DE1495544A1 - Process for the production of self-extinguishing synthetic resins - Google Patents

Description

U95544

DEUTSCHS GOLD- HMD SILBEH SCEISIDÄAiiSTALT VOiLMALS ROBSSLEB Frankfurt am Main, Voissfrauenstrasse 9

Ancestors for the production of selbetlöechondan Kunsfcharzen

Bo are hardly flammable or so-called ο self-inflicting Plastics have become known that are either ale hardenable Casting resins or Tlfermoplaston can be prepared, You look into the group of flame-retardant, un «· saturated polyeater jelly resins and in the group of heavy flammable thermoplastic arts peat e oinfceilon «,

The self-cleaning, unsaturated polyester glass lens usually contain chlorine and / or brost and / or phosphorus incorporated. In addition, the plan is being enforced to slow down the use of small amounts of antinone oxide is recommended They are mainly flat or profiled with Glass fiber reinforced panels, see B «Light panels, manufactured. However, it has been found with these products that their weather resistance is inadequate «Yes After a course of outdoor weathering, it shows a strong yellow color and the glass fibers become visible. Simultaneously the surface gloss, which is very important for self-cleaning, is reduced during their manufacture Antlmontrioxvd is also used, this creates a cloudiness, by which the character of a light plato is lost · Their fire behavior can be adversely affected by increased smoke development. This is particularly noticeable when fighting fires

BAD OWGINAL 909807/0948

The self-extinguishing if thermoplastic synthetic material · are mainly through the addition of the usual flajameahemic substances, in particular halogen ™ and phosphorus-containing substances and also from antioxidant, from normal thermoplastic «! horsesteiled »SIo have a low strength and v« r al lea a low temperature permeability · you are for the Manufacture of slaafaeorrerttSiktea panels because of yourβ not suitable for unfavorable behavior during processing Its burning down, causing flammable plastic parts The fire is spreading further · They therefore do not offer sufficient security, especially in the case of roof cladding against flying sparks and radiant towers.

Not a satisfactory solution for making plastics with good victor strength, high inherent stability and surface quality with sufficient resistance to flue fire and shining yttrms was not known so far

It has now been found that self-dissolving, under the action of fire or radiant walls, were practically non-existent dripping synthetic resins through polymerisation at least one * ■ onosoric polymerizable organic compound, given · if In the presence of a polymer of these compounds, in the presence of a phosphorus and optionally halogen-containing one The substance and preferably using a polymerization catalyst * or system can * kaan, if auua sin Geaisch polymerized, which of at least about 5 parts by weight of at least one copolymer satee from Vinylohlorld (▲) · at least ·· tone about 1.2% by weight - ^ phosphorus la Fei an optionally halogenated · containing and F-O-

- 3 BAD BiG '^ ^AL

909807/0948

14955W

Phosphorus compound (B) containing compounds, preferably organic ₍ preferably at least one monomeric, polymerizable, ritual compound (C) _# and, given-TaI- * β, a betrayal (d) in amounts of less than about 3 GeWe- ¹ J *, before eye wise there is less than about 2.5 wt .- ^

The copolymers dos vinyl chloride * (a). which must be soluble in the moaraeren, polymerizable, organic compound can be used as cocomponents, for example, esters of acrylic acid or methacrylic acid and in particular ί maleic acid υβν. contain. However, they should preferably contain methyl methacrylate and, in particular, vinyl acetate. Phoaphorbaltlge copolymers can also be included. The cocomponent can be present in this copolymerization in the liblicfaen amounts, taking into account the solubility required. In general, the content is between about 20 and about Uo wt .- ^ t.

Dom aengenmäaeigexi addition of copolymers of vinyl chloride (a) If no particular limit is approved upwards. It is only made possible by the possibilities that exist in the selection of the co-components and by the properties and the intended use of the polymer to be produced. In general, iodoeh amounts are used from SO Gew ~ -j & not exceeded. Preferred are about tO to about 20 wt .- ^ rd.

The »phosphorus can be used in the starting mixture both in the form of a inorganic ale also preferably an organic one Phosphorus compound. This can also meee;

tftt »tf / ttü

_BATH

Pho sj borate you au? welaen »Dor Phosphor καββ However, gen * odor partially bound to floor Sauers toffatoaeo. Examples of this group of Vorblndunfen are Orthoplkoepltereäurv t organic Phoepbate and Phosphonato · Particularly go · 6iga <t are Trlalkylphoephata, vlo Trlaethylp & oepbet, then Triciloratbylphosphat, Bis "(chlpopyl) -proponyl-2-Phoeihouat

CH ₂ CB ₂ O -PO-CH-I- OCB - P (OCB ClCB ₂ CH ₂ CH ₃ OClI ₂ CM ₂ Cl

Also unceaatticte PboephorrerblBdeee · », άί · bol dor Berit ation" It olat ^ obaut werden "fcnwn In the milling machine · piping T <blnd-oDgen contain polyMerleatleacfJahlse self-sustained or non-substituted vinyl, allyl« ip, acrylic or lttt -itothacrylyl-athan-i, 1-bia- (pho sphoncäurediaethy! ester) and 1-MetheoryIyI-Äthanphos; ih <meKuredinethylester.

