DE1811166C3 - Process for the production of foams - Google Patents

Description

~> 4

^ \ ^ t! ^^ f ^> ^ ^a '- ^h ^ - ^ ^{asahmd} m} ^ product from the maleic anhydride polymer with

smdAmmoBiak and / or pnmare and secondary or the amine can dam the polymeric hemiamide or

tertiary amines or mixtures thereof can be used, the salt of which can be used by carefully removing the suspension

at pnmareAmme preferred gecgnetsmd. sion or solvent.

In addition to ammonia, aliphatic 5 Diezar process-based production of foam

SCÄe, cycloaüphatisearaliphatic, cal and aromatic substances to be used homo- or copolymers

called, for example butylamm propylamine, ethyl from α J-di-

amine, ethanolamine, cyclohexylammon, benzylamine, carboxylic acids or their salts, with preferably Halb-

Anihn, toluidine. Di- or polyamine amides or hemiamide salts also come from alternately

m öetracüt. ...... "built maleic anhydride copolymers and especially

However, special N-methyl half-amides or N-methyl half-amide

and optionally the formation of the half amide salts amine salts of maleic anhydride-isobutylene copolymers

Amines with a low boiling point can be used such as marisates without using them

thylamm, which is particularly popular as an amine-com propellant, such as nitrogen donor,

?? ^nen i * "* ο u u ^er J ^experienced accordingly for the i _S C0 ₂ -dispensers or volatile hydrocarbons

Production of foams with particularly favorable foaming, although the additional use

Homo- or copoly- nation of such blowing agents required for properties is entirely possible

sate is predominantly present as half-amides.

«, ^ - unsaturated dicarboxylic acids or their amines are preferably used for foaming

salt has proven to be suitable. _ao the process according to the invention serving poly

The polymeric half-amides or the underlying merizates in compact form at room temperature

the maleic anhydride polymers should be used in a stable, homogeneous form for foaming.

thylformamide measured at 25 C, viscosity numbers are set, the polymer being quite low

(intrinsic viscosity) [η] dl / gr from 0.05 to 5, preferably amounts of suspending agent, solvent, about

0.1 to 2.5. ₂₅ water, or excess amine.

They can, although they predominantly have the structure. These residual substances should, however, preferably of half-amides or salts of half-amides to less than 20 percent by weight of the amount used should, still make up minor amounts of other long-lasting polymers. The polymer From the structure of the built-in dicarboxylic acids, however, additional contain subassemblies to be dissipated, such as anhydride additives such as fillers, nucleating agents for pore-forming structures, Imide structures, half or full esterification, dyes, plasticizers or flame retardants structures or dicarboxylic acid structures or their additives.

Salts. However, these structural elements should be used in the polymer as a compact, homogeneous form of use for the

If possible in smaller numbers than the half-amide structure foaming suitable polymers, an additive

be included. ₃₅ understood form of preparation, in which the procedural

The preparation of the polymer, if appropriate, used in moderation polymer not in the form of a fine

Half-amides present in salt form evolve from advantageous powder, the individual particles of which are inherently still

admittedly due to the conversion of maleic anhydride copolymers are used, but rather than not

merisates with primary amines. substantially porous material in the form of a largely

It is expedient to use at least 40 homogeneous, closed film or granules per anhydride group 1 mole, preferably 2 moles, of amine, although. Here, the layer thickness of the film or the same also applies to the use of an amine under-or granulate particle 0.1 mm, not significantly under excess is possible. step, preferably 0.1 to 10 mm, whether-

The reaction with the amine can also be carried out with the technical possibilities of the heating process such as benzene, methylene chloride or gasoline in a suspension medium, such as benzene, methylene chloride or gasoline are limited in terms of foaming,
Neither the starting material nor the conversion The conversion of the process to be processed with the amine is soluble. It is also possible to carry out foaming polymeric hemiamides or the amine reaction with the amine in a multiphase salt in such a favorable or multicomponent system for foaming, which is achieved from preparation form either by compressing a nonsolvent and a solvent for the in corresponding machines , for example a rolling mill reaction product, if necessary using or better in an extruder, with the addition of additional dispersing aids, for example the process can be connected immediately, or the toluene-water system may be mentioned. A further 55 by converting the polymers into solution, the working value being that the reaction both organic solvents, such as methanol, such as the maleic anhydride copolymer with the amine in preferably also water, and driving off a solvent for the starting polymer of the solvent under conditions , in which the and / or reaction product is carried out, for example in Me-foaming does not yet occur, preferably in the case of ethanol, acetone or dimethylformamide, with temperatures below 150 ° C. Here, the polyhave can be water. merisate mass, for example by evaporation of the aqueous

The reaction in aqueous Me solution of the polymeric hemiamidamine salt is preferred, at 30 to

diuiri isolated at temperatures below 150 ° e, preferably at 140 ^c C in the form of tablets and

10 to 12O ⁰ C, carried out by converting amine and Malein- lieren into a foamable form

anhydride polymer are combined in an aqueous medium.

