DE1946819A1 - Process for the production of polymer dispersions in inert organic liquids - Google Patents

Description

Process for the preparation of polymer dispersions in inert

organic liquids

The invention relates to a process for the production of Dispersions τοη polymers in inert organic liquids.

It has already been proposed, a dispersion of a polymer in an inert organic liquid in which the poljTBer is insoluble, by producing a α, β-ethylenically unsaturated monomer in the liquid below Formation of a disperse polymer is polymerized in the presence. of a polymer stabilizer that works with the polymer associated and the dispersion sterically stabilized. The representation is generally achieved by using a fraction of the batch of unsaturated monomer, polymerization initiator and dispersion stabilizers to the selected polymerization temperature heated inert liquid was added, the reaction taking place and a polymer dispersion a low solids content is formed. This level of the Procedure is usually called "Keisstufe" beaoichnöt and typically consumes up to 5% of the total economic

009812/1680

batch based on weight. The best of the batch will then gradually added to the mixture over a predetermined time, the reaction temperature being maintained until im substantially all of the unsaturated monomer is converted to polymer. The speed de :? Must be added carefully can be controlled in order to reduce the risk of unstable dispersions to avoid, which in turn results in the attainable minimum Processing times are limited.

It has now been found that the lower limit of the process P Duration can be reduced and that other advantages emerging from the following description can be achieved if in the Dispersion certain classes of stabilizers can be used and the procedure in the manner described below is carried out*

According to the invention, a process for the preparation of a dispersion of a polymer in an inert organic liquid, in which the polymer is insoluble, is provided by polymerizing an α, g-ethylenically unsaturated monomer ψ in the liquid to form the polymer in the presence of a polymer Dispersion stabilizer in a two-stage reaction consisting of a? One step and one speed step are proposed, which is characterized in that .1. the seed stage consists of the inert organic liquid t, to which the unsaturated monomer and the copolymerizable polymeric stabilizer of the type described below are added in a weight ratio of 1:10 to 15 × 1, the added amount of unsaturated monomer? ~ 70 Sew %

BATH ORIGINAL

of the entire monomer from which the disperse polymer

is formed, is §
2 · the step from the bed of unsaturated monomers and the polymeric Rahratufe stabilization room. tte 1 of

type described below; and J. the sowing of poljaeren stabilizers in the dispersion 0.5-30% by weight based on the disperse

Polymer is.

In a preferred embodiment of the invention, less polymeric stabilizing agent is generally used in the Kähratufe Dispersion added, the more unsaturated monomer, the same is added, has been added.

under an - inert organic liquid a liquid should are understood to be the one for the disperse polymer

Visual solver and compared to which the stabilized

en
parse polymer forming reaction / inert.

The disperse polymer is produced by the polymerization of at least one α, β-ethylenically unsaturated monomer. as Suitable monomers can be mentioned, for example, the following

halogenated vinyl compounds, r.B. Vinyl chloride and

Vinylidene chloride;

aromatically substituted vinyl compounds, e.g. styrene, a-methylstyrene and the technical mixture of isomers, known as vinyl toluene;

009812/1680

Xther of vinyl alcohol, e.g. the ethyl, n-propyl,

Isopropyl, η-butyl, isobutyl, 2-thethosyl and bensyl ethers country

Allyl esters of mono- and dicarboxylic acids, such as acrylic, Hethacryl- * Haiein- and fumaric acid, old saturated monohydric alcohols, for example methanol, Ithanol, n-propanol _t loopropemol, n-butanol, s © K.-But * nol,

and dodeeanol.

™ Hoberpolar «Polymers can be polymerized or Hieehpolyaerie & tion of highly polar monomers * such as ffi.B. the o.a. unsaturated acids themselves, their acid esters »and their polar derivatives, for example acid chlorides, and HithjlolaBiden, arise.

Si · polymeric stabilizers for the present invention have the following general characteristics. The stabilization means are polymeric in the sense that they only have three or four However, mostly see or see more repeating monomers "Contains units per molecule. The stabilizing agent, which is initially in the nonaqueous liquid of the dispersion is soluble, must associate with the disperse polymer and contain one or more components that are liquid to be solvated and a stabilizing sterile protective cover around the disperse polymer particles form.

The force of association between the stabilizing agent and the disperse polymer can be a force dependent on the mass

009812/1680 - 5 -

■ ORIGINAL BATHROOM

-L ti ,.

be moving between those of the organic liquid non-solvated components of the stabilizer and the dispersed polymer developed * on the other hand, it can be a force that is characterized by a strong specific interaction between polar groups of the stabilizer s and complementary polar groups of the disperse polymer developed. These association forces that exist between of the disperse polymer and an expedient as Anchoring component to be designated component of the stabilizing agent arise, are essentially on an electrostatic attraction between polar and / or dipolar charges in the disperse polymer and in the anchoring component of the stabilizer} they include those dependent on the Hasse Forces of the London or Van der Vaal kind created by attraction between numerous weak dipoles in the disperse polymer and in anchoring components of the stabilizer arise up to specific interaction forces between significantly fewer, strong polar or dipolar groups, u.IT. between only a few or even a few very strong polar or dipolar groups.