»« Aeeeftttiete oopelyaerlalexbare Phoephor ^ eri ▼ tjrw> nd «earth., Can these the sKmeswre» polyswrlelerbere, or ^ ailsohe Terbindon «(C) eans or partly erseti

The »rfiadnnfseemasee PalyjMrieatloa sell la present wen

"Indisteae about 1.2 Qew * - £ phosphorus is threatened"

Wach oeea the PhospherettsatB nnr dares dl · Ae-

ford "run" -en ₍ which is divided into the Folyaerleat c "<*" eelle "" be "x> nst. As is known, nüsit old dough — de * the" eohanisehe firmness, the mtter "n""1 ax aeevsaimxgKei * ejeejeji iraeeer esss' Teejewniviir wmg die feieiar »it» d die ii niüdrnT nmum ** .- tü # eite

U95544

An * ' WJbXOfBfZlIt * koomen dencnaoft Phosphor "narrow question" the uct> r about 10 wt. ~ £ 11 open. The mentioned quantities ontepreohon ± λ JLlgos: eln9n a «Elnaats τβη about h bla about 90 before: ro & aweieo ron about 10 bia about 30 Gev * - £ on a phorverblndung ·

The erflcdungageaftaee procedure is carried out as a precautionary measure in the course of a bonoaaren, polyverialable, orjaniecaen Ψ * τ— bix »^ u3 £ (c) dnroheefOhrt, the quantities given are the above-mentioned quantities to 100 percent aolloH. Advantageously let ea, van Gea: acben to go out, which contain the compound (c) in quantities from about 40 to about 85 0ον · - £ · To dleeen TerbiD <ungen born inabeeondare cat of acrylic acid «ad Meti jtcrylaaare. Beaendora suitable are the prayers of the Acr ^ 1- or. Methaorrleftttre, on it aliphatic alcohol content 1 to k carbon atom "contains oowle set with cyoloallphatleohen baw hoterooyollechen alcohol components," le cyclohexyJUaethaorylat, Tetrahydrofurfwrylauotl aorylat. MethacryleAureaethyleeter is boToraugt eeetat »

The monomers mentioned can also be used or several other polyaerialable compounds, Ina beecndoro vinyl compounds, oimgeaetat become · Beiapiele for the connection a rinyllerte aroaatieohe Xohlanvaeeerateffe, via styrene, vinyl toluene. Vinyl ester, vie Vinjr lace did. Anhydrides baw. Qatar won unconditional Dloarbonelaren, such as Maleineaareanhydrld, ruaarelwredialkyleeter. Styrel, MaJ.einalureanhydrld, F «amrsauredlaethyleeter, PuemralnredlAthyleeter. Advantageously let

- tf -

909807/0948

bal

free, these compounds in canteens at about 30 wt. see the geaaate exit notification, elnsusetsen.

A wider variant of the invention thread Laeen VerfaJ

envisages assuming such an assumption that the polymer included in the monomers mentioned. Ha" Polyverlsit can belepielawelae In Hangen bla au 20 wt present join. However, you can also use kneadable Hassan expenditure.

According to another variant, it is also possible to use the mono acre compound (C) in Font a β in a prepolymer obtained by partial polymerisation, which is known as a prepolymer, whereby ee also nttglloh lat, the other polarizable compounds aULtbaaan. Duroi dieue variant is given as erallgllolit * umm Oawlaon «ine bell> bige Konis tens. One can therefore proceed from syrupy approaches, in which vlekoaitaten advantageously lie about 50 tu id 5000 op. Xh ecause the more "el wan Koemi 'n biii below about 60 0AW .-] (be it in the form Mononaren ainaa Vorp> lyeerisate · · This variant lat baaondara door rbelten appropriate in the presence of unlBsllchen Pigaanten and Füllitoffon the \.

