DE2234271A1 - POLYIMIDE POLYMERS - Google Patents

Description

The SrfindtHig 'refers see. on. eynthetieohe polymer resins * It looks in particular at new polyimides and on a new process for the production of the same * It also looks at thermoplastic, fast curing, stable, high molecular weight polyimides, which have superior thermal and oxidation resistance and which are made by pyrolytic polymerisation low molecular Vorpolymerer be prepared at elevated Sempsraturen _o Vorpoly "wsröon iaere prepared by reacting a polyfunctional amine _s, <si.n polyfunctional anhydride, maleic anhydride and reacted with each other iiiQn _a VorpolLymere This polymerized"

209884/1269

BATHROOM 0RK31NAL

then Sieren, v / hen they are heated to elevated _{temperatures,} and continue wherein finally by a ·-average molecular weight * of about 10,000 or more he will hold ~ end to end Polymore.

The currently known polyamide resins are known because of their extraordinary physical and chemical properties, and in particular because of their stability at higher slump temperatures. Because of their attractive properties, the polyimides have numerous applications in technology where high strength and high temperature resistant materials are needed. While the currently available polyimides are very good, they still suffer from a disadvantage encountered in the cure stage of these polymers. For example, most of the polyimides produced to date have been obtained by reacting a dianhydride with a diamine in the presence of various end capping groups such as S5 * B ₉ a monoanhydride 4 st a polyamic acid by chain extension. When the polyamic acid was ready, the intermediate product was kept in solution, hermetically sealed and cooled if it was not to be processed further. »This special packaging for storage and subsequent use was expensive, which had a particular effect on the consumption of waste. During the hardening of the amic acid, the intermediate product must be heated to an elevated temperature for 16 hours or more, with the development of volatile materials which arise during the reaction and during the evaporation of the solvent;

In US Pat. No. 3,528,950, significantly improved, fast-curing, stable polyimides are described _. that you have a special monoanhydride with a mixture of one

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Dianhydride and a diamine converts * to produce torpolymers, which have the following indais closing group

This Torpolymere are then polymerized by pyrolysis to high molecular weight polymers out share "In this way the Polyimidsäuren can be circumvented _e The finished Polyimidpolyinere" possess exceptional physical properties "as _ζ β Β β an exceptionally high temperature resistance and an exceptional Inerthext to chemicals" Besides having the Torpolymere5 from from which the finished resins are derived, have an excellent shelf life and do not have to be refrigerated to keep them stable; rather, the gate polymers can be stored for long periods at room temperature Thus, there remains a need for a method that yields polyimide polymers that have the desired properties but that are cheaper.

Object of the invention to provide a new and improved method for the preparation of Polyiraidvorpolymereni is now the Tojjpöly * · mers are prepared that ₉ is a jpiplyfunktionelXes anhydride Male4nsä, ureaiihytoid "ad cyclopentadiene are reacted with each other a polyfunlctionelleB JmIiI" The cyclopentadiene is the polyfunktiönellen amine and the polyfunktioneilen anhydride added simultaneously with or subsequent to the addition of the maleic anhydride, the individual amounts of the various components are chosen such that a _s Torpolymer formed "which is more than 0% and" up to 100 $ of a compound of TTorrael

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_B AD

9 Q

R.-ft XJU- ¹ X S > v

ο χ

Q ο

Around

contains, wherein «R« is hydrogen or a lower alkyl group

β an aliphatic or aromatic one

Hydrocarbon group, and η κ is an integer of at least 1

wherein the remainder of the gate polymer is composed of a compound the formula

X.

- ■ "■ R ^ i

Ci I! O

₀ 8th

H-

consists in which R ^ and Rg »an aliphatic © or aromatic

Hydrocarbons group and. & α is an integer of at least 1.

These prepolymers polymerize when heated to Ütemperaturen tiber about 180 ⁰ O further Inde to Bnde, wherein finished polymers having a molecular weight of about 10 0OG or more receive "are, pas obenbe β einrieben © method allows the production of superior poly & midpolymeren with a substantially reduced cost , and with good control of the binding properties ^

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* 5

The method of making the prepolymers and in particular is the order in which the participants in the reaction are united critical,,

Up to 100 ^a ß> of the prepolymer according to the invention can be obtained from a compound of the formula

^E ? - σ

- R.

