SK281498B6 - Process for the polymerisation and/or copolymerisation of vinylchloride - Google Patents

Abstract

A method of homopolymerization and / or copolymerization of vinyl chloride, in particular suspending with the inhibition of the formation of inhomogeneous so-called. fisheyes, is carried out at a temperature of 5 to 85 ° C using initiators, dispersants and / or emulsifiers and auxiliaries, wherein the inner walls and agitator are treated with water vapor or an aqueous solution containing at least one polymerization prior to feed of the raw materials into the autoclave reactor. an inhibitor or compounds having an antioxidant effect, wherein at least one water-soluble strong reducing compound and / or at least one water-soluble and / or oil-soluble antioxidant is added to the aqueous phase or even to the vinyl chloride or mixture of monomers, in an amount of 1.10exp (-5) to 1.exp10 (-2) wt. %, calculated on monomer or monomers. After the addition of the other raw materials and the tempering, the polymerization or copolymerization is carried out until a conversion of over 70% is achieved and the suspension and / or dispersion is processed in the usual manner.

Description

Technical field

The invention relates to a process for the homopolymerization and / or copolymerization of vinyl chloride, in particular suspension polymerization and copolymerization with suppression of the formation of macromolecular inhomogeneities, the so-called polymers. fish eyes, as well as a significant retardation of the increment of the reactor walls - autoclaves and their internal equipment, using specific, technically readily available compounds.

BACKGROUND OF THE INVENTION

Vinyl chloride (VC) homopolymers and copolymers, especially suspension types, intended especially for demanding applications, such as the production of transparent films, transparent plasticized and solid products, electrical conductor insulation, sound, light, magnetic and other record carriers, etc. provide quality products, if the PVC powders and copolymers are as homogeneous as possible, with a minimum content of macromolecular inhomogeneities, so-called " fish-eyes (Fischangen). These are particles in PVC powder and VC copolymers which are not capable of gelation under the processing conditions of the actual homopolymer or copolymer, as a rule, do not absorb the plasticizer. Therefore, they usually form discrete gel particles in the final product - "fisheye", which, as non-homogeneous aggregates in the final product, significantly impair its physical-mechanical, particularly strength, transparent and aesthetic properties. Therefore, it is the object of many studies and the invention to look for the effects of reaction, respectively. technological parameters for the formation of "fisheyes" and a way to prevent or suppress their formation.

Thus, the formation of "fisheye" in suspension polymerization according to U.S. Pat. No. 3,627,742 suppresses the use of alkanolamines and esters of polyhydric alcohols with higher unsaturated acids as excipients in suspension polymerization environments, as well as linear polyvinyl alkyl ethers (U.S. Pat. No. 2,886,552) or organic phosphorus compounds. 026 308). Several publications (Balakiskaja VZ, Starkman BP: Colloid Journ. 23, 653 (1969), Leuchs O,: Konstoffe 50 227 (1960), Skraga J. ex al .: Polimery 24, 229 (1979), Barclay LM, Bemdtsen N: Kunstoffe 66, 735 (1976), Defife J R: J. Vinyl, Technol 2 (2), 95 (1980), Horacek I., Pankova I .: Plastic Kautsch 20, 30 (1982) suggest some characteristics and trends in solving this problem, such as "fisheye" may be higher density polymer particles, and it is most commonly assumed that these particles contain cross-linked PVC macromolecules. However, they do not present proposals useful in VC polymerization and copolymerization. Similarly, the application of these and other patents, while reducing the formation of "fisheyes", is of little significance if the reactor - the autoclave of the PVC residues - is not thoroughly removed before each batch. Interesting, but less effective, is the process of using dialkyl ether admixtures in the polymerization or copolymerization environment of CS 245 419. However, we have made significant progress in the process of CS 223 066 by treating the walls of the polymerization apparatus with an inhibitor or antioxidant before adding the initiator. Reducing the formation of "fisheyes" or at least reproducibly suppressing them to levels below 5 pc / g PVC powder is not always achieved. Similarly interesting is the method of suppressing the incrustation of the walls of the autoclave by the ratios and copolymers of VC according to the Italian invention (Polaxxo F .: 83 459 A (24.12.1986)) with an aqueous-ethanolic solution of polyvinyl alcohol at least partially esterified with p-aminobenzoic acid.