In addition to these general characteristics, "those of both the germinal stage and the are also common to the level stabilizer " must be the copolymerizable seed stage stabilizer at least one polymerizable ethylenic double bond per molecule of the stabilizing agent that are involved in a polymerization reaction with the monomer, including the disperse Polymer arises, can enter, while the Bährstuf © n-Stabilisierungsmittei ' preferably no such double bonds

having. Suitable m ^ ep% iy% 4Jr%! Abar · Kei »etuf« n-

Stabilizing agents are described, for example, in the German patent application of the applicant Ir · P 17 TO 812.2, of which those are selected which have a mixed polymerisation reaction with the diapered polymer with the formation of 1 to 10, preferably 1 to M, covalent bonds. per molecule of the stabilizing agent that reacts with it.

The choice of stabilizing agents for the speed level is greater than that of the stabilizing agents for self-leveling. Although the same stabilizer can be used in both the glue stage and the speed stage of the process, it is generally preferred that no polymerizable stabilizer is used in the speed stage, since the aim is to create a robust process that can withstand the normal fluctuations of the actuator conditions is relatively insensitive. Basically it means that the stabilizers resemble the polymerizable stabilizers described above, but do not have any polymerizable double formations, which are the preferred stabilizers for the safety. Suitable stabilizers for this stick are described, for example, in German patent applications P 15 70 804-O and P 15 70 805.I.

It is also possible, for the production of mesSiaaiseh vaiä thermally high-resistance bispersioja, to use stabilizing agents for the driving stage that do not have polyaerizable double bonds, but are chemically reactive

capable groups include »those with complementary chemical reactive groups of the disperse polymer react to 10, preferably 1 to 4, fragile bonds

per molecule of the ait ilm® stabilizing agent reacted to

009812/1680

BATH ORIGINAL

give. Suitable stabilization tools of this type can B.B. aua daa in the German patent application P 15 95 826.6 as described, can be selected.

The polymerization takes place by daee maa da Konoewr, daa Keiaatofea - Stabili8iercsigS3aittel and daa Folyaerieetione imitiator within the specified committees for the Hiscnungavarbaltni — a in the case of the chosen lacktioaetasparatttr are inert organic fluidity gives u & d the opening temperature like this Aufraohtarhalt, until aiaa permanent people aas disperse Polymer continues. Baa bavotrsygta weight-

yarhiltnla by Ronoaer au «iaefcyolyarjLaiaa Stafeiliaiaruiigs- ■ ittal in dar laiaatnfβ for the gSBetigetaa Bataciababadi ingwngan iat via Λ t 5 lsi · 9 ι 1 · la ie« confesses, daisa dia Efeaaa & tration t. IraizadikalaB (dia wiadertm roa dar Art da Boljaariaa-

md dar Ha "kfcI" MFteep * ratiir aibbanft) "ad daa,

Tarhaltsiie worn 8twbiliaiar «agaBi. Without the experience on it, it is assumed that the Stabiliaiamagamittal with the baaebriabenen nmc da * Yaefahreaa ioaaarat is well aua ^ aotst,

wouroh the seed particles aiaa unexpectedly small and equal- ■ iaaiea. Particle size beaitsaa. The surprising effect of the "Stabiliaiaruag iat Tarautlioh" is the reason why the sun can use an unusually large "narrow Honoaer ia " r Xsiajatufa, and the fact that the invention lake is robust. In the Eeiaatafa the Miechpo3jaerisable polyurable stabilizing agent is not necessarily used as a uniquely · Stabilization ·

309812/1680 -β - -.

medium, although ββ knows how to be thorough. For the calculation the above ratio of monomer and stabilizer in the germination stage, however, becomes wedge »back-adjusted to any existing non-polymerizable stabilizers are taken. Optionally, all of the stabilizer for the dispersion can be dispensed during the cooling stage of the process.

Aa the end of the keiabbildung becomes the best of the polyaerielerbaren Monomer ·, the initiator! and the stabilization means to the Dispersion added, whereupon the polymerization is completed. Optionally, one of a copolymerization can be used different reaction between the stabilizing agent and the disperse polymer at the same time or after the polymerization reaction be effected with the formation of an addition product "

The reactants of the Bahrstuf β can pre-ash and the Dispersion from the germination stage supplied as a single edible mixture will. In order to achieve maximum operational stability, however, preferably a proportion, see B. 20-80 GewJt, des Geeaatetabilieierüngsaittele for the speed level of the completed Dispersion of the keia level added before the polyaerizable Monomer and the initiator is gradually added, with the best of the stabilizer · gradually in smaller and smaller Amounts are added with the horn. The one that is getting smaller and smaller The addition of the stabilizing agent is controlled in such a way that it increases the surface area of the dispersed polyamide particles but is not critical.

