DE1745053A1 - Process for the production of shaped structures from polymers with cyclic imide units - Google Patents

Description

ralle Aktiengesellschaft ^^^

Uni.r · Ζ «Μι · η day Matt

1786 PP-Dr.S-in November 8, 1967

description
to register the

KALLE AKTIENQESELLSCHAFT Wiesbaden-Biebrich

for a patent

Method of manufacture

of shaped structures

Polymers with cyclic imide units

The present invention relates to a process for the production of shaped structures from polymers with cyclic Imide units, which are intramolecularly imidable, in the ß- or / -positions to the carbonamide groups Polyamides containing carbalkoxyl or garbaroxyl groups by conversion into the shaped structures with the aid of solvents and subsequent chemical and / or thermal conversion into polyimides develop.

Aromatic polyimides are particularly popular in insulation technology because of their chemical and thermal resistance Gained importance. A number of methods for their production and processing into foils, coatings, threads or the like has been described.

J0H31 / 2069

IMtM * ZaIdMn Tog Matt

17: 0 FP-Or. 3-in 1.11.57 J * »

A method is known for ci ^ r. the foiyani <- 'T ".ur ~ - structures aur the soluble unset for.r; sproc'u': ton before."etracarbons'iurec-ianhydriden with primary diarrins are rolled out and the following tifcerf ^ runr in the polyir.idlforr . änre under the influence of ^{1T 0} and vorpsnonnen Dehydratisierunpsmitteln.

? Due to the instability of the Polyanidsäure appointed -.I .n soon cla ° ec it zv ^r: mäaif 13t to replace these aurc'i at r'ern process more stable derivatives. So it is already known that the poly aiii dc "ure sun example in Polyininol ^ ctono 0 ' ¹ ^ r in special metal salts of Polyar.idsäur ^ ur-su' .. 'ar. ^R " .oln.

From these Ζν "\ τ. ^Α - . i considerably inconvenient.

Hs is also a process known in the nan, from the Dianhydrides of the tetracarboxylic acids starting over the Intermediate stage of the acidic diesters is the diester dichloride and this nit the diarin in a polycondensation reaction to the polyamic acid esters.

• However, the split will give rise to significant disadvantages of hydrogen chloride, such as the impurity by the by-products that arise as a result.

109831/2069 BAD original

Unix · Zaldian Tog Matt

? -Dr.S-ir. 3.11.57

.-, s was. '. uf: a' · ο ^ r present ^ rfindung, in a process for "'larstsllur.r," eforinter structures' iun? oly: .ioren ::. i *: - cyclic: - . I-J'.oinheitcn t'r'.e known Ir> c}. Parts to vcrr- ^ i: -? R. u ~ c ""^; ./. :: ". resembled oinfac'ier /.usf'i:irun ^r · roine? ol" ^r cr? to. "^

This upbeat becomes invention SEeniif, thereby r.el "st, dr.? Nan

.'w ".hydri ^r lc vor. Polvon.rV.ons'iuron in inert organicc :: er. Λ

^T i ".3-1 .-. Ti '-.-: tt ^ l:.,' T pliphatischeii unn / o ' ^: T r ^^ rt ^ c ^ cn Γ'ν i""~: ·: τ ;: ¹ :: r: üur. ~? N ru r) icr.r:? Or.3Üursn rit ri; I 'ctor.u 3i: - .: r ^r -:,'? R / -sf: '. r.:l:.fcn Ccrl al'.zoxyl- c '^ r Cirbcroxvl-?: i'·; * · ^ c u'T.etzt and "read anschlio ^ enü ir. Holvcr '-. ^ ltnis ve · ¹ 1: (1 to etvo. 1,3) r.it Diisocr.'anr.t-ir., Rarebener.if ir. -La ^ enwart vor. au ·? the isocyanatchenio known "atalvsators and / o ^ or increased Tenerife nature, in linear polyar · \ de" 5b he leads.

The inventive ingredients according to the dicarboxylic acids to be used are f

acidic esters of polycarboxylic acids, plural marriage at least at one of the SS to the carboxyl groups or Y ~ ständip: en Ko'ilenstoffatoine aine Carbalkoxyl- or Carbaroxyl-Grunpe met. They are obtained, for example, from their anhydrides by adding one mole of an aliphatic or aromatic ionohydroxy compound per equivalent of carboxylic acid anhydride, it being irrelevant which carbonyl run of the anhydride adds the hydroxy group, since isoric mixtures are also used.

