DE1570819A1 - Round-grained agglomerates containing a homopolymer of vinyl chloride or a copolymer of the same - Google Patents

Description

PATE NTAN WALTE
DR.-IN α. H, FINCKE D IPL. -ING, H. BOHR DIPL.-ING. S. STAEGER

Telephone, 22 49 41

8 MUNICH 5, Müllerstrasse 31

M 20 403

Oasis Z / P. 18 410

Description ■ K \ m Patron search

dor Firiaa IMPERIAL CHEMICAL INDUSTRIES OF AUSTRALIA AKD NEW ZEALAND, Melbourne C2, Victoria, Australia

concerning

"Rim & granular. Agglomerates containing one Homopolymer of vinyl chloride or an oopolymer

same "

Priorities: November 2, 196Ä - Australia

Di «? Invention relates to and relates to better polymeric compositions in particular stabilized compositions containing polymers by VisylSialogenldoonomerea. .

It is known that the polymerization products of halogen "switch" Vinyl monomers tend to crush when exposed to heat and / or exposure to light, which in some cases results in a Deterioration of the color »and the properties of the polymers leads. To counteract this effect, it is a well-known one

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Admitting practice certain Gtabilisatoren to the polymeric resin before ea oinea llioch-, kneading, or Strangproß- Formprcßarboitaeang, one of v.olchon all. Krhitsen of the resin require respectively öaiai iüJAroa, is subjected. However, it is difficult to obtain an equal dispersion of the stabilizer in the polymer.

In the German patent application I 27 030 XVd / 59c of Imperial Chemical Industries Tiimited int a process for the manufacture of a mass with oiuen uniformly dioperative stabilizer, wherein vinyl chloride old 0 to 20 wt. ^L / a oinea ethylenically unsaturated monomer in an aqueous medium in Polymerized in the presence of a polymerization catalyst and the polymer is separated off from the aqueous medium, which process is characterized in that a lead acid is suggested in the polymerization mixture before or during the separation stage.

The obisso procedure provides a hatred with better qualities and also simplifies the Goaamt process of making manufacture polyvinylchlopid measures by incorporating dea ' stabilizing lead salt and / or other optional. additions in the polyhydration perforation before or during the Trejma stage Necessity for a separate or special stage of the Verroxschen3 the dried polyaerization producta with the above stabilizing lead sais and / or other fa & altative zueifti ^ n eliminated »It's d $ like with the herkösnailioaeii. Dispersion polymarisatlojasveirverfahren still necessary to filter and dry the polymerization product. Since the latter is an extremely? is finely divided powder, it is difficult to filter it

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The amount of water adsorbed is considerable, and an expensive device, especially apparatus, is required in the drying stage in order to handle the pulverulent polyvinyl chloride without significant losses to the gas flow of the drying device and to prevent the health hazard or dust nuisance to the operating personnel and the environment of the company.

Another with finely divided and ready-made respectively ready-made polyvinyl chloride, the so-called "dry blends" of the prior art The problem is generally based on the fact that this Masses are more dusty than ground and kneaded polyvinyl chloride masses, the so-called post-mixed or compounded polyvinyl chloride materials, and that at "Dry mixes" are therefore more prone to mutual contamination (cross-contamination) between batches or batches and dyes and handling losses as well as a larger one There is a health risk. Another disadvantage of the "dry mixes" in comparison to post-mixed or compounded polyvinyl chloride is that "dry mixes" entrain larger amounts of gas and / or moisture in extrusions and for the production of more porous extrusions tend. To overcome these disadvantages, it has been proposed that the additional stage of tabletting the "dry slurry" to introduce.

It has now been found that the incorporation "in situ" of auxiliary additives, such as stabilizer salts and carbon black, antioxidants * ·

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1S70819

means or other optional additives in the polymerization vessel, dispensing with a requirement peculiar to the prior art of polyvinyl chloride dispersion polymerization, namely the requirement that the polymerization product is finely divided and that the polymerization process can be controlled in such a way that large ball-like ( quasi-spherical) some granular or rounded (globular) Polyvinylchloridagglomerate with fixed or prescribed characteristics likely Eb Wurd © found that by generating round grain agglomerate the filtering and drying the polymerisierton polyvinyl chlorides ^ ttiiä can be simplified by polyvinyl chloride compositions and proportionate · * excessively large agglomerates can be produced from ready-made or pre-prepared polyvinyl chloride without a separate, bi-directionally special tableting step *

