CHgCl-lfcd groups converted into CH ~ -group owing to the Analysis is therefore inferred that conventional Yinylohloridpolyiuerisata on average about 10 CH ^ groups and Contains 3 CHgCl groups per 1000 ΟΙ ^ & ΗΦροη

It has been found that the vinyl chloride polymers according to the invention have almost no tactiality, ie these polymers have almost the same percentage of syndiotactic and isotactic components. In these polymers, the branching is growing with the same GröesenOrdnung with which the polymer is increased anauwendende onstemperatur from 90 to 165 ⁰ C · Thus, according to analysis containing these polymers to 1000 CHU groups 10 to 15 CH ^ end groups on the branches!; the highest CH, group value was detected in a polymer which was produced at the highest polymerization temperature. The same analysis of the reduced polymer gives values of 13 to 27 G & y end groups per 1000 CHg groups. The increase in the content of CH, groups in the polymers of the invention accordingly amounts to between 3 and 14 CHj groups to 100 GHg groups after the reduction. When comparing the number of end groups to be found in the conventional vinyl chloride polymers, the increase mentioned is attributable to the larger number of CUgCl end groups on the side chains. In contrast to the conventional polymers, the vinyl chloride polymers of the invention contain on average 3 to 14 CH ₂ C1 end groups per 100.1 CHg groups.

It was found that melting point measurements on the reduced polymers indicate no degradation, i.e. during the run the reduction did not cause chain cleavage.

0098 1 3 / T709 _{BAD 0RlGtNAL}

ν- ■■.; .. .. ■■ '■ ... ■. ■■ - ■ ίο - ■■■■■■ -, - ■ - - ■■. .

Wei tore analyzes showed that a polymer of the invention has a higher average molecular weight than some other conventional vinyl chloride polymers, but it always has a lower one Limiting viscosity number than conventional Vinylohloi & JpolYmerisate has what can be ascribed to a higher branching.

A vinyl chloride homopolymer or a random copolymer According to the method of the invention to produce »is in a suitable Container containing a dissolved in an aqueous medium

"Contains suspending or dispersing agents, vinyl chloride or a mixture of the same with one or more copolymerizable therewith toonomers introduced »The aqueous suspension of the monomer is then brought to 90 to 165 C heated, whereupon enough water is pumped into the reactor to achieve a pressure which is at least the same under the reaction conditions used, but preferably over is the vapor pressure of the at the given polymerization temperature Monomers used oi the monomers lies »During the stirring The ftonomer suspension is continued, the free radical becomes generating catalyst is added to the reactor at once or, as an alternative, the required amount of catalyst is added continuously during the reaction. The special kind The addition of the catalyst is dependent on the particular catalyst as well as others described in more detail below Pactors dependent. During the reaction, something else becomes necessary Water is pumped into the reactor around such a Maintain pressure, deac at least equal to or above that The vapor pressure of the monomer or the monomer mixture which has not yet reacted in the reaction device should be.

To prepare graft polymerization products according to the invention, the process is carried out essentially as described; however, prior to the addition dee Vinylchloridaoaomerβ dae optionally to be grafted polymer in the reactor and dxBpergiert In the aq membered medium. Auseerdem is prior to the addition of any catalyst, according to the current adding dee Mononere, heating the reaction mixture to the gewünsohte polymerization temperature and after thy achieving a sufficient Reaktionadruckes the reaction mixture, preferably during a period of for example 15 - 30 minutes stirred at swells this way, the suspended polymer and is finally partially dissolved by the monomer, whereby the grafting effect is increased.

J) ae method according to the invention can be carried out in 3 ^eci em suitable reaction vessels which are provided with a stirrer and which are made of corrosion-resistant material, ζ · Β. made of stainless steel, made \ * grounding. The reactor must be designed so that it can withstand pressures that are at least equal to, if not greater than, the vapor pressure of the monomer or the monomer mixture at the polymerization temperatures particularly suitable and effective.

As has already been pointed out above, the process is generally carried out at a pressure which is at least the vapor pressure of the vinyl chloride monomer. Lonomer mixture is the same at the specific polymer ion temperature. The required- :; Pressure in the container is increased by pumping in sufficient heat at Y / ater .heryoetollt “At the present

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BAD ORfGINAL

; :; _ ₁₂ _.; ■ 194792V

practiced »preferred implementation of the invention; After the polymerization temperature has been reached and before a catalyst is added, let the reactor fill essentially bit of liquid. Accordingly, the pressure in the container is then essentially above the vapor pressure of the monomer. This embodiment is preferred because, in conventional arrangements, heat-degraded polymers on the walls of the editor above the surface of the liquid due to the extremely high polymerisation temperatures used If one proceeds in such a way that no too high local catalyst co-concentrations develop, - 2.B ₀ by inserting the catalyst below the surface of the reaction mixture »the reactor does not need liquid to avoid the formation of products which are not thermally degraded almost completely filled Similarly, to its - v / ie stated earlier ~ _f the entire required amount of catalyst are introduced at the start of reaction in the reaction mixture. However, the required amount of catalyst can also be added gradually as the reaction progresses. Z-. The continuous addition of the catalyst is currently preferred, since this technique is used to control both the reaction rate and that of the indirect reaction temperature. The process of continuous or portionsv / iron addition of the catalyst allows the use of many catalysts aueserst unstable at the applied Polymerisatiönetemperatur these catalysts would be ₀ When this initially completely Ziirn reaction material, where v / ground, ί decompose very rapidly and for. the incipient polymer! Station reaction ineffective at Audi you could ■ ± share a danger that an explosion might tend to occur.