N-hr

IF

consist, in which R is hydrogen or a lower allyl group and R ₁ and R2 represent an aliphatic or aromatic hydrocarbon group, β toffgruppe and η is an oil number of at least 1. The remainder of the prepolymer can be represented by the following formula

N-

R ₄ -

R ₁ -

j.

wherein R, j and Rg an aliphatic ^ or aromatic hydrocarbon groups and η is an integer of at least 1.

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This prepolymer is produced by reacting a polyfunctional amine, a polyfunctional anhydride, maleic anhydride and cyclopentadiene with one another. Usually the reaction will be carried out in a liquid solvent. The composition of the! Solvent is not critical «However, it should be compatible with all components» A wide range of solvents can be used, such as ζ, B ₀ organic liquids »for example Pural, butyrolactone, 1-methyl-1 _f 2- pyrrolidone, oluene, dimethylformamide, benzene, benzonitrile, dioxane, xylene, cyelohexane and mixtures thereof

A critical feature is the order in which the various ingredients are added. According to the invention, cyclopentadiene is used simultaneously with or preferably after the addition of the maleic anhydride to the polyfunctional amine and the polyfunctional anhydride added. The preferred way of making the torpolymers is by using maleic anhydride to a mixture of a polyfunctional amine and added to a polyfunctional anhydride and then added cyclopentadiene "

The molar amount of the polyamine used is equal to the sum the molar amount of the polyfunctional anhydride and maleic anhydride which are used. The relationship too of the moles of maleic anhydride from the moles of the polyfunctional Anhydride is usually in the range of about 0.05 to about 1.0, and preferably in the range of about 0.15 to about 0.50.

The amount of cyclopentadiene ₉ added depends on the desired properties of the finished cured polymer *

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Xm general, the ratio of, moles cyclopentadiene au are the moles of maleic anhydride in the range from about 0.01 to about 1 _f. 5 Therotetically, a ratio of 1 _f 0 gives a prepolymer _? which consists essentially entirely of one compound, the end groups of the formula

wherein R is hydrogen or lower alkyl. However, an excess of cyclopentadiene can also be used will,,

Larger amounts of cyclopentadiene result in! OlyB ©: p © with a high strength (Crlaelaminatbiegefestigköit 5600 kg / cm) and with a high thermal stability (1000 st at 290 ⁰ O with only little _{loss of strength) β} However, these polymers have the disadvantage that they high Härtungatemperature ^ 250 et example, until about 30O ⁰ G, and relatively long HärtungBtemperaturen, for example, to below about 1, gene benb'ti *.

On the other hand, smaller amounts of cyclopentadiene were rapidly curing polymers at lower temperatures example ", about 200 to 250 ⁰ O harden _{o t} These polymers can be AUOH at lower 5? Emperaturen form" but in general they have a lower resistance and thermal stability, according to the invention in any 3? all cyclopentadiene present _P even if the amounts small leg can "the larger amounts of up to one mole xmd. more per mole of maleic acid go ₀

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A person skilled in the art is able to determine the amount of cyclopentadiene to dimension that a prepolymer is obtained which, after pyrolytic polymerization, a polyimide with the desired Properties results.

The temperatures for the preparation of the prepolymers are not critical, βie of the solvent to the boiling point can extend, but generally in the range of about 100 to about 180 ⁰ O, and especially in the range 150-165 ⁰ Oo

In preparing the Torpolymere can polyfunctional amines _s as Z ₀ B.! Ssriamiuaund Setraamine use the diamines are preferred but "The following examples illustrate polyfunlctionelle Amine? which can be used in the production of the polyimide * prepolymers:

para-phenylenediamine

me ta-Phexiyiendi amin

4,4 * -diaminodiphenylpropane

4,4'-diaminodiphenylme t'hanbenzidine

4 _f 4 • -diaminodiphenyl sulfide

4,4 * -diaminodiphenylsulfone

3,3'-diaminodiphenyl sulfone

4 D 4 ^f -Piaminodiphenylether

1, 5-Dlaminonaphthalm

3,3 '"-Dimethocybenesidine

2,4-bis »(beta-aiaino ~ butyl) toluene

Bis (para-beta-aminobuty! Phenyl) ether Until «(para'-beta- = iaet'i3.yl *» "delta" "aminopent3rl) bensol Bis- ~ para «~ (1,1 -dimetbyl-S ^ aminopentyl) -benzene 1 -Isoprcpyl-2 «4-" met £ «« paenylsndiamisi

■ ni-xylylenediamine

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BAD ORfGINAL

Hexamethylenediamine

Heptaraethylene diamine octamethylene diamine

lionamethylenediamine

Deeamethylene amine

Diaminopropyltetraraethylenediamine 3-methylheptamethylenediamine 4,4-dimethylheptaraethylenediamine 2,11-diaminododecane 1,2-bis (3-aminopropoxy)> -ethane 2,2-dimethylpropylenediamine 3-methoxyhexamethylenediamine 3 t 3'-dimethylbenzidine 2,5-dimethylenediamine 2,5-taiaethylenediamine ~ Difflethylheptamethylenediarain 5-methylnoname thy leadiamine.