Ee i it also eiOglioh, the Pol feriaa tion la Oegenwejrt flfcl those Cross) ters, such as functional vinyl compounds plaerylates and) iaetbylaorylate ven glycols "and polyglycols," le Xtfay.englykoldiMethaorylat · Trlftthyleneglykeldiaethylaorylat, Tetraethylene glycol and Polr & ttaylene glycol dimetkaorylate, durol on watches. These networkers are «Travel up to about 2.0 0ew .-) l, drawn on the au polynerl-

CHIGiNAL

»OSffT / ttU

H95544

yawing Goeaa mixture, eugeeotsst «. You can be present at the production of the ο prepolymers

Furthermore let os IaOgIi.ob _r ssw «8. *: Nlic? *? Asa? 6» ape "" ie glass fibers "

in the form of mats, pieces, woven fabrics, ο flat fibers, inorganic or organic fillers cad dyes dem Polymerisatlonegoniech jsumiae tacan * On this ¥ ei.ao can strength and Au3 «K» h «m d © T P« »lyi3» rls2to "varies f be o

The PolyMerieation aelbor is in at Oich known Velae dureb ^ efünrt _v belepleletreioo s under the influence of Wlrae, UY-Stranlnn £ or ener ^ ieroiener radiations "Verteilhafter is Jedocb, Eatalyoatoren as radical forming Startwdttelt beioplelaweiee ABonrerblndtm ^ s and particularly peroxides oinstusetxen, «. Pre-cattle catfish, however, have seven known catalyst systems. Here, ice ^ it pfieblt SLCB _r eolcne catalyst "and StartBittelsyeteno au _t use the farbbestSndlff and weather test are"

(! Hose conditions are, for example, -of iOl ^ end-

eten combinations satisfies _"f Poroxyde as Laaroylperoxyd

alone or ansiiin mi * hydroperoxides such as

ketone peroxide, sonwofeUM ^ -tice Terblndnneen, like © - (p-Tolnoleulfonaetnyl) -äscin · Lanrylawrcaptan n »a. , orcanloebo StA-stanBon Kit a * lonogeu sobundKnen Halo ^ enatowi, Tor all Cnlorldo or Bydroenlorlde oreaniscner bases »aB Pnenylathylda-btttylawcUtrnlorid, Solnrenaetallspuren, weiso Köpfer ale Kwyfernapbtnenat

BATH

- 8th

The generally known PolTKerisatAonastartmittol PeroyydOf as L & uroylperoxydp Benzoylperoxyd, Methyl * thy 1 «* ketone peroxide can also be used in ellain or goal sola side by side used «if the hardening occurs during the fur the effect of the peroxide is carried out at the necessary temperature.

If no special requirements have been made on the Farbbestandigkeit, anen k & eucib all other cold-curing Sys been used most _f in particular the known Redoxsystetsop vie ZOB »tertiary amines additionally having diacyl =" peroxides "

The hardening takes place even in thick layers, 10 MB «without any particular difficulties and without turning the bridge To ensure optimal stability Is it sweoSn & ssig »according to the main polyaerleatioaa sequence Another 1 to 2 hours at 60 to 100 ° C night-time tubes. You can also use the usual amounts of PVC stabilizers and UV <*> Absorbor are added «In addition, the Mixtures of old laudable dyes clear and transparent and can also be colored with opaque dyes »

The products manufactured according to the ornational processes are not only equally dissolving and do not drip under the effect of fire or radiant weather, but are also characterized by high mechanical strength and resistance to weathering. "Clear and colorless polymers can also be obtained" Surprisingly the polymers can be, for example, “drawn deeply by vacuum * or subsequently deformed, loaned and processed without difficulty using the blue process. _BATH

909 807/0 94

• i

The iW düi naolurelgcaiden B ^ iepl ^ tön ervÄhnton burn test vrardien in Anlotitnme am- die Voreoitriit ASTiI 635 56 T «ue led» You LBttge der SCtndfXeHsso amount approx (ie »h ₆ nwh 30 see. Asüakreniazel ^ l stated»

Not otherwise stated, ale copolyraorleate dee vinyloolorida a suepenslonspelyaorisafc aua 60 βόν " ~ i" polyvinyl chloride and 'kQ Gew "^ polyvinylacetate * K ^ Vert" 55, - was used. ■ '■ · ■ · ■.

XMLe Before | "ely" erie "to were duroh partiolle Polynrarlaation according to known Verfabron (Belgian patent very Ift 572 359 » frans ^ eieete "patent specification: 1 221 537" deutoehe Auelege " eohrift 1 083 057) i »an aogenam & ton sintopf reaction

Torpolyarerieat des used in the examples b «saes a Vloln» 9ltfit of 3500 cpo

In Example 6, there are 1% tiares in the polyeerieatione · Kioonung noon 1 eetr »- ^ © ib» i * ylBinndilauret al »Polyvinyl chloridegtatdlieator and; 0.1% by weight of a common UV absorber "

Stir the. BresHtevte «orden plates as well as glass slices seeoveen nnet at lfcMiw» w «perat« «r aaecenSrtet« Lt a »flcUtelt aas. ' O _V 5 Oei "" ^ Le "rtrflperoxy4 _v 0" 1 Gev "- ^ an IfcUietltr1phtfiala *> Lggung _t the kO Gw,