00 98 1 3/1709

Türlich can prepare su start aur reaction mixture is added to the polymerization vorauegesetet, the catalyst daae not unstable at the Polynerieationetemperatur is "It should have a half-life" the except-calibrating itt, sur by free radicals during a sufficiently long period of time maintaining the polymerization reaction up to to produce their essential conclusion »

Any of the "monomer-soluble" free ones currently available Free radical generating catalysts previously normally used for the polymerization have been used to advantage, e.g. for vinyl chloride in aqueous suspension, provided that it has a suitable decomposition rate at the polymerisation temperatures and are reasonably stable during storage and handling, can be used as suitable catalysts. When selecting the catalysts, their half-life at the polymerization temperature is of primary importance «This should be such that the catalyst can be distributed throughout the reaction mixture before it decomposes »on the other hand, it should be the half-life should be short enough that the catalyst during the polymerization is essentially completely decomposed and none of it remains in the final polymer, depending on the im The individual polymerization temperatures used are especially suitable catalysts such as 2,4-dichlorobenzoyl, caprylic, and lauroyl peroxide, tert-butyl peroxyisohutyrate, tert-butyl peroxypivalate, Benzoyl peroxide, p-benzoyl peroxide, hydroxyheptyl peroxide, Cyclohexanone peroxide, Üi-tert.-butyldiperphthalate, terto-butyl peracate, terto-butyl perbenzoate, dicumyl peroxide, terto-buty! hydroperoxide, ethyl ethyl ketoperoxide, di-tert, -butyl-

0098 13/170 9 _{toAr% Ä}

SAD ORJGiMAL

"■■■ peroxide, Acetylcyolohexansulfonyljseroxid, i> i ~ _(o sec -butyl) -peroxydicarfconat and Isobutyrylperoxicu Of these compounds of the invention, after the catalyst is introduced in portions for the preferred implementation, those particularly suitable that a half-life within the Polymerisationstemperatürbereiches from 0.1 sec to 12 min _o ", preferably from 0.5 to 5 minutes, have * Those catalysts are presently preferred ZABO benzoyl peroxide, tert, -Butylperoxypivalat _p * lauroyl peroxide, caprylyl 2,4.-dichlorobenzoyl _B, Terto terto.-Butylpe.race.tat and p-chlorobenzoyl peroxide «, general information

to the
carries the / applied concentration of the catalyst 0.01 to 2.0 fi _s based on the total batch of monomers / The preferred concentration is 0.05 to 0.5 wt _o - #, calculated on the monomer,

Apart from the extremely high polymerisation temperature, the process is generally similar to the known suspension polymerisation.Every proportion of vinyl chloride moriomers or a mixture of monomers requires 0.4 - 6 parts of water. The ratio of water to monomer is from 0 _t 5 to 2: 1 =

To a stable suspension of the monomer in. Tauerhalten the aqueous medium to compute, can be any of such _a Zt = available dispersing agents or protective colloids, are usually used in the system for vinyl chloride polymerization can be used isjt "prerequisite is that these agents both stable are completely soluble at the polymerization temperature ^ Suitable suspending agents are currently aB, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone and copolymers thereof, as well as the nonionic alkylene oxides »alkylene glycol /; 0098 13/1709

ORIGINAL

~ 15 -

Adducts ο The concentration of the suspension agent is generally between 0.05 to 4 percent by weight, based on the monomer or the monomer concentration. The concentration of the suspension agent is preferably between 0.1 to 2 percent by weight, based on the monomer or on the monomer mixture, more preferred are O ₁ .2 to 1 _f 0 wt. ', -,

The "'geinäss method of the invention is in general carried out in a i'emTiei'aturbereicii 90-165 C ,, As expected: _p isi the polymers prepared in Oer upper limit of this temperature range have a lower Durchschnittsmolekulai'gewieht and more branched as those polymers _f , rlj.o are produced at lower temperatures = measurements au:; '^ - u / id dor reduced viscosity are used throughout, 1.UU comparative molecular weight of the products on average to eiiia'i th., -üie Gx' eiizvisk-ositätßzabJLen and Durchschnittsmole-] cu "iargcwicliY.e of products l.assen compared with conventionally produced Poj.ycierisaten HüclcFchlüsse on ate degree of Vsivzwc-igimt. : ^r 'ir procedure: to determine this fourth _} will be described later «

.The end of the traversed Pi measure of the invention is in Igenieinei al .'- iniiorhalb 1 to 12 hours prior to and at-hän -, - .. Au vol. ^1st specifically arigewa-ndten Teiuper ^^ ture, - the specific catalyst UNCs its Xoin:; SRTL, ration "The entire Heaktions · = _f .isuer d.-iic the Polymerisatioiis-geschwinäigkeit ^ is also on _t i .händig, In! vclehcm circumference die'Heaktiorisv / ärmß from the polyme-Λ · ι. · - ·· \ ΐ3 onsmißch-. ^1. ·! ^ Ied v / ird _o In the ζΛ-Χ * usual practice>'■·.' ■ (. 'Tj.ii / .r ·' · ..; ■ '".Vj-Ii-.; : iitfei ';. n.'. n _t ·; the heat of reaction through the • ■ ·. .-- '. i-jy ■ - ν -. \ j-. ■ .- ■■■ ·.'. : / ·.: ■: ■ ;! .-:; -: J -; - i.!, R! - ■ or, in front of parta "tfc.c-. Tiurch s: '..- ie

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BATH ORIGINAL

Cooling coil, which is in the Reäktionegut j vörgenöinmön. At the ziZt «. Preferred embodiments of the process are carried out using such a cooling coil and with the addition of the catalyst in portions during the course of the reaction, 90 to 95% of each monomer reacted over a period of 1 to 3 hours. Accordingly, the process according to the invention is extremely economical Method used for vinyl chloride polymers

The reaction lcann proceed öiöh * At least Brüek within a guide Ueru ^ Kbereieiies. Is hiirideBteiis gleiek üiefti Daiiipfäruck des Monomers or tier i ^ hbniöreniaisfehüng at ter i teiäißeratüri The hijbhs ^ e bridge is next lent to the "broth strength of the reactor limited iJ§r

Drüök amounts to 28 % 3Ö kg / Sin ² ; äii

30 UM 15 kg / eiii ² are typical
Mfe a

en | 0 Wed 4§δ

ti siiiä p NäSä ihrSi Äufbäil wiftvöll äsB * ali i j älä Ireriibei-ijünifeiiilisiuitlei füf äiätiii iölfliiiiItI ^ i öö

in iöiyyinfisiiiilil üii Miifeö

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and vöü versiMiiäehSn ÜbirgugöiaaEieil ÖUfän MöiälÜiüefi 'Öder

i ten Muli von -füsäiien "E! eäghiBfeiiii $ giIS§i§ii von ÜberMiön äut ver ^ öMifed§
by feeäfeulönä kleinirir

f according to aef Erfiniitii ^ i Wiün

BATH ORIGINAL

polymerizate as dispersion, latex. or when using clay upper eye material should be used in dissolved form , among other things the fine particle size of the polymer should be preserved, bit modifications carried out. For this, a small amount elnee emulsion or wetting agent, for example, sequentially or simultaneously eye passed with the suspension means the Polymerisatlonaaneatz to reach the gowünsciite reduction of the average particle size de? 3 polymer ,,