Thus, the advantages of these last two processes in particular are followed up and their drawbacks are solved by the method according to the invention.

SUMMARY OF THE INVENTION

The present invention relates to a process for the homopolymerization and / or copolymerization of vinyl chloride, in particular in a suspension with the suppression of the formation of inhomogeneities, the so-called " of fisheye, carried out by homopolymerization and / or copolymerization of vinyl chloride with at least one olefinic unsaturated monomer, at a temperature of 5 to 85 ° C, with the initiating effect of at least one free-radical oil-soluble and / or water-soluble initiator in the presence of protective colloids and / or emulsifier and / or excipients and by acting on the reaction space of the homopolymerization and / or copolymerization, such as the internal walls of the reactor - autoclave and equipment coming into contact with the reaction medium before addition of the starting materials and / or initiator or initiator mixture, by at least one polymerization inhibitor and / or combined with an antioxidant effect , and / or a higher molecular weight to markomolecular compound having a reducing effect by adding to the aqueous phase at least one water-soluble strong reducing compound at a temperature of 0 to 85 ° C and / or at least one water-soluble, and / or the oil-soluble antioxidant in the aqueous phase and / or at least in part to the monomer, of a total of 1.10 "to 1.10 ^{5 '2} wt. %, calculated on the monomer or monomer mixture, whereby after addition of other raw materials including monomer or monomers and initiator or initiator mixture, the contents of the reactor-autoclave are allowed to reach the desired polymerization and / or copolymerization temperature of vinyl chloride while stirring and after conversion % of the monomer or monomers above 70%, the homopolymerization and / or copolymerization of vinyl chloride is stopped and the dispersion and / or suspension is worked up in the usual manner.

An advantage of the method of the present invention is to suppress the formation of "fisheyes" inhomogeneities in PVC powder or VC copolymer, or at least to minimize their formation. Further reducing the formation of incrusts on the walls and stirrers of the autoclaves, prolonging the periods of cleaning the autoclaves and thereby increasing their production. Preventing or at least significantly suppressing the formation of impurities in the PVC powder at potentially lower monomer quality. Last but not least, improving the quality of the PVC types and VC copolymers produced, and thus their application possibilities.

In particular, the auxiliaries of the process according to the invention include secondary dispersants, pH regulators, molecular weight regulators and the like.

The highly reducing water-soluble compound or compounds for carrying out the process of the invention are selected from sulfur dioxide, sulfuric acid, alkali metal sulfite, alkaline earth sulfite, alkali metal sulfite, alkaline earth metal sulfite, ammonium sulfite, alkali metal pyrosulfite, alkaline earth sulfite, , hydrogen sulphide, alkali metal sulfides, alkali metal hydrosulfides, alkaline earth hydrosulfides, ammonium polysulfide, alkali metal polysulfides, ammonium polysulfide, sulfoxylic acid and its salts, hydrazine hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride and its salts, hydraxylamide hydrochloride its salts, phenol, cresol and xylenols.

At least one oil-soluble oxidant is selected from tert-butylphenol, 2,4- and 2,6-di-tert-butylphenol,

SK 281498-6

2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,2-methylene-bis (4-methylbutylphenol), tert-butylhydroxytoluene, di-tert-butylhydroxytoluene, sec. butylhydroxyteluenes and tocopherol. The oil-soluble antioxidant or multiple antioxidants are at least partially added to or added to the aqueous phase and / or to the monomer or monomer mixture prior to the addition of the initiator or initiators.

According to the method of the invention, at least a portion of the polymerization inhibitor / or antioxidant, respectively. mixtures of antioxidants used to treat the reaction space, in particular the walls and other surface of the reactor - autoclave, to substantially slow their clogging with the inclusions of the polyvinyl chloride and / or vinyl chloride copolymer may be left in the autoclave reactor. A compound or mixture of compounds with a strong reducing effect can also serve as an antioxidant.