109831/2069 _0R1G1NAL

Under · Ζ * ώ · η Toe sheet

K 17 86 FP-Dr. S-im 8.11.67 J> r

In addition to the dianhydrides of tetracarboxylic acids, IToroanhydrides of tricarboxylic acids are also used in the reaction. They can be used alone orter in genic in any weight ratio with one another. . As for the erfindunrspenä ^ e process pteeißnete anhydrides include: Pyronellithsäuredianhydrid, Eenzonhenon-3, 3 ', ^, ^ ¹ tetracarboxylic dianhydride, Haph Thalin-1, ¹ J, 5.8-th tracarbons * uredianhydrid, ii aphthalin-1 , '1,8-tricarboxylic acid monoanhydride, trirellitic acid monoanhydride.

E3 is also n ^ pjlic'-;, in the reaction solution the acidic Ester partially by carbalkoxyl or carbaroxyl-free aliphatic or aromatic dicarboxylic acids, first by isophthalic acid: up to about 30 mole percent of the dicarboxylic acid ester su replace.

As aliphatic and / or aromatic hydroxy compounds ^ v; earth primarily used ionohydroxy compounds, for example methanol, ethanol, propanol, butanol or Phenol. The hydroxy compounds met with suitable substituents, etvra a hydroxyl, nitro or amide group, in particular, however, they carry Xther groups, such as an alkoxy Irruppe, which refers to the solubility of the acidic esters and the polymers synthesized from them in the inert solvents have a beneficial effect. Be like that 2-methoxy-ethanol, 2- (2-methoxy-ethoxy) ethanol, 2- / J- (2-methoxy-ethoxy) ethoxy / ethanol and p-methoxyphenool

Tdt ends with a particular advantage according to the invention. it) 9831/2069

BATH

Under · Z »l <*« n day sheet

K 1786 FP-Dr. S-iin 8/11/67

Inert solvents are those of the carboxamide type such as dimethylformamide, dimethylacetamide or Dimethyl sulfoxide used, which are used alone or in a mixture with each other.

According to the invention, aliphatic or aromatic diisocyanates are used, which may also contain heteroatoms. Diphenyl methane-4 is preferred , 4'-diisocyanate, diphenyl ether- *! , 4 'diisocyanate or hexa ^ .ethylene diisocyanate is used. The diisocyanates are also used individually or in any Relationships used with each other.

The catalysts used are those generally known from isocyanate science, such as tertiary amines or metal acids, for example copper, cobalt or lead naphthenic, in proportions of about G ₃ I to * -Ocwiohtsorosen '; based on the diisocyanate used.

The formation of the polyamide3? .Us the acidic internally u. · ': -. ti; -n Diisocyanate ^ 3rfol ;; fc by Umaetzunr. · d? -r :: 'T' - »oner.;. or, be it in molar circumstances, let 03 Li"hen:;:'::' ■ / - ■; diisocyanate to zn etvra "50 üol -rozent. The iicai; t 1:;:. ^ψ ·; λι · - iii inert organic solvents. Τ ·:; :::.: · Ϊ́ " ^h 'ir ■■■. Performed between ¹ U) and I ¹ IO ⁰ C, vicbf-i :"' ^! : "■:.: · - ■» - · ,, :: - sohlu; ';;; esor * ft; ■ - ■: ■; ■ - '■ -vi ru' .. V'enn un ^1. ".: ¹ ?. \ ': ^{F .l:.:.} ... ^r 'h .ΐΠ'.ΊίΠ'J ^ri ϊ' ¹ * ■ - ~ ix \ "" ■ '' ■ - '·''",''' / I! '''" -. '■■■■ .'.- i v' ¹ ·> ρ I ¹ T. "**" ■ '' ■ "·, ■ '" - ν :: ¹ "·.!.: ·· -V'.'Π·.; -.-.: ■>-;»; ur ^; .: I au; ·: be t; ^>; 1? J-; L ι,: ..

10 9 8 3 1/2069

1745653

Uniir · Ztlttitn Tog sheet

K 1786 PP-Dr.S-im 8.11.67 * & ~

at O ⁰ C. With the implementation is a r-erinpe ,. easily controllable carbon dioxide emissions; tied together. It is not necessary to isolate the acidic esters before they can be reacted. Rather, it is possible. and it is advantageous to treat the reaction mixture which is obtained in the reaction of the anhydrides with the hydroxy compounds directly with the diisocyanates.

The resulting viscous polyamide solutions can be, for example, to process coatings films, other shaped articles or who ^: own ute mechanical properties and can be, imidate by dehydrating reagents, or by heating at temperatures higher than 150 ⁰ C to form insoluble and thermally stable products .

You can see the polyamides as well as well-off W cases isolate as a powder and processed by conventional sintering methods.

The products have excellent application technology Properties and are for packaging and electrical applications or suitable as ■ thermal insulation material. Through additional other polymers, plasticizers, P'lll- and dyes or compounds can be used to determine the properties Modify the products in a known manner.

109831/2069

BATH

To »r · character day sheet

Y [Y ■ FP-Dr. S-im 3.11.67 -f-

The process has advantages due to the fact that isocyanate compounds are easily accessible and produced on a technical scale, by the fact that the execution is not possible. there.! pure sensitive polymeric intermediate stages -> nfall, as well as by the extraction of pure? cl; ^r H ^ r'-r.