The rate of addition of the monomer for the mahretufe Is not critical, and in practice there will be a maximum

009812 / 1S80 - 9r.

Speed determined through trials. If the addition is eu quickly, the dispersion will coagulate or become labile on storage.

In general, known catalysts, initiators, chain transfer agents, etc. can be used for the polymerization, which is preferably carried out at a temperature not above 100 ^{° C.}

In this way, dispersions can easily be obtained have a content of dispersed polymer of a few percent up to 60% by weight or even higher.

The invention is illustrated below with the aid of exemplary embodiments explained in more detail, where! parts are parts by weight and some components are identified as follows:

Hydrocarbon liquids

I. Hydrocarbons without aromatic components: Hydrocarbon A - boiling range 180 - 210 ⁰ G Hydrocarbon B- ^w 40 - 60 ⁰ C Hydrocarbon C- "114 - 144 ° C Hydrocarbon D-" 55 - 72 ° C Hydrocarbon H- "32 - 67 ° C

2. Hydrocarbons with a low aromatic content: Hydrocarbon G - boiling range 33 - 82 ° C

Content of aromatic Ingredients about 1.5% by weight A Seibet polyester of 12-Hydroxy8tttrine «ure with a molecular

009812/1680 - 10 -

weight of about 1,700 condensed with glycidyl methacrylate to Introduction of a polymerizable double bond (hereinafter called the monomer A) was carried out with methyl methacrylate and glycidyl methacrylate in the weight ratio 66x30: 4 in the presence of hydrocarbon A, hydrocarbon D and ethylene glycol diacetate Miechpolyiierieiert in the weight ratios 0.7 ^ 9: 0.519: 1t732, by a 50% strength by weight solution (based on the Dry content) from a polymeric stabilization intermediate with a molecular weight of 70,000.

This intermediate was then used to introduce polymerizable Double bonds modified as follows:

A mix of:

Parts stabilization intermediate product *

Solution (as described above) 5279 * 0 Methacrylic acid 39 «β

hydroquinone 0.6

tertiary amine of coconut fatty acids 3.0

was placed in a heating vessel equipped with a return condenser Heated under reflux (about 110 ° C) for 5 hours. The thus obtained Solution of copolymerizable stabilizer identified as stabilizing solution A.

Stabilization solution B

A monomer, methyl methacrylate and glycidyl methacrylate in the weight ratios were 45, "50: diacetate Xttaylenglykol-5 in the presence of hydrocarbon 0, and N, N-dimethylformamide in the Gewiohteverhältnieaen 0.556: 2.223: 0.221 miachpolymerieiert at 130 ⁰ C. Thus, a 50% strength by weight solution (based on the dry content) of a polymeric stabilizing intermediate was obtained.

009812/1680 - ^ ₁ .

BATH ORIGINAL

The intermediate product then becomes polymer upon introduction τοη! - modifiable double bonds as follows *

line scoffing out

Stabilizing agent solution (as just described)

Methacrylic acid 62.0 Srdroquinone ~ 1.2

tert-AHin τοη Lokosfettsäuren 5.0

Hollow binding material B 200.0

was generally heated in an old reaction vessel, which was built in a soot condenser, for 5 hours under Buekflu ·· (about 110 ⁰ O). The mixed-polymer stabilizing solution obtained in this way was identified as stabilizing solution B.

established parts of the bisohen product Losum «(as for stabilization- ***** losune; B used) 2 * 00.0

p-nitrobenoic acid 50.0

tert-amine tob Lokosfettsäuren 2, $

ia a rersebenen with a Röcklaufkonnsator reaction (• barrel 3 hours under Buokfluss (C) is heated about 130 ^0th Di · • so rhaltem · Losun "τοη polrmerem 8tabilisierunesmittel was« 1 · Satbilieierunfslösunf C identifisiert.

Ha · Lo «uae of polymeric tabulation agent, which is used as a stabilizer D is identified ·, became closer to the general

009812/1680 '" ¹² -

Hethode für etabiliiierungsiöming B errengt, but the Content en methacrylic acid τοη 62.0 to 4O ₉ O Xeile herahgesetst

became.