Therefore, according to the invention, a method for producing Polymer compositions, 100 to 80 parts by weight of vinyl chloride gtts & ffiiatn with a total of 0 to 20 parts by weight of at least 1 äthyieaisöh unge « saturated monomer in an aqueous medium in the presence of oil poly merization catalyst are polymerized, which thereby ga ~ indicates that the polymerization product is a sphere-like one round-grained or rounded agglomerate with ®iß & m average Diameter from 0.51 to 12.7 ram (between i / ^ 0 and

lh · »

|| inch), a packing density of 0.4 to 0.8 g / cnr and total amount of volatile substances of less than 0.20 g pae © dry product, the procedure being determined volatile substances as indicated in examples 1 and 3,

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seen.

It should be pointed out that the method according to the invention a special form of suspension polymerization, which thereby is characterized by the fact that the round-grain agglomerates formed are larger than those in conventional suspension polymerization received.

For the sake of simplicity, those specified above will be spherical-like round-grained polyvinyl chloride agglomerates hereinafter referred to as round, grainy Called agglomerates

One advantage of these round-grain agglomerates is the larger one Ease of filtering, drying and handling in the dry condition.

It was also found that an effective respectively z \? angular process by which the desired round-grained Agglomerates can be obtained which comprises adding asbestos fiber to the polymer mixture.

Accordingly, the present invention is a method of polymerizing ■ from 100 to 80 parts by weight of vinyl chloride together with a total 0 to 20 parts by weight of at least 1 ethylenically unsaturated monoxide in an aqueous medium in the presence of a polymerization catalyst, which is characterized in that fiber asbestos is present during the polymerization, is provided.

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The term asbestos is defined in book Asbestos Fandamentale ⁴¹ by H. Berger, Chen. Publishing Company, Now York, 1963, page 1, paragraph 1 and page 2, table 1 and page 55, table 2.

All forms of Asbosb, e.g. Ohrysotil, Crocidollt, Montasite, amosite, antbophyllite,! Ere & olit or actinpiite, different geographical origins are suitable, the amphibole relationßv.Oiso Homblendon types of asbestos, however, require a certain precaution, -.vio C3 is given below. Other side is the seropontin type of asbestos that is called chrysotile, although it is is pre-improved by pretreatment, even without it being effective. Accordingly iab Chry3otil the preferred fora of asbestos.

For the purposes of the invention, the asbestos is preferably subjected to a pretreatment process. Without being bound by theoretical explanations, it is assumed that the effectiveness of the pretreatment is due to the reduction of the fiber size and the fiberization or comminution into smaller particles *. Sin first preferred pretreatment method comprises treating the asbestos with an acid, a strong mineral acid, in particular hydrochloric acid, at temperatures of from 1O ⁰ C preferably up

Boiling point of the acid · Bin second pretreatment process comprises stirring or moving the asbestos in a liquid, generally water, preferably with heating under reflux, in the presence of a surfactant in a concentration range of 0.01 to 5 wt -.% In weight concentration expressed . Useful surface-active agents can either be cation-active, for example Oetgrltrimöthylammoniumbrojaid, or

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anionically active, for example sodium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate, or non-ionic, for example the condensation products of alkylene oxides with long chain alkyl phenols. Another, so a third Pretreatment method, which, however, is only effective with chrysotile, involves simmering in water for periods of from 1 to 4 times 6 hours. A particularly preferred pretreatment process is the combination of the first and second of the above-mentioned processes.

The manner in which the pretreatment process according to the invention is carried out is not very critical; for example, higher or lower concentrations of the agent and higher or lower temperatures are used; Usable conditions for any type of asbestos are found in a few simple experiments routinely easily determined.

Usable asbestos concentrations are 1 to 11%; in the case of untreated chrysotile, the preferred range is 4 to 8% and for pretreated asbestos the preferred range is 1 to 4%, where all percentages are based on the sum of the weights of the vinyl chloride used and the ethylenically unsaturated comonomer used or refer to the ethylenically unsaturated comonomers used; however, the concentration is not strict critical. The addition of other inert solids, such as pigments, somewhat diminishes those for the formation of satisfactory ones Round grains or globules (globules) required amount of asbestos; the degree to which such fixed Substances can replace part of the asbestos »depends on their type

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and focus off; it is easily determined empirically.