Further, when the hydrates or salts of the strongly reducing compounds are applied, their application rate is calculated on the basis of the pure reducing chemical substance. In carrying out the process according to the invention, the water-soluble strong reducing compounds and polymerization inhibitors or compounds with antioxidant effect, applicable to the treatment of the reducing space, in particular the walls and the other inner surface of the autoclave reactor, are also interchangeable.

A total amount of strongly reducing antioxidant compounds and a polymerization inhibitor to reach the environment of the polymerization and / or copolymerization VC, can range from 1.10 ^-5 to 1.10 ^'2 wt. % based on VC or monomer mixture, most preferably in the range of 1.10 ^-4 to 1.10 ^-3 wt. %. Lower amounts are no longer effective and higher usually require higher concentrations of initiator (s) to avoid a marked decrease in polymerization or copolymerization rate. In order to reduce the need for reducing agents and polymerization inhibitors, care should be taken to remove air, i.e. oxygen, from the raw materials and reaction medium, as well as to prevent the accumulation of incrustations on the inner walls of the polymerization autoclaves.

Other non-limiting data as well as other advantages are apparent from the examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

50 dm ^{3 of} demineralized water, 325 g of a mixture of cellulose ethers as protective colloids are charged into a non-pressurized tank equipped with a stirrer, heated to 80 ° C and stirred for 1 hour. 1700 cm @ ^{3 of} an aqueous solution of 11 wt. % of partially saponified polyvinyl acetate with an acetate group content of 30 ± 2 mol. % (PVAL-X, product of NCHZ, as, Novaky) and 15 g of sodium pyrosulphite Na ₂ S ₂ 0s or potassium pyrosulphite K ₂ S ₂ O ₅ . It is then diluted to 100 dm ³ by adding demineralized water and pumped into the water phase reservoir where 1033.4 dm ^{3 of} demineralized water is impregnated. Thus, 1134 dm ^{3 of the} aqueous phase is prepared for 9 autoclaves of 250 dm ^{3 each} .

From the aqueous phase, 125 dm ³ are pumped into each autoclave with a volume of 250 dm ^{3 by} pre-spraying the walls of the autoclave with an aqueous-ethanol solution containing 6 wt. % of polyarylphenols bound to polyvinyl alcohol, respectively. and polyvinyl alcohol partially esterified with aminobenzoic acids (e.g. NOXOL WSW). Spraying the walls of the autoclave with said water resp. water-ethanol solution of 20 g per autoclave is conducted with steam. Next, 2 g of dissolved antioxidant oil (2,6-di-tert-butyl-4-methylphenol or butylhydroxytoluene), 100 g of partially saponified fat as a secondary protective colloid, 20 cm ^{3 of} oleyl alcohol and then 130 cm ³ are added to each autoclave. xylene solution of initiator mixture (EHP-80, product NCHZ, as, Novaky) of the following composition (in wt.%): 50% xylene, 35% bis- (2-ethylhexyl) peroxydicarbonate, 14% benzoylperoxy-2-ethylhexyl carbonate and 1 % dibenzoyl peroxide. The autoclaves are then closed, the air is removed and 87.0 kg of vinyl chloride are pumped into each. The contents of the autoclave are then heated to 56 [deg.] C. with stirring and the polymerization proceeds to a pressure drop of 0.3 MPa. The hot content of each autoclave of this first series of experiments is "degassed", then drained into a vat where it is pumped for demonomerization by steam stripping or, in addition, a polymerization "stopper" is added to the suspension in water before stripping. It is further centrifuged and finally dried under reduced pressure at a temperature of about 50 ° C.

The most important qualitative parameters of this obtained suspension PVC (S-PVC) are summarized in Table no. First

The results of further experiments carried out under otherwise similar conditions but without the use of Na ₂ S ₂ O ₅ additives as reducing agent in the aqueous phase of each autoclave are also shown in Table 2. First

In the third series of experiments, which was carried out similarly to the first series, only 1 g of hydrazine was added to the aqueous phase of the autoclave in the form of a 17 wt. %.

Finally, in a fourth series, similar to Series 3, only the PVC slurry is added to 1.5 g of ammonium nitrite and 0.5 g of the xylene mixture, also as polymerization "traces", calculated on the amount of product from the PVC prior to demonomerization by stripping. one autoclave.