The reduced viscosity values for the polymers according to the nfe are used to measure the molecular weights ₀ These advertisements are determined by the preparation of a solution of 1 g of polymer II IOC ml of cyclohexanone with a measurement at 3 ° G: the leakage since this solution is calibrated by means of a calibration Pipette compared to that of the cyclohexane. The reduced viscosity is then calculated as follows;

¹ I ¹ Q - solvent outflow in seconds T ^ - outflow of the dissolved polymer in seconds Viscosity- = - = - ¹ ·

m
* °

Red, viscosity -

C is the concentration of the polymer in g / polymer 100 ml solvent. ,

According to the specific polymerization temperature used and the catalyst used, the vinyl chloride polymers have a reduced viscosity ranging from 0 _f ) 2 to 0 _? 58 is sufficient ο It must be noted that in those cases where a homopolymer with an extremely low average molecular weight is desired, a chain terminator is used

0 09813/1709

BATH ORIGINAL

"■■■■■■■ - '■ \ .- 18 -

can be added to the reaction. In this way ■ kürmer *. Polymers with a reduced viscosity value as low as 0.08 can be obtained. Suitable chain transfer agents are the lower aliphatic alcohols such as isopropanol, and halogönxerte ,, a, B ₀ chlorinated or brominated _t KohlenwaeseratofXe having 1 to 6 carbon atoms,

The examples illustrate the invention in parts dao Gewicütο

Manufacture of clee Vinylc-hloriüpo iymerisats A 3f8 liter reactor made of stainless steel, which withstands a pressure of 350 kg / cm ", ** / iai-t a mechanical stirrer, a cooling coil, - e / bieui iherm-oeleiasnt, an i -iruekmesser, with inlets to the -Beschickuiiß, a Sicherheit3v'erit.il ₂ that eats verbimöen with a vent line, -. Equipped "'In this reactor' A '1.5 liters ^; .s 7 »2g of dissolved polyvinyl alcohol, given, Dsr hc * al-: tor is then closed. Lina is freed from acid by repeatedly pumping out to a pressure of 10 Torr, whereupon the vacuum is replaced by the introduction of vinyl chloride . The reactor is then charged with 908 g of distilled vinyl chloride under lüihran, whereupon the reaction mixture is heated to 90 C. » Then it becomes zw-ecks.

■■■ "■■ 2 ^: ""- - -

A sufficient amount to achieve a pressure of about 35 kg / cm fully desalinated, degassed water is pumped into the reactor. With this one Pressure the reactor is almost completely filled with liquid.

While stirring is continued, 5 ml of a ^ solution of terto ^ butylperoxypivaLlat in trichlorotrifluoroethane (40 g of catalysis

^ - _; ι 0098 13/1709

tor with 75% activity in 200 nl LtSaunganittel) is pumped into the heater. One läset öiQ polymerization without further addition of catalyst to run 'at least 30 f> (about 15 minutes Re actions duration) conversion; are achieved . Thereafter, the t \ m rollsuändigen course of the polymerization every 5 minutes 2 ml are eye specify catalyst solution _t wherein additionally in a suitable manner the required Wasoer, is pumped to achieve that ä '- r reactor is filled with fluid substantially "The Gefeamtkonaentration the catalyst beträ _o t 0.57 Gewo-jS ,, based on the monomer _a 'if & chdem the addition of the catalyst ISTF stopped the reaction mixture is for 15 minutes at 100 ¹⁹ C geriihrto the entire lie nude ions ze it belauft to about 75 Minutes.

Reactor contents äahzi cooled, taken out, and the Pöly merisat eye flung Ss is repeated with deionized water washed and finally under reduced l) fuek to a moisture content of less than 0.1 pbw, - ^ ge ^ dried This polymer '- _t which 95 ^ of the theoretical yield is obtained § has a reduced viscosity of 0.4O ₆

Use of the PölymeriBäts.als flammhemmenäerÜusäiä In order to test the effectiveness as a flame retardant additive, a portion of the polymer according to Example 1 is mixed with different low-pressure polyethylenes and with a polypropylene _# on the total mixture in the polyolefin by means of a heated 2 ^ Waläenstuhies mixed ο Jfach 5 ^ mintitigem rollers of the mixture is it from the chair as Foil äbge-

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BATH ORIGINAL

So-called "GewalLate" skins of polyolefin are manufactured as a control material. Samples are cut off from the pelts and tested for flammability according to AS'JiM - PaHIf standard D 635-63 *

The following results "were obtained:

Polymer

Poij'äthylen D «0.921, Schinels-Iiaex 3.0

Polyethylene Γ = 0.9 21?

hIndex- 3J0 ·! ■ PVC

Polyethylene D ₉ = 0-962, ..Sctnelz-TndSx 6, ό

Polyethylene J) _? - ■ * O _f 962, Iridsx 6.0 -v

Polypropylene Ij - O «905 _r

5 _f 0

Polypropylene P ~ 0.905. Melt Index ..5.0 +

IaDeIIe _- I , Inflammation
area ß "~ burning
so windy-
speed Whale tempc burns -18.5em / min " 138 self-conscious-- "
delete u ti 1358 burns 168 seibetter-
lying 168 bx'emit I9't5cm / min » 177 selves?> ··
lÖBchenü 177

fc Those samples which contain the yinyl chloride jiolyruerate

and burn in without dripping or dripping in or out for 1.5 minutes, before they scale.

Determination of the physical properties of verpreseteia

Samples of each of the polymer and polymer mixtures listed above show that the addition of the vinyl chloride polymer according to Example 1 results in a significant increase in the strength of the α. olj olefine is achieved, which when comparing the higher Z-ufjfeatiglr.tsitsraoduli for the samples from the
Polymer} aatittisehung compared to tfomm der -y. r-adhett-i ^ en "polyclefi-

009813/1709

5he eye-sight, will.