Without being limited by theoretical explanations, it is assumed that the fibrous nature of the asbestos has a major influence. ' the desired agglomeration of the polyvinyl chloride particles to rim grains or globulites.

As already mentioned, the lower limit is that in the invention Method of using asbestos not strictly critical; if significantly too little asbestos is used, the extreme cases form solid polymer blocks; with less lack of Asbestos occurs some undesirable build-up of polymer; the degree to which such accumulation both from Can be admitted from the point of view of material effectiveness as well as from the point of view of the expediency of the operation the lower limit of the amount of asbestos required.

Eg it has now been found that the lower limit of asbestos required in a given system can be reduced ... if a protective colloid is added to the reaction mixture. Useful concentrations of protective colloids are from 0.005 to 2% by weight of the total polymerizable monomer used. Usable protective colloids are known from the prior art; a list of such colloids is given, for example, in the book Polymer Process by Calvin E. Schildknecht ¹ (High Polymer Series Vol. X of the Interscience Publishers Inc., New York, edition 1956), pages 78 to 81 inclusive.

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* ο 157081a

jparüberhinaua was also found to have a similar reduction the lower (! renoe dor Asbsntmonge may have been received j ' if an obox 'surface acuivea agent is added to the reaction mixture will. Usable) obox surfacealctive agents are cationic active agents,

otyltrinethylammoraiimbromide, anionic active agents, dodecylbonzolsulfonaauroa sodium beniehungowoino

Hatrituadodccylbon ^ olsulfonat, odor nioht ~ ionogone means, for example the condensation products of alkylenodene with an alkyl phenol. Usable concentrations are xi 0.005 to 2 wt .- # der all polyacrylic monomers used.

The invention relates to the "in situ" incorporation of Well applicable in polyvinyl chloride beaondors.

Accordingly, according to one embodiment according to the invention, too the conception of ready-made or ready-made products nmtikoViiigGii Polyvinyl chloride agglomerates which polymerize from TOO to 80 wt .- ^ share vinyl chloride with a total of 0 to 20 parts by weight of at least 1 ethylenically unsaturated Monomer in an aqueous medium in the presence of fiber asbestos and non-inhibiting or non-inhibiting additives includes, provided.

among non-inhibitory or non-inhibitory effects The additions »which? when adding in a particular Polymerization stage the desired degree of polymerization of vinyl chloride and / or the comonomer respectively do not hinder or impair the oomonomers *:

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Understood. It is known from the prior art which of the conventional polyvinyl chloride additives inhibit or inhibit or disrupt the course of polymerization. So are certain organic ones Additives such as the organic phosphites, thiols or mercaptans, α-phenylindole, certain organotin compounds, for example Tin (2- [ethyl / capronate) or tin octoate, Benzoquinone, chloranil, m-dinitrobenzene, p-dinitrobenzene, pyrocatechol, tert-butylpyrocatechol, nitrodimethylaniline, hydroxydimethylaniline and thionyl chloride, known polymerization inhibitors when added at low conversions and therefore undesirable. from of these, benzoquinone and chloranil are special inhibitors of the polymerization of vinyl chloride.

A group of non-inhibiting or non-inhibiting additives are those used as hydrochloric acid acceptors (hydrogen chloride (acid) acceptors] acting salts, such as organic lead salts, inorganic lead salts and basic lead salts, cadmium salts, Barium salts and zinc salts. Examples of such acid acceptors are lead stearate, basic lead carbonate, triple basic Lead sulfate, dibasic lead phosphite, dibasic lead phthalate, lead silicate, lead chlorosilicates and mixtures of basic Lead sulfate and lead silicate, cadmium (2- [ethylj-capronate) respectively Cadmium octoate, barium laurate, cadmium phosphite and mixtures of these salts. The use of triple base lead sulfate and lead stearate is preferred.

The stabilizer can be added to the monomer suspension in water before beginning

become even or 009811 / U00

be added to the polymerization or it can be added during the

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- 11 -

merization can be added. For the sake of ease of work it is preferable to add the lead salt to the aqueous phase ^ to which the monomer is then added and in which it polymerizes will. In some cases, however, it may be necessary to add the salt later if the polymerization is too early Stages inhibited or inhibits or otherwise interferes, but can be allowed during the later stages. Inhibiting or inhibitory additives can optionally be added to the reaction product in the reaction vessel after completion of the Polymerization can be added.