Results in table no. 1 represent the average powder values from at least two autoclaves.

Table no. 1

K-M- Mta g-PVC <! »*> AbMipdi tone O * pl VC Md VC t rvc WU HU rjtófe OK M M jAatóldto l) 4 «to > rite MO ivyfak ta dfe • 3 » 1.7 SM 99.4 12 -M i M 1.7 62.1 574 993 β, α 13 M 4/5 1.7 67.7 582 99.4 14 9.4 4 ' - 0.0 553 993 9.69 13 «4 M - - 67.6 566 99.2 9.78 * 1 04 9 / LI

- 674 566 »3 <1 · 14 04 9/11 - - I73 They are »4 13 M 1M2 IMiO. 1.7 04 569 994 6.41 13 04 2Λ Iwo, IN 93 514 »4 04 » 12 M 2/3 1.7 M 674 574 »4 IN· 12 M 2/3 ΉΠΏ w M w · 5 * 9 »3 043 12 04 20 NHJKh xrieaok v • A w ‘03 * 579 994 044 12 0.7 1/2 1.7 * 14 «3 582 w 045 12 w 1/2

(a) used as a 'tracer' for polymerisation

Example 2

The procedure is similar to that of Example 1, but the composition of the autoclave feeds and the polymerization temperatures are different, since the aim is also to prepare suspension types of PVC with different

K-value. Thus, batches of slurry polymerization autoclaves carried out at 52 ° C to produce S-PVC with a K-value of 70 ± 1 are weighed up to 117 g of partially saponified fat at a melting point of 38 in addition to the aqueous phase as in Example 1. Butylhydroxytoluene as antioxidant 4 g, 68 cm ^{3 of} oleyl alcohol. Alternatively, up to 1.8 g of Na ₂ S ₂ O ₅ and, more particularly, to the aqueous phase of each autoclave of 0.9 g of Na ₂ S ₂ O ₅ or in addition of 1 g of hydrazine in the form of a 17 wt.% Aqueous hydrazine hydrate solution. %. However, for the reference production, reducing agents were not added to either the pre-prepared aqueous phase, or even to each autoclave.

For the production of S-PVC with K-value 68 ± 1 a polymerization temperature of 56 ° C and for the production of S-VPC with K-value 65 ± 1 a polymerization temperature of 58 ° C, and in addition to any of the autoclave as an adjuvant was added 117 cm ³ trichlorethylene as regulator mol. and for a K-value of 62 ± 1 at a polymerization temperature of 59 ° C to 370 cm ^{3 of} trichlorethylene. The additives of other excipients vary insignificantly.

The type and amount of reducing agents, the polymerization temperature as well as the achieved K-values of the S-PVC powders, the "fisheyes" as well as the vinyl chloride in the S-PVC powder are given in Table 2. Second

Table no. 2

TcHvta mrjBMBCj) 4puriUd <(* 1 * <3) PifcaianJAtycfa K-Mwta frMdPVC VCtPVC (N ') PeCrt ** ** w M Mbtn «-« d * » 52 703 0.7 20/12 52 IHAOj U + V 70.4 03 5 R 52 1,8 + 0,9 p 703 03 2Λ 56 - . «1 03 22 / M 56 BhNNHb 13 + 03 67J 03 4/6 36 ÍMjOi HjNNHj 1,8-QJ 0.9 «.I 03 M 58 - 65.4 0.6 LIM 58 NfcSA 13 + 03 «53 0.7 5/6 58 WibSjO, HzNNH: 13 + 03 65.3 0.6 2/2 59 - Í2J 0.6 15/16 59 HfcS.0. 13 + 03 62.0 03 4/6 39 NfcSjOj HaNNH » 13 + 03 W «u 03 2/1

