DE1669923A1 - Process for the production of shaped structures from acrylonitrile copolymers - Google Patents

Description

German Academy of Sciences too

"/ experienced in the production of shaped G-ebilden Acrylonitrile copolymers

The i; ring relates to a process for the production of Shaped j-c form from powdery acrylonitrile copolymers without the use of a solvent »The moldings obtained are lasaen due to their good physical and use chemical isigoiischaften versatile.

As is well known, polyacrylonitrile has excellent usefulness in terms of isestiindi ^ ity ^ euen over purple and literal solutions in "3 & ine solvent in the case of processing, but does not give rise to the missing!" hernioplasticity the greatest difficulties ", since the origin point is above -J.eeiii In the literature there are therefore only a few studies dealing with the production of I.'oruküipei-n from powdered polyacrylonitrile or copolymers can be hot pressed into a flour or less compact l.las £ e "by pyrolysis at 220 to ujeiuperaturen ⁰ Q as well as in li'aaern blackish brown materials {recovered therefrom opposite Lüstaiiiaiai;. stuffs, strong and corrosive 3üuren öasen cL-J'-rordejatlicn reals tent 3ind "Daa pressed material is, however, even at higher ^f j] öitiperaturen deformable only to a very limited and instead ge et therefore koine processing too

· £ Μ <αg'.i der ^ i-xindurig consists in forming shaped ü-ebilde i · j ..- eijtig ^ üit, which against xiitae and solvents rcai.j U, juI; oinü, uüb tixermoplastiscuen A

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is the A ^ gJb © on; i-unde _f a procedure 109877/168 »

BADORiSlNAL

Production of any shaped body from powdery! Ac * 7 "l & £ tril-GopQlymeren without the use of ' ζα develop »

it was found that when using certain copolymers !? The aorylnitrile allows compact thermoplastic material to be obtained under high pressure, which is easily deformed at higher temperatures and, through subsequent heat treatment, obtains the same or similar resist properties as polyacrylonitrile with larger proportions of strongly plasticizing premdcokomponenten · i) ädarch "internal plasticization is achieved that contain the subsequent thermoplastic is it lit causes · the output products 35 to 75 öew _t $ acrylonitrile and 5 to 25 G-ew.jo of the softening ■ ' Comonomers »Acrylic acid esters, for example, are suitable as comonomers for these purposes» Even the cold pressing of these copolymers with a pressure of 3000 kp / cm τ. t usable white materials with a smooth surface. As a result of the sintering that has occurred, they have a relatively high breaking strength and can be machined (e.g. with a turning tool), whereby under otherwise identical conditions the strength is a puncture of the applied pressure. At higher temperatures, z, B · 180 ° 0, the sintered Ha Serial becomes soft and

can be easily deformed. A ¹¹ Ch in boiling water is a W- yerformung "possible. This thermoplastic zwisciien-

stage is of .great advantage for practical processing into plastics »before the polymerizate is press sintered, the air trapped in the powder is removed from the powder · during subsequent hardening for several hours. '. V at 230 ⁰ O the moldings turn black, inside sohwarsbiauü · The end products have a high breaking strength _s are resistant to thermal loads of up to 230 ° C, and moreover for a short time at considerably higher 2 © mp @ ratv! Ren belaafbal? and extremely resistant to solventsa * Bi® end products are also Ia Biiae chyl- * -ünSolösIofe- »■■■" · ■ """'-·' ■ ■""■ ■ - ■

j ^ latiy high content of plasticizing economic monomers

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BAD OPJQIMAL; - 3 -

In the polymerizate (ζ * Β · 20 $) there is a noticeable rise in the softening point discoloration (yellow-brown) to "curing takes place again at! temperatures around 220 ⁰ C * Further, one can be prepared by the inventive method using copolymer consisting of 80 ßew, $ acrylonitrile and 20 percent * $ acrylate and" certain in compliance versuehsbedingungen molded articles obtained with a density C 1 which are buoyant and a heat- and lö'sungsmiütelresistente outer layer have "According to the invention the powdery copolymer by" preßsintem at high cold pressure or deform under slight pressure at ioemperaturen treated over 200 C and to "closing several hours annealed at 200 to 225 ⁰ G · The layer thickness should be less than 2 mm A partial decomposition of the acrylic acid ester built into the chains occurs. The resulting gases act as an internal blowing agent and cause a porous structure. The fi lm body then has a density of 41 g / egg and floats on water. Equilateral to form a solid black outer layer * changes the molded body to heat to 250 ⁰ C and solvents, also makes bulb thylformaiaid, resistant The density of the molding check with the Bahanälungstemperatur · At low temperatures, ζ · Β · 180 ⁰ C, no mass capable of sciawiim has yet been achieved. It has also been found that the copolymers of 90 to 80 wt. Acrylonitrile and 10 to 20 wt fibers can pull out when emperaturen the deformation at the IiUft or under protective gas at £ 140 ⁰ C or in a liquid medium, for _# b · oil, about 1oo ° C makes · According to the GeV / ählten initial diameter arise solid filaments desired strength · X-rays show that the