1 _V O f ^ K Ko ^ er als HejKbtAenat and llBlf 1 iite _T ■; the ans

^Bass

Di («p-toluoleulfonHiei; hyl) affiin, 23 wt» ^ ß-pitenylätliyl. dibutylaainhydt-ochlox-ici and "5% by weight of dibutyl phthalate insisted ο The Flattenditske was fraudulent; ca »3.5 to.% caa

Example 1 The polymer! 3leronde mixture consisted of:

fc 15 Gewo = ^ monoaoröiH methyl methacrylate

59 ^M prepolymerized methyl methacrylate

5 ⁿ Copolynierieat dea vinyl chloride

2O "trichloroethylphophate

The burning time after lighting is 192 and 213 seconds, the burned length after the first /, ollmarke was 22 and 29 mm, the polymer was self-extinguishing and did not drip «

In contrast, showed a polymer that consists of a Mixture of:

- # prepolymer of methyl ^{methacrylate 25 w} trichloroethyl phosphate

BAD ORfGi-NAL

90 9007 ^ 004

-H-

was polymerized, a burn time after lighting of 386 and 358 seconds _t a burned length after the first inch mark of 33 and 32 ram, awar extinguished. but dripped heavily.

Example 2 The mixture to be polymerized consisted of:

15% by weight of monomeric methyl methacrylate

6h "Prepolymoriaate of methyl methacrylate

5 ^w copolymer of vinyl chlorine! Ds

15 * trichloroethyl phosphate

The burn test showed: "

Burning time of 352 seconds «Burning length of 50 mm, self-extinguishing and no dripping »

In contrast to this, a polymer which was polymerized from a mixture of 8h wt .- ^ prepolymer of methyl taethacrylate and 15 wt

Example 3 The mixture to be polymerized consisted of:

30 wt .- ^ monomeric methyl methacrylate hh "Vorpolymerieat des Methy! Methacrylate 10" copolymer of vinyl chloride 15 * Trichloräthylphosphat

The burning test of the polymer showed:

Burn time 172 and 118 seconds, burn length 15 and 10 mm, self-extinguishing and non-dripping

BAD OHiGiNAL

Λ **

-aft -

With »η i el k . . , _v

The mixture to be polymerized consisted of:

KO GeW ₃ - monomer «» Methyl methacrylate 39 ^{«prepolymer of methyl methacrylate 10 n} Copolym« rieat of vinyl chloride 10 ^w Trichlojratliylphosphat

The burn test showed »

Burn time 151 seconds _E BrönnlUnge 21 esa, 3olbetlc5aohend and not dripping »

Example 5

The mixture to be polymerized consisted of:

69 Gewo = ^ monomeric methyl methacrylate 30 ⁿ copolymer of vinyl chloride

The burning test showed:

Burn time 300 seconds, burn length 100 not self-piercing _and dripping.

Example 6

The mixture to be polymerized consisted of)

lh weight of monomer em methyl methacrylate 10 ^w copolymer of vinyl chloride

15 ^{n of} an organic phosphorus compound of the formula given above with 27% by weight, - ^ chlorine and 15% by weight <. <- ^> phosphorus, molecular weight about 6II

as well as polyvinyl chloride and UV stabilizer

BATH ORIGINAL

. 909807 / 09A8

H95544

The burning grate revealed!

Burn time 1 ** 9 and 160 seconds «Burning length 26 and Z6 m, self-seeing and not dripping» The poly »morleate was colorless and very weakly opaque»

Example?

The su polyaerlslerende mixed breed consisted of:

hh Gewo «$ monomere * methyl methacrylate 30 GeWo-flt prepolyester of methylraethacrylate

10 wt «» ^ copolymer of vinyl chloride «f

15 Gew .- ^ of Ih Example 6 specified phosphorus compound

as well as polyvinyl chloride and UV stabilizer

The burning test showed;

Bronndauer 200 and 163 seconds focal length 11 and 13 na _t eelbetlöechend and not tropfendο Dae Poly "merieat was colorless and klarα

Example 8 The stimulating mixture consisted of:

7k Gewo-i » monoaerea methyl methacrylate

10 ** Copolyasate of vinyl chloride »

15 "of an organic phosphorus compound

(Pnoegard B 20, Ilandol product from Monsanto) with 0.9 wt. Rp chlorine, kZ Gow .- ^ bromine and 8 Qew.- £ phosphorus, boiling point 180 to 182 * C / O _t 1 mn Hg

as well as polyvinyl chloride and UV stabilizer

The burn test revealed Burn time 137 and 138 seconds, burn length 13 and

11 MB “self-extinguishing and not dripping” The polymer was almost colorless and clear

909807/0948

» Lh -

Example g.