Monone? A ₁ Methrlaethacrylat and ulycidylaethaerylat were in the Oewiehtsrerhaltnissen 52140? 6 in (blessing Wart iron hydrocarbon C, Itbyiangiykol diacetate and K _# K "* Dlnetbylforaaaid in eewi & htererhal ^ iieeen (^ 556" 2,223iO, 221 bei'-IJO ⁰ O "leohpo ^ aeri- • i «s? t · Thus aan received a 50 weight (lied to the frookengehelt) solution τοη a polyeeren stabilization wisdom

_{ . This intermediate product was then modified as follows but introduced τοη polymerizable double bonds

A mill from Γ

etabiliaierubgssisehenprodukt « gel solution (as just described) 6504.0

Methacrylic acid 4O ₁ O

lftrdroohinon 1 »2

, tort.-lain τοη eocos fatty acids 5 * 0.

Hydrocarbon 0 20O ₉ O

was converted into an old "Bucklaufkondensator Tereehenen Beaktions" The vessel is refluxed (about 110 ° 0) for $ hours. Me so obtained solution τοη aisohpolyKerisbarena stabilizing agent was identified as stabilization solution S

Stable? • i

Sine Hisohung aust

0 0 9 8 12/1680

Stabilization intermediate product gel Solution (as for 8 stabilization ~

solution E used) 2400.0

p-nitrobenzoic acid 50.0

tertiary amine of lokoefettsäuren 2.5 was in a "kit" a Rücklasfkondensator Reaktionegefäss provided heated for 3 hours under reflux (about 130 ⁰ C). The resulting solution of polymeric stabilizing agent with free epoxy groups was identified as stabilizing solution f.

example 1 Representation of a dispersion of 40 wt% poly (mathyl methaorylate)

in an inert organic liquid. ,

The egg stage consumes 11 8ew% of the total polymerize Monomer and comprises a weight ratio of polyaerizable Monomer su polymerizable stabilizer like 9: 1. The stabilizer for the nutritional stage was found in smaller and smaller amounts are added, the more monomer is added had been.

A mix of*.

horny hydrocarbon A 102.0

Hydrocarbon C 74.9 Hydrocarbon D 110.0

was heated to flow temperature, and a mixture of 1 parts of n-butylbenzyl phthalate, 18.1 parts of methyl methacrylate, 3.1 files azodiisobutyronitrile and 4.1 files stabilizing solution A was added, whereupon the reflux temperature was held at 79-80 ° O for 20 minutes. Thus one formed

. 009812/1680. ^ .

Wölk made of stable dispersed polymer seed particles Am mixture of parts Methyl methacrylate 144.0 Asodiisobutyronitrile. 1.2

primary octrlaercaptan

(10% solution in aliphatic Hydrocarbons - related to the froeken content) 0.8

was prepared and divided into equal proportions of animals. Stabilization solution A was added to each of these parts Hange from 7.90, 5.75t 2.20 etc. 0.65 parts sugar given.

These animal sparing solutions were added in the given sequence at an equal speed within 5 minutes of the dispersion kept at reflux temperature (about W ¹⁸ Q) , whereupon the reflux was held for another 50 minutes.

Soeit # rhl @ l ^ mm a® stable dispersion of dea Poijaer.

ί Example 2

For comparison with Example 1, a test can be similar

^: 40% by weight dispersion of FoljCaethylKethaerylat), the concentration of the monomer in the seed stage, however, was reduced to 6.5 3ew £ on the total polyaieri & lable honey · The stabilization side for the bar stage was in constant slopes during the addition of the 9 stage ~ Honomers su the dispersion

Am «Hisehung ausi

• 15 -

^; 009812/168 0 W.

Toil » λ 2022.00

lohleeweeaeretoff B $ 80.00

n-Butylbentylphthalate 106, $ 0 8tabiliaierungalö "aune A 49"

Hetbjrlsethaorylat 148.50 AiodiiaobutjToaitril 15 * 20

pritt8rea Ootjlaeroaptan

(1OJf-IM L8 * mf in «UpUfttleotü * lohlanwaaaeretoff) 4,

wttrde in #in ait tin · "Rüoklaufteondeneator and agitator reraehenea leaktioaagefäae tlaeebrmcht, avf TO ⁹ O ervärat, whereupon the -ptg iim * rh * ll) 10 minutes" n * uf 8O ⁹ O and there another 20 HiSMriMtt gtliftlt "was brought ·. Bcrnlt bild * · see «In« f * lav «rt * ilt * Volk · by diaporMA PoO / m» j? K «Äjit« lloh «n, 41 · was stable,

Xta Ötmiech auei Tail »

2070.0

A 285.0

Aeodiieobutyt ^ nitrtl 15.0

priAär ·· Oo ^ fiatrcapt «n 6.0

will · tu dMi iBitar Räckfluae aiadenden content dta Baaktione-

* ■ - ■ '■.