2,17 diamino eicosadecane 1,4-diaminooyclohexane 1,10-diaminor-1,10 * dimethyldeean 1,12-Dlaminooctadecane.

Examples of olriamines that can be used are:

1,3 »5-triaminobenaol 2,4 9 6-triainino-0-triazine 1,2,3 * -sriarainoprppan 4,4 ·, 4« -triaminotriphenylmethane 4,4 », 4" -triaminotriphenylcarbinol.

Polyfunctional anhydrides that can be used in the manufacture of Polyimidvorpolymere invention are generally dianhydrides, although tri- and letraanhydride in the scope of the invention fall "polyfunctional anhydrides which have been found suitable ₉ can be selected from the following exemplary list :

,. '209884/1269

Pyromelll dianhydride

Benzophenontetracarboasäuredianhydrid 2,3,6,7 ~ l! Iaphthal © ntetraeärbonsä ^I ureäianhydrid 3 '3', 4 '4' ^ Mphenyltetracarbonsäuredianhydrid 1,2,5, ö ^ Naphthalentetraearbonsäurediaiihydrid 2,2 ', 3 ₉ 3' ~ 3) iphenyltetraearbonsäuredianhydrid 2 , 2 * -Bls ~ (3 »4-dicarbo2gyphenyl) -propane dianhydride 3» 419,10-perylenetetracarboxylic acid diahydride bis- (3 »4-dicar" boxyplienyl) ~ ether diacid dianhydride xthylenetetracarboxylic acid dianhydride Haphth.alen-1,2,4 "» 5 bon8äuredianhydrid ITaphthaleii-t, 4, 5 »8-te traoarbonsäuredianhydrid Decahydronaplithaleii 1,4,5» 8-tetracarteoB3ä "aredianhydrid 4.8 ~ Diaiethyl-.1,2,3,5,6,7 ~ hexahydronaphthalen-1,2 , 5.6 carboxylic acid diajihydride

2 y 6-Dichloroiiaphtlialeii-i, 4,5 _f S-tetracarboxylic acid dianhydride 2 j 7-dichloronaphthalene ~ 1,4 * 5 "8-tetracar" bonsäuredianhydrid 2,3,6,7-SetrachlorGnaphtliale] a «1,4, 5,8 th traoarboxylic acid dianhydride phenanthrene-1,8,9,1O ^ tetraarboxylic acid dianhydride cyclopentane-1,2,3 "4" tetracarboxylic acid dianhydride pyrrolidine-2,3,4 * S-tetracarboxylic acid dianhydride Py3? A3in "! - 2 , 3 "5" 6-tetracarboxylic dianhydride 2,2-bis (2,3-dicarbo3 ^ ypfee ^ yl) "- propane dianhydride 1,1 - ^ BiS- (2,3-dicaipboxyphenyl) ethane dianhydride 1,1 '-bis - (3,4-dicarboxyphenyl) ethane dianhydride bis (2,3-dicarboxyphenyl) methane lanhydride bis (3 »4 ~ dicarbo: ayph, enyl)» methane dianhydride bis (3 »4-dicarboxyplienyi) -sulphon dianhydride benzene -1,2,3,4-tetracarboxylic acid dianhydride ϊ1ι1ορ1ιβη · -2,3,4 »S ^ tetracarboxylic acid dianhydride.

The high molecular weight finished polymer is made by pyrolytic polymerization of the gate polymers produced at temperatures above 180 ° Ö * Temperatures are preferably in the range of approximately

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200 to about 350 ° 0. Pyrolytic polymerization occurs below t80 ° 0 not on »

The interpolymerization begins at the same time as the evaporation of the solvent and continues with further heating. The result is the formation of a stable polymer with a molecular weight of more than approximately 10,000 thermal stability even at a temperature of more than 35O ^{0 O.}

Due to its superior characteristics, the finished polymers can find a variety of uses * Examples include the production of laminates, reinforced composite products, plastic parts ₉ SPenaettteke and coverings.

