SE190810C1

SE190810C1 -

Info

Publication number: SE190810C1
Authority: SE
Publication date: 1964-01-01

Description

Uppfinnare: IV M Edwards Prioritet begard frau den 13 mars 1961 (USA) Foreliggande uppfinning avser en modifikation och en forbattring av sattet enligt patentet 174 964 och det enligt detta satt framstallda formmaterialet (plast). Patentet 174 964 hanfor sig till ett satt att framstalla polyamidsyror och kannetecknas hi. a. darav, att man omvandlar minst en polyamidsyra med den aterkommande enheten: I vilkenbetecknar isomeri, R betecknar en fyrvard radikal innehallande minst 2 kolatomer, varvid hogst 2 karbonylgrupper i varje polyamidsyraenhet dro bundna vid var och en av kolatomema i den fyrvarda radikalen, och R' betecknar en tvavard radikal, innehdllande minst 2 kolatomer, varjamte angransande polyamidsyraenheters amidgrupper var och en är bunden vid skilda kolatomer i denna tvavarda radikal, och polyamidsyrans egenviskositet är minst 0,1, foretradesvis 0,3-5,0. Inventor: IV M Edwards Priority requested from March 13, 1961 (USA) The present invention relates to a modification and improvement of the set according to patent 174 964 and the molding material (plastic) produced according to this set. Patent 174,964 relates to a process for producing polyamic acids and can be described herein. a. of converting at least one polyamic acid with the recurring moiety: In which isomerism, R denotes a quaternary radical containing at least 2 carbon atoms, wherein at most 2 carbonyl groups in each polyamic acid moiety are attached to each of the carbon atoms of the quaternary radical, and R 'represents a divalent radical, containing at least 2 carbon atoms, each amide group of adjacent polyamic acid moieties each being attached to different carbon atoms in this divalent radical, and the intrinsic viscosity of the polyamic acid is at least 0.1, preferably 0.3-5.0.

Enligt patentet 174 964 framstallas dessa polyamidsyror darigenom, att minst en diamin med strukturformeln 1-12N—R'—NH 2 i vilken R' betecknar en tvavard radikal, innehallande minst 2 kolatomer, varvid diaminens bagge aminogrupper arc bundna vid var sin kolatom i den tva.varda radikalen, i ett organiskt, polart losningsmedel under i huvudsak vattenfria forhallanden och vid en temperatur understi- ... gande 60° C (foretradesvis under ° G) under hela reaktionen, omsattes med minst en tetrakarbonsyra-dianhydrid med strukturformeln: 0 0 C C / \ / \ 0 R 0 C C II 0 0 I vilken R betecknar en fyrvard radikal innehallande minst brâ kolatomer, varvid hogst tva karbonylgrupper i dianhydriden aro bundna vid var och en av kolatomerna hos den fyrvarda radikalen. According to patent 174 964, these polyamic acids are prepared in that at least one diamine of the structural formula 1-12N-R'-NH 2 in which R 'represents a double radical, containing at least 2 carbon atoms, the diamine ram amino groups arc bonded at each carbon atom in the The two radicals, in an organic, polar solvent under substantially anhydrous conditions and at a temperature below 60 ° C (preferably below ° G) throughout the reaction, are reacted with at least one tetracarboxylic dianhydride of the structural formula: In which R represents a quaternary radical containing at least brad carbon atoms, at most two carbonyl groups in the dianhydride are bonded to each of the carbon atoms of the quaternary radical.

Ett syfte med sattet enligt patentet 174 964 är att astadkomma polyamidsyror, som kunna formas till formade strukturer. An object of the kit according to patent 174 964 is to provide polyamic acids which can be formed into shaped structures.

FOreliggande uppfinning avser nu en forbattring eller en modifiering av sattet enligt patentet 174 964 och kannetecknas av att reaktionen mellan tetrakarbonsyradianhydriden och diaminen genomfOres vid en temperatur Over 60° C under en tidsperiod tiiracklig att astadkomma en polymer, innehallande minst 50 % av polyamidsyran. Foretradesvis genomfores reaktionen vid en temperatur mellan 60 och 175° C under en tidsperiod av minst 1 minut. The present invention now relates to an improvement or modification of the set according to patent 174 964 and is characterized in that the reaction between the tetracarboxylic dianhydride and the diamine is carried out at a temperature above 60 ° C for a period of time sufficient to produce a polymer containing at least 50% of the polyamic acid. Preferably, the reaction is carried out at a temperature between 60 and 175 ° C for a period of at least 1 minute.