This example states that it is a thermally degraded vinyl chloride polymer arises when the reactor is in progress of the procedure according to the decision is not essential is filled with liquid. In a reactor dea! "Yps geiaäaa Example 1 1715 ml. Of fully demineralized, degassed water, wel-

solved
ches 4j, 6 £ / contains polyvinyl alcohol, given. The apparatus is closed and, as in Example 1, degassed, then up to 5 g of the purified vinyl chloride monomer are sucked under pressure. While stirring is continued, the pressure is in

ο
the system about 28 kg / om **. The reaction mixture is then on

100 ". ' heated 4 ml of the tert-butyl peroxypivalate solution with trichlorotriilluoroethane as solvent (see Example 1), then pumped into the reactor and the resulting mixture was kept for about Stirred for 15 minutes. Thereafter, a total of 44 nil of the catalyst solution are added in poison ions of 2 ml each after every 5 minutes. The pressure in the reactor has now fallen to 7 kg / cm is then cooled, the polymer is separated, washed and besehrieben as in example 1 dried. the yield is about 85 fi theory, the polymer has a reduced viscosity of 0,3.9ο in contrast au the product of example 1, this polymer but partly corrodes, as can be seen in the dark ...-. particles, a considerable percentage of which it contains 1 can be used wherever

0 0 9 8 13/1709 BAD ORIGINAL

19Α792Λ

it does not su & omrat on the degree of fer coloring,

Examples 3 and A

These examples use vinyl chloride homopoly agents 130 and 160 C according to the method described in Example 1 using the same apparatus. With every attempt was the addition of the total amount of catalyst required 8 continuously pumped in during the reaction and demineralized water as required to maintain the working pressure © also pumped in ,, The Polylaerisatiorisvorschrift and the reaction conditions are as follows:

Polymerization temp, 0

2 working pressure, kg / cm total heating time, Hi :: i _: fully demineralized water., Ml

Aqueous suspending agent solution, g (2 ¹ Jo polyvinyl alcohol in water

isT> i8l 3 Be game. _ _ti 4 130 160 42 84 45 90 1000 1000 360 342 908 913 1.0 .1.9 72.P-5 0.25 0.14

Vinyl chloride, g

(overall concentration of the catalyst, i>

I yield, ^c ßi of theory

Reduced viscosity of the polymer

Example 5

Polymerization products of Examples I ₁ 3 and 4 and is selected ■ th sample of conventionally produced PVG be dependent Ge on the CH * "groups _Y which are located at the ends of the branches, analyzed by means of a specially developed IR method, In this case, to compensate for the interference of the CH _O absorption bands for the amorphous part, which are usually in the range of 1360 cm to 1350 cm "in the spectra of polyvinyl chloride

-nVÄi: ü- * v 0098 13/1709

occur «a linear high density polyethylene is used, by this becomes this area, which is analogous to that of polyethylene is switched off and a sharp, symmetrical band of the CH, -

■ -1 group kaxiB in the vicinity of the area of 1580 cm "observed The procedure is as follows:

High density polyethylene, Karlex 6050 (Phillips Petroleum) vird _f after of M ₁ and L ₀ Cc Harvey Lc Peters, AnaIo Chemistry, -VnI 32, Mr ₃ 12, 1900 ₁ p 172? reported method a wedge produced The wedge is tapered and has a different _{thickness a ve> n O 1} -076 to O ₈ 46 nanu, ^ r is, cut up to a sample of 31.7 χ 62.-5 su. which is then mounted on the metal frame of the variablenuij Wegaelle von Barnes (the block of salt is removed). "The frame is attached to a Teflon glider with a holder of ropes" The sample is rotatably attached to 2v / eclis change in thickness-

In order to be able to analyze every Pi / ij-nieribat _r , a PiIm is produced by pouring a solution of dc-ε polymer in tetrahydrofuran (0.25 g polymer in 5 parts of solvent) onto a KBr plate the one

any reduction pressure prevails "währenu 30 minutes at 80 ⁰ C. The dried film is evaporated on residual solvent by

up to 6.0 μ
Test in the iR of the 5.5 yes / and 9 _f 2 to 9 _r 5 ju areas examined. The completely kneaded film is then mounted on the holder

Bi α. "Spectra of polyethylene and PVC are marked with a bead in L-liaej-, Ηού- ^ Γ ¹ ). 52I _1. Infrared Glttex speictrophotometer on ge ™ aeii.'h?; Et- ir · ς . '"' Jitsblende is located at 332 ji; the ver

0098 13/1709

ORIGINAL

atärkungefalctor heträgt 4 »The writer is at 1600 cia ^ manually set aiii '90 ^ rrarchläss'iglceit <■ The Probefilra is ätln'lenkeil in ahn beam path for samples and the Poli / in the Re;! ence beam path Ce ~ placed the wedge; --o lung rotated "until the writer is on $ 90> permeability _e Üiu Procramgeschle · - - is 50 cm""/ mine _f where the zero order interference is suppressed we" d _o Uenn the two wings

l;. 5öO ο na "band iingleichmä sig & sina, they are compensated for _r that the on ze ictaiunks drum au.f.." · 3 6 9 om '"" zurücle- and rotates. den PölyäthylenkejJ eo lan ^ e A ^r erstfcJ.lt _r bn .s. the two wings of the 1380 cro "gang evenly., Then the drum is rotated back to 16OC waves / cur"'Euro \ i ; d. -. as far as eo roi.-agile is · »· the tfusti & ?: un ^ 3knopf des' SpeJri.roii ^ oijoruotfirs εο set _r daSv ^ der Scnreibni. on 90 ⁰ Yes DurchiäPTsigireit ateht «Now the area from 1600 to 1100 cm *"'isaböi.;: ·.! -en, In the J.'YC-i-peit- Voi J ^ 'ÖO cm bec.-T> ~ the intensity of this band is corrected if the absorption ratio is proportional to the effective thickness of the film (K value) ο-

The absorption of the corrected band bej- about .1333 cm '* "' - is ^: ΊήΤ-- Ijicke" of the Filni sample in etv / a proportiorjijl, JUas ratio "dex- / ib sorptions A 1380 cm ' to. H 1338 cm" represents the KV / ert = oils branching of the not: reduced PVC-. ^{; i} r (; dui: ta. is determined from the calculated K values (A 1380 //. 1338) - "and converted into the Verliä-i i.ni s GH ^ / 100O CH ₀ , - using as the basis - the ratio 1, iiGH ^ / lOOö CII2 serves as a branching sinusx ei new haadelsüblj chon PVC (Karlex. "6O5O). _a " Uie ^ rgfebiii.ssfi d: iAiHt! x · .Beet ^ niinungeii show aiii ·;: · hsvdPlrmtvLi chr> ^ ier in .tJorJ'.Öi ^rt iiil.ioJi -.- i-- ■ Vi'o.ia «hc; r, 'j; eo part 11

,; ..: -, 0098 1 3 / T7Q-9

PVU materials have a K value in the range of O _a 1200 and a Geha ¹ ! - vo: i afcv / a 3 0 ÜK ^ groups to 1000 Oily " groups, vrie dUr: / ι -or The outer bevel ends of the table can be seen _t xxii or.

