DE1745083A1 - Process for the halogenation of vinyl polymers - Google Patents

Description

Process for the halogenation of vinyl polymers

The invention relates to the chlorination of vinyl chloride polymers and / or copolymers, wherein a polymeric material with a high proportion of chemically bound! Vinyl chloride is ciioriert so that one obtains polymeric products with a high degree of orientation, which have such properties, that they can be further processed in a simple manner on conventional devices can be.

It has long been known that by chlorinating vinylpolyraerenes which are dissolved or suspended in organic liquids which cause normal polyvinylchloride to stand, polymeric materials with a high degree of chlorination can be obtained greater affinity S 2 ^e have ^en solution Tiittel ale ^ angsmatgriallen the corresponding from ·

(Art 7 11 from. 2 No. I 3 & tt

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ν. 4. 9.1. -

These processes of chlorination are free, even then they lead to products with a high level of chlorination, useful . manageable, require high respiratory repair and devoted Products that have poor thermal stability and unsuitable for the manufacture of heat-resistant objects are another disadvantage of these known methods is that the highly chlorinated polymeric materials difficult to separate from the organic liquid in which the chlorination reaction was carried out.

fe j5s is still started, there '? many Jigenschoften the Pol7 / mere

and iischpoliermere of vinyl chloride, e.g. the lower temperature of use and the preservation of mechanical properties at high temperatures, can be improved by special) chlorination processes. The Aucaa'i represents improvement this / Uiganschaften depends on your special in fcüns?! - the procedure applied declines. See some of these procedures the chlorination of Polyvinjrlchloi i ^ s in S-isnension in one organic medium which has no or at least only a very low level of swelling capacity for the polymeric raw material, before. The suspension medium can be made up of a jin-phase system e.g. chlorofluorocarbons. ^ 5s can but also a system with heterogeneous phases, 2.B

"» Siasser / Ohloroforai or aqueous solutions of the hydrogen chloride

act acid / chloroform.

Processes of the last-mentioned type lead? .U highly chlorinated Polish materials, which are used in particular for the manufacture of everyday objects with? Higher thermal bathing ability are suitable. However, they have the large ion iSocht ^':????, Il on, dai they use large ier I iangen pn Ssu pencionBaiecJiii.m require so dai - s is difficult iCon ^ ntrptionen nn' _ol7 ^r m ^ r ^ ia. "iaterial in the Susp ^ nrvLonsniedi'im can reach over 55% '* u.

109832/1310

D? C again leads to the fact that 3 the iden; re ^ n S'lppens d ie 'iT »In ^ e d-? r wb.lorierun ^ sreaiction 7 ^ nic'-c ;; ev; onnen be • τιί, is particularly high.

dsrf invention ^ s ^ eiia '^; ( ^'1 e method collsn S the previously -H'iten method "" adhering wax parts can be avoided.

By des? Rf i ^Ti da.n2; s [remä? E process, pich jrolymere and / or .. liFciipolyn-sre of vinyl chloride with high thermal stability, high low temperature and high self-extinguishing ability can be obtained, which are made the "beneficial possess d? ^1? pie on SST-ndard ^ ^ Verarbeitan smaschinen are for limststoffe v ^ rarbeitber. the erfindungssemäie method for ChIoriervm ^ Vin ^ lchloridpolinieren and / ocer -Mischpolymeren is d ^ CDCR ^ £ ii 3X3nnzeichnet that nan Vinylchlo2? idpolyaiere and / oier -misehpo! ^ ηα.τβ in form of powdery, essentially anhydrous xäipchtine-en, which are known to be chlorinated by mixing such polymers with small amounts of a chloralicäns ^ e ^ lnnt ^ in what is well known . the ^.ie; nperatur, wherein the Jhlorierun ^ ^ d.virch eführt is not; critical: preferably operates Ή η at a temperature -mterhalb the G-lcrüber- anTstemperstu ^ ^ (./armeStandfestigkeit ")? des pol ^ 'meren material «? lies, η] in the preferred temperature range for the process lies between 0 and °

The orfird'infs ^ em ^ ie ghlorierungsverfahren la. ^ T sicn both on ηο mo ίο lines of the vinyl chloride as well as on liischpol ^ mere of the vinyl chloride ε lit «other monomers like vinyl acetate, vinylidene chloride, acrylates,« «ethacrylate, P.niarate etc. as well as polymers! They hang in the propppo ^ mers of vinyl chloride.