Stfitaa «in gUiete ^ aeigan Manganese within 3 hours ao auge ·

give daaa da «Gemiaoh through the tos return condenser flieaaasda Ilüeei ^ ity has been thinned well, is the end of the addition the diapereion became unstable.

Beiapiel 9

Representation of an Oiaparaion toe. 40 Qew9 (PoIj (bethyleethacrylate) in an inert organiaeban Huasi ^ ctit. Dia Zaiaetufe T needed 67 Qew% daaasted polymerizable HonOsera and Uttfaaate

009812/1680 - 16 -

Weight ratio of polymeric monomer to polymerizable stabilizer is 2.4t 1. Ala stabilizer for the highest level, a non-polymerizable polymeric stabilizer was used. . ^! _#

A mixture of parts Methyl methacrylate 9000 Stabilization warning B 7500 A «odiieobutyronitrile 250

priairaa octyl mercaptan 4

lehlenwaaeratoff A 18300

Kohlamraaaavatof f C '5000 Coal Waiaeratoff D 15000

was introduced into a Taraahanaa Raaktionagefäaa with a reflux condenser, ^{heated to reflux temperature (80 0} O) and kept under S & okfluaa for 20 minutes. Soait formed looks tint ftinrtrttiltt, ttabilt people aua diapereen Polymarkeimt ei lohen.

The following late loaungans were overridden

Parts of 1 Kethyl methacrylate 2250

AaodiitobutTonitrile 9 Stabilization solution C 500

primary octyl mercaptan 5

K * .2 methyl methacrylate 2250 Aaodiieobutyronitrile 9 Stabilization solution C 400

primary octyl mercaptan 4

The two salivations were given in the order given

. '- 17 τ

00981 2/1680

BADOBIGINAL

at a constant speed within 25 minutes added to the refluxing dispersion, whereupon the pool temperature was maintained for a further 15 minutes. the The low-boiling liquid was then evaporated in vacuo until the solids content of the dispersion was 40% by weight.

Thus, a stable dispersion of the polymer was obtained. Example 4

A dispersion similar to that according to Example 3 is shown wherein the amount of polymerizable monomer in the seed stage has been reduced to 33% by weight of the total monomer, the weight ratio of polymerizable monomer to copolymerizable * Stabilizer was such as 1.4: 1, the concentration of total polymeric stabilizer in the dispersion was kept constant and twice as much non-copolymerizable stabilizer was used, that was added in the speed step.

A mixture of » parts Methyl methacrylate 4500.00 Stabilization solution B 6500.00 Azodiisobutyronitrile 150.00.

primary Oc ty! mercaptan 1.25

Hydrocarbon A 17,000.00 Hydrocarbon C 4000.00 Hydrocarbon D 15,000.00

was placed in a reaction vessel equipped with a reflux condenser introduced, heated to reflux temperature (80 ° C) and Refluxed for 20 minutes. Thus one formed

009812/1680 " ^1β "

finely divided, stable population of dispersed polymer seed particles

The following feed solutions were prepared; Mr. 1 methyl methacrylate ■ · -> 4500 Azodiisobutyronltrile 9 Stabilizing solution C 1000

primary octyl mercaptan 10

Kp.2 methyl methacrylate 4500 Azodiisobutyronitrile 9 Stabilizing solution 0 900

primary octyl mercaptan 10

Both of these feed solutions were added to the refluxing dir J ¹ Sion in the order given at a constant rate within 40 minutes, whereupon the reflux temperature was maintained for a further 15 minutes.

% '-C ί

The low-boiling liquid was then evaporated in vacuo, bia der iietatdffgÄtialt der Möperaion 40 G · * ^ betrue?

A stable dispersion of the polymer was thus obtained. In particular

ι this example shows, compared with Example 5 _r ^ that \ a stable dispersion of poly (methyl methacrylate) satisfied "■ either from an very different process conditions within the limits of the invention can be produced. ,

Representation of a dispersion of 55% by weight of poly (methyl methacrylate) in an inert organic liquid. The germination stage is consumed 18% by weight of total polymerizable monomer and comprises a weight ratio of polymerizable monomer to

009812/1680 ^ ¹⁹ "'

BATH ORIGINAL

Polymerizable polymeric »stabilizing agent such as 2.5t 1 * In addition, the best of the stabilizing agent, the consists of a non-copolymerizable polymeric stabilizer, used in the seed stage.

A mixture of: ropes Stabilization solution C 1000.00 Methyl methacrylate 1000.00 Stabilizing solution D 800.00 Atodiieobutyronitrile 50.00

primary octgr! mercaptan 0.75

Hydrocarbon A 3000.00 Hydrocarbon C 1230.00 Hydrocarbon 6 2500.00

n-butybenayl phthalate 500.00

and agitator was placed in a Beaktlonegafäaa provided with a return condenser introduced, heated to reflux temperature (80 ° C) and then refluxed for 40 minutes. Thus, it formed a divided, stable dispersion of polymer seed particles.

I'm horny Gemlaoh

• methyl methacrylate 4560, ο

Aaodiisobutyronitrll 7.7

primiraa Octylmarcaptan 12.5

was allowed to reflux for 2.5 hours Give the dispersion an eye, whereupon the low-boiling liquid is poured into VakttUR was evaporated until the fast substance content of the dispersion 55 oew%. A stable dispersion was thus obtained.

- 20 109812/1880

Example 6

Representation of a dispersion of 42 wt # of a carboxyl-modified one FolyCmethylmethacrylats) in an inert organic Liquid. The egg stage consumes 18% by weight of the total polymerizable monomers and includes a weight ratio from polymerizable monomer to copolymerizable polymers Stabilizing agents such as 3.3: 1. The best of the stabilizer consisting of a non-copolymerizable stabilizer is used in the germination stage. In addition, the disperse polymer reacts with the non-copolymerizable one Stabilizing agents brought about the formation of covalent bonds by adding carboxyl groups of the disperse Polymer react with epoxy groups of the stabilizer.

A smack from ». Parts Stabilizing solution F 800.00 Methyl methacrylate 1000.00 Stabilizing solution E 600.00 AEodiisobutyronitrile 50.00

primary8 octyl mercaptan 0.75

Hydrocarbon A 3000.00 Hydrocarbon C 2150.00 Hydrocarbon D 3000.00

n-butyl benzyl phthalate 400.00

was in a reflux condenser and stirrer provided Eeaktionsgefäß introduced, heated to reflux temperature and Held under reflux for 40 minutes. Thus one formed finely divided population of stable dispersed polymer seed particles.

A mixture of:

- 21 009812/168 0

BAD ORiGtNAL

(Peile methyl methacrylate 4-360.0

Azodiisobutyronitrile 7.7

primary oety! mercaptan 12.5

became refluxing uniformly over 2 hours The contents of the reaction vessel are added, whereupon a mixture of 55 parts of methyl methacrylate and 55 parts of methacrylic acid were added over 8 minutes. The dispersion was still Refluxed for 20 minutes and a stable dispersion of polymer was obtained.

A mixture of 2500 parts of hydrocarbon was added to this dispersion C and 15 parts of tertiary amine from coconut fatty acids added, whereupon the solids content of the total mixture through Thickening in vacuum was increased to 42 wt #. The mixture was then heated under reflux (at about 115 ° C.) for a further 2 hours in order to remove the carboxyl groups of the disperse polymer To bring reaction with the epoxy groups of the stabilizer. Thus, a stable dispersion of the polymer was obtained.

Example 7

Representation of a dispersion of 40 wt # poly (methyl methacrylate / ethyl acrylate) in an inert organic liquid. The germination stage consumes 11 wt # of the total polymerizable Monomer and comprises a weight ratio of polymerizable monomer to copolymerizable stabilizer such as 0.67: 1 · The stabilizer for the nutritional stage was made added in smaller and smaller amounts, the more monomer is added had been.

A mix of:

- 22 -

0098 12/168 0

Parts of hydrocarbon A 366.0

Hydrocarbon C 120.0 Hydrocarbon H 390.0

was at reflux temperature (80 ° C) in an old reflux condenser provided reaction vessel heated, whereupon a mixture of:

Methyl methacrylate 30.0 Azodiisobutyronitrile 3.0

n-octyl mercaptan 0.044

Stabilizing solution B 90.0

was added and the reflux temperature was still 20 minutes was held. Thus a cloud of stable ones formed disperse polymer seed particles.

A mixture of: Ethyl acrylate 120.0 Methyl methacrylate 120.0 Azodiisobutyronitrile 0.4-

n-octyl mercaptan 0.6

was divided into four equal weight jackets, and the following

Food mixes were shown:

Hr.1 Mixture as described above stabilizing solution A

Hr.2 mixture as described above - stabilization solution C

Hr.3 Mixture as described above stabilizing solution C

Hr.4 mixture as described above Stabilizing solution C

009812/1680

60 , 2 - 23 - 35 , 0 BATH ORIGINAL 60, 2 ' 25, 0 60 , 2 15th , 0 60 , 2 5

These food mixes were added to the refluxing one in the order given for 15 minutes each The contents of the reaction vessel are added, whereupon the reflux temperature was held for another 20 minutes.

Then the low-boiling liquid was evaporated in vacuo, until the solids content of the dispersion was 40% by weight. Consequently a stable dispersion of the polymer was obtained.