The Polyui &^>"i.Ä;3.ic; four examples I _8. 3 and 4 _f o" ov / -X3 selected, conventionally manufactured. ^Τί 7Π - products with im ^ l '& hr the same mean »] mole ^ ^i: a, birg <3Wiei> t w-yi-atHi in einar iJtic.jLSif · Cfatmoerphäre • ü; known -.- re iv.; isö, at ii ->. ^ UiAJfI ^ is used as a catalyst »'iei- reducingC ¹ Ji Ii>' dri« rurr- uatiei'sogeiu laeae flothode is from k, Jlakaji '?; · -. y- · al in «MaleicoUelölla * · Ch ^ fi«: 9'v 1966, p. "40" öingehend!, - asciirieben ^ Xd. ee? s "ce Keduitfeionsphaaa v / i cd at 65 ° 0 during 3C-) Hours, with tetrahydrofuran as Jjue-'i / i du.rohgoführo The second R-sduktionaphase is below 10C ⁰ C imter

aimsv - ΊΌ urahvclrolV.ran — DekalinniiBchunE., during 155 hours -. ', - rgfcitcciuieiu Iiach. onephaße each Redukti -.? 'v rd dae reduvierte polymer by gev / may that ιηειι dis Heaktioxismisühung in libersionüssigöö \ Vasser singiesst, au lot of H ₂ SO, bi admits "a pn is achieved by 2 and then filtered off the Msohung. The polymer is washed again and then dried.

The branching values for the reduced PVC samples were given below Use of the JBich curve A 1370 cm '"" "/ A 1'568 cm" "

) That the linear 0-> r - Cg wurde- aufge0tej.lt ₀ hydrocarbons o.chaltan, details sur obtaining these Bichkurve be of Boccato, A "et al _ä in" Macromolecular Chemistry, 108, 1967 * 218 S. -?>"given» based on the measured A 1378 om " ₉ k . 136B oai""" * values and the calibration relationship;

00 98 13/1709 SAO

- ■ 26 -

A 1378 / A 1368 = 20 (CH ₃ / ^) + 0.2939 "*" ***

the ratio of CH, au 1000 OHg in the analyzed

PVC samples determined. The results are shown in Table II

reproduced «

SafeaLl® II

sample

Conventional V (red, visc. -1.55)

Conventional PYO (red = visco G, 63)

PVC with 8 Gewo4 chain

carrier

(red, Yisko 0.17} product according to example =! product according to example ₀ 3 product genaass Belsp-, 4

CH ₅ ZlCOO CH ₂ reduced
polymer Polymeriaa-
tlongtemp., not redu
adorned bottom
lymer 10, O ⁵ * 55 9 10, O ⁺ 55 9 13th 71-74 10 . 13th so 10 23 130 11th 2? 16Q 13th

-z / ICCO OH ₀ - values from literature,

These results aeigen that the Vinylehloridpolymerisate _f contain mass of the invention, a higher percentage of CHoCl-Enügruppen than that conventional FVC indicated by the retrieved enlarge the number of CH ₇ is obvious to IGCO CH _{2 0}

The limit viscosity of the polymer samples was measured in tetrahydrofuran at 25 ° C. in a modified eastern forest Capillary viscometer measured.

The melting point of the .reduzierte Vinylchlorlapolymerlsate and that of the polyethylene are equal to each other and Wuruen. itach the

00 9 8 1 37 17 09

ORSGlHAL

Perkin-Birner Differential Scanning Caloriaetry method on three different Aufheiegeeohvindheiten found. Dieee Vereuche show «that the realized products have a« polyethylene structure and that no dismantling of the chain took place during the BeduktloK

In the sequence are Zahlenaittel and weight average molecular weights, the einu listed in Table II relate alttela the Gel Permeation Chromatography for some of the polymers specified and also the homopolymers prepared at 100 and 120 ⁰ C gemäee the invention. The Greneviekoaider polymers are cheating

Table III

Polymer! - Grenevie HL M satione- koeitäts- * ⁿ temp «, C number, dl / g

Herlvörcn ;! 3 ciios PV C. weary tr 55 0.52 38 000 13th 600 Pv'C - lv; l Ki? Ttemi hert sp. f-he ' 71-74 0.188 36 800 5 OCO PVC «16? · Kei.t · .. ι above 1 55 0.162 10 200 4th 100 Polymerizat gesv, • rei 90 0.438 36 800 18th 700 rolywerieat gc :. Ifi 100 0.39 25th 100 12th -500 V ilymerisat ^ em _t sp. 3 120 0.25 17th 500 9 000 fo ^ meri.Bat _b oiP, at 4th 130 0.145 13th 000 7th 800 Tolvmerieat j ^ eir- at 160 O ₁ 09 10 561 6th 164

The cncegebeiifii · Verte show that the homopolymers geioäss QUJ liriinduiigf 'AEIA hei higher polymer? : sations tempera door were brought about. c? n höhu-i-es Dnrciischjiit'.aaol'olcular weight alB

like e.g.

r>: -vU-j: - ·: ··,; i-tv> r «r? i h '- ^ :: rx-? il ^ Zt vTt.r <1c ^j n- The high, .009813 / 1709 Ba ₀ OR _161n A ₁ .

however, branched structure of these products is shown in a significantly lower intrinsic viscosity limit

£ s ale can safely be assumed on the basis of the found for the Homopolymerieate Kolekularstrukturdaten that the Vl nylchloridpolynierisatketten * th ren of random and graft Oopolymeri prepared by the same procedure, a different structure than other similar polymer! Satketten, on The conventional way of obtaining _e Jiine Support IUr these assumptions are the various improved processing> properties of these products ",