The foils;:.: · :! PgI spat Io ο oil ion. the rirfindunr * vreiter

"'example 1

3 ^ 3V ¹ * '■ < ' -dir ^ hv-ir'd and · 1 ₃ ? 7 - ■■ (1,:. ■ * !? ■ T-ol) p- 'phcnol vrerclr-n in Γθ ^ ; water-free, "-i_, T-Dirr.ethylforrexiid -cl" st and -c 1 ptunde at ^ίΛ ° and 1 ^ 0 ⁰ C in a heated bath '■ er'.; ärnit. Ilan ll'-3t then the resulting solution of the acidic bis (p-metho :: yphenyl) -ber.KO ₄ ih2non-3, 3 ', ^J fs ^' ~ tetracarboxylic acid ester - cool down to CO ° C and f ' _{jrrt 5 5} 01 g in portions within a quarter of an hour. - (0, .024.MoI) Diphenylmethane-4, - ¹ I '-diisoe ^ / anat added. The solution is then stirred for a further 15-30 minutes. The solution has an RSV value of 1.1 ¹ I and is then cast on a glass base to form a film. After drying in vacuum at 100 ° C, the 7olie can be pulled off and condensed by 2s.t Uendi "ge &'heating at 200-22O ⁰ C. The film is then insoluble, has the typical yellow

Color of the polyimides and has their 109831/2069 in the ultra red

Unj »r» Ztldian day sheet

K 1786 PP-Dr.S-im November 8th, 67

characteristic absorption (e.g. at 5.6 ** / u).

example

The Esterbildung carried out as in Example 1. The solution of the acidic bis (p-methoxyphenyl) benzophenone-3 '3' ^ »4 ¹ -tetracarbonsäureesters allowed to cool to ⁰ ° C, as the catalyst is 1 wt.% (Based on Gesaintfestkörper ) of 1,4-diaza- / ^< 2 ~, 2.27bieycloogtan and adds 6.01 g (0.024 mol) of diphenylmethane-4,4 · diisocyanate within a quarter of an hour. The solution is then ^{stirred at 0 °} C. for 4 hours; your RSV value is then 1.37-

The Pilmbildung made on a glass substrate, llach drying at room temperature and condensation at 22O ⁰ C to obtain the polyimide film.

Example ?

To 5.71 g (0.01ο mol) of bis (p-methoxyphenyl) benzophenone-3, 3 '»4 ^' - tetracarboxylic acid ester and 0.15 g (0.0025 mol) of isophthalic acid, dissolved in 30 g of anhydrous N, N-dimethylformamide, 3.75 g (0.0125 mol) of diphenylmethane-4,4'-diisocyanate are added at 60.degree. The solution is then stirred for 2 hours and then has an RSV value of 1.4. · _Ν ^; · '■'; .. ■ ■■., · · ■ '. ·' ■ '■' ■■ '■ ^: -

The film formation, fröekming and condensation are done like in $ €> game 1.

/ 2Ö69

University·!" Sign . Day sheet

K 1786 PF-Dr.JS-im -8 ..Ii.67

example

As in Example-1, 5.25 ε (0.025 mol) of trimellitic anhydride and 3 ₃ 10 g (0.025 mol) of p-methoxyphenol are converted to the corresponding acidic ester. After cooling, the solution is added portionwise 7 ₃ 50 g (0.030 mole) of diphenylmethane-4, 4'-diisocyanate au. The solution is stirred for 1 hour, its RSV value is -1.00. Film formation, drying and condensation take place as indicated in example t *

^108831/2068 BADORIG.NA,

Claims (2)

κ 1786 * tr- Pa t e η t a η 3 ρ r ü c h e 1. Process for the production of shaped structures from polymers with cyclic imide units, which are composed of intramolecularly imidable, carbalkoxyl or carbaroxyl groups in the P> or K positions to the carbonamide groups Fe-containing polyamides by conversion into the molded Structures are formed with the aid of solvents and subsequent chemical and / or thermal conversion into polyimides, characterized in that anhydrides are used of polycarboxylic acids in inert organic solvents with aliphatic and / or aromatic hydroxy compounds to form dicarboxylic acids with at least one ß- or ß-position carbalkoxyl or carbaroxyl group and these then in a molar ratio of 1: (1 to about 1.3) with diisocyanates, optionally in the presence of from ™ Catalysts known from isocyanate chemistry and / or elevated temperature, converted into linear polyamides. 2. The method according to claim 1, characterized in that the aliphatic and / or aromatic hydroxy compounds used are those which are provided with ether groups. KALLE AKTIENGESELLSCHAFT I. 10M31 / 2069 BAOGRIGINAL '