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17A5083

In the case of polyvinyl chloride, it is preferred to use for the process according to the invention, a homopolymer which is obtained by normal polymerization in aqueous suspension and a molecular weight - determined as viscosity in cyclohexanone - from 0.4o%, parts / volume, at 25 ° C., with a range of variation from 0.3o to 0.75, preferably 0.4o to 0.60 and a particle size of 150 to 50 microns.

Particularly suitable for the purposes of the present invention are homopolymers of vinyl chloride with a 'particle size distribution, determined according to ASTM! 5 11-61, as follows:

% Residue on a test sieve with approx. 245 meshes / cm ¹ "=

70 " dd It dd It Il 576 It = 0 ^c / o " Il dd It Il Il 12oo It - 0 9a " ti It It It It 16oo It = 0 % " dd M. dd It It 33oo It - 4o Γ / ti It It It It It 64oo It = 4o % Passage by a Sieve with approx. 64oo It = 2o

These polymer products have the following additional characteristics: approximately 56.4% chemically bound chlorine; specific gravity about 1.4 g / cnr; 2nd order glass transition temperature (thermal stability) 73 to 85 ⁰ G; Vicat Sindring temperature (5 kg in oil, 1 mm penetration depth) about 85 to 90 ° G; mean porosity, expressed as the volume of the voids, 0.2 to 0.4 cnr per gram; mean diameter of the pores between o, 3o and o, co wlikron. According to the invention, the chlorination is carried out in the customary manner well known from practice. Dry gaseous chlorine is preferably used. The reaction itself can - also in a manner known per se - be activated, both by physical and chemical aids.

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So it is possible and advantageous in the presence of photochemical to work active light rays or to carry out the chlorination in the presence of small amounts of radilcal-forming substances.

In this regard, it was found that in addition to the usual radical-forming catalysts such as azo-bisisobutyronitrile, Lauryl peroxide, benzoyl peroxide and others also peroxide compounds with a high decomposition constant (low half-life in that required for the chlorination reaction according to the present invention Temperature range) such as t-butyl perpivalate, diisopropyl peroxydicarbonate among other things can be used to accelerate the chlorination process.

In the method according to the invention, the chlorination speed is relatively high; it will - provided that the light intensity or the amount of catalyst and the concentration of gaseous chlorine are the same through The type and length of the chloroalkanes used are regulated.

The Keaktionsdauer is adjusted so that the product -nan fflit AEE> n receives desired percentage of chemically sebundsneiii chlorine.

Chloralkanone required for the process according to the invention, r'i? for pretreatment of the polynerma torial before serve the actual purpose, it can be different Trade ties. Particularly suitable are chloroform, Carbon tetrachloride, 1,1-2 dichloroethane, and others again - mainly for reasons of economy and Easily obtainable - chloroform.

The amount of chloralicene contained in the polymer according to the invention

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and / or mixed polymer of vinyl chloride is absorbed one of the most important factors of the process according to the invention, because it depends on the optimal course of the chlorination action and thus the production of chlorinated products with the desired properties depends.

The determination of the amount of chloroalkane depends on the type of that polymer material used, primarily on the degree of comminution or the porosity of the same, as well also on the type of chloroalkane used.

In fact, it has now been established that if the amounts of chloroalkane are too small - among other things the same Reaction conditions - a post-chlorination product with poor thermal stability is formed; when using too large Quantities of chloroalkane swell the polymer material too much, so that the mixture has its normal flowability (T-fluidity) loses. This can lead to the formation of incrustations on the walls of the reactor and, in the final effect, to an inhomogeneous one Chlorination come. The polymer could then be used in addition, no longer win in a powdery state.

If chloroform is used in the process according to the invention as a chloroalkane, amounts of 1o bip 551 are preferred 4o to 55 1 / part oluric chloroform to too weight parts Polymer material as particularly favorable for achieving excellent Results proven. The parts by volume relate to parts by weight like grams to cubic centimeters,

The powdery mixture of the polymer material present in powder form and the chloroalkanes is erfindungegemä 'i prepared by lä'it, absorb from the Polymermatarial, preferably at room temperature, the chloroalkane. Preferably!

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"one works in apparatuses that correspond to those that usually for the production of mixtures of polyvinyl chloride 'and' vieichraachern are used. It is still advisable to carry out the procedure with complete exclusion of moisture. The presence of very small amounts of water both in the polymer material and in the chloroalkane. can, however, be tolerated. The best results can be achieved when the amount of water used is below 0.2 percent by weight.