The ssu polymer! Egg ring consisted of:

V: Oeν. ~ $ f. ^ on ^ niorp ^ Mothylraothacrylat

'30 ^w Vorpoiytaeriuat von Hethylraothacrylat

10 "copolymer of vinyl chloride

15 ^w phosphorus-containing compound of the example

as well as polyvinyl chloride and ÜV = »stabilizer

The burning test showed:

Burning time 15 ^ and 156 seconds, burning length k and 15 mn, solbot-quenching and non-dripping. The polymer is almost colorless; 3 and clear «

Example 10

Dio Ku polymerizing mixture consisted of:

69% by weight of methyl methacrylate 15 "copolymer of vinyl chloride 25 "tritaethyl phosphate

as well as polyvinyl chloride and UV stabilizer

The burning test showed:

Burning time lh and 10 seconds, burning length lnm in front of the first customs mark, self-extinguishing and not dripping

The polymer was colorless and slightly clear *

-

WHEEL ORiGNNAL

909807/0948

14SF5544

The mixture to be polymerized consisted of:

39 <* iBW ^ 3 Kionojceren «. MethyXraethacryXat

30 Yorpaly »e: Risate of methyl methacrylate

15 ^i; GopbXym6risat des ViiiyXchlorid »

15 *

e as well as Polyv-liaylchlörld- and \ 7V-Stabi3.ioat: <ir

i) ei "Kresüivoct resulted in:

Duration 3 seconds _£ Bfösinlünge 3 i »jr vox 'the first EolXraarJca, neltsstXöachend isiid not dripping,

The polyacrylate was farbXos 12nd kJ.aro BejLspieX X2 The EU poXymerleierende His & uuig consisted of:

6h wt. ^ Btononerem HothyXmethacryXat

15 ** GopoXymerieat from VinyXcliXorid

20 ^w bleachXoropropyXj ^ propenyX-Z-phoophonat

as well as FoXyvinyXchlorid · =. and UV-StabiU'eator

The burn test revealed

Burn time 80 and 120 seconds, burn length h and 15 VBOi _x . self-extinguishing and not dripping »

The polymer was colorless and clear « Example 13

The mixture to be polymerized consisted of:

7U Qew <- $ monomeric »methyl ffethacrylate

10 of a Copolymerisatob of vinyl chloride and 20 percent ⁿ -.% Maleic

15 "X Trichloräthylphosphat c ^J olyvinylchlorid ·» and UV - Stabilinator

- I ₆ ~

9.09.8.0.7./0.9A8 'EAx

- 16 Dev burn test showed:

Burn time 168 and 165 seconds, burn length 25 and 32 mm, self-piercing and non-dripping «

Pci.ywerieat was colorless and clear. Example Ik The mixture to be polymerized consisted of «

71.9% by weight of mononerera ethyl methacrylate 10 "copolyestericate of vinyl chloride 15" trichloroethyl phosphate
2 «triethylene glycol dimethyl acrylate

Polyvinyl chloride · = and UV «* stabilizer The burn test revealed

One sample plate _r 8 esa dio & 50 cat wide and 100 cm long; was, lengthways in the middle of a rabbit »with the clear Veite ho x. 60 cm and the HShe 1OO it hung. For the distillery the chimney was placed with the plate on two feet. The plastic plate was then flamed on the lower edge for 10 minutes using seven burners, which were evenly distributed over a plate width of 50 cm. The distance between the burner opening and the lower plate edge was 7 cn, the Flemings »length of the burner approx. 11 on«

After a burning time of 10 minutes, the burners were switched off, after a further 4 1/2 minutes the fire went out. The plate did not drip, the burnt spots were heavily charred and formed a solid framework. Weight loss of the plates was 10 i *

The mechanical properties of a h mm digital plate of the same composition were <

Flexural strength: 1025 kg / cm (according to DIH 53 * 152 Dyns tatprobe) Base bending strength: 10 "J" cm kg / cm "(according to DIH 53 & 53 Dynstatprobe) -

9 0 9 807/0948

1Ü5S44

Example 15

The asu 'pefiBgmmvX β * «ί *« 3β * ϊβ mixture consisted of:

5 * »wt. - # SKaMBHMReW Hötfeylmetnaerylat 10 "BKMttnsereate styrene

15 <* CopolyoMtzdleat dee Vinyl chloride

20 ^u trichloroethylphophate

The burn test revealed

Burn time aear 143 ratal 82 seconds, porridge length 7 and 3 to, self-XSscItend, not dripping _{or similar}

The Polyeerlaat wkx> far 1> 1 ob and schirach opaque,

l 16

The painting to be por.yaigrende consisted of:

kz Oatw «~ ^ nrWa methyl methacrylate 20 ⁿ aottOBraro« butyl acrylate

15 * CvBolymvrZm & t atm Vinylcblorldo

2O "

2 * Tiriathyleneglykoldlmethylacrylat

PolyrlnylGhlorld and UV stabilizer The Bv «ont« et yielded *

Burning time 8 ^ seconds Burning length 1 aa » _t even thaws without dripping.