Vid faststallande av en specifik tid och en specifik temperatur for formning av polyamidsyran av en specificerad diamin och en specificerad dianhydrid behover dessutom manga faktorer tagas under tivervagande. Maximum tillaten temperatur kommer att vara beroende av anvand diamin, anvand dianhydrid, speciella losningsmedel, procenthalten polyamidsyra, som onskas i den slutliga kompositionen och minimum av den tids- 0 0 HO—C C—OH \R/ / \ NC—N—R'— 0 H IIIIII H 2— — period, man onskar for reaktionen. FOr de fiesta kombinationer av diaminer och dianhydrider fallande inom ovan angivna definitioner är det mojligt att bilda kompositioner av 100 % polyamidsyra darigenom, att man genomfor reaktionen under 100° C. Emellertid kunna temperaturer upp till 175° C tolereras far att astadkomma formbara kompositioner, vilkas polymera del innehaller minst 50 % av polyamidsyran. Den speciella temperaturen under 175° C, som ej far overskridas for varje speciell kombination av diamin, dianhydrin, losningsmedel och reaktionstid for att astadkomma en reaktionsprodukt sammansatt av minst 50 % av polyamidsyran, kommer att variera men kan faststallas genom ett enkelt prov, utfOrt av varje fackman. In addition, when determining a specific time and temperature for forming the polyamic acid of a specified diamine and a specified dianhydride, many factors need to be considered. The maximum permissible temperature will depend on the diamine used, the dianhydride used, the special solvents, the percentage of polyamic acid desired in the final composition and the minimum of the time-0-HO-CC-OH \ R / / \ NC-N-R ' - 0 H IIIIII H 2— - period, one wishes for the reaction. For most combinations of diamines and dianhydrides falling within the above definitions, it is possible to form compositions of 100% polyamic acid by carrying out the reaction below 100 ° C. However, temperatures up to 175 ° C can be tolerated to produce moldable compositions, which polymeric moiety contains at least 50% of the polyamic acid. The particular temperature below 175 ° C, which must not be exceeded for any particular combination of diamine, dianhydrin, solvent and reaction time to produce a reaction product composed of at least 50% of the polyamic acid, will vary but can be determined by a simple test, performed by each professional.

Efter formning av kompositionen sammansatt till overvagande del av polyamidsyran, foretradesvis fortfarande i losningsmedlet, till anvandbara alster, exempelvis fibertradar, film, ror, stanger etc., och torkning av desamma, foredrager man att omvandla polyamidsyran till en annan polymer for att modifiera egenskaperna hos den formade strukturen. Salunda kan polyamidsyran omvandlas genom varmebehandling eller kemisk behandling till motsvarande polyamid, sasom framgar av patentet 177 293. Polyamidsyran kan aven omvandlas till nagot av dess salter eller estrar medelst konventionell teknik. After forming the composition composed into the predominant part of the polyamic acid, preferably still in the solvent, into useful articles, for example, fiber radar, film, tubes, rods, etc., and drying them, it is preferred to convert the polyamic acid to another polymer to modify the properties of the shaped structure. Thus, the polyamic acid can be converted by heat treatment or chemical treatment to the corresponding polyamide, as disclosed in patent 177 293. The polyamic acid can also be converted to any of its salts or esters by conventional techniques.

I stallet f Or att forma polyamidsyrakompositionen till vanliga artiklar, kan polyamidsyrakompositionen i losningsmedlet anvandas som en flytande belaggningskomposition. Sadana belaggningskompositioner kunna pigmenteras med foreningar, sasom titandioxid, i mangder av 5-200 viktprocent. Dessa belaggningskompositioner kunna anbringas pa en mangfald av underlag, X. ex. metaller, exempelvis koppar, massing, aluminium, stal etc., varvid metallerna kunna vara i form av folier, fibrer, tradar, dukar etc., glas i form av skivor, fibrer, skum, tyger etc., polymera material, exempelvis cellulosamaterial sasom cello-fan, tra, papper, etc.; polyolefiner sasom polyetylen, polypropylen, polystyren etc., polyestrar sasom polyetylentereftalat, etc.; perfluorokarbonpolymerer sasom polytetrafluoretylen, sampolymerer av tetrafluorroetylen med hexafluoropropylen, etc.; polyuretaner; varvid alla polymera material kunna vara i form av ark, skivor eller Rimer, fibrer, skum, vavda och icke-vavda ytalster, siktdukar,,etc., laderark; etc. Instead of forming the polyamic acid composition into ordinary articles, the polyamic acid composition of the solvent can be used as a liquid coating composition. Such coating compositions can be pigmented with compounds, such as titanium dioxide, in amounts of 5-200% by weight. These coating compositions can be applied to a variety of substrates, e.g. metals, for example copper, pulp, aluminum, steel, etc., whereby the metals may be in the form of foils, fibers, threads, cloths, etc., glass in the form of boards, fibers, foams, fabrics, etc., polymeric materials, for example cellulosic materials such as cello fan, tra, paper, etc .; polyolefins such as polyethylene, polypropylene, polystyrene, etc., polyesters such as polyethylene terephthalate, etc .; perfluorocarbon polymers such as polytetrafluoroethylene, copolymers of tetrafluoroethylene with hexafluoropropylene, etc .; polyurethanes; wherein all polymeric materials may be in the form of sheets, sheets or rhymes, fibers, foams, woven and non-woven surfaces, screen cloths, etc., loading sheets; etc.