Example 8

Representation of a dispersion of 40% by weight of Foly (methyl methacrylate / ethyl acrylate) in an inert liquid. The Seimstufe consumes 11% by weight of the total polymerizable monomer and comprises a weight ratio of polymerizable monomer to copolymerizable stabilizer such as 9: 1 * Das Stabilizers for the Hährstufe became smaller and smaller Amounts added the more monomer was added.

A mixture of: parts Hydrocarbon A 534.5 Hydrocarbon C 124.3 Hydrocarbon D 192.8

was in a reaction condenser provided with a reflux condenser

Gefäes heated to reflux temperature (80 ⁰ C), whereupon a

oemiech from:

H »thTls» tB * exylate 22.5 Ethyl acrylate 7.5 Stabilization process Bl 6.8 Asodlisobutyronitrile 5.1

n-Butylbeneylphthalate 24.8

- 24 009812/1680

was added and the reflux temperature was still 20 minutes was held. A population of dispersed polymer particles was thus formed. '

The following food mixes were prepared:

Parts

# 1 methyl methacrylate 44.8 Xethyl aerylate 15 # 0 Asodiisobutyronitrile 0.46

n ~ Octy! mercaptan * 0.03

Stabilizing solution B 11 »95 Hr.2 methyl methacrylate 44.8 Ethyl acrylate 15 to Azodiieobutyronitrile 0.46

n-octylatingcaptan 0.05

Stabilizing solution B 8.97 Hr.3 methyl methacrylate 44.8 Ethyl acrylate 15.0 Aiodiisobutyronitrile 0.46

n-octylaercaptan 0.03

Stabilizing solution C 5 * 98 Mr. 4 ethyl methacrylate 44.8

ithylacrylate 15.0

AEodiisobutyronitrile 0.46

* n-Octylaercaptan 0.03

Stabilizing solution C. 2.99

These food mixes were given in the following order for 15 minutes at a time to the refluxing

, - 25 00 9 8 12/168 0

The contents of the reaction vessel are added, and the reflux temperature was held for another 20 minutes. The low-boiling one Liquid was then evaporated in vacuo until solid content the dispersion was 40 wt #. So you got one stable dispersion of the polymer.

Example 9

Representation of a 55% strength by weight dispersion of poly (methyl methacrylate / n-butyl methacrylate) in an inert organic liquid. The germination stage consumes 18 6ew% of the total polymerizable monomer and comprises a weight ratio of polymerizable monomer to copolymerizable Stabilizing agent such as 1.1: 1. The stabilizing agent for the nutritional stage is added in smaller and smaller amounts, depending on the food more monomer has been added with the final feed mix containing no stabilizer at all.

A mixture of: parts

Stabilizing solution B ■ 1800.00 methyl methacrylate 1000.00

Azodiisobutyronitrile 50.00

primary Octy! mercaptan 0.75

Hydrocarbon A 3000.00

Hydrocarbon C 12 J 0.00

Hydrocarbon G 2500.00

n-butyl benzyl phthalate 500.00

was in a with a reflux condenser or provided with a stirrer Reaction vessel introduced, to reflux temperature (80 ° 0) and then refluxed for 20 minutes. A finely divided, stable dispersion of

0098 12/1680 - 26 -

Polymer seeds.

A mixture of:! Parts

Methyl methacrylate 4-100.0

n-butyl methacrylate 460.0

Azodiiaobutyronitrile 7 »7

n-Octy! mercaptan 12.5

was divided into three equal parts of 1529 parts by weight each divided, whereupon the following food mixes were prepared:

Nr »1 mixture as described above 1529» 0

Stabilizing solution C 200 _f 0

No.2 mixture as described above 1529.0

Stabilizing solution C 75.0

Mixture as described above 1529.0

This food was added to the refluxing contents of the reaction vessel in the order given for 20 meows, after which the reflux temperature was maintained for a further 20 minutes. A stable dispersion of the polymer formed.

Example 10

Representation of a dispersion of 55 Gei ^ .PolyCHethylmethaerylat / -2-lthylhexylacrylat) In an inert organic liquid. The germination stage consumes 18% by weight of the total polymerizable Monomers and comprises a weight ratio of polymerizable Monomer to copolymerizable stabilizer such as 1.1: 1. The stabilizer for the speed level is always in

- 27 -

009812/1680 :: · '

BATH ORIGINAL

«Fl If

Smaller amounts are added, the more monomer has been added is.

A mixture of: parts Stabilizing solution B '1800.00 Methyl methacrylate 1000.00 Asodiisobutyronltril 50.00

primary octyl mercaptan 0.75

Hydrocarbon A 3000.00 Hydrocarbon C 1230.00 Hydrocarbon G 2300.00 '

n-butylbeniyl phthalate 300.00

was introduced into a vessel equipped with a reflux condenser and stirrer Beaktionsgefäss, brought to reflux temperature (80 ⁰ C) and then kept for 20 minutes under reflux. A finely divided dispersion of polymer seed particles formed.