The amount of lead salt used can be of the order of 0.1 to 10% by weight, based on the polymerizable monomer, respectively on the polymerizable monomers, and is preferred 0.5 to 5% by weight.

Another class of useful additives are those from the Prior art known inert pigments or fillers, for example Büß, OaIciumcarbonat respectively Titanium oxide. Useful pigment concentrations are 0.05 to 10% of the Sum of the weight of vinyl chloride and ionomer, · the concentration is but not strictly critical. Canoe at higher pigment concentrations the amount of asbestos required to achieve the same degree of agglomeration with round-grain polyvinyl chloride may be somewhat reduced.

Components including lubricants or lubricants and additional stabilizers, for example lead stearate, double acid lead stearate, calcium stearate, oadmium stearate and Cadaium laurate and waxes ^ kbjmen, .iiL · incorporated into the mixture and

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in many cases at the same time as adding the lead salt to the mixture will give.

Other ingredients that are either used to disperse or to have arisen Polymer can be added, include processing aids, such as methyl methacrylate / ethyl acrylate copolymers, Styrene / acrylonitrile copolymers and chlorinated polyethylene, and Agents for improving the impact strength, such as calcium carbonate, preferably coated with a fatty acid such as stearic acid, Acrylonitrile / butadiene / styrene copolymers and ethylene / vinyl acetate copolymers.

It was also found that organic plasticizers ζυ Reaction mixtures according to the invention "in situ" without any disadvantage for the process can be added. This enables the production of completely manufactured or completely attached round grains or globulites of plasticized polyvinyl chloride; this eliminates the one hitherto in the art Applied preparation or post-mixing stages (formulating steps) and leads to a considerable simplification of the polyvinyl chloride manufacturing process .

Accordingly, one embodiment of the method described above is characterized in that a plasticizer from the group of the saturated phthalic acid esters, as described in Encyclopedia Issue for 1965 of "Modern Plastics", Vol. 42, No. 10A, September 196 * _t published by McGraw-Hill Inc., pages 370 to 373 »under the upper

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is described below in Examples 1 to 3, determined.

Monomers that can be copolymerized with vinyl chloride, include vinyl esters such as vinyl acetate, vinylidene chloride, alkyl esters of unsaturated mono- or dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid and fumaric acid, in particular the methyl and ethyl esters of such acids, acrylonitrile, Methacrylonitrile and maleic anhydride.

Brewable polymerization catalysts include the oil-soluble Peroxides such as benzoyl peroxide and lauroyl peroxide, peroxydicarbonates and azo compounds, such as diazoaminobenzene, «, (X'-azodiisobutyronitrile, (^, oO-azodibutyric acid esters, for example the methyl, ethyl or butyl esters, o ^ oc'-azo-Cdi-ßx, ^ - dimethyl] valeronitrile) and ft, * '- azo- (dicyclohexanecarboxonitrile) (alpha, alpha'-azo (dicyclohexane carbonitrile ^. The amount of catalyst used depends on the type of catalyst and the polymerization temperature, However, it is generally 0.005 to 2 wt .- # of the polymerizable monomer (s).

. Advantages of the method according to the invention are: Elimination of a separate mixing or tableting or compression stage, elimination of the thermal degradation that conventional polyvinyl chloride does during the post-mixing process (compounding process), avoidance of dust and simplification of the filtering, washing and drying stages. So is by the way: conventional processes are water adsorption, as it is in Example 1 shown is about 28 grams per 100 grams of polymer when it is under

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ßAD ORIGINAL

has been filtered under the specified conditions, while the beads of Example 5 <according to the invention had 10 g of water per 100 g of polymer. The respective periods of time required to dry the two materials to 5% by weight volatiles under the stated conditions were 4½ hours and 3 hours, respectively. In addition, the beads of the invention reduce gas and / or moisture entrainment into the extrusions; They are easily handled and fed to extrusions and can be extruded at unexpectedly higher speeds than the ^{throughputs achievable with "dry mixes 11 of} the prior art and / or" re-smeared "or" compounded "polyvinyl chloride or ready-made (formulated) "dry mix polyvinyl chloride masses", which is characterized in that the aforementioned hats are round-grained agglomerated polyvinyl chloride masses as defined above.