Foreliggande uppfinning belyses ytterligare med hjalp av efterfoljande exempel. Dessa exempel, som visa specifika utforingsformer enligt uppfinningen, avse emellertid icke att begransa Lippfinningens omfattning pa nagot satt. I exemplen angivas kvantiteterna av reaktionskomponenterna vid framstallning av forrnbara polymera kompositioner corn molara mangder och koncentrationen hos kompositionen i losningsmedlet angives i viktpro cent. The present invention is further illustrated by the following examples. However, these examples, which show specific embodiments according to the invention, are not intended to limit the scope of the Lipp invention in any way. In the examples, the quantities of the reactants in the preparation of formable polymeric compositions are given in molar amounts and the concentration of the composition in the solvent is given in% by weight.

Exempel 1. Detta exempel visar temperaturens .betydelse och dess relation till varaktigheten hos reaktionen vid framstallning av polymera kompositioner Mom definitionen for foreliggande uppfinning. Enligt detta exempel framstalides en losning av 20 g (0,1 mol) av 4,4'-diaminodifenyleter 1120 ml N,N-dimetylacetamid. En losning av 21,7 g (0,1 mol) av pyromellitindianhydrid i 250 ml N,N-dimetylacetamid framstalldes a.ven och sattes snabbt till diaminlOsningen. Reaktionstemperaturen och reaktionstiden varierades, sasom visas i efterfoljande tabell for att astadkomma en polymer komposition innehallande minst 50 % polyamidsyra. Egenviskositeten hos polymererna (mutt som 0,5 % losning i N,N-dimetylacetamid vid 30° C) angivas aven i tabellen. Example 1. This example demonstrates the significance of temperature and its relation to the duration of the reaction in the preparation of polymeric compositions within the definition of the present invention. According to this example, a solution of 20 g (0.1 mol) of 4,4'-diaminodiphenyl ether 1120 ml of N, N-dimethylacetamide is prepared. A solution of 21.7 g (0.1 mol) of pyromellitic dianhydride in 250 ml of N, N-dimethylacetamide was also prepared and added quickly to the diamine solution. The reaction temperature and reaction time were varied, as shown in the following table, to obtain a polymeric composition containing at least 50% polyamic acid. The intrinsic viscosity of the polymers (mutt as 0.5% solution in N, N-dimethylacetamide at 30 ° C) is also given in the table.

Tabell for exempel 1. Table for example 1.

TemperaturTidEgen- Experiment(cc)(min)viskositet A85— 882,44 115-1191,16 125-1281,00 135-1370,59 165-166 3-4 0,89 Exempel 2. Exempel 1 upprepades med anvandfling av N-metylkaprolaktam som losningsmedel stdllet for N,N-dimetylacetamid. Man observerade att, ndr temperaturen hos reaktionen mellan 4,4'-diamihodifenyletern och pyromellitindianhydriden hi011s mellan 150-160° C under 2 min, egenviskositeten (matt som en 0,5 % lOsning i N,N-dimetylacetamid vid 30° C) hos den resulterande polymera komponenten innehallande till overvagande del polyamidsyra, efter isolering och aterupplosning, var 0,51. Nar temperaturen tillats stiga till 175° C kunde en egenviskositet storre an 0,1 endast erhallas out reaktionsperioden minskades till 0,5 min. TemperatureTimeExperience-Experiment (cc) (min) Viscosity A85- 882.44 115-1191.16 125-1281.00 135-1370.59 165-166 3-4 0.89 Example 2. Example 1 was repeated using N- methylcaprolactam as solvent for N, N-dimethylacetamide. It was observed that when the temperature of the reaction between the 4,4'-diamihodiphenyl ether and the pyromellitic dianhydride is between 150-160 ° C for 2 minutes, the intrinsic viscosity (matt as a 0.5% solution in N, N-dimethylacetamide at 30 ° C) of the resulting polymeric component containing predominantly polyamic acid, after isolation and redissolution, was 0.51. When the temperature was allowed to rise to 175 ° C, an intrinsic viscosity greater than 0.1 could only be obtained if the reaction period was reduced to 0.5 min.

Exempel 3. Polyamidsyralosningarna enligt fOregaende exempel anvandes f Or att belagga filmer av polyetylentereftalat, cellofan och ickevavda mattor av fibrig polyetylen och polypropylen. I varje enskilt fall var vidhaftningen av polyamidsyran tillfredsstallande. Example 3. The polyamic acid solutions of the preceding example were used to coat films of polyethylene terephthalate, cellophane and nonwoven mats of fibrous polyethylene and polypropylene. In each case, the adhesion of the polyamic acid was satisfactory.

Claims

Patentanspr It

Modification of the kit according to patent 174 964, characterized in that the reaction between the tetracarboxylic dianhydride and the diamine is carried out at a temperature above 60 ° C for a period of time sufficient to achieve one. polymer, containing at least 50% of the polyamic acid.

2. A kit according to claim 1, characterized in that the reaction is carried out at a temperature between 60 and 175 ° C for at least 1 minute. Request publications: