DE2025100A1 - Flame retardant acrylic molded articles - Google Patents

Description

DR. MOLLER'IOie DIPL-PHYS-DIiMANITZ DIPL-CHEM. DK. DEUFEL DIPL-ΙΝα FINSTERWALD DIPL-INa GKXMKOW

PATENT ANWXLTE

WSh * J. 1038 21 NAI

Japan ExIan Company Limiteä 1-25 »Bojl & a Bamadori 1-ohome, Kita-toi, Osaka / JAPAN

Flame retardant i.cryl ~ 3? Ora objects

Priority: Japan ν. May 22, 1969, Mr. 39975/69

The invention relates to novel, flame retardant b2w. Flame-resistant or flame-retardant & e Acryl-Itormgegenatande and in particular a subject, ζ. B. a jade, a fiber or a film, which an acrylic polymer with a Contains lactone ring in the main chain of the polymer. The invention also relates to a method for producing such molded objects.

It is well known that an oxycarboxylic acid generally forms a lactone ring under acidic conditions. Z * example, it is known that a lactone ring by saponifying a Oopolymerisates of Yiny3s "and Metnylacrylat with an alkali and subsequent Be * action thereof is formed with an acidic solution,"

DarÜb «rhinaue is in the German patent application P 17 20 9 ^ 7 * 1 * ^ · a process for the selective production of a lactone ring3

SAD ORIGINAL 109883/1493

Dr. MMhr-fc »4 Dr. Month · Or. OwM · OfeM ««. RmIwWoM Oipi.-lmj. Grtmhtm

(• MM fCStl) 2 «4 V 1 "Ufon (Mil) B 5110, Utaf XOHD mbpd MarUdroe · J, T" t * (o. "TTtl) U73" l

; ■

wrote, in which an acrylic copolymer, which is composed of acrylonitrile and a mono * · "kidney" having a hydroxyl group, is treated with a medium which contains an acid in a concentration of less than 40 % and a pH value of less owns as 2 *

On the other hand, different working methods are known, ta an object., A »B. a thread, a paisei» or @inar Sole ₉ . which consists of an acrylonitrile polymer to give gravity * «» flammability or flame retardant property * For example, there is a method _T in which a Sionomer containing halogen or containing phosphorus together with a halogen, to produce a non-combustible Gaisee as. Oo · »polymer! onskoiaponente is introduced into an acrylonitrile polymer, or a polymer, which consists of _{an 'eolohen' non-separable gas arzeug®adea Component® '9} and an acrylonitrile polymer3? isate, moreover, the development of f ! Lamb-resistant or flame-retarding agents progressed "There is a working method in which such a flame-resistant agent is kneaded into polymerizate for the production of fiber, or in which a textile product is post-treated with such a flame-resistant agent" known working methods are used to read the combustion of an object by generating an effective, non-combustible gas in the largest possible amount.

Ira general, however, it is not easy, a molded acrylic item, or especially an acrylic yarn flame "" resistant bsw see / do it retardant au To get the desired effect, it is necessary, a large amount of the _above;.. Non-flammable ( Jas-generating component or the flame-resistant agent to copolymerize ₉ or "use".

109883 / U93

BATHROOM ORIGINAL

and generates aiii β gp? size Kange a toxic gas zvs & point of combustion, has a post-flowed on the dyeability _s increases the specific Öewleht and be * einträchtig.ch remarkable grip * Bariibsrhinaus is many * times the toxicity de a flsEmenbe ^ ändigen Means feared myself.