The masses produced after the experience according to the invention are particularly useful for the production of rods, tubes or hoses and other profiles by extrusion processes.

The invention is not intended to be limiting in light of the following Examples to be understood in more detail, the parts being parts by weight and the percentages being percentages by weight.

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00 9811/14 0 0

- 16 - Examples 1 to 23

The runs and resulting products of Examples 1 to 11 are compiled in table 1; Examples 12 to 23 are in Table 2 compiled.

Example 1 shows an Ifa lake according to the prior art. Examples 2 and 6 illustrate the production of round-grain polyvinyl chloride agglomerates according to the invention by adding asbestos, but in the absence of optional additives. Examples 3 to 5 and 7 to 11 inclusive «own the invention in the presence of optional additives, namely blelstearate and buss »Example 4 illustrates the effect of a lower stirring speed, Example 5 shows a higher asbestos concentration and Example 11 shows

a lower asbestos concentration *

Examples 12-13 illustrate the use of a minor amount of vinyl acetate and Example 14 demonstrates the invention in the absence of cojaonomers.

In Example 15 the comonomer is vinylidene chloride. Example 16 shows that the plasticizer dlisooctyl phthalate in an amount of up to Sa 20 wt .-% in weight concentration (20% w / w) can be incorporated as an additive.

Example 17 illustrates the advantage of combining a protective colloid (partially hydrolyzed polyvinyl alcohol) with the Asbestos. In this case, a lower proportion of asbestos is possible, with the accumulation of solid polymer still at a low level

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is held

Examples 18-20 show the advantages of combining. surfactant with asbestos in the polymerization process, in which combination less asbestos was required to produce a to achieve low accumulation; the surfactant also aided in particle size control.

Examples 21 to 25 illustrate various pretreatment

lungs. In each of these examples the asbestos was in 5,000 cm ^ Slurried water, stirred or shaken and 20 Simmered for minutes; the asbestos was then filtered off and used in polymerization. In example 21 was the pretreatment agent Water. In example 25 the pretreatment agent was water acidified with 20 cnr 50% hydrochloric acid and in example 22 If the pretreatment agent was dilute hydrochloric acid as in Example 25, however, it was also the specified amount of dodecy! benzenesulfonic acids! Sodium or sodium dodecylbenzenesulfonate added. In Examples 1 to 25 inclusive, the polymerization was carried out in one of 2 autoclaves (A and B). In the Examples 1 to 5 inclusive, 14 and 16 to 25 inclusive was the autoclave A and in Examples 6 to 11 inclusive, 12, 15 and 15 the autoclave B was used. The polymerization process was as follows in all examples;

There were water, asbestos, lauroyl peroxide and optional not inhibiting or non-inhibiting additives (protective colloid, surface-active agent, pigment, stabilizer, soft *

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Bacher ι etc.) introduced into the autoclave. All solids were ground in water in order to form a dispersion before addition.

The autoclave was tightly closed or sealed, evacuated and the monomer or monomers were introduced.

Eb began stirring, and the feed was to the reaction temperature of 75 - heated 2 ⁰ C. The reaction vessel was relieved of excess pressure or vented when the operating pressure at the reaction temperature fell from its m »t1« v by 2.80 atu (40 psig).

The product was removed from the autoclave and washed free of asbestos on a coarse sieve using a stream of Vaesian.

The measurement of moisture retention, if necessary, was made as indicated below. The product was 24 hours, tang at 60 ° C in an air-heated oven (air oven) dried.

The particle size was determined using a projection microscope measured.

Her autoclave A was a jacketed cylindrical pressure vessel made of stainless or stainless steel having a length of 264.16 mm (10.4 inches) and a Durohmesser of 202.2 mm

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1570813

(8 inches), its capacity was 7,340 cm *. The one used The stirrer was a flat winged one pointing 4-5 ° upwards Paddle (flat bladed 4-5 ° upthrust paddle) that is close by of the floor was arranged. It was through the thermometer pocket respectively -sleeve provided a rebound effect (baffling) »

The autoclave B was a cylindrical, electrically heated pressure vessel with an insert or an insert (liner) made of stainless or corrosion-resistant steel. The liner or insert had a length reu 517 * 5 ^ m (12 * 5 inches) and a diameter of 114.3 söst (4.5 inches). Its or its capacity was 3 13 ^ · '- ^% m- \ The stirrer used was a' flat paddle provided with wings 45 ° upthrust paddle (flat bladed 4-5 ° upthrust paddle), which was at the height of the Bcdens was arranged, "Lederum was intended to have an impact effect through the thermometer pocket or sleeve."