Example 3

In a 250 dm ³ polymerization autoclave equipped with a 300 rpm duplicator and propeller stirrer. after rinsing the walls with a hot (75 ± 5 ° C) aqueous solution of ascorbic acid at a concentration of 0.2 wt. % in an amount of 2.5 dm ³ , weigh 110 kg of an aqueous phase containing 51 g of methylhydroxypropylcellulose (Metocel 50 F) and 27 g of hydroxyethylcellulose (Klucel J). Furthermore, 80 g of partially saponified fat EC (average molecular weight = 493 g / mol, acid number = 4.3 mg KOH / g, saponification number = 1757.3 mg KOH / g, iodine number = 35.3 g 1 / 100 g, wt% OH = 61, H ₂ O = 0.24 wt%), 10 g oleyl alcohol, 1.5 g 2,6-di-tert-butyl-4-methylphenol and optionally at least one at least partially water-soluble reducing agent compound. After mixing, 120 g of a 50% by weight xylene solution of di-2-ethylhexylperoxydicarbonate are added. % and after removal of air 82 kg of vinyl chloride. Thereafter, with stirring, the contents of the autoclave are heated to 52 ° C and at this temperature the suspension homopolymerization of vinyl chloride is carried out for 8 hours when the pressure drops by 0.3 MPa. The unpolymerized vinyl chloride is then discharged from the autoclave. The polymer slurry is then separated and dried at 60 ° C while washing with demineralized water. The yield of suspension polyvinyl chloride (S-PVC) was 89%. Its K-value is 69.9, bulk density 540 g / dm ³ , plasticizer absorption 7 min. The sieve residue determined on a 0.250 mm sieve is 0.4% and the sieve residue is 0.063 mm is 94%. The volatiles comprise 0.1 wt. %. The "fisheye" determined by the method according to STN 64 3200 is 24 kg / g.

However, under otherwise similar conditions, but without pre-rinsing the walls of the autoclave with hot aqueous ascorbic acid, the quality parameters of the PVC powder are similar, but the "fisheye" content is around 40 pieces / g.

In table no. 3 shows the results of the effect of other reducing compounds in addition to the above-mentioned rinsing of the walls of the autoclave with hot aqueous solution of ascorbic acid and 1.5 g of 2,6-di-tert-butyl-4-methylphenol as an antioxidant, on PVC powder yield and in particular called. fisheye in it.

Example 4

The procedure is similar to that in Example 3, but instead of the diluted aqueous ascorbic acid solution, a hot (75 ± 5 ° C) aqueous solution of the partially esterified polyvinyl alcohol with 4-aminobenzoic acid in an inert atmosphere is used to rinse the autoclave. salts and conjugated coupling with p-aminophenol. Aqueous solution applied for each rinse, at a concentration of 0.9 wt. % is 1,5 dm ³ . However, it is retained as part of the aqueous phase. The results obtained are included in Table 2. 4th

Table no. 3

howl S-PVC (H) Č »ränraMde W FvMrjHth MTjrtfct PVC DN * 2J * dfcrttatyM rtyifcaoi NtÄOs 1 2 122 2:44 > 9 4 M) 2.1 x x butyttiod 1 122 88 á 4 ' NaCRHd 2 144 90 X6-dUcrcbutyU- N1H3O> SQ> 1 2 05 122 2:44 041 88 « 4/5 -tayiftmi (MU) » 1 1 1 122 122 122 99 6 4/3 4-Methylfinol cyanotrifluoride 1 1 1 122 122 122 88 6 M down H »3 Nim R.NNR.TL0 05 OJ 041 OJI 041 88 6 2XJ 24, these very KAO, 05 OJI OJI OJI OJI 87 6 2Λ 2J-xyleeol 05 0J1 OJI 0J1 90 6 3A njwwii ^ iy) wJrf wf kytefay atatWvei 05 05 122 0,61 OJI 89 6 3Λ 22 * αβΜ6Μ) β4 ety ethyphthatifa (fa) HÄNBÄO 05 05 0J1 0522 90 6 M kyudutbwi Na & 1 05 OJ 122 OJI 041 90 4 M tenAfltylijrdraxy> tetofa EôNNHiJbO KÄO, 2 2 2 2.44 2:44 2:44 78 8 1Δ knwttMoi attaytaiaMty HjNNHj-HJO OJ 1 OJ 1 0J1 123 «41 122 88 6 1Λ