Ea was found min, it daö "in acrylic yarns make flasuabeständig au is important that erseugte Meng © a combustible gas significantly belittle" It was also been found that such a reduction of generated lleag "eiaee 'brennbe ·' can be achieved by gas by reducing the segueal position la acrylonitrile polymer. In addition, as a series of extensive investigations on various poly merisates for reducing the acrylonitrile length in the polymer, a new fact was found that a. Aoryl polyate which contains an octone unit with a lactone ring "as described above", a very remarkable Sohwer · * ent ^ saambarkoit, b?, W. Flaitaenbeständi ^ ceit possessed ^ and d & B eiiij ana such a lactonized polymer obtained Seganstand a very useful ilasmea-resistant Fons "· object forms, with all the disadvantages of tone conireationflame-resistant form textics eliminated

The aim of the invention is to provide a novel * permanent, bisw. Delivery of flame-retardant acrylic objects. Another object of the invention is to use an AcrylpoXjm®3? I sat, which contains a lactone unit in its main chain, as a material for forming an acrylic molded article "to give the molded acrylic article flame resistance". Furthermore, it is Z1 © 1 of the invention to provide an aoa * yl * molded article which, as far as possible, reduces the generation of a toxic gas when it is irrigated, with other useful properties of an acrylic, telephone article, or, in particular, a padane, "or a? jaser, e.g. . B, the degree of whiteness and the handle, will not *

10 98 83/1493 _BAD

Goals of the Krfindimg Touching »

eiofc « aser

The above-mentioned keels of Erfinditog be erreitihtf: by a JOrjegegenatand-forming polymer is an acrylonitrile used oopolymerieat having "wtdtes In a" ia "r- Sanptkette a lactone _s soft by dl · .folgend * wirdi reproduced forael

E i Q

fi

where B is hydrogen © dar «tine» Eethylrest «

a desirable «.»

cashless » Acrjl ^ fümgßsmMtmA Be ν special bwora-ugt alsdeeteoe 5
! »Aotonelnheit la foxed article«. The oeere Ö3? ® »ae of Öehal * · tea of the lactone unit described above la tat Foregegenstead. should be planned depending on the type of VoxsgegeAetaadee des Auasasses && r desired Vlsin resistance. If a * B · the. form gegenetaad a f sdea bsiw. # is fiber, it is desired ». Aase de »content of the © bea ten Ifaetoneinheit less than 30 ββν®« «^» -wmtng & w & tee ger than 25 Crew # «$ _s 1st« Bie einfüliriiiig tob den oten. Jjaotoneiahelt ia üsn ladea "bsw« di® ^ a * ser advertises a remarkable amount of material, including the thread and the fiber.

In addition, by introducing a halogen, s ^ e & ttelte & «f the Monoaeren in the AorylnitrileopolTaerlsat ^ - which 'the The above-mentioned lactone content has the aws. a "such Polymer! Eat educated? OrmartikeXn an aeiu? remarkable Plaom-proof can be granted «If therefore one from one such acrylonitrile copolymer, which ®ia @ Laetonainheit

109883/1493

and contains a halogen-containing mono Moree, formed FormgegenBtEna and are compared from a Acrylnitrilcopoljmexlsat containing the same amount of the above-mentioned halogen-containing monomers, 4 ^ö & oeh no I »actanöinheit ,, each other, the former, the invention v / eist corresponding" The form object had a more notable flaaabeity than the last-mentioned, well-known, flaraabeganganstand “If a by the introduction of a Lactonelnheit; produced which containing monomers by copolymerizing a halogen in € fa halogenated 's Acrylnitrilcopolyaeriaat "Wurs ^ Ml ^e i £% l $ ^ g |? lienatand forming Polymerißat is used, especially a can more desirable laaabe be ~ ßtänaigfceit achieved if the fonsgefenetand a Halogen-containing monomers in an amount of Ϊ Qew, · ^ and one «lactone unit in a Henge of 1% by weight, which satisfy the following general equation:

at.

The required level of plammability of an? Ona article differs depending on the use, and therefore it is difficult to define in positive terms the upper limits of the halogen-containing monomers and the content of lactone units in the yorogd article. However, it is generally preferred that the lactone unit content is not more than 30 <* ew. ~ # And that (X + Y) is not more than 50 *%.