With. Using the "method according to the invention produced Polymers and / or interpolymer oil vinyl chloride stand out due to consistently good characteristics with regard to thermal. Stability off; these characteristics are better than those of than Starting material used chlorinated polymer or mixed polymer. ■. '

The "thermal stability" is determined as follows:

a) by-ASIM D-793-4-9: one determines first the fetch amount is not developed in the stream of nitrogen at ⁰ C Ί80 of 1 g polymer during a heating period of less than 60 -Minuten-. Then graph the amount of HCl as a function of the heating time

-1. The slope of the curve is expressed in hours and referred to as the "dehydrochlorination constant" (DHG). The D3h7 ^r drochlorination constant is lower, the higher the stability of the polymer is »

b) lan determines the time required XSt ₁ until a "mustard color" develops in a sample of the powdery, non-stabilized polymer, which is in a special aluminum glass in a convection oven at a temperature of 1 ^{l 90 ° C;} then the time is determined which is necessary to develop "an" amber color "from the" mustard color ".

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D'l.poh ^ ie .iinf'ihrunp * vcn Jhlor 'nit; ffilfe of the inventive 0 · "1 c ri - ^{j 10} Hn- s process in the vinyl chloride polymer ^{- ode 71} vinyl cb.] oridiiir? ohpr-polymer mixtures lesson the properties ^ oq a ^] P ^ enc ^ waterials change ·

'.vvirde are located, d.e3 the specific G-ewi ^ bt, the G-Ips-

rot ⁱ ir, C ¹ Ie S ^ Tbstverlosohfahip.x ^ it and the 'V ic at pa ^ ur mit ^' lnehmender 'irhö'nm «· der rflcn ^ en an in di °" iisc] ¹ ι ¹⁰ er 9in' ■ '■■■? F'ii ^ rte'Ti Gb.lor "nst" eicr © n.

Po] 2 ^r m? Re des Yinylr.hlcrics, the 6 ^R , 2% chemically (r \\ ov o ^^ bglten, W ⁰ IvSeP the following lion data call:

roe ζ if i ° cries weight "1.5 ¹⁷ O""/ c

'tI ^q 5 ³¹ M bor ^ pn ^ pteiio ^ rs .door

The thermal stability (BHO'j according to the definition above is 1, h ^ o. Io 'for a non-chlorinated Vin7 ^r lcbJ oridpo.l ^^ tnsr; for a nee hch ¹ edited Proda' ct nit 6 ^ρ ,? ./ ό chemically TebMndenem OrD.or cheats them o, 4 ° o. ίο "?.

Surprisingly, it was found that through the invention the ivioleteular weights - f-uisg-pressure due to the viscosity - there is a nominal change in it suffer, but praictically via the external media. remain unchanged.

Ingenious of a preferred form of the guide according to the invention Procedure, the odorization is carried out in a jar in which firstly a thorough mixing of the. -Polymer material "with the ChloreIfcan and secondly a continuous one / juführunp; the chlorine gas trenes at clever

BAO OBlGiNAU

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removal of the hydrochloric acid formed during the reaction is possible.

The activation of the reaction is preferably carried out with the aid of suitable lamps that emit photochemically active light, preferably with lamps that light the "wavelength between." Radiate 35 ° and Λ5ο millimicrons, reached.

one äJrreicht the other hand, the activation with the aid of radical-forming catalysts, so the latter can in dam ühloral'xan prior to treatment of the polymeric material dissolved Λ or continuously während.des course of Chlorierungsreaktioh be added in the form of concentrated solutions in a suitable solvent.

At the end of the chlorination reaction there will be excess chlorine and excess hydrochloric acid removed by uian iramer still stirring - a nitrogen flows through the powdery mass presses.

The polymer powder thus obtained is then mixed with an aqueous Solution of HaIiCO, treated to remove the last traces of acid to remove. It is then filtered. That in this tfeise obtained polymer is finally with a solvent ™

washed like methanol to remove the last traces of the chloroalkane.

As a result of the "removal of the solvent, the Values for the average size of the particles of the chlorinated polymer material and for the particle size distribution Values of the raw material.