2 of the advantages of the generated, iäassen *. namely the lower one Moisture content after filtration and the higher drying rate can be illustrated by comparing Examples 1 and 3 as follows?

The product from the autoclave after the polymerization was washed free of asbestos using a coarse sieve to hold back the polymer mass. 200 g of this moist product were filtered on a mountain pine or a Büchner funnel of 152.4 mm (6 ") under t .: SxBTH. Vacuum of approximately 508 * 0 mm Hg (20" Hg) for a period of 5 minutes . The wet product was weighed and

009811/1400 -20-

then dried under controlled identical conditions in an air circulating oven maintained ^{at 60 0 G.} The results are illustrated in FIG. 1, in which the curves show the decrease in volatiles (expressed as a percentage of dry weight) as a function of drying time.

Example 24

There were high fidelity records respectively high accuracy with regard to the fidelity of the reproduction using the product of Example 7 as follows:

The round grain agglomerates were (full 2-mill) is ground in a two orphans mill for 15 minutes at a temperature of 140 ⁰ O. The crepe or whale skin was removed from the mill and cut into appropriately sized panels or plates by pressing in a high fidelity record press designed to make a 304.8 mm (12 inch) high fidelity record at 55x revolutions per minute.

The panels were then preheated to 150 ° C. in an oven immediately before pressing.

The board or plate was placed in the press, ^{heated to 155 °} C. and the press was closed. After 15 statements, the press plates were cooled with cooling water. The press was then opened and the finished record removed. The records produced in this catfish were made with commercially available be *

- 21 -

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loved. State-of-the-art records and it was found that they behaved equally well.

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Table 1

Example no. 1 - 2 3 k 5.7 5 5 · « Vinyl chloride in g 1 919 - 1 919 1 919 1 919 1 919 Vinyl acetate in g 386 - 386 386 386 386 Lauroyl peroxide in g 5.75 550 5.75 5.75 5.75 5.75 Water in g 3 838 101.6 3 838 3 838 3 838 3 838 O Polyvinyl alcohol in g 9.22 - mm - mm « 09811 Asbestos in g - 230 115 115 230 "ν Blelstearate in g - 31 31 31 t »
O
O Rufi in g - 10.3 10.3 10.3 Drilling speed in revolutions
per minute 550 500 200 500 Stirrer length in mm lüi, 6 101.6 101.6 101.6 Asbestos type * 7R2 7R 7R 7R Average diameter of the
round-grain agglomerates in mm 1.2

Asbestos type geaäA "Committee on Uniform Classification and Grading of Asbestos Mines Produote ", Quebec, Canada, formed in 1931, revised in July 1959 Chrysotl asbestos was used in all of the examples in Table 1

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Table 1 (port setting)

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Example no. 6th 75.6 - 7th 52.9 8th 52.9 9 10 52.9 11 30.2 Vinyl chloride In g 630 425 630 10.2 630 10.2 630 630 10.2 630 10.2 Vinyl acetate In g 126 88.9 126 126 3.4 126 126 3.4 126 3.4 Lauroyl peroxide In g 1 ₉ 86 7R2 1.86 425 1.86 425
88.9 1.86 1.86 425 1.86 425 Water in g 1,260 1.6 1,260 88.9 1,260 6D2 1,260 1 260 1 33.9 260 88.9 Polyvinyl alcohol In g - - 7R2 - 6.1 - 4K2 - 7R2 Asbestos In g 4.3 52.9 7.2 5.5 Blslatearate In g 10.2 Soot In g 3.4 Stirring speed in revolutions
per minute 425 Stirrer length in mm 30.9 Asbestos type 5R2 Average diameter of the
round-grain agglomerates in mm 6.9