Is Seibat when a mixture of a Acrylnitrilcopolyiaeriaates which has a L & ctoneinholt and a Acrylnltrilcopolymerieates which * containing monomers ·· unit a halogen _t has instead of a Acrylnitriloopolsmerlsates, täLehes the abovementioned lactone unit, and halogen * containing Konomereneinheit possesses used, a wirksa «Se yiaüBjabeetehandkoit of the molded article will be issued, if the in the. The amount of lactone and the amount of halogen

■ · 5 - ■ ■ 109883/1493

unit meet the above general formula ».

According to the invention, the applied amount of halogen containing homomers lower than in the conventional, Flame-resistant EOrffi objects} so that a form article can be obtained in which the production of toxic gases is lower * and the. useful properties an acrylic hair dryer on the other hand, will not be affected

As described above, according to the 0rfi & manure ^ atatB @ ii Yerfah "ren Schwerentflaaiiftbarkeit erreieht _f by the Se ^ uensl & OGE BAW. ! folgclängQ dös Aorylnitrils is redusiert in Oopolymerisat) and to this purpose is the obm-called standardized in dae copolymer sat elEgdfiüäfi * Xn these should be noted Dajs itself, ιϊθώά §ine grolle a etatietiach copolyaerisierenden component is introduced * the Aerylnitril ^ SequeasBlängia 4 * icrylnitwilcopoljmeri - "- aat to downsize, the BinführungiBg a" large a Weaga τοη vinyl acetate, 'methyl acrylate or methylaetfcaerylat as eia®' such copolyaeriflierenden Kompoioente iie Bigeiiaohaftea the? A large number of such a high value as 7iu.ylch.orid or vinylidene chloride copolymerized with acrylonitrile will block the shape of the shape obtained from such a polymer, and it will have a detrimental effect on the convertibility , and the feature of the so-called Bauschiglreit in the Acrylgege & etand go t lost and there will be a large amount of. toxic gas is generated, the form object is burned.

In contrast, the invention uses a. Acrylonitrile « copolymerisate which eiuo Lactoneiahelt with a liacton · ring contains that by copolymarisiöreja of acrylonitrile with a conomer, which is a Hydroxylreat and / or a Jioao * »Ierad, dae veiiaag to produce a Hydroxylrest, possesses,

r 4

44 * «« Ik *

furthermore in a few cases a with any other yinylaonoaeren and lactone formation of the resulting acrylonitrile copolymer by a treatment, β. B. an acid treatment was obtained. The act of a unit introduced into the polyamide chain restricts the mobility or freedom of the polymer chain and makes the polyamide chain stiff, and when a large henge ftji lacto unit is introduced, or, in other words, a large henge of a honey, the one Hydroxyl radical possessed, or eluoo monomers, which produce a hyroxylreat RU vensag, is copolymerized, the useful igenacliafton of the aoryl molded article are not influenced in the bad sense | The acrylonitrile sequences were introduced by the lactone formation reaction, so that the forum material obtained from this oil can have a very high level of stability and can do most of the conventional work picks in we3 & er such Aoryl <the useful properties - are 0rmgegen "stands _Λ as described above eerstört, * Vei * terhin can Flainmbeständigfceit by introducing such Halo" genetically ^ nthaltender Honotteren as Tinylohlorld, vinylidene chloride or bromide in a A lactone unit containing 7or ^ snet «and su better. Values increased, and there & gnn a sufficient "de FleÄtbeatändigkeit with a lower Terweaäungeaenge dee Halogea ^*> entha3.t monomers are granted, they ale for one. Aoryl form object is required in a conventional manner to produce a (yiaaabeständi ^ CQit. Therefore, a fiaaabetandiger form object can be obtained "which has a low level of suction el", nes toxic A C-aaes * <

The Aerylnltrilcopolymerisat old Iiactoneinheit can be obtained ₅ by an acrylonitrile polymer is lactonized obtained by OopolynexiEation of acrylonitrile as the main component, aes * B · mindöstens 50 Ggw. · * · ^, With a Konomeren which a hydroxyl · rest besitet, and / or oinem Honomeren, which is capable of producing a hydroscyl residue, and in some cases further-