Example 6

Production of a ^ Copol ymerisate

A copolymer of vinyl chloride and propylene is produced in a 38 liter stainless steel reactor of the type described in Example 1. 11.3 liters of deionized water and a solution of 72.6 g of polyvinyl alcohol in 3.6 liters of water be added to the reactor, whereupon the reactor is closed and is gemäßs example 1 freed from oxygen. with stirring, the reactor is further charged with 8808 g of distilled vinyl chloride and 272 g of propylene ₀ the reaction mixture is heated to

100 C heated, whereupon a sufficient amount of deionized water is pumped into the reactor, until the pressure is 35 kg / cm * o At this pressure the monomers are liquid The reactor is then essentially filled with liquid continues, a solution of 20 ml of tert. ~ butyl peroxypivalate solution geinäss example 1 in the reactor is then pumped _f "is the Reaktionögemiach a further 15

Stir for minutes, ^ until the end of the polymerization ^^ I0P3 ^ 0 0 9813/1709

after every 10 minutes 10 al of the catalytic converter solution and but maintaining the working pressure! WtiHV neon needs in Mhnlioher WeI ee pumped in. The full duration of the reaction is 2 1/2 hours. Bie ine ^ eeamt verwtnitte Konsentration of catalyst used is 0.23 1>, be absorbed on the Gewioht the monomer charge.

The copolyester is obtained, purified and as in Example 1 ^! dried. The yield is 90 Ji of theory The Polymeri sat has a reduced viscosity of 0.44- and contains about 3.0 Gevfe- # of polymerized propylene *

The use of the Go polymer as a binder in polyvinyl asbestos iüssbode- ibelai ?;

A floor covering material, which contains the copolymer and asbestos, is produced according to the following approach:

Oopolymer 100 parts

Butyl benzyl phthalate plasticizer 25 parts

Epoxy type softener 5

V-1285 ⁺ 3

Calcium carbonate 360

Asbestos 120

Titanium dioxide 48

Stearic acid 0.5

Pest nitrogen-containing organic stabilizer that is used in the Polyvinylfussbodenbelag. ':' (Kuodex Products Co,) "

0 0 9813/1709

. '. ■■■■■■ '■. ■. ■ ~ 30 -; .- .; ■ .. ■ - ......

The ingredients given above are mixed with one another , the mixture is placed in a Banbury mixer and then treated at a temperature of 148-163 ° C. for 3 minutes. The hot-treated material is then placed in a 2-roll mill and processed at 121 ° C. After the material treated at this temperature for 5 minutes has been mixed, Θ8 is peeled off as a thin, 3-175 mm thick skin. Another approach for similar purposes is processed in the same way. This other 'approach

^ i.sii the same, but with the exception that instead of the vinyl chloride -...

^ Propylene Copolymarisäts according to the above example, a conventional vinyl chloride copolymer (containing 15 wt <> - ^ vinyl acetate), as "usually apply for the flooring aur application is used * The vinyl acetate CopolymeriBat has a reduced viscosity of 0,6I ₀ ■ ■

For each batch, samples of the rolled skins are made according to the regulations of the Revised Federal Specifications for Vinyl "Asbestos Floor Tile, L'- I" 00345 (COM-NBS), August 28, 1959 k Based on these regulations, the following results were obtained:

Table IV

- 25th , 4 iDia plate * VG vinyl acetate properties ~ 26 »4 mm VC propylene Gopolymer- ...: «25 ι4 · mm Copolymer Notch / test (McBurney) ■ _N .. Oj, 007 Room tempo, 1 kin ₀ 0.007 OV0ÖÖ75 ' 10 · ». ' 0.0005 46 ⁰ G, 30 sec. 0.014 ■ '- ■■} ; -v. ; - »■ Abrasion (taber) 0.40 g / 1000 cycles 0.23 Deflection test

Deflection} kg / cm. . '. 213 , ^ g ^ angle of fracture, (irad ₅ - j - ^ -. t ^ 10 _.: 7.

; * ν · .ϊ-ν ^χ '"" - ^ "ö & B-ifi / 1 709

BATH ORIGINAL

- 31 -

These values show that the copolymer of Example 6 gives a floor covering where a test bag is more resistant and more resistant to abrasion . The floor covering material, which was produced with the copolymer as shown in the example , is more flexible, which is clearly visible through the application of a greater force when bending the sample until it breaks

To the Waaserfestigkeit the plates gemäes above approaches check ,, mx samples were weighed from each plate and immersed during ₅ I 2 and 3 Vvoaheii-at room temperature in water, kept on. On Jiude each storage period, the samples were removed ,, the water freed from the coarsest part by wiping and weighted by a percentage of water absorbed during storage was determined from the weight differences, was being made to the Origiiialgewicht I ³ robe reference. If this method is used, the following results will be obtained!

Table V

Water absorption, f>

Plate sample storage: 12 3 ^ ___ ^ V / oche weeks weeks

YC-propylene copolymer O _f 25 0 _R 60 0.78

VO-Vinylacetat'Copolyasriijat; 0.90 1 * 17 1.43

In the approach to the production of a plate which contains the copolymer according to Example 6, is more resistant to moisture than one which is produced with a vinyl chloride-vinyl acetate copolymer of the prior art ₀ Accordingly, a plate produced according to the present example may be used during use - stay true to size "

009813/1709

BATH ORIGINAL

-.32, 19,479.2 *

It is difficult to use vinyl chloride-propylene copolymers conventional methods because long polymerization times, 18 hours or more, because of the low degree of catalyst efficiency are needed. It is characteristic that only up to 70 # are implemented. The conventional copolymers cannot contain all asbestos-containing binders FussbotLen covering material are used because they are because of the in their manufacture, temperatures used only so badly suitable for further processing ,, '

For example T

A rigid foam was made using the following approach

produced with the polymer according to example 1: Polymer 2500 parts

Stabilizer * "75 parts

⁺ T-31 - liquid organotin-mercaptid-statiilizer-Metal and Thermit Corp »

The ingredients are mixed together and ο milled at 235 ° for 5 .G Hinuten The soft material is drawn off as a thin layer and formed into pellets ₀ The existing cubes material is immersed for one hour in trichlorethylene, -said about 35 wt _o ~ $ > of the solvent have been absorbed *

The cubes treated in this way are processed in a 25.4 mm injection molding machine that contains a simple _{worm worm. The machine has a 3 f} 175 mm slot nozzle «The screw speed is 20 rpm and the« temperature of the injection »molding machine between the funnel up to the nozzle is 93

009813/1709

BATH

177 ⁰ Co The die temperature is 146 ⁰ C. The foam has a density of 0.320 g / CONU

Example a

This example shows the use of the polymer according to Example 1 as a processing aid for a high molecular weight polyvinyl chloride (reduced viscosity 1 _→ 55).