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Table 2

- Example no. 12th - 1, 52, - 39 13th - 1 10 - , 7 14th 9.2 15th 52, - - 89 16 9.2 17th 9, - 2 '■ Vinyl chloride in g 720 1200 10, - 637 1,260 3 - 2 305 3,340 720 10, - 2 304 3 840 2 305 5 840 - Vinyl acetate in c 36 - 3, 425 68 - 425 .89 - - 3, 425 -. U - 15th Vinylidene chloride in g 88 9 88 - 230.5 36 88 9 - 161 - 23; 05 Lauroyl peroxide in £ 7R2 2 7R2 - 1* 7R2 2 50 5500 009 V / ater in g 1 , 4 1 , 9 - 1,260 2, 4th 7.5 101 OO Polyvinyl alcohol in g , 2 - - 460 7R2 ν ». Asbestos in g .4 - - 1 ο Lead stearate in g 500 500 O Soot in g , 9 ιοι, β 9 101.6 , 6 Plasticizer diisooctyl phthalate in g 7R2 7R2 Surface active agent in g »0 • 9 1.0. 0 1.2 , 5 Stirring speed. in revolutions
per minute Stirrer length in mm »0 Asbestos type
llf "* .- ■■■ - ■ '..' ■ Average diameter of the
coarse-grained agglomerates in mm

2 (continuation)

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Example no. 13th IJb η 6 - 19th 5.75 > - 20th -46 - 21 5.75 HG 22nd 5.75 31 23 Vinyl chloride in g 1 919 3 838 31 2/5 ⁱ 1 919 3 B33 U ₅ U ^T 1 919 31 1 919 3 833 31 1 919 3 333 10/3 1 919 Vinyl acetate in g 336 - 10.3 ', 50 386 386 ^ / 5 550 386 - 10.3 386 - 386 Vinylidene chloride in g - 101.6 - h 6 IUi, 6 101.6 - - 1.1 ³ CW
J Lauroyl peroxide in g 7R2 31 Airioc! it 5.75 Crocido 550 5.75 Water in g 1 » _<5 10 _v 3 3 P. 33 3.2 101.6 3 83ft Polyvinyl alcohol in g - 101.6 Amosite Asbestos in g '-ν-I - τ
lit YR2 46 BIe stearate in g 2.5 31 Soot in g 10.3 Plasticizer diisooctylphth ;. > a · ;; p; Surface active Hittul) n? - Stirring speed in revolutions
per minute 550 Stirrer length in mm 1.01.6 Aebesttyp ** Crocddo «
lit, Average diameter <la
round grain agglomerates in rome . ^s . ·. ^6. ,

cn σ

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Table 2 (continued) In Examples 12 to 13, chrysotile asbestos was used

1 "Lissapol" N (a condensation product of ethylene oxide with octylphenol) 1 OetyltrlMethylammoniumbromld

3 Sodium dodecylbenzenesulfonate, for example sodium dodecylbenzenesulfonate

_o Asbestos type GNU "Committee on Uniform Classification and Grading of Asbestos ° Mines Products", Quebec, Canada, formed in 1931, revised in July 1959

Cnrysotll

33

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Claims (1)