1098S3 / U93

BATH ORIGINAL

»It

Disturbance of the subsequent iactonieieruagsresktioa sbaren "like s <B · Allyl sulfonic acid or llethallyisttifon""acid or its SaIa, styrene or such balog © nfchalfcenden. Monomers such as vinylidene chloride or vinyl bromide were obtained using a well-known polymerization catalyst. They were also copolymerized by the hydroxyl group of the monomer and the equivalent of the eqao iasren, which produces a hyroisyl group in aesr 3 «« ge iet _f \\ ^r lrd by the gewüneohten content aa lactone in © riaaltexien polymer "determined"

The formation of accton can generally be a b0li © big®n _; geöig & eten Vi © iee · be carried out, S · B # tdrd h @ ± d @ a LaotonbildungSYerfatirexi by a direct acid treatment process in Aorylait5? ilpoly · aerieat, which was obtained as above »ia an acidic hedium _s the axLt © inen pH- ¥ ert voa little · set than 2 (if the pH * value is less than 2 1st »ee & r © it © t the!» Reaction to laiagseiE Yoraa) waJs s © lcfeea suorgssiseh ^ n Schwefelßäm? Β, Ohlorwaesdretoffäure, .nitric acid or dsr Äosphor "acid and / or such örganisohen sauces wi © Amelsensä ^ r _©} acetic acid _t oxalic acid or ^ © laetonisiert oluolsulfonsäur? The ZiaotonisierungsausfiisüS ia Copolyiiörisat can be regulated ₉ by the acid treatment b © diagön @ sn appropriately selected, ζ * B * the Behsndluiiigsteaper & tur wad ° »% ® ±% - with the above mentioned further aiHat; e entration: acon This acid treatment can either be used in a lioaogenea system or ija eiaea & ichthoxaog®nen system until the structural change to be brought about by the diolactonization method is as follows

ι d ι

O O

C = OI

H ₂

"* Ο33Γ ^ιυ

OH GOOH

Z wi Bcheastuf -a

10S833 / 1483

BATH ORIGINAL

OH «* OH <· OBU * OH *

J "c * ο

This reaction can be carried out in a sfcufa »■ and it constitutes such an effective technical peat honor

If this direct acid treatment process is continued, the aoryl nitrile unit will not be used . Formation of Iiactoaringes contributes practically not hydrolyzed j ναχά therefore AorylnifePilainliait x ^c? IPK · "Ben remain in the polymer can" Barüberhinaus seigt the formula above the formation of a Laotcneinheit ei-Hos 5-gliedjrf.Ken lUngee from an acrylonitrile unit mod a Vinylacetate unit * Bs is essential that a 6-membered ring of allyl * alcohol or hethallyl alcohol or its derivatives and. an * Acjpylnitrileinhait can be formed * Not only the above-described Iiactonsieiöruagsmethoda, but also *, if any other Itactonelelerungsotethode »through which a lactone ring in an Acrylnltrilpolyexdsat can be sucked, can be used»

The Monomora is an Eydroscylrest a copolymerizable with acrylonitrile Monomera, z. B. Allyl alcohol Qder allyl alcohol. The monomers capable of dissolving a hyaroxyl residue are monomers which can be copolyraerated with acrylonitrile and are capable of producing a hydroxyl residue _; however ee under the

»Ereetat vdrd, to B · Viaylmethyläther, Vinyläthyläther, Vinyl propyl ether, vinyl isopropyl ether, vinyl butyl ether, VinyXioobutylathexr, Vlnyl ^ butyla * thor, Vinyloctyläther » VinylphenyläthöJT, Allylmethyläther, Ällyläthyläthei "A3, lyX-" propyl ether, allyl isopropyl ether, allyl butyl ether AXlyX teobutyl ether, allyl t-butyl ether, allyl octyl ether, illyl phonylether, vinyl formate, vinyl acetate, vinyl propionate, vinyl vinyl caproaa. Yinylisöoapront ;, VinyXcaprylat *

109383 / U93

BATH ORIGINAL

• · '

Vinylpelargoat, 7ix & ^ * tiÜh & X-hsxBmMisQ3 & l * t ₉ Yiayl * stearate, Vinyllevuli & t, ttlxyXvinyXox & Xat, TiBylchlor * acetate, TinylciiehXoracetafei Vinylbeii & oat ». Vinylcyclo ·· hexanecarboxylate * Vinylno ^ bannaB ^ Ksarboxylatj Allyl * - aeetat, Allylpropicmat, Allylbufeyrat, AlXyIXaoreate _s AXlylbenzoat _} ÄXlylcycloheptanoarboxyX & tj AllyleMoracetatjbtjayropropenylacetyl »

oaer Metliallylpropioiiat "

Sols AcryXaitriXoopolyaerlsat; with; a "& a ^ tone: U3 &el1; kajan to a Fadöüj a Faaer or eloer Folia nmh in itself belcaaatör Arbeiteweiss r®Ttam, t become« Bq wirt das -Oopoly »merisat ia a» as IiÖsuns ^ ittei for J.oa? yl » ii5ri3.polysft © ri · * eat © "bekaantea solvent dissolved _? The measurement can be made into threads or foils in a way that is pre-formed, as previously explained, it is also possible to use an insulation made of acrylic glass, which has a lactone unit, and mix it with others use »over a flansbes stand iieraustelleii. Sa ^ iiboiiMnaiis laaa äurch Yerwexiduns read well-known flanab0st8» dig # a mttole isu ^ aauen ad.t eiaett AcrylBitrlXcopol ^ aeriBftt, which one has j de »^ locality ^ netcid be granted a higher

The following examples explain the fication without them aBusohränkaiit Xb the following see "eiott all ^" - information and ^ eil ^ submissions unless otherwise stated «

Some reference is made in these examples genosia9ii; in the drawing are »

yig. 1 shows an IH absorption spectrum of an acrylonitrile acetate / polyisocyanate from Example 1; and FIG. 2 shows a lii absorption spectrum of a lactonized polymer ₁ which was obtained by ligating the abovementioned 0opo3.yraerisataß mwäw *

.09883 / 1493

BATH ORIGINAL

25 He * of an acrylonitrile copolymer, which consists of 80% acrylonitrile and 20 % vinyl acetate, were dissolved in 100% of an aqueous solution containing 3 % p ~ 2to3 / uolauline acid and 20 % sulfuric acid Inhomogeneous system for 5 h at 100 ⁰ O vx & bv Bükren s & ure ^ behssndelt * The solid was separated by filtration and washed old waaaer "During the heating of the Hwty" g * e of lectonicity in the polymer treated in this way was found that it was an acrylonitrile copolyttortaa -fe old was 18 % lactone.

The «θη ^ β an!» Actoxiolnheit was in Gow. «#, Based on the Polymorieatee, the beetee

-OH- CffiU -OH-, 2,

0 ■■ '' - 0 «O

The amount of lactone content is indicated by ti a control a Copolsfmrisat ntt «ine» "known salary on the lactone unit made up of a copolymer of methyl acrylate and Tiuylaoatat after the "? ol" in "Kobttnahi Kagftkti" 7 (1 ^ 5C), S «142 to 154- described method dergeotiellt \ iad the amount from dee IB <» Ab8orptlonab * reiQ & from 11? 6c. * · ^ In the e ^ haltanen Gopoly ripped off all coffeemakers while defeating control was done. .

Acrylonitrile copolyerate old from Laotona was found to have a pinning solution on 15 et, so that there was a polyoconentration of 10 % in 50% by Käfirigor Löaxing from Hatriuatiiiocj-ajiat. This spinning solution is pressed into a fiaibad of 10% watery solution of Hatritimthlobei 0 ⁹ O through a spinneret with 50 openings with a diameter of 0.09 mm to form threads. The ϊϋίίοη were used ait Vas sor and were then in Vaaser to ten times the original length

• 11 · 109883 / U93

BADORIOfNAL

From the comparison of the physical properties of the threads in Table 1, it can be seen, by the way, the thread physical characteristics are those that are common above. or liTbe ^ legea are _a