The invention will now be explained in more detail using the following examples *

example 1

Moles of cyclopentadiene _ moles of maleic anhydride

Approximately 4O ₉ 7 Gew _e ~ 3Jeile 4 ₅ 4 ^! Methylenedianiline, 32 * 8 wt -0 _e? Rush 3 ₅ 3 _»f 4,4 'benzophenonetetracarboxylic dianhydride, 20" 2 0e \ f _e ~ rope maleic anhydride and 26 ₉ 8 öewe iüeile-cyclopentadiene in 170 ml of dimethylformamide and 400 ml toluene dissolved, the solution is 13 "st refluxed» during which water is collected ,. at the end of refluxing the Löaung is cooled to room temperature and. filtered. It is striking an insoluble! fraction ;, collected which and overnight at 110 ⁰ C dried under vacuum

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The filtrate is slowly poured into 3 liters of rapidly stirred water and stirring is continued overnight. While stirring, a second precipitate forms and is collected by filtration and dried overnight at 110 ⁰ O under Yakuum. The first and second dried precipitates are separately ground into a fine powder with a mortar and pestle. The yields of the first and second precipitation are 32.9 parts by weight and 60.9 parts by weight, respectively, f part by weight of the second fraction and 1 part by weight of the first fraction are in 8 parts Ν, Dissolved Ν-dimethylformamide. Bin glass fiber cloth is impregnated with this solution and st in a forced air oven for about 1 to a temperature of about 120 ⁰ G heated. Then the temperature is heated an additional hour at about 190 to 200 ⁰ C to imidization of the impregnated material to effect "Dae tissue is cut into several pieces, at a temperature of about 275 ⁰ G and at a pressure of about 14 which kg / cm to produce laminates. These © laminates are thermally stable at a temperature of 290 ^{0 O for over 1000 hours.} Its flexural strength is approximately 5600 kg / cm.

Example 2

Moles of cyclopentadiene _
Moles of maleic anhydride

Approximately 40.7 parts by weight 4i4 ^! Methylenedianiline, 32.8 wt parts by _a 3,3 '^^' - benzophenone tetracarboxylic dianhydride, 20 ₉ 2 wt "parts by weight maleic anhydride and 13j4, parts by cyclopentadiene are dissolved in 170 ml of dimethylformamide and 400 ml of toluene" The solution is 18 at reflux held ^ during which water is separated _e At the end of the reflux time, the solution is cooled to room temperature and filtered. The precipitated or insoluble fraction is collected and at 110 ⁰ O under vacuum overnight.

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dries. The filtrate is slowly poured into 3 liters of rapidly stirred water and stirring is continued over 1-fold. While stirring, forms a second precipitate which is collected by filtration and dried over Haoht at 110 ⁰ C under vacuum. The first and the second dried precipitate are ground separately into a fine powder with a mortar and pestle. The yields of the first and second precipitation are 30.2 parts by weight and 56.4 parts by weight, respectively. 1 part by weight of the second fraction and 1 part by weight of the first fraction are in 8 parts ^^ dimethylformamide dissolved. ^ a glass fiber fabric is impregnated with this solution and at a temperature of about 120 ⁰ C 1 st long in a forced air oven dried "Subsequently, the temperature is raised for a further hour at approximately 190 to 200 ⁰ C, the imidization of the impregnated material to cause "The tissue is cut into various pieces ·, which are pressed min at a temperature of 225 ⁰ C and at a pressure of 14 kg / cm about 45, to produce laminates. These laminates are 1000 pcs thermally stable at a temperature of 29o C ^0. Its flexural strength is approximately 5250 kg / cm ² .

Example 3

Moles of cyclopentadiene moles of maleic anhydride

Approximately 40.7 parts by weight 4.4 ¹ ~ methylenedianiline _s 32 ₉ 8 parts by weight 3äi3 ^5, 4,4 ^J ~ benzophenonetetracarboxylic dianhydride, 20.2 parts by weight of maleic anhydride and 6 ₉ 7 parts by weight of cyclopentadiene dissolved in 170 ml of dimethylformamide and 400 ml of toluene. The solution is refluxed for 18 hours, during which time water is collected. At the end of the reflux time, the solution is cooled to room temperature and filtered. The precipitated insoluble fraction is gsaammelt and dried overnight at 110 ⁰ C under vacuum.