SK 281498-6

Table no. 4

VýflM PVC (») HyKMtaAd · w P »M tjMch PVC frrftí Dré avfeolcktorit taMfanl qbm creols I 1 122 90 « M 2,4,6-triJtra. taeknaotov Η, ΧΗΗ, ΒΟ 1 1 I 1 # I # 122 M 4 and awiaao 1 122 122 M 6 2Λ bWlfiMl 2 2.44 W 6 9/10 BaHNHiHO 2 2:44 6 12 HiinäfcÄo 1 1 122 122 89 6 2/3 i «« »and 1 5 122 «, 10 10 Ί wl

Example 5

The suspension copolymerization of vinyl chloride with vinyl acetate is carried out in a stainless steel autoclave with a volume of 15 ^dm3 equipped with a turbine agitator with a number of obrátok.min 105 ^L, also a discharge valve, and other conventional equipment. 8500 g of an aqueous phase containing 8.34 g of methylhydroxypropylcellulose (Methocel 50 G), 0.68 g of hydroxypropylcellulose (Klucel J) and 0.03 g of partially saponified polyvinyl acetate as a 16 wt. %. Furthermore, 6.5 g of dilauroyl peroxide and 0.6 g of bis- (4-tert-butylcyclohexyl) -peroxydicarbonate, 49.3 g of trichlorethylene and 546 g of vinyl acetate. After closing the autoclave and substantially removing the air, 2715 g of vinyl chloride are added. Then, with stirring, the contents of the autoclave are heated to a copolymerization temperature of 64 ° C and maintained at this temperature by automatic cooling jacket temperature control for an additional 8 hours. During this time, the pressure in the autoclave drops by 0.3 MPa. Thereafter, the contents of the autoclave are cooled to a temperature of about 30 ° C and the uncondensed vinyl chloride is drained. The entire contents of the autoclave are then discharged into a demonomerization column where residual vinyl chloride and vinyl acetate are removed by tracing water vapor. Next, the suspension is centrifuged, washed with demineralized water and dried in a leaf drier. The yield of vinyl chloride / vinyl acetate copolymer reached 86% of the theoretical yield. The bulk density of the copolymer powder is 701 g.dm &^lt; -1 &^gt;, the viscosity value is 49 cm &^lt; ^{3 &gt;} g &^lt; -1 & gt ^; . The "fisheye" of the copolymer powder determined by the method according to STN 64 3200, only the plasticization temperature reduced to 73 ° C, reaches 60/65 pcs / g.

However, in copolymerization under otherwise similar conditions, only in addition by rinsing the walls with a warm aqueous solution of ascorbic acid in an amount of 0.6 kg with a concentration of 0.6 wt. % and leaving this solution as part of the aqueous phase, the copolymer yield is similar, except that the amount of non-homogeneous ("fisheye") is 15/20 pcs / g. In addition, the walls of the autoclave remain virtually free of copolymer inclusions.

In a third batch carried out under similar conditions, also rinsing with an aqueous solution of ascorbic acid, but additionally with the addition of 0.2 g of hydrazine in the form of an aqueous solution of hydrazine hydrate at a concentration of 17% by weight. % and 0.1 Na ₂ S ₂ O ₅ into the aqueous phase as well as 0.1 g of di-tert-butyl-4-methylphenol, with a similar copolymer yield, the content of "fisheyes" is 4/6.

Example 6

The procedure is analogous to Example 3 except that after each batch the walls of the autoclave are treated with water vapor containing an aqueous-ethanolic solution of polyvinyl alcohol partially esterified with aminobenzoic acid with a dry matter content of 6 wt. %, in an amount of 20 g / autoclave as anti-encrusting agent. This aqueous, respectively. the aqueous-ethanol solution is kept in the autoclave as a component of the aqueous phase. In addition, the ingredients as in Example 3 were added to the aqueous phase with 1 g of 2,6-di-tert-butyl-4-methylphenol, 1 g of Na ₂ S ₂ O ₅ and 1 g of H ₂ NNH ₂ .H ₂ O as inhibitor formation of inhomogeneities - "fish eyes". The resulting suspension PVC for 15 batches contains 2 to 3 pieces of "fisheye" in 1 g of powder and from 15 to 25 batches it is 3 to 4 pieces / g and after 25 batch it is necessary to remove the deposit of PVC increments from the walls and mixer autoclave.