109827/1559. '^ φ ^ ⁰

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filamentary material produced under these conditions has good orientation '

As is well known, thread-like structures based on polyacrylonitrile have hitherto only been produced from suitable solutions using the dry or spinning process the properties are affected · the Torteil the method proposed here is the ElAminierung of the solvent, with "is moved erfindungssemäßen the iiögliehkeit au a solvent-free processing of Acrylaitril-ßopolyjneren. with more than 75 fo acrylonitrile any optionally heat- and solvent-resistant pormkörpern given * This could mean that these polymers, which have hitherto been mainly used for the production of fibers, can also find broader use in the ■ sector.

The invention will be explained in more detail in the following examples explained

Example 1 ■

A polyacrylate made of 86 -Qewrf acrylonitrile and 12'-Itiij'iacryl.at with a particularly wide distribution of seciuence is exposed in powder form ⁵ Bi at room temperature to a pressure of 4GOO kp / cm> with the air being sucked off beforehand 'the jjruck zurückgenoiamen "the thus obtained;. white Schei has a high breaking strength · In 2emperung -ütosi * 180 ^Ö it is transparent and soft · they verformuiig erßö-u * iw boiling water © .the in air at' jjeiaperaturen 180 ⁰ G",

Example 2 : ■ ■ "

A 6 hours' at 230 ⁰ C according to Example "IHER ^ estellter li'ormkörper is annealed j it is black * .. B'er i ^ mkörper is break-proof, has a .glänzende öberflüche and is resistant to solvents and heat,

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example 3

Powdery oil-polymerizate made from 80% by weight of acrylonitrile and 20% by weight of ethyl acrylate is ^{deformed at 215 0} O under light pressure on a cylinder. pormkörpeä? with a * density of ^ 1 g / ora '' »this float has a sohwarae, heat and solvent-resistant exterior sciiiehi«

Example 4

Sin oopolymerisat aua 80 © ew * ^ acrylonitrile waä 20

is ia pulverf or »Taei Zimoierteiiiperatyi? a pressure of 400Q & p / eia aüsgesetat "uach 20 se we ο 4 of 2urückgenoüiruen # The sq erhaltönQ white disk with thickness of 3mm 10 hours at £ 10 ^Ö 0-Kan sustaining a SohwiMnkörper porous and solid black outer layer ''

Example 5 '

jjjin powdery eopolymer from 85 and 15 eew »^ Ithylaerylai. is at

a Dzx & k van 6000 kp / om press-sintered · The m white disc is laid out in strips »This wejeäea is thawed for a short time in a sSÄitoaa oil bath of 18 © ⁰ Q and then immediately pulled out to a multiple of its original length» pie resulting lerstsa are with ₉ firm and flexible * ". _;

Example ^

puiverföria% ea oopolym @ ri © ai from 85 and 1? öew * ji Xthylacrylat wirä at room temperature? a sruote of 6OÖOkp / om press-sintered ^ t, Baoh dismantling into strips we α the sintered material in süikonol at 120 ⁰ O hoehverströokf * You get a firm , flexible ©

109827/1559

Claims (1)

~ 6- ffate atanspruehe t 1 * T process for manufacturing wa shaped structures Gopoljnere & j d &<characterized by the fact that powdered oil-finishing which, in addition to acrylonitrile, contains 5 to 25% of an internal plasticizer, s »B _e acrylic acid esters ^ * and? high pressure free room stone peratua? press sinters, - daiiaca hardens at temperatures above 100 ⁰ O tiiermoplastisoii Yerfonat u & 3, if necessary, subsequently at 180 to 340 ^{0 0 for} several hours * 7 © rfaiiren aur hot formation of shaped sebilden aiis olymerenj daäurcii keiiniseiohiiet that one Aeryl nitrile copolymer ait 15 to 25 of an inner white egg, a "B" aoryl acid ester ZQQ ° ß with the application of a little or more then several hours at 18o up to 24Θ ^G € tesipert ». 3 _# ? Erfahnen laaoh Aüsprucix 1 öder 2 * da & uroh marked, äaS msji ei »oopölymerisaf _f which in addition to AergMifcril 20 (? $ W * ^ Aerärlsäujeeester, contains, on a jorjn mass with an iöliißhtiiskö ^ 2 is® shaped and at 200 to 225 ⁰ Q 4 # Yerfalires "ah Aiispruoh" I ₁ characterized in that one ia ööföiymerisat »which mTo & n acrylonitrile 1Q bis Contains 20 GrOWf ^ Aerylsä «i? Eester, at dimmer temperature holies l ^ uck pi * ei3sintert and including at Qjem * labet leo ^ O to spring-shaped structures,