17th

The su polTBHwlelereii ^ e Genisoh consisted of:

6h wt .- ^ M methylsethaorylsite 15 * Copolyeerleate dee Vinylchloride 20 »l-Methacrylylttthanphoneauredleetliyleeter

eowle Polyrlnyl Chlorid-Stable! eat or

Burn test gave ■. · ,. ■ - -.f.- · - · .. · ■■ - ^ iV Burn time ld ^r / and Ϊ98 seconds, 9 and XS

lengtha _c self-extinguishing: and not dripping ο

Bae Polyiswri. aa * vase fartföes-, spawn, opaque and good:

■ ■ · '.-: ■ ^r ■■ / {- verfor «bar ₀

Example 18 Daa su polynierlolorenüa mixture consisted of:

Me thy lmetliacrj ^r lat

52 ", 4 * Copolymexisat dos Yiaylchloride 19 Trichlorosthy! Phosphate

as well as polyvinyl chloride and UV = stabilizer The Hlschuiig lies al ο Knötaiaae © in front of ο

For the hardening, Z% of a 5Q-igen Bensoyl "peroxydpaetö was exposed". According to the usual working technique, an inner, thick plate was pressed at 90 ° C.

The burning test showed:

Burn time 1 and J seconds, burn length first inch mark, aeXbstlue'ohend and not dripping.

Example 19 The su-polywerisier * ende mixture consisted of atwsi

30 ßew. «=> $ Raononerea» »taylaietliacrylat kZ " prepolymer of methyl methacrylate

10 "Copolyraerisat of Vinylchlorlda

15 * trichloroethylphophate

2 "triethylene glycol methacrylate

and was two hours lia water bath at 60 ° 0 cured with 0.2 Qffi. · ^ lauroyl peroxide and 0.05 wt $ _r a L8eung the ^ O drinks. MetaylSthylketonperoxyd contained ο Thereafter, with XOO ⁰ C wOhrend one hour nacherhltsto

ORIGINAL BATHROOM -

90980770S48

r r * rc; i * nteet resulted in:

ir ο «unique: *. ' 103 SoStKUden, Bjritfmlängö U nas in front of the ore ten _v celbctl Boohend and spawns:

DIo «u polymer!« J.orexide Miselumg consisted of:

73 Gewo <- $ iTii-ti
10 ^M nopolyinoi ^ sat dec "vinyl chlorides

13 "Ts ¹ Ichior Ethyl Pliotphate

2 "TrlfithylcaglykolöisaetliViCrylat Λ

xwö. wturd "at 6O C ^for iia y ^ 2 ineerljad Stxtndon ausgahürtet with 0 2 _r tr" u * "'/ i latiroylpcroxydt anachliceacad still" ί ^ β hour, wherein

The Erontitcrit revealed:

? .12 seconds, Bratuiliingo 4 now before the first esa " _t colbotlösendem ttnd not dripping« - '^ ^f ^

BoAapiol 21

The eu iiolytserizingm odor consisted of:.,

4 2 Gew r - raoiiomcrem methyl methacrylate

30 ^w prepolymer of Hothylmothacrylat ""

10 ^w Copolytnerieat doe Vinyl chloride ^ a

15 "trichloroethylphophate

2 ·· Trläthylonglykoldimethacrylat *

The burning test was carried out on the basis of DXN 4102 sheet 3 as carried out as follows:

The planar plate 70 χ 150 χ 0, ^ cm is mounted in ^ 5 * Daclineigung a Geotoll and tested in the same VeIse · 600 g Eo "lcwolle be on in a wire basket (in 1 Distance

-20 -

bad or'g :: -: al 909807 / 09A8

from the plate surface) burned off for 3 minutes »high 3 kt grooves the basket is removed test advice» 3 ■ porridge. £, h m long, closed on all sides 2 hj high, open at the top, on each side air tni.nla00cb.il t «E«

After 90 seconds, the top of the plate had caught fire. After 60 seconds after removing the wire basket, the fire was extinguished ο The lower side of the plate remained tight and feet «I did not see the fire penetrated, the burned area above was 0.105« * »

™ »he mechanical properties were

Flexural strength (according to DIN 53 ^ 52 Dynstat sample) 1050 kg / cia ² Impact flexural strength (according to DIN 53 ^ 53 Dynstat sample) 9.2 am Aeg / cm ²

In addition, a dome of 23 cm cows could be blown from a k am thick and 90 χ 100 ca large plate.

Example 22

The mixture composition was similar to Example 21, "for the combustion test, a sample plate of h2 χ 77 e" is suspended vertically and 6 Bm thickness and down medium with a normal bit Bunsen burner flame is applied FlatnmenstMrke w in the middle of the lower edge. Distance between plate and burner »opening approx. 5 cm.

The flame was applied for 15 minutes. Follow up 9 minutes from the beginning of the deflation «the record had gone out. The burned area was 100 cm «. No dripping, the residue was charred.

In comparison, the burning time for a test panel of pure polymethyl methacrylate in the size of 70 χ ko cm and 11 mm thickness was 30 seconds, the fire increased very quickly, it had to be extinguished after 2 hours.

- 21 -

BATH ORIGINAL

909807/09 48

ΖΊ

- 2-4 -

Example 23 The Oemiflchaueas HaeneptÄung corresponded to example 21 «

The bromine "teat at a Preboplatt" ύοιι 32 jc fro about 8 uad bob thickness was performed with a glowing HlIjTe screw. Kino Eisenachraub M 12 with a weight of 47 g was obtained in two strongly set Bunsen burners to a bright red glow and placed lengthways on the test plate.The plate was immediately ignited, it continued to burn for 1? ** seconds, but it did not burn through were about 5 me heavily charred. ™

If the same burning test was carried out on a test plate made of pure polymethyl methacrylate (Grusse kO frO cm, 11 ma thickness), "then - the plate was immediately deflonated - had to be fanned after 20 minutes. The screw almost fell through the plate, the heated and softened material burned down from above. «The fire spread more and more«

Example 2fr The polyaierlslerende mixture consisted of:

7fr »9 Gev» - £ Mononerea methyl methacrylate 20.0 "copolymer of vinyl chloride fr, l "orthophosphoric acid,

The hardening takes place nltt

2.0% Lauroy peroxide paste (50 pounds) 0.2 % methyl ethyl ketone peroxide solution 0, accelerator paste used for example 1

IfO ppm Cu as naphthenet

during eft. J hour »at + 50 ° C la Vaaeerbad, followed by post-heating for 1 hour at +100 ° C in the Otaluftofen.

909007/0948

-22 -

BATHROOM OBiGl

»- ■ 2 2."

? 'β3 · Brozuttest orgabi

Burn time h GO Sol, .undon., Burned LUr ^ iJ after dar

nroteu 2oll ^r ·., rk. ¹ ! hQ ma. Pu>Polymos'iuaiS -w * ¹ aolbat- "luchend mjuJ. iropft" not.

to polymeriftieroiule mixture; consisted auoi 69 »Ο G © w,." ii ü: oi? .oc »8reBi Hothylmothaci '/ lat 23.0" Copolyiaerleate doe Vlnylchloridu 7 ₀ O Orthophosphoraaure (lOO ^ lg)

Ira Ubi-lgen will proceed as in example 2k » P * r burn test e »rcab»

Burn time 9 and h8 seconds, burned length according to the ereton customs mark h and 16 camouflage » The Polyraorloat is

xatd does not drip ..

example Z6 The mixture consisted of:

$ 9 , 0 G-ow, "^ laoncinorea Hetliylm © thacrylat 20.0 ^M Trichloroethylphoephat

P 15.0 "copolymer of vinyl chloride 5 (0 ^tt maleic anhydride 1 _w 0 ^w PVC stabilizer

The hospitality took place with »

0.05 i> ethyl ethyl ketone peroxide solution: (ko £ ± g) 0.10 i> lauroyl peroxide

for 3 hours at + 6O ⁰ C in the vase bath. Naoh-tempered for an hour at +100 ⁰ C,

BATH ORIGINAL - ZJ -

909807/0948

0er Bi emv t »-st o £ * gave;

: · .. <}: · β seconds _t spent JJHnQe O must be

i »d for the first customs mark * The polymeric at iet uoxt; tlüachenc and does not drip.

Example 27

Sa will proceed as in Example 26. Instead of maleic anhydride, fumaric acid methyleter is used

The result:

Burning time 85 seconds, burned length 6 mm after the first inch mark · The polymer is self-piercing and does not drip "Bs is clear and colorless, hard"

Beigplel 20

The polymerizing mixture consisted of:

6k Uew »~ £ Totrahydrofurfurylaiethacrylat 20" Trichlorotthylphosphat 15 ⁿ Copolyerisat the Vinylchloride 1 ■ PVC stabilizer

The HUrtung took place with 0.05 ^ Methyltlthylketonporoxyflösung (^ ODtig), 0.05 i> Diisoproyplolpercarbonat at + was rted 60 ° C in a water · Kachgoh one hour · at +100 ⁰ C.