For example, an assignment is made, according to which 80 parts each of the high molecular weight PVC 20 parts of the polymer according to the example 1 konuneno per 100 'file of the mixture - with 3 parts a liquid Oiganurvuiw-üierkaptid-Stabilizer added.

Me components are mixed together and 5 minutes' at 177 Ό on a 2-toalaenstuhl treated "Am part of this softened material is verpresat at 177 ⁰ C, a lauryl

2 '

fende increase in pressure up to 3500 kg / cm takes place and the The duration of the exposure is 8 minutes in total. For comparison purposes, an approachρ of only the high molecular weight PVC and the stabilizer (3rd parts to 100 parts PVC), rolled in the same way and vfirpresst.

Test pieces from each pre-prepared approach are tested for their strength in accordance with ASTM D 6-38 - 64 T. The results are as follows: i

Table VI

Checked Molecular weight PVC mixture

Tensile strength, kg / cm ² . 536 534

Tensile modulus, kg / cm ² 255 x 10 ⁵ 262 x. 10 ⁵

Elongation at break,. ^ 85 93

BATH ORIGINAL 0 09813/1709

The rheology of the melts of each of the above genanut ^ ji ^, mixtures is determined with the Sieglaff-Mo & elyey rheometer, in which a 25? Kap j Hart measuring 4 mm long and 1.01 mn its diameter is used, determined at 216 ⁰ C. The results are as follows:.

Table VII

Viscosity (poises)

S cherpeschwind iK ness, lake Mge "of PVC Mix g

10 ° 58 χ 10 ⁴ 35 xlO ⁴

IC ¹ 17 χ 10 ⁴ 11.4 x ΙΟ ⁴

10 ² 4.3 x 10 ⁴ 3, -0 χ ΙΟ ⁴

10 ⁵ 0.98 χ 10 ⁴ O _? 57 χ ΙΟ ⁴

Shear rate at
Schmelabruch,

see "' ¹ 110 490

These results aeigen that the mixture containing 20 vinyl chloride homopolymer according to the invention, in Compared to the one whose plastic only has a high molecular weight has, has significantly improved pleating properties Accordingly, they also have excellent processing properties

The use of the product according to the invention as a processing auxiliaries for other high molecular weight plastics reduced in no discernible form the physical properties of the the former «, This is evident from the equivalent values for the properties from Table VI.

Example 9

According to this example, using the procedure and

■ ' - 009813 ^ 1709 _BAD ORIGINAL

the apparatus NaOH Example 1, a vinyl chloride-vinyl acetate copolymer at 100 ⁰ C. After 1850 ml of demineralized water, which contains 7 g of polyvinyl alcohol and 180 g of vinyl acetate monomer, has been added to the reactor, the reactor is pre-closed and evacuated. While stirring, the vinyl chloride (1020 g) zubegeben _r is then heated whereupon the Reaktionemischunfi to 10O ⁰ C and pumped quantity of water in the reactor is to e: is reached in .Druck of 35 kg / cm (line pressure) ". Thereafter , the yellowest tert-butyl peroxypivalate catalyst (as in Example 1) is added in proportions of 2 ml for the duration of the reaction. The transfer concentration of the catalyst is 0.68%, based on the total weight of the monomers introduced. The reaction lasts from min , 37t

This product has in solution s an excellent Viskositätsverhalt. "- 'W each have the _f the following results which were obtained ketone for solutions of different concentrations of this copolymers in Methyläthy1-, reveal Concentrations are based on the weight of the copolymers to. Comparison will be übereinstimmende.Lösungen for a vinyl chloride copolymer prepared according to a customary type, the 13 - # contains vinyl acetate, also indicated - 15 wt _o.

BATH

0 0 9 8.1 3/170 9

- 5ο «·

Concentration of the solution (weight)

Copolymerization according to example

Conventional copolymer

Tabel VIII . Gentipoise * viscosity 20% 25? 6 41 71
? 8 194 20th
39

Determined with the Brookfield Viscometer i'Wodel RV) ₅ using the spindle Wr, 3 at 100 rpm « ₀

The low viscosity of the solution of the vinyl chloride-vinyl acetate copolymer according to Example 9 suggests its use for coatings on paper “in paint sutures and in other areas where flowable solutions of polymers with a large proportion of pesticides can be used advantageously”. near _e

ß of Yinyl Chloride- P for graft copolymers

Using a 3β l / iter capacity stainless steel reactor, which is equipped according to Example 1, is a Graft copolymer prepared as follows. '";

In the Keaktor a solution of 72 »bg polyvinyl alcohol in 3600 will ml vollentsalzteiu water _(J 5 _V I liter vollentEalztes water and 1, 816 g of ethylene-vinyl acetate copolymer which 26 Gev / _O ^-.! Includes ^ vinyl acetate (Melt Index -. 3) is entered, 'wax and the Versehliessen .Rinse the reactor as described in example 1, 7 g of distilled 264.- vinyl chloride monomer is added thereto, after which the heated jKeaktionsiüischung on ICO ⁰ C wirdV

■ "· ■"'■"' ^v 2 * ^; """"'Vbilent's most water is pumped up to 35 kg / cm«

^^ ¹ ^ · '^;'0Q9813 / 1709

Thereafter, 20 al of a solution of tert-butyl peroxypiralate (40 g of catalyst are diluted to 200 μl with 95% strength ethanol). Poured into the heater, whereupon the reaction mixture is stirred for 15 min. as the· can be recognized by the necessary addition of water, then the The reactor remains essentially filled with liquid. Each of them will continue to operate until the polymerization is complete 5 minutes 10 ml of the catalyst solution were added; no further addition is necessary. “The entire reaction time is 90 min. The total concentration of the catalyst used for this experiment is 0.29 pounds based on the weight of the vinyl chloride monomer charge "