1570813 - - & - Claims 1.) Round-grain agglomerates with a content of a homopolymer of vinyl chloride or a copolymer of the same aua 100 to 80 parts by weight of vinyl chloride and 0 to 20 parts by weight of at least 1 ethylenically unsaturated monomer, optionally at least 1 non-inhibiting or Contain non-inhibiting polyvinyl chloride additive from the group of stabilizers, pigments, plasticizers, auxiliaries for processing or processing, agents to improve impact strength, lubricants and surface-active agents, characterized in that the polyvinyl chloride agglomerates mentioned have a spherical shape, an average diameter from 0.51 to 12.7 mm (between 1/30 and tj inch), a packing density of 0.4 to 0.8 g / cnr and ^a "* eamtmenge of volatiles of less than 0.20 g per gram of Completely manufactured or fully attached on a carriage of 152.4 mm (6 ⁿ ) under a Va A vacuum of approximately 308.0 mm Hg (20 "Hg) filtered over a period of 5 minutes and dried in an air circulation ^{oven kept at QO 0 C f} ¥ product. 2 «) agglomerates naoh claim 1, characterized in that they are additionally added after the end of the polymerization to inhibit or inhibit the polymerization Contain polyvinyl chloride additives. 00981 1 / UOO _BAD OPJSiKAV. 3 ·); Process βατ production of the agglomerates according to claim 1 or 2 by polymerisation of 100 to 60 parts Vinyl chloride together with inage all 0 to 20 parts by weight ! von Dlndeetena 1 copolymerizable athylenically unsaturated uronobor in a hot medium in the presence of a Polymorisatlonakatalyeatora, because it is worth knowing that one used Yasoraabest during polymerization 4.) The method according to claim 3, daduroh gekennselehnet that one Vinyl chloride polyairized on its own. $.) Method according to claim 3, dadnxoh gekennaelohnet that one Vinyl chloride together with vinyl acetate polymer 1alert 6 ·} Method according to claim 3 · da rtfa ^ ch C ¹ W ¹ ^ ¹ If ftl ^ n ^ t _t that vinyl chloride is polymerlelert sueamman with vinylidene hollow world. 7.) Procedure according to Anepruoh 1 ble 6, daduroh gefcennaeiohnet thatB one ale faaeraebeat one from the Ohrysotlltgrp β.) A method according to Anapmoh 5 Me gekennselohnet 7% daduroA, DAB is ale AalMst been subjected to a eolohen, the comminution of the aeernng beslahungeweiae Aabeatfaeer before Tweg in PoIyaeriaatloneTerfehren a ohemlaohen pretreatment door Verainderune the size and tellwelaen Zerf 1st 9 ·) Procedure according to Anepruoh 9 IA * 8, daduroh gakennielohnet, dafl ale asbestos one whose pretreatment is 00981 1 / UOO BAD OWG'NAL deal with an acid, preferably a strong mineral acid, has been performed. 10.) The method according to claim 3 to 9i, characterized in that that asbestos is one whose pretreatment is by dispersing it in water in the presence of a surface-active agent Means has been used. 11.) Method according to claim 3 to 1 ^, characterized in that that one as asbestos is such, for its pretreatment as a surface-active agent, a cation-active agent anionic agent or a non-ionic one surfactant has been used. 12 ·) Process according to Anepruoh 3 to?, Characterized in that the asbestos used is one of the chrysotile type, the pretreatment of which has been carried out by dispersing in water and allowing it to boil for a period of ν to 6 hours » 13.) The method according to claim 3 to 11, characterized in that the asbestos is one whose pretreatment with stirring or agitation at temperatures of 10 ⁰ C to ^! _{ has been carried out at the boiling point of the solution, turns 14 «) Method according to claim 3 to 7, characterized in that the asbestos in a concentration of 1 to 11 wt. 00981 1 / UOO - 2? - 1F70819 len, preferably 4 to 8 parts by weight, per 100 parts of the Total weight of polymerizable monomers used 15 ·) Method according to claim 3 to 13 »characterized in that that dop pretreated asbestos in a Conseatration of 1 bio 4 parts by weight per 100 parts of the total weight of the polyacrylatable monomers used. 16.) Method xutoh claim 3 to 15 »marked by this, that one 0.005 to 2 parts by weight of a protective colloid per File the total weight of the polymerizable monomers present during the polymerization. 17 ·) method according to claim 3 to 7 or 14, characterized in that 0.05 to 2 parts by weight of a sonic colloid used per 100 voiles of the total weight of the polymerizable monomers present. 18.) The method according to claim 3 to 17t, characterized in that that one 0.005 to 2 parts by weight of a surface-active Average used per 100 files of the total weight of the polyaerionable monomers present. 19 ·) Method according to claim 3 to 7 «1 * or 17, characterized in that 0.05 bio 2 parts by weight of elneo surface-active agent per 100 parts of the total weight * of the poly- 89 ·) Method according to spoke 5 Mo 19 _1, characterized in that 009811/1400 -2β- BADORlQiNAL-; 1F70819 - se - _yi that BA does not act as an inhibitor during the polymerization or non-inhibiting additives used for polyvinyl chlorides « 21.) The method according to claim 3 to 20, characterized in that an inorganic lead salt is used as a non-inhibiting or non-inhibiting additive. 22.) The method according to claim 3 to 21, characterized in that that a saturated phthalic acid ester is used as a plasticizer during the polymerization. 23) Method according to claim 3 to 22, characterized in that that dialkyl phthalates with alkyl groups with 6 or more carbon atoms in the chain are used as plasticizers. 24-) process sum extrusion of polyvinyl chloride masses, characterized in that the agglomerates according to claim 1 or 2 are used. 25.) Method sum compression molding of records, characterized in that the agglomerates according to claim 1 or used. 00981 1 / UOO -32-blank page