If the autoclave rinse is to be carried out with a warm solution of ascorbic acid only after 22 batches, up to 36 batches can be achieved without the need for autoclave cleaning, the "fisheye" powder content not exceeding 4 kg / g.

Industrial usability

The process is useful in the chemical industry in the production of homopolymers and copolymers of vinyl chloride, especially suspension types, practically avoiding or minimizing the formation of "fisheyes".

Claims (6)

PATENT CLAIMS A process for homopolymerization and / or copolymerization of vinylchlodir, in particular in a suspension with the inhibition of the formation of inhomogeneities, the so-called polymers. of fisheye, by homopolymerization and / or copolymerization of vinyl chloride with at least one olefinically unsaturated monomer, at a temperature of 5 to 85 ° C, with the initiating effect of at least one free-radical oil soluble and / or water-soluble initiator and the presence of protective colloids, and / or emulsifier and / adjuvants and by acting on the reaction space of hompolymerization and / or copolymerization, such as the internal wall of the autoclave reactor and equipment coming into contact with the reaction medium prior to addition of the starting materials and / or initiator or initiator mixture, at least one polymerization inhibitor and / or antioxidant compound and / or a higher molecular weight to macromolecular compound with a reducing effect, characterized in that at least one water-soluble strong reducing compound is added to the aqueous phase at a temperature of 0 to 85 ° C and / or at least one water. orozpustný and / or oil-soluble antioxidant in the aqueous phase, and / or at least in part to the monomer in a total of 1.10 "to 1.10 ^{5 '2} wt. %, calculated on the monomer or monomer mixture, wherein after addition of the other raw materials including monomer or monomers and the initiator mixture, the contents of the autoclave reactor are allowed to stir to the desired vinyl chloride polymerization and / or copolymerization temperature while stirring and maintained after conversion of monomer or monomers above 70%, the homopolymerization and / or copolymerization of vinyl chloride is stopped and the dispersion and / or suspension is worked up in the usual manner. The suspension homopolymerization and / or copolymerization process according to claim 1, characterized in that at least one strongly reducing water-soluble The compound is selected from sulfur dioxide, sulfuric acid, alkali metal sulfite, alkaline earth sulfite, ammonium sulfite, alkali metal sulfite, alkaline earth metal sulfite, ammonium sulfite, alkali metal pyrosulfite, alkali metal sulfite, sulfonate, metals, alkali metal hydrosulfide, sulfoxylic acid and its salts, hydrazine, hydrazine hydrate, hydrazine hydrochloride hydrazine sulfate, hydroxylamine and its salts, nitrous acid salt, ascorbic acid and salts, phenol, cresols, xynols. A process for the suspension homopolymerization and / or copolymerization of vinyl chloride according to claims 1 and 2, characterized in that the at least one oil-soluble antioxidant is selected from tert-butylphenol, 2,4- and 2,6-di-tert-butylphenol. 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,2-methylene-bis- (4-methylbutylphenol), tert-butylhydroxyltoluene, di-tert-butylhydroxytoluene , tocopherol, at least partially being added to or added to the aqueous phase and / or monomer prior to the addition of the initiator (s). A process for the suspension homopolymerization and / or copolymerization of vinyl chloride according to claims 1 to 3, characterized in that in the aqueous phase of the suspension homopolymerization and / or copolymerization at least a part of the inhibitor and / or antioxidant compound used in the autoclave reactor is left. treating the reaction space, especially the walls and the other surface of the reactor - the autoclave, to substantially retard their fouling by the polyvinyl chloride and / or vinyl chloride copolymer inclusions. A process for the suspension homopolymerization and / or copolymerization of vinyl chloride according to claims 1 to 4, characterized in that, when applying hydrates and / or salts of water-soluble strong reducing compounds, their applicable amount is calculated on the pure reducing chemical substance. A process for the suspension homopolymerization and / or copolymerization of vinyl chloride according to claims 1 to 5, characterized in that the water-soluble strong reducing compounds and polymerization inhibitors and / or compounds with anti-encrusting effect, applicable to the treatment space, especially the walls and other inner surface of the reactor - autoclave, are interchangeable.