A mixture of: Hetbyl methacrylate 4160.0

2-ethylhexyl acrylate 400.0

Aiodiisobutyronitrile 7.7

n-octyl mercaptan 12.5

was divided into three equal parts of 1529 parts by weight each divided, whereupon the following food mixes were prepared:

Iv.1 mixture as described above 1529.0 Stabilizer C 220.0

> r.2 mixture as described above 1529.0

Stabilizing solution C 100.0 Br.3 mixture as described above 1529.0 Stabilizing solution C 50.0

009812/1680 - 28 -

These food mixes were made in the order given

for 20 minutes at a time to the refluxing The contents of the reaction vessel are added, whereupon the reflux ' temperature was maintained for a further 20 minutes * A stable polymer dispersion formed.

Example 11

Representation of a dispersion of 40% by weight poly (methyl methacrylate) in an inert organic liquid. The germination stage is consumed 11 6 wt% of the total polymerizable monomer and comprises a weight ratio of polymerizable monomer to copolymerizable stabilizers such as 9: 1. That Stabilizing agents for the driving stage are becoming smaller and smaller Amount added, the more monomer has been added.

A mix of; Parts Hydrocarbon A 334 * 5 Hydrocarbon C 124.3 Hydrocarbon D 192.8

JLN was brought one provided with a Hücklaufkondensator Beaktionsgefs'se on Bückflusstemperatur (80 ⁰ C), whereupon a mixture of:

Methyl methacrylate 30.0 Stabilizing solution B 6.8 Azodiisobutyronitrile J>, 1

n-butyl benzyl phthalate 24.8

added and the reflux temperature was held for a further 20 minutes. A colony of dispersed polymer formed.

The following food mixes were prepared:

- 29L-0 0 9 8 12/1680

BATH ORIQINAL

Hr »1 methyl methacrylate

Azodiioobutyronitrile n-octyl mercaptan Stabilizing solution B

No. 2 methyl methacrylate

Azodiisobutyronitrile n-octyl mercaptan stabilizing solution B

No. 3 methyl methacrylate

Azodiisobutyronitrile n-octyl mercaptan stabilizing solution C

No. 4 methyl methacrylate

Azodiisobutyronitrile n-octyl mercaptan stabilizing solution C

Parts 59.8

0.46

0.03 11 x 95

59.8 0.46 0.03 8.97

59.8 0.46 0.03 5.98

59.8 0.46 0.03 2.99

These food mixes were 'in the order given added over 15 minutes to the refluxing contents of the reaction vessel, whereupon the reflux temperature was maintained for another 20 minutes.

The low-boiling liquid was then evaporated in vacuo, until the solids content was 40 wt #. Thus one obtained a stable polymer dispersion.

- 30 -

009812/1680

Claims (1)

Claims 1. Process for the preparation of a dispersion of a polymer in an inert organic liquid in which the polymer is insoluble, by polymerization of an α, ß-ethylenic unsaturated monomer in the liquid to form the polymer in the presence of a polymeric dispersion stabilizer in a two-stage reaction consisting of a germination stage and a nutrient stage, characterized in that that 1) in the seed stage, the unsaturated monomer and the polymerizable polymeric stabilizer of the type described above in a weight ratio such as 1:10 to 15: 1 to the inert organic liquid are added, the added amount of unsaturated monomer being 7-70% by weight of the total monomer to which the disperse polymer is formed is; 2) in the nutritional stage, the remainder of the unsaturated monomer and adding the polymeric nutritional level stabilizer of the type described above; 3) the total amount of the polymeric stabilizing agent added 0.5-50% by weight based on the disperse formed Polymer is. 2. The method according to claim 1, characterized in that in the nutrient stage the monomer gradually together with a part of the Stabilizer is added, the ratio of stabilizer to monomer getting smaller, the more more monomer has been added. - 31 - 0098 12/168 0, 3 · Method according to claim 1 or 2, characterized in that the nutritional level stabilizer is a non-copolymeric sable polymeric stabilizer is. 4-. The method according to claim 3t, characterized in that the High level stabilizers chemically reactive Groups entaalt that with complementary chemically reactive groups of the disperse polymer to form 1 to 10 covalent bonds per molecule of the stabilizing agent reacted with it can react. 5. The method according to any one of claims Λ to 4, characterized _f that in the seed stage the ratio of monomer to mischpolyaerlal «rbarem stabilizing agent such as 1: 5 to 9 * 1 - based on the weight - is. 6. Method according to one of Claims 1 to 5, characterized in that that aas polymerisation process at a temperature does not is carried out above 100 * C. 0 03812/168 0