After the polymerization has ended, the copolymer is recovered, purified and dried as in the previous examples. The yield of copolymer (6,626 g) is somewhat higher than β 95 i> theory.

heal «

Extraction tests were carried out on this copolymer with / cyclohexanone. Ee has been found that the lagging, ' insoluble fraction (a copolymer based on ethylene vinyl acetate) contains at least about 60 pounds of chlorine, based based on the weight of the vinyl chloride contained, similar extractions with hot toluene resulted in a soluble fraction. Huh After evaporation of the solvent, it was found that this fraction contains a percentage of chlorine which is equivalent to the percentage by weight of the yinylochloride contained in the graft polymer. Based on these results, it can be assumed

009813/1709 ^BAD

- that the Ffropfoopolymerieat not a free copolymer substrate contains more, but straight-chain Viaylchlorid-Honiopolynisat included

Physical properties of the gfropfoopolymerieate As a result, the physical properties of samples which have been obtained by an injection molding machine using a Go-polymer, _o determined These samples after Verwalzen and dismembering of a lug (100! Feile copoly> oerisat to 3 parts Stabilizer) obtained using a Mini-Jector Injection Molding Machine, Model 65-HA 100 (Newbury Industries, Newbury, Ohio). Deformation conditions: cylinder temperature 177 ^° C .; Nozzle 165/171 ⁰ C; Forms room temperature; Injection

2
pressure 84 kg / cm j deformation cycle 30 sec (injection), 10 sec.

(Filling), 5 sec. (Hardening).

Table IX

Tensile strength, kg / cm ² 210-280

Tensile mo ^ ul, kg / cm χ 10 '..' 8.4-13.6 Elongation at break (ASTM D 638-64Ϊ) 40

.Izod Impactness .ft · lbs. / In.

Notch (ASTM D 256-56) 9 -10

■ ". '■' ■ '■ ■ ■■." .. ■ -.' ■■ ο
Distortion speed at 18.5kg / cm,

⁰ G (ASTM D 648-56) 46-49

• Brittleness at low temp ₀ , ⁰ C

(ASTM D 746-64T) -10

Flammability? ' self-redeeming. ·

In comparison, a Mischunt, 80 parts of the homopolymers of Example 1 with 20 parts of ethylene-Viny 1-, acetate Copolynierisats which is verwalzt at 121 ⁰ C, friable and not fixed. The mixture can not be as

! tough Fei? «be ab & jgeii-

Mixtures of conventional PTC (reduced ^'r iscosity - 1.10) with 15 - ZO parts of ethylene ~ Vinylacei; at-copolymers are at 171 * C, rtiva-IEFC "withdrawn as coat and deformed by means of pressure samples _t lieser mixture have an average impact strength Ton et '«! .-! 1.5 - 2 ffco ibSo / inph notch,

Be with Celoiutnoartonat, As st and glass fiber filled approaches! Mixed ρ oei 14O ^v> 0 'marry choosing 5 minutes and then Drude boi 149 Ό and 70 Jcg / cm ¹¹ "during a 2i> itdauer verformto 5 minutes Physical Eigeixschairven these briquettes beef according to the ASW. 6 ^ 8-64-T like

Fill quantity par tensile strength. "Kg / -

Tensile modulus _y kg / cm " χ 10

-ffempo at 18c5 kg / cm, C (ASW- 1) b48-56).

Calcium
cixbonate 100 asbestos Glass
fiber 50 308 75 25th 28h- . 242 501 401 181 476 ♦ 312

66

CO98 13/170 9

BATH ORIGINAL

Claims (1)

P ate η t a η s ρ r ü c h e 1- "Thermoplastic vinyl chloride polymers which contain at least 50% by weight of polymerized vinyl chloride, the chains of the vinyl chloride polymer being highly branched and having up to 14 CHoCl groups on the branches per 1000 CH ₃ groups * -. -% 2, vinyl chloride polymers according to claim 1, characterized geke η η ζ eic h, net that they are vinyl chloride homopolymers with an essentially non-oriented tacticity (random tactieity) _{or the like} 3 ο vinyl chloride polymers according to claim 1, characterized in that they are copolymers of vinyl chloride with an unsaturated monomer copolymerizable therewith from the group of C ^ _- .j-olefins, the vinyl esters of ^c 2_i2 ~ ^{monocartlonic acids} »maleic anhydride, the unsaturated Cj ^ -carboxylic acids and their lower alkyl esters. 4 _? Vinyl ciiloridpolymeri sate according to claim 3, characterized geke P η η ze ic h η et that it consists of 50 - ₉ 5-bis ^ consist of vinyl chloride and 50 parts by weight O-ji ethylene or propylene - 99.5 wt.. 5 * vinyl chloride polymers according to claim 1, d ad o r C h geke ri ze ic η h η et _t that they Vinylchloridoopolymerisa- * te are based on a homopolymer of a C - ^ - olefin or its chlorinated derivative, a. Homopolymer of a vinyl ester of C ₁ -a monocarboxylic acids, a homopolymer of acrylic and methacrylic acids or their lower alkyl esters, a copolymer. sata of the C _2- ^ olefins with vinyl ethers of the C ^^ - hunocarboxylic acids ^! »^^!« .. tx the graft copolymer 60 - 95 grafted vinyl chloride and 5-40% by weight substrate polymer contains. 6. vinyl chloride polymers according to claim 5, characterized in that d 'e Substratpoiymerieat lacetat-Copolymerieat an ethylene-Vin ^ is that 10-40 Grew _e - £ contains vinyl acetate. 7a process for the production of vinyl chloride polymers according to Claims 1 to 6, characterized in that t, | that in an aqueous, suspending medium, monomeric vinyl chloride, a mixture of vinyl chloride with an unsaturated monomer which can be copolymerized therewith or a mixture of vinyl chloride with a solid polymer which can be grafted with this, with a catalyst which forms free radicals and which is soluble in the monomer, at temperatures of 90 and 165 ⁰ C and bridges 28 and 35Ö kg / cm for 1 to 12 hours transposed, 8 ο Method according to claim 7, dadurehgeke η \ n -zeiohnet that tert-butyl perosypivalate is used as folvme- \ riaationekätalysator · 9 · A method according to claim ₉ characterized ge I k e η - zeiohnet that one carries out the method for a time period of 1 to 3 hours. BAD ORIGINAL C3 98 13/1709