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The filtrate is slowly poured into 3 1 rapidly stirred water is ~, lind, stirring is continued overnight * While stirring, forms a second precipitation "represented by Filtra ~ tion is collected and dried over Haeht at 110 ⁰ C under vacuum" The first and second dried precipitates are ground separately into a fine powder with a mortar and pestle. The yields of the first and second precipitates are 29.0 parts by weight and 55.0 parts, respectively. 1-turn portion of the aweiten fraction and 1 wt _o -part of the first fraction are dissolved in 8 parts of N, ^ dimethylformamide * A glass fiber fabric is impregnated with this solution and temperature long introduced at a! Of about 120 ⁰ O 1 St in a forced air oven . Subsequently, the temperature is raised for a further hour at approximately 190 to 200 ⁰ O, to cause imidization of the impregnated material. The tissue is cut into various pieces, which are pressed at a Temperatur.von about 200 ^G G and at a pressure of 14 kg / cm in about 45 min Laminate "These laminates are thermally stable at 290 st 1000 ⁰ O. Its flexural strength is 5250 kg / cm ² .

Example 4

Moles of cyclopentadiene
Jflole maleic anhydride

Approximately 40.7 parts by weight 4,4 * -methylene dianiline, 32.8 parts by weight 3 9 3 S 4 »4'-benzphenonetetracarboxylic dianhydride ₉ 20.2 parts by weight maleic anhydride and ₉ 37 parts by weight cyclopentadiene are dissolved in 170 ml of dimethylformamide and 400 ml of toluene ,, the solution is refluxed for 18 st, during which water is collected ₀ at the end of Rüekflußzeit the solution is cooled to fcur RaumtempcJra- • and filtered. It forms an insoluble precipitate "which is collected and dried under vacuum overnight at 110 ⁰ O _e is dried slowly Piltrat The rapidly stirred in 3 1

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Pour in water and continue stirring overnight. While stirring, forms a second precipitate which was collected by filtration and dried over Haeht at 110 ⁰ C under vacuum ge * · is "The first and second precipitation are dried separately with a mortar and pestle to a fine powder ground. The yields of the first and second precipitation are 2B _f 6 parts by weight and 53 »0 parts by weight. 1 weight part of the second! Fraction and 1 weight part of the first fraction are dissolved in 8 parts ^^ - dimethylformamide. A glass fiber fabric is impregnated with this solution and at a temperature of about 120 ⁰ O about 1 st hours in a fan oven. The temperature is then raised to approximately 190 to 200 ° C. for a further hour in order to bring about an imidization of the impregnated material. The fabric is cut into several pieces at a eah? Emperatur of about 200 ⁰ C and at a pressure of ungefälii? H kg / cm are pressed for about 45 minutes to produce laminate herßus'c @ llen _o These laminates are thermally stable for up to 100 st long at a temperature of 24 ° C , their flexural strength is about 4200 kg / cm *

Claims

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Claims (1)

P a t e li t a π s ρ r ü c h e tKmki <* r ** ι ** - ν -.t. 1 "prepolymers, characterized in that sYou the Reaktionsproöukt from a poiyfunktionellen amine, a polyfunctional anhydride" maleic anhydride and cyclopentadiene, wherein the molar ratio of maleic anhydride O to about 1 _P to polyfunctional anhydride approximately ₅ 05 0 ", zn the mole ratio of cyclopentadiene Maleic anhydride is about 0.01 to about 1.5 and the cyclopentadiene has been added during or after the addition of the maleic anhydride to the polyfunctional amine and polyfunctional anhydride * 2c prepolymers according to claim 1, characterized in that the ratio of maleic anhydride to polyfunctional anhydride is approximately 0.15 to approximately 0 _y 50. 3 * prepolymers according to claim 2 «characterized in that the polyfunctional anhydride is a dianhydride. 4 ₀ prepolymers according to claim 3? characterized in that the polyfunctional anhydride is a diamine. 5 «prepolymers according to claim 4, characterized in that the cyclopentadiene was added after the maleic anhydride is. 6o polymers, characterized in that they have been prepared by polymerization of the prepolymers pyrolyti BCHE according to one of claims 1 to 5 to a temperature of at least 180 ⁰ C are C PATBfTANWXLTE RHHOC & DlPL-ING. 14. DRILL WHANO. i.8TA £ G « 209884/1269