Furthermore, from the comparison of the factories shown in Sabelle _? although the erfinduagsgea & Be FADEA A no Halogea ^ onthaltenAee tSononeso awfwoiet ₅ .he a far kShere Flamabeständi ^ ince than the · ', one who bathing-B ₅₁ dia ordinary acrylic thread is "\ xnd © ine same as that de © Äcryltadeas _C9 the copolymerized halogen-containing monomers have a division of a Vlanni involvement, shows *

The end. the otan

Acrylfadaa _s the out
merie & t ait der

knew lorylfSdtm

'. ■ ■. 2925100 '

from the comparison of the pliysifciijischen apnaecliaftea of the flctoa in table I can be seen, b »@it» t_der evfiaeu & gegen & Ba physical Bigöaeotoft® », the deaddalgeti € @ ϊ · IiWLi * ■ equal to octer superior aini«

is it from the? ergl @ ieli which in fmfeelle Il showed FXaEBa resistance evelcbtlloli »claÄ, oteolsl € er iinduagsgöaöse thread 4 no halogen ^ etitluiltanäee tlononexii on white» «3? a much higher S'XemTbeetSndeit from the few of the thread B _{3 of} the one.-ordinary .AcryXfadea is ₉ and a similar vrid that of the Aerylfadens C "€ er cofpoljaörßierteSi HaXogen * contain because monomers with ®c""division of a? la & abeet? time contains,

From the comparison given above is clear _? dad the aerjlfadent, which consists of the »inventöngegjBeEßea" Aorylaltpilcop merieat xait the LaGtoneinhait, in your ¥ elae Acrylfade "unterigon 1st, wp / BL " in "retains.

109883 / U93

BATH ORIGINAL

(cto?)

(cto?) i'ocrö & i

Fn ι fr

din J ^ ι ^Γ 4 ν 3 ^ Su ^ HS ⁴ / 5ώ @ § - ^ j ^ - 21 _δ 4

ti i \ fij τ ι

■ fQ

taaaeceajiiaie =

2Pa *

thread B (tararea * «.-.«, * "*

f tdea α

(ktuairen ^ $ *% <m 30 "8 - '25 *

thread)

109883/1491

Three types of acrylonitrile polymers, which 76 *? 0.8 baw »70 % acrylonitrile, 15.8? 19.6 baw. 17 % vinyl acetate and 8 * 2; 9.6 bfcw · 13% vinylidene chloride contained, three types of laetonized Acrylpolyiierisatea with the ratio of 71.6; 66.6 or * 67s2 % acrylic! «·· trll-rf13.1> 15i8 or 16.5 % lac ton ·» and 9 »3» 9 * 6 eg, 1J _} 1% vinylidene chloride units to be obtained «in each of the above The three braids of laotonized acrylic polymers mentioned above were a very small amount of the unreacted vinyl acetate unit and units which contain a carboxyl radical and hydroxyl red which did not contribute to the formation of the lactone unit.

The lactone formation or lactonation was carried out in a catfish, in which 25% of a polyamide was poured into an aqueous solution which contained 10 % po-foluenesulfonic acid and 15 % sulfuric acid, and the suspension was poured into an egg. * * nea nloht homogeneous system 5 h at 100 ⁰ C while stirring it "Hitat.

Each of the three types of lactonized polyacrylate obtained was dissolved in a 50% aqueous solution of sodium thlocyanate to produce a spinning solution which contained 10 % polyamide. Each solution was dissolved in a precipitating bath of 10% aqueous solution From NatriuathiooyÄn * t at 0 ⁰ C through a spinneret with old 50 openings "with a" diameter of 0.09 on the formation of threads. They filaments were washed old water and then 10 times the original length in boiling * Water-ver 8treckt, then at 105 ⁰ O at a relative? Euchtigfc »lt of 60% and then dried old überhitztoa Saapf at 130 ⁰ O hitiebeh * ndalt _t vm three scripts from fädan, nayalich D ₁ £ and f, asu received. Iode dar three

109883/1493

Varieties of threads contained about

aw point in time of a Lftotonldlerunga reaction

Seared Oarboxylreat contained ha & cationic oil in 5 " lead dyed, kosate eew-like acrylic fiber dyed

J | 5se »aji des?

i S «ad t _s Ä © s 0 VEO & o

β (la if @ I © ä © ii. © la

e 1® fl

which one! »!» © Its als tl © Jä & © st © aül! | Qii

Like «f§

the
but #iae

is it?

t _D

wi © i

uad S.
itt

fp © a

Qqo ^ adoas

is ft «p Jadca © ₉ II
) j £ and

_Φ he occupied liwtrleMlfeti

oriff seta

son nlenaXs

BATH ORIGINAL

Table III

Together Flam- ' set the aen ~ form thread * height ' don Polymeric (cm) sates

Combustion time (eec)

G
appropriate threads:

AKsLAsTdOl
= 711
9.3

Jaden 2 = 66.6ϊ15.8 * 1 - 2 31 9.6

Fadea W "67" 2H6.5 "1 - * 2 20 13.1

Thread 0 ANsMAiVdOl , 5 3 * - 3 50 Thread Q AH) HA
* 90:10 - 2 43 Notesι

glow · Verbrenaiuags de Bück » aen ^ e ,. , stands (sec)

16

1.7

1.3

10

25 -

20-25

ANt aoryl nitrile unit - LA: Lactonicity

YdOIt vinylidene oXoride unit Methyl methacrylic oil unit

contains 18 % ifö? ie (2,3 »dibroaa? ropyl) phoepaÄt ale not ontilamaibaree means i» thread »

Example 3

25 x acrylonitrile copolyesterisatee with a solution of 02% acrylonitrile and 18 % allyl alcohol became 100 tin. egg"·

108883 / U93

■ J i. «Rf * ■ > -

A boiling 20% sulfuric acid solution was added, and they were treated by continuing the boiling in a non-homogeneous system for 5 hours with stirring. Then the treated polymer was filtered off and washed with water, and the infrared absorption spectrum was measured. As a result, the band at 3450 cet of the hydroxyl residues had decreased and an absorption of 0 * .Ο, Ö-0-0, which shows the absorption of an ole-membered ring lactone, was shown at 1735 and 1165 cm Lactonized polymer was determined by the amount of decrease in allyl alcohol is polymer by the lactonization treatment (the hydroxyl radical of the allyl alcohol is consumed to form the ionic ring), it was found that 15 % of a lactonity of a 6-membered ring is contained in the laotonized polymer was *

A di »ethylforaamidlÖ8ung which 20% of the Acryipolymerisates thus obtained contained lactonißierten _t was applied to a Glasplat · * te for producing a film of approximately 0.1 nm thickness applied On the other hand, for comparison, a film according to the above Köthode hergeetöllt by © in acrylonitrile polymer with a composition of acrylonitrile. methyl acrylate of 90110 was used. "When the" white types of oil were burned, it was observed that the 7pXie " was burned than the film obtained from the ordinary acrylonitrile polymer for comparison, therefore it was confirmed that the first film had better non-flammability than the latter poly.

1.5 TIe. an acrylonitrile copolymer, which consisted of 58.5 % acrylonitrile, 18.6 % vinyl acetate and 22.9 vinylidene chloride, were suspended in 10 TInu of an aqueous solution,

- 18 -

109883 / U93

which 15 % sulfuric acid and 10 % p-Tpluolsulfoneäw © The suspension was heated for 7 h to about 100 ⁰ C under RÜhraa, to carry out the non-homogeneous lisctcnl beer reaction "A lactonized polymer was obtained" which J> 1.2 acrylonitrile , 20.0 % lactone unit and 2 ^, 9 % vinylidene chloride

Daa lactonisiert® polymer; was produced in dimethylformamide atar a Sfrinnlöeunis ,; The 20 % polymer is entüidelto aufgel0st _t Die ^ inalBmang is dtycck a Spinaafs © (50 Mt ™ uuageii »0.09 ffi» Burohfteeßer ^ in @ia felling bath from BolyEtliyli »» glyicol (Holelrolargewiclit β H®Q) at 50 ⁰ C ata? Sllduoe verfeatigtta threads expressed "Me lädea warÄom" on the before the length ^ extends and further the 15 * Äch.o der in a Ba.d aue Bolyäthylea ^ l ^ al boi ⁰ Däds became the l "ädea aur -Schru ^ ftm ^ 1 "18 % generally a bath of polyethylene glycol relaxed at 140 ⁰ G, old haters" ge * we.0Ch.en " ^{dried at 110 0} C" one

Subject to 110, ° <3, and eelilloillleh at 140 ⁰ G bltsabeAandt, including IPaden of 4.3 g / dea Feetigkait and 26 % Debuone ^r *

Ke became a yerbxwanuagsteet for the eo. received. 7ädes> led .. The 2fioht-Batfle «Bi> ia? Keit or real this. thread was since the ^ enlgea Hodacrylfaden (AerylÄitrilsTinylchlorid ^^^^) t ä * le. fXwM?> stable? äd © n are well known, comparable to "S® kaam g ©""it is said" that when using a β, lactonized aoryl "nÜPilpolyerisates, even if the content of a halogen-containing monomer is low, an excellent, non-flammable molded object can be "grounded"

Example 5

Sin aorylaitrile copolymer, which β consists of 60 »0 % acrylonitrile,

109883 / U93

15 _S 2% vinyl acetate and 24.8% vinylidene chloride was lactonized in the same manner as in Example 4 to give a. lactonized polymer containing 55 % acrylonitrile, 12 % clay and 25 % vinylidene chloride *

The lactonized polymer obtained was formed into threads in the same manner as explained in Example 4. This jade was subjected to a combustion steat and it was found that its lambeet properties almost those of comercial modacrylic threads, containing 37-5 % vinylidene chloride,

109883 / U93

Claims (1)

Claims Λ * xm an acrylic method, "molded article to give Flaiambeständigköit, characterized in that the material for the formation of the molded article is an acrylonitrile" copolymer is used which has a _f Laotoneinheit in its polymer chain, which is again given by the following formula: B or R ι «■ OH ₀ - 0 ■ * · 0 -OH-0 * = 0 -0-0 = 0 wherein R represents a hydrogen atom or a methyl radical. . _% Method according to claim 1, characterized. known that the molded article is a thread, a fiber or a film. Method according to claim 1-, characterized ge. know net that the Acrylonitrilöopolymerisaij at least 5 contains laoton units. 4. The method according to claim 1 »characterized in that the Acrylrdtrilcopolymerisat contains less than 30 & ew. * ^ Irfioton units · Method according to claim 1, characterized net that the Laoton unit used by the following Structural formula is represented by J CH ₂ - 109883 / U93 6 «travel cm. according to claim 6, characterized t that the acrylonitrile copolymer used still has a halogen-containing "monomeric unit". 7. The method according to claim 6, characterized in η et ι that the used / ended acrylonitrile copolymer the Iiac ·· Tonunit in an amount of Y wt .- ^ and the halogen ~ contained * tende, monomeric unit in an amount of X% by weight, based on the object of the business and with the fulfillment of the following Formally contains * 8. The method according Anapruch 7> characterized gokennseich ~ net, that the total amount (X + X) the halogen-containing monomer unit and the lactone unit is less ale 50% 9. Method according to claim 6, characterized in that that as halogen-containing monomers vinyl chloride, Vinyl broaid or vinylidene chloride is used * Acrylic molded article molded from an acrylonitrile copolymer eat, which in the polymer chain dine Luc tonunit dcrr Formulas: • OHg - 0 · OH ₂ - or B I σ - _β - CH * * 0 r 0 ^β O contains, wherein R is a Vaeeerstoffatos or a Kethylreet divided " Acrylic molded article according to claim 10, wherein the acrylonitrile «* eopolyeeriaat also contains a halogen © Sinness contains ^ - 22 .. « 1 0 9 8 8 3 / U 9-3