The burning test showed:

Burning time Ίο seconds, burned down length 0 nan, d. H not above the first customs mark. Since polymer 1st self-extinguishing and does not drip Ea is slightly opaque, colorless and guawlartlg pliable.

BATH

90 980 7/0948 '

U95544

The nu JJ0.I3 .lox'it errende Mi editing consisted of:

(Wi 0οι # 7 * - / ί CycJohexylmoth & erylafc
PO "Ti-lchlorütliylplioehpat

15 ⁿ Copolyiaerleate of vinyl chloride

i ⁽ⁱ PVC stabilizer

The UäTUiiii took place at BelopieZ 28

Bi'onndurance 225 indicate, burned length 28 M after the first ZoJlioarlto The polymer is self-draining and does not drip. E * 1st. Slightly cloudy and guanal-like bendable »

BATH ORIGINAL

909807/0948

Claims (1)

Pat "atan" prttoh · t 1. The procedure was Heratellon «τοη telb« tl «« eneaden, nater linvlrkun «vom Fouar« tar »traaleader was« practlaoa aloht drip aden Kvra «taars * n daroa F« lirae> rl9atloa ada4 «* taa • a uotumoron , polya «rl * l« rbar * n, '«rgaalJiea · * Verblaaaae, gee · - ¹ base case · la Oafaawart« la ·· Falyaerleat ·· ^ 3L * mmv ▼ • οι »la O« c «avart« ine · Paoepaor- aad Substance ·· and before *** · * ·! · * Under ο ine · PolyMorl «« «l« a «k« t «ly« ». tor · admr -m-fmtmm, eekenax« iolmet, da ·· «ma oia Ooaleoa polya * ri» i «rt _t wolefe ·· au «Are ·· th ·« tv · 5 Q «v * - £ ■ iitnrt» «t« la ·· Copolfaorlsat ·· des Tinylokl «rld0 (a), aimdeeten *« tw * 1 _t 2 O * w.-in For «a g * f * b« aoaf * ll · E «lO (t» aatoa · contains «ndea aln4 * «t« a ₉ polyw »rl« l «rbarea, orcani ^ o ** ^ V« rbladaa # (θ), and «effebeaeaf all · olaeM Toraotaor (i>) la Kencen less al · etira 3 O * v.-j ( _t T« rsac «irei ·· w * alc« r al · 2.5 Ge * .-%, ordered . 2. T * rfalirea naeb Aaopraota 1 »dadarca geJrejm-loaaot , da ·· da · Cepolyaerleat (a) la M * ae * a bl · sa otva 60 Oov« - ^ »v * rau« a «el · · vea otva IO bl ~ about 20 Chwr .- ^, 4 «a * a« * pa «r is N« a «« a bl »a« about 10 0e « _{- ^ t} die aoac-re Yerblnrteag (θ) la Mee v «A about kO bl · otwa · 5 0 · * · * 4 « nd ffb — wiafal 1 · dea Vernetser (D) la Mensen bl · «twa 2.0 Qev.-jl rerwendet. J · Terfaaraa aaoa daa Aa «prttob« a 1 ed «r 2» dadarob gak — n » ■ eloaaot, da ·· am al · Sabataaa (a) «la Oepely * erl * at d ·· Tlnyloklerlde old, ror «u« «vel · · about 20 bl · about kO vinyl acetate 909807/0 9 4.8 _BATH U95544 %. Method according to claim 1 or 2, dadttrdt «okaauaeloanet, • daea «an« le Subs tans (α) a Cepolyaerieat de · Vinyl-Chloride with oinen ester of Kaleinetture or old methacryl " JiMureaiethylester used. 5 · Method according to the AjoopxHohan 1 bie k, daduroh net, daoe Man ale Pboephorrerbindim «: (B) Trieblorfttfcyl- or a Paeephonat d * r Torwml 0 0 CJH. Ο ₂ O -PO ^ CH-V »OCH - P (OCH ₂ ClB BO ClCH ₂ CH ₂ O - ClCB ₂ CH ₂ CB. OCB ₂ CB ₂ Cl or an oopolyaerielbaren Phoepborverbmdtma> used· 6t method according to de »Aneprfiohen 1 ble 5, dadnroh 4> e can» elelmet _t daee stan ale eioneawre, polyaerleiorre »organlecne compound (c) methacrylic muremetbyleeter, ere ^ level trap also in the form of a prepolyer leatea, used. 7. Method naoh Λ · η Aneporfiohen 1 ble 6, dadareh daee aan ale Verneteer (D) aebrfnnktlonelie and / or Diaorylate and / or Di «ethaorylate of aiykolen o4mr Poly ^ lycolen used. BATH 3I.e
Dr.Wo / Ha 909807/0948