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The polymers and / or ivlisch ^ olymers of vinyl chloride ε, the inventive-S have been prepared fc ^ n ^ ¹ he euf ·-'I ^ scf and devices are further processed, which usually does not nachchlo-- for further processing of normal. -ated polymers and ivfish polymers.

Shall - a rigid vinyl sheet on top of one. If a salt is produced, it is possible, for example, to work with particular advantage at temperatures between 18 o and 22 o if a post-chlorinated polyvinyl chloride with an aluminum content of 55.7 to 70% is used.

The chlorinated polymer materials made with liil fe d.es inventions Process are produced, »tons in the same Similar to normal vinyl polymers and vinyl polymers softened, although normal Jeichmacher in post-chlorinated Polymers are often not as effective as they are post-chlorinated polymers.

By mixing the chlorinated ones produced according to the invention Polymer materials with common additives such as fillers, stabilizers, Plasticizers, dyes, pigments, G-Ieit- and Spotting agents commonly used for normal Po ^ vinyl chloride can be used, molding compounds can be produced. «/ earth.

Example 1

Sine Probe "SICRÜN 548 FM" is a commercially available polyvinyl chloride high porosity, which is obtained by suspension polymerization from Societa iMison Aziend ε Ohimica, Milano, is kept in animals has been chlorinated. The polyvinyl chloride sample had the following characteristics:

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rs ^ -y'i - P-Vpc'ie "Vis'x ^ sitat at Ί ^ ■. <ο, 4-67

j -'ν- · ' ¹ -crt ^ ¹ Id fl'if aii test sieve "lit more f ^ hr 24-0 rio see / c · ⁰ " O

• I -I Il 11 H Ί "77ο" O

.-, ■■ ''■;'"i ¹ it it 12oo" O

., μ Μ Μ it ι Ii 16oo .- '". ■ G

II. M: l Il U Il AAi ^ ci " UA

: i M- Il II - ■ tt II ~!. \. r \ c * "': O

wi Ij "π ^" η "-" η-- "'' -η.- · <■» fi oi-ρ! "-" i ^ f 3 i ^ b Π? it ■■ * 54-ΟΟ "I '"'

C -inte3 "· Sti '■: ·?" "" Ff, h "^ ^, 62ο. 1o ~

Ο-

technical 1; Nepalese stability at 1 ^u c "'u

faglini ρ ·>! ΐ3 fhgpMi grt | -ig St ° · bj 1 it '^ t V ¹ ^ _V t 1 ο oi ^ [V) J ■> - »o ^¥ .o" O ^{l = I%} c>+;f>in'n'3-v<o-jj- ^ Tri P. ^ τιΛηιιηρ ¹ · [

^{ty /} C.

■ ΐ> η - * r-ν c: ^ rr * ~ 1 j _ (^ ¹ ^ Civ ^ ^ -XJ- ¹ , '^ i ^ v ^ - ^ - Ti ^' iti ^ f ^ nHuY ^ • ■ ^ ■ r \ r 'q ί nom f ° ¹ ^ t ¹¹ ^ t ^ Ί. "^'" ¹ O- ^ P ■ Deil bep ^ snd .. The rotieraiic ¹ e part-consisted aas einia Eea ^ ions ^l co ' ben (in the following examples 2 flasks 'nit verpeaiedener Sspacity, na-ilicii 2 bz-rr * 2o 1 vsr ^ used), whose roc "ütioTisβ ■ * iise' -itü Jp" ^ s ^ sn the riorizontple n 'enei'T't' .vcr · 1) 3 "aßl'D3T!? ΐΓ ^Λ ι iTi with the help of a ♦ ilejEtrc ^ otor pro ■ '/! invite' -rnd is the case of the 2o 1-Kclbens with 1 '> ilradrehanffen pro ■ ^; ' iiriate · *. -

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The fixed part, which was connected to the rotating part by sine spherical fully dense compound consisted of the Cblorzuleitungssystem, a grater jfühlei · • ^with: n lo ^ ö en veer and returning the Chlorelkandämpfe and a graduated cylinder, either ale ~. R3servet8nk for the Chlcr? -Lkan or ice tank was used for the catalyst solution.

The excess of chlorine or carbonic acid developed during the reaction was introduced into an absorber with WsOi-Loruns. At the beginning of the reaction, the rotating 2 liter was first flushed with nitrogen and then with 200 g of powdered polyvinyl chloride charged of the type described above. After stirring was started, at a temperature of 2j? \ i slow bo

TeiDe pro Ίοο Crewicbtstei] e Pol ^^ ner) Chloroform zu2; 3? Eti5t. Hach termination of Gblorofor.mzugabe the flask was still ^T * reitere 7 ° niinuten in rotation held.

A stream of dry chlorine was then passed in, which reacted with the powdery ifesse; men worked while in GSM genwart photocheiiisch of active light, which was emitted from a 125- * Vatt-.V "oodlanipe. The chlorination was carried out at 3iner 'temperature of 3o C in j> hours. Thereafter, the chlorine feed was shut off, the Lairrpe switched off and the post-chlorinated polyvinyl chloride separated.

The end product obtained in this way had the following characteristics:

specific viscosity at 25> ° C o.463

Chlorine 65% particle size

% Residue on a test sieve with about 240 meshes / cm '"

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■ "'■■■■ / 2

-fo eücfcstand on a test sieve with about 1200 l / cm

cig, ii it it ii ti it 1SoO "

ψ ₀ """" ■■ '"■■." 64oo "

% Liurch ^ axisr through a test sieve with about 64ο ο '"

specific gravity 2o / 2o C g / cm
Vicat penetration temperature 128 C

thermal stability, worth the D.H.C. constant 0.375'1 ^ "h technical thermal stability at 19o O

"Mustard" 60 minutes

technical thermal stability at 19 "^ C

"Amber Color" 1 '^ Q ^ Limits.

Example 2

In an apparatus of the type described in Example Λ , a polyvinyl chloride of the type described in Example Λ was treated. -

The procedure was as given in Example Λ , the chlorination time being 2 or M hours. In this way, 2 types of post-chlorinated polyvinyl chloride were obtained, the characteristics of which are summarized in the following table:

Reaction time 2 hours 4 hours

specifis': ae "viscosity at 25 ⁰ C o, 468 o, 465 chlorine 64 % 68.2

specific gravity 2o ° / 2o ° C g / cm- ⁵ 1.52 1.57

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2 Stand 4 hours anno η

Vicat-3indrin3teraperatur, in "G 12? 14-6

DKw constant at 1 «o ° G, h""" ¹ ο, 4 ^ρ ο. · 1ο ~ ⁵ o, 2 ^Q o.1o ~ '

Glasiibersans ^ steiiperatur,! Tg »in CJ ^ o ^p- " -Mo

technical thermal stability:

"Mustard color" at 1 ^α ο ° ϋ ^ o .iin. 'ο.! in.

Amber color at 14o C 1 ^ o / iin. iib ^ r Ί4 · ο, -li ^.

ivian. ercen-'t, that ^ at ^ rhöh-in ^ the G'-lori3r'An «-srii? le ^ der tr ο ζ s- ^ t ^ an cne.aisC-h ^ bounded chlorine in the ns ^ hcpiori ^ rton polyvinyl chloride ens ^ eigt. Simultaneously; is ^ In ^ betr irböhun? the thermal stability and ^ er vice ^ - ^ i.-n ■ z>mx> evetav to be observed.

Example 3

To carry out this example, an apparatus and a polyvinylciloric ^{1 of} the type described in Example 1 were used.

n worked b-? i different weight VoImnen-Ratio ^b "" i tnissen of "polyvinyl chloride to whloroforifi, so that 'the possibilities times to the recovery of dry, powdery vtir". ⁱ n'i.r>-; en? us Pol7 ^rv '.er and chloroform resulted.

The reaction conditions are in the following i'ob ^ llo I ", 'i n""-? Represents:

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^ a at le I.

B C D

Si-TO

erjn-hi ^ tje -eit bi-s ¹ ^ ur

"C ^iVU 5T)

ΠM ⁷ I ¹³ '

¹ ] - T ⁵ Ierankste 2neratur, 2on 2oo 2öo 2oo O '1o 55 Pi?

- 1ο 5ο ? '. 4 4 4 4 2 = 3 2 * 25 2-

In d?. "Fo] /"? N (i3n Tr be 11 β- II are "lie tVennds ^ er ¹ of so obtained" fc9n ^ r! Ch ¹ r '^ iei'ten. J? Oliners ζ xsa "im3n ^ '- represents ;.

• fabeile. II

1)

Ohlcr

specific.a "viscosity specific ue ^ richt 2o ° /? o "Ο in ° 0

in

Yic? T- '3Ir ¹ '? Rin ^ f amperatur in thermal stability Dehydrochlorierunss-Konstejite at 1PoC, h '

technical thermal stability at 1 ° o ° ü ■ 'mustard color " * Amber inf color *

?? Z - ö-la «HÜ b'3r33iigste ^r üperatar 59/0 61, '/ jo 63, y / o 6 ?, 2 / ό

.o, 441 ο, 45ο ο, 46ο ο, 465 1.45- ι, 49ο ι, 51 ο 1.56ο RR 93 1ο1 95 1ο3 116 14ο

1.35ο. 1, ο3ο.ο, 68ο. ο, 37c.

-3

1ο

1ο

1ο

1ο

3ο M. 4ο

? ο Μ.

8ο "1οο" '11ο "14ο"

_ΒΛ0 OB »» »·

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The results compiled in the table man. that the increase in the amount of chloroform (or the amount of chloroalkane) under otherwise constant conditions a considerable increase in the rate of chlorination (and consequently the 'little chemically bound chlorine'; leads to so there are end products with significantly better characteristics the resilience and thermal stability arise.

Example 4

In this example one worked in a "i .Regletionsgefä''3 with a capacity of 2o 1 and performed various prejudices under different conditions in different proportions the ruling participants through to each other.

In a first experiment (-0) 100 g ^: 'Sicron ^ MP- Fw' in powder form with ^ ο ο cm CHCl ^ at 23 (; mixed in the course of 3 hours; after this time the powdery mixture was dry.

The chlorination was then carried out in the usual ./eise with the same ■ early exposure of the mercury high pressure ÜV- " Lamp outgoing radiation carried out. The chlorination lasted 4 stages at an intermediate temperature from 16 ° -J.

> 0 in the second attempt (?) Was carried out under the same conditions, with the only exception that the period of advice 6 hours.

The results of the experiments are in the following table ■ ip ^ compiles:

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Table III.

Attempt ■. 'B P

specific gravity 2o / 2o ° C, £ / r.nr 1.51o 1,

Chlorine, %

specific viscosity porosity:

Pore volumes, cm / 3 Pore diameter, micron Vicat penetration temperature, G. Glass transition temperature thermal stability:

Dehydrochlorination constant at

ο -1, -5 ^ ^ -3

I80 G, h o, 4bo.1o o, 2oo.1o

technical thermal stability:

"Mustard color" 5o min. °> o i / iin.

^ir amber color ". over 14o iiiin. over 14o min.

63.3 67.0 o, 467 o, 462 o, 16 0.15 o, 7o 0.70 118 14a 1o2 130

Example 5

Working as described in Example 1, using the 2 l flask, activating the Eeaicbion not photochemically, but with the help of a peroxide catalyst *

Various experiments were carried out under different conditions with different peroxide catalysts at different temperatures carried out.

In a first attempt (G) we put 300 g in the xolben;

4 λ ft α * s in 11 ί ft

"Sicron 54 ^ß FM" in powder rf oral as well as 12o err '> JnOl., In 7/0 leno: ti 3 g t-But2 ^r lperpivalat ^ iö' ⁵³ ^ were, iian rimrte the leg in r components 85 four minutes at 15 G; risen, this time 1ρρ · a completely dry powder before. The chlorinating agent rubs in the same "if it is as described above"; ef ^;; After a reaction time of 4 hours at 45 °, its characteristics are given in Table IV below

4 votes reaction time at 45 -J Iss ^e i ⁿ the product before,

On a second attempt (H) nan worked in the same way as with Vor sue. ¹ (G), but ended as K ^ it ^ V ^ sa- ^ tor 3 Z Di-isopropyl perox ^ delicarbonate, which is dissolved in chloroform

was resolved.

After 4 hours of reaction was at 36 C; a c ^ lor-ized before, whose characteristics are also in derl'obelle IV iMsa-n places are.

Table IV

Experiment G Ή

specific gravity 2o / 2o ^o C, s / cm 1.535 1.5bO

Chlorine, ^c , o 65, ^ 67.3

specific viscosity o, 46o o, 466

Porosity:

Pore volume, cm / ^ ο, 11 ο, 11

Pore Darclifflesser, Mikron Vicst-. 'Iindrinp ^ teraperatur, J Glasübergan.'TsteMperatur, ⁰ C

thermal stability: D3hydrochlori-

o -1
at 18oO, ho, 4 ^a o

0.6b o, 7o 1 ιη 14-3 111 131

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Try GH

technical thermal stability:

"Son color" 4o min. 5o

"Amber color" 14o " > 14o

Example. 5

• -lirt prob? before "Sieron 945", "in" Jischpol ^ mer from vinyl chloride and vinyl acetate, w2lch.es ^ -. 0 chemically £ ebunden2s / Vi ^ lscetst contains and norh der Saspensionpol ^ erisatio ^ smetiioas lierge - A'O-rdsn i? t , vrirde clalorized. This? S ^! 'iiiEClipoJ.ym.sr pointed

the following Sennds.ten aaf:

specific viscosity at 25 ° C

ο 3 ■

specific gravity 2o / 2o C, s / crr 1.598

Chlorine, % 55j2

ο% residue on a sieve with ~ 24o! Aachen / cm O

'"■. ■ O

¹¹ 1 \

11 Il fl t (It vi y- _ Il

"4o

It II Il ti ¹¹ 576 " It ti Il "~ 12oo ti Il ti It "16oo ti II It Il "■ ^ 33oo ti ti 11 It ti an

Il OC.

through 3in sieve with 64oo "52

Vicat- ^ indrinste ^ erstur, G 85

Glass transition temperature, Tr ₁ G 78 thermal stability: dehydrating chlorination constants at IBo ⁰ C ₁ h "' ¹ 1,460.1ο' technical thermal stability at 19o ° G:

"Mustard Color" 25

"Amber color" 5o

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- 2ο -

One worked in the 2o l vessel described in Example 1, in which 1ooo g of copolymer mixed with 4oo ml of chloroform and were chlorinated with dry gaseous chlorine at a temperature of 20 ° C in the course of 4 hours.

The reaction was carried out by irradiation with a 70% mercury high pressure UV lamp activated ■>.

The chlorinated product has the following properties:

specific viscosity at 25 C. o, 455

spe3ifinches weight 2o / 2o C, g / cm 1,5 ^ °

Chlorine, % 63, o

Particle size:
-Residue on a test sieve with "-'24ο meshes / cm" O

Il Il II 11 It Il It 11 U It Il It Il ti It II ti Il Il It

"O

"4

"16oo" 5

"f ^ 33oo" 48

"64oo" 22

% Passage through a sieve with 64oo "21

Vicat indentation temperature, ⁰ C 110

Glass transition temperature, Tg, C I00.

thermal stability: hydrochlorination

o -1 -

Constant at I80 C, h o, 45o.1o ^

technical stability at 19o ° C:

"Mustard Color" (minutes), 4o

'' Amber color ¹¹ (minutes) Ho

It can be seen from the above data that the inventive Chlorination of polyvinyl chloride achieves improvement in thermal stability and resistance even with appropriate chlorination of vinyl!

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174S033

Vinj ^ lacetate copolymers can be achieved.

Example 7

Using the procedure described in the preceding examples, a propylene-VinjT-lchloride copolymer, which contained about 4% chemically bound propylene, chlorinated, with -man starting from a mixture of 1200 g of the copolymer and 4-o.ml chloroform.

The reaction temperature read at 20 G, the reaction temperature was 4 · hours and activation was done with a GTV-Ijampe carried out the type described in Example 6. The following table lists the properties of both the non-chlorinated and also compiled of the chlorinated copolymers.

Table Ϊ

- non-chlorinated chlorinated

Mixed polymer i "iischpol ^ mer

■. "i

specific viscosity at 25 ⁰ C 0.345 0.327 specific weight 2o / 2o ° G,

Chlorine, 'it 55.3 63.8

Particle size:

% Huckst.a.ein ßiob m .- ^ 24O Mq./cm "C) C)

> V "" "" 576 "C) O

% "" "'" "16oo" 18 27

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_ OP _

non-chlorinated chlorinated

nil sc hp ο Iy me r Mi sch ·> o .1. y ifie

% Backward a. a sieve m. 33oo rla./cn ^ 9 i? o

ίό """""β4-οο" Ίο Μ ·

d.a sieve tn.64oo "4 Λ

, OO «^; 117

Glass transition temperature, Tg, G 7 ^ - ^ 06

thermal stability: dehydro-

o -Ί

chlorination constant at 1 ^P o C, h 1.4 ^ o ο, 5Ίο

technical stability at I90 J:

"Mustard far be" Ti'Iminutes) Ίο 3 ο

"Amber color" (wünuten) 4-o, 7 °

The improvement of the thermal stability όγΛ dar v / idsrs-tandshaftigkeit 3333η Hitse can also bsi a ·.! Vinyl chloride pro-P3 / 'len - yiis ^ npol3 ^r m3r3n can be achieved by the inventive chlorination.

Example R

The chlorination was carried out in a device as in the example

1 described; used as the A LsgangS'.iafcerial r ¹ 'chloride Vienna the same properties vie e'er. ^ ^τ οη rtei - ^ '^ ial 1.

was by t'etrach " ¹ orkionl Tstoff ^ r ^ etzt, the ratio if ^ weight amount - jrOlyvinyl ^ hl ^ rid to L'etraehloricarbonstoff was 2oo: 42, i> The Re ^ Kt gen are in the following Tabolllo VI ^ uraminn ^r e fp ⁴ t.

BAD ORiGlNAu 109832/1330

1745093

- a - '.. ■■■■ .;

T0.b9l.le VI

-WHERE. , 3

d ?! ¹ Η5 ^ν "3Ϊ-3ΐ1'Λϊΐ5 of the Palvergemisohs

Hoo 5 42, wiin. V'O Hours. 4th G OS ⁰

The; i "-enscheft3r] des chlorinated. PoD.yvir ^ ylcii.lofic'.s sin! from this fol ^ andeη i ^ belle VTI au can be found:

Table VII

Chlo-p'3 ^: ih.alt _y (\ e ^.% 63, ο

Vicat-Temperatar ..- 126 G.

Thermal condition

ο -1-5 n ^ s — characteristic at 180 G in hours o, 62o.1o

■ i'echnisclie therii. Stability at 19o G

^{: i} mustard color "- - '. .. 4o <-iiin.

"" Amber color "11 ο iJlxn.

Example 9

Example 8 was repeated, replacing the carbon tetrachloride through symmetrical dichloroethane. The reaction conditions are summarized in Table VIII:

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Table VIII

PVO, s 2oo

GlCH ₉ -OHpGl, crn ^ '42.5

Duration of the preparation of a powder mixture = - 90 min.

Chlorination time 4 hours

Giiloration temperature 25 ■ G

The properties of the post-chlorinated polyvinyl chloride can be seen from the following table IX:

Table IX

Chlorine content, wt% '65.5

Vicat temperature 1; So ^O C

Thermal resistance

ο -1 - constant of dehydrochlorination at 18o G in hours o, 58o.1o Technical thermal resistance

"Mustard" 45 min.

"Amber color" 115 min.

BATH ORIGINAL

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Claims (6)

1745 033 claims 1. Process for the chlorination of Viny lc hloridpoly kidneys and / or -mixpolymers ,. in powder form, characterized in that the powdery polymer with small amounts of a chloroalkane mixes in the absence of substantial amounts of water and that Mixture at a temperature below the glass transition temperature of the polymer lying 'temperature under irradiation or in the presence a catalyst treated with chlorine. 2. The method according to claim. 1-, characterized in that one the Ur leads, the reaction at a temperature between 0 and 55 C d'xrch- 3 = method according to claims 1 and 2, characterized in that since the chloroalkane consists of chloroform and amounts to: ■ -. Io to 55 parts by volume for every 100 parts by weight of the vinyl. Chloride polymers and / or polystyrene is used. 4 ·. Process according to claims 1 to 3, characterized in that the reaction is carried out in the presence of small amounts of a catalyst of the raditcalbildenden Peroxydtyp _e | 5 · The method according to claim A-, characterized in that it the peroxide compound is t-butyl perpivalate. 6. The method according to claim 4, characterized in that it the peroxide compound is di-isopropyl peroxydicarbonate acts. 7. Process according to Claims 1 to 6, characterized in that that the water content of the powdery mixture is below 0.2 percent by weight Weue documents (Art 7l 109832/1330 17450S3 8o shaped fibers, foils and others; -? Ever educate, thereby.?. eic im. ^ t, d ^ 3 them from Vinylctiloridjr ^ lmeren and / ^ er - · ?? Ir ^ h "^ ο l kidneys are made by the process i ^ v? ' ^A * d ° claims 1 to 7 have been created. For Montecatini "ildison lüailand / Ital Lawyer BAD ORiGiMAL 109332/1330