will. However, there are also higher conversion stem- After other isolation methods, e.g. B. Spray

peratures possible. drying or azeotropic drying of a

From the solution or suspension of the reaction suspension of the polymer solution in a non-solvent,

the polymer can also be poured directly into foaming B e i s ρ i e 1 1

capable or foamed form. Even

it is possible, with the solution of the 150 parts almost alternating insulation

venvendendeo.Polymerisate to coat a surface with a butylene-maleic anhydride copolymer

and the coating after drying in situ to a value of 5% of 0.74 is applied in 400 parts of 30% aqueous

foaming. dissolved methylamine solution. Then the

The foaming after the solution according to the invention is ^{evaporated in a circulating air cabinet at 80 °} C. and the process is carried out by heating the homo- or resulting polymer sheet onto a medium-sized grain copolymer of predominantly as a HalLamide "ore diameter of 2 to 3 mm. / ^ - Dicarboxylic acids or from the amine io standing granulate is exposed to a salting of these half-amides at temperatures between hot air flow of about 200 ° C for about 3 minutes, whereby it foams between 120 and 250 ° C, preferably at temperatures between to a pure white foam , which has a 125 and 220 ⁰ C. Here, the foam density of about 0.04 can be used,
The resulting polymer is also a mixture of poly- The foamed material will be in Ethylmerem hemiamide and its aluminum salt for 5 minutes, ie only acetate or benzene will be stored and will lose its partially neutralized form. Not the form. Similarly, coat the foamed material mung takes place under Itnidbildung in the homopolymers with a 30 minute storage at 150 ⁰ C in the hot or copolymers. airflow not together.

The foaming can after the extrusion ". . ,,

driving are carried out, whereby the schäu- 20 ueisp

is observed at the exit of the extruder or 150 parts of an approximately equimolar isobutylene

by heating granules or preformed maleic anhydride copolymers with a q value

Formations, e.g. films, molded parts, fibers and fibers of 2.03 are in 500 parts of 20% aqueous

Layers of the methylamine to be used according to the process are dissolved, then raked in a vacuum

Polymers. »5 excess methylamine together with a

The heat treatment can be carried out using hot gases, in a small amount of water. With the obtained viscous

In the simplest case by hot air or steam solution, metal wires are coated and kept at 80 C.

can be made or dried in a heat bath. The wires are now with an approx

or with high frequency or radiation. The 0.15 mm thick polymer layer is encased. She who-

Polymer parts can be heated to a stream of hot air for 3 to 5 minutes in a one-step process

or foamed in several stages. exposed to about 200 ° C, whereby the polymer

The foams according to the method according to the invention and the wires with an insulating tough common foam surrounds, depending on the starting foam layer. Another part of the poly material and degree of foaming densities of z. B. merisate solution is suspended with the addition of some talc in 0.03 to 0.8 and also have without the addition of auxiliary 35 methylene chloride. With stirring, substances for nucleation are now azeotropically distilled off via a very fine-pored water. The remaining structure. They are slightly discolored to pure white and granulate particles are dried and ^{heated in hot air for more than 30 minutes at 150 °} C. for about 5 minutes at 200 ^° C., during which they are stored without collapsing. The foam, a foam with a density of about 0.12, can foam thermoplastically after foaming.

further processed, they can be printed, another part of the polymer solution becomes

heat seal, glue, coat and feature a cast plate. After drying at 80 ° C

has a very good resistance to water and so it has the mass of about 2 × 200 × 200 mm. she

aggressive solvents such as ethylacetate or toluene are placed between two tarpaulin metal sieves and 3 to

and alcohol. Pre-foamed for 6 minutes at 160 ^° C. in a stream of hot air

The foams are also partially filled with foam and then for 3 minutes at 210 ° C. It is

tough-elastic and can, for. B. without breaking with a foam sheet with an average

Rolled at room temperature, resulting in a paper density of 0.1. Such accessible

similar material can be obtained. Foams are an excellent insulating material.

They are suitable e.g. B. for purposes of thermal iso- so _. . . .
lation, especially when improved heat resistance B e 1 s ρ. e 1 i
speed is required; However, they can also be used for electrical 150 parts of an equimolar maleic anhydride insulation and, as soil butylene copolymers with a j value of 0.18, better in the agricultural sector or for elasticizing, 18% aqueous methylamine in 500 parts can be used Surfaces, or to cover 55 solution dissolved at about 60 ° C. The surface of the liquid is then concentrated, for example in the form of a foamed solution, to a solids content of about 30%. Granular particles. Plates are poured from the solution by adding the

Allowed to evaporate at about 8O ⁰ C, the foams obtained according to the method kön- water. These can NEN with acidic agents or acid agents, examples through about 3 minutes of treatment in HeißluftspielsweiseCQ ₂ or SOG, be post-treated, vm 60 current of about 185 ° C to form a foam with the possibly occurring amine odor elimination density of about 0 , 07 foam up, which remains dimensionally stable at 120 to ren, but strong ventilation is usually sufficient at 130 ^{0 C,}
at temperatures between 30 and 150 ⁰ C. Another part of the solution is in a spray

The following examples are intended to explain the process in the case of a dryer at a drying air temperature of approximately. All Viskositätszahleh (intrinsic atomized 65 100 ° C. It screened from the obtained PoIyviscpsjty) [η] dl / gr in dimethylformamide at 25 ° C merisatperlchen a fraction of medium through-measured, the parts given are parts by weight, diameter of 1.5 to 3 mm and sets them in one unless otherwise noted. Sieve basket a hot air stream of about 200 ⁰ C for

about 2 to 4 minutes. The material foamed to 10 hours at 5O ⁰ C and dries the Polymerisateinem contiguous foam material with a powder at 5O ⁰ C in vacuo. The mean density of 0.06 is then resolved. it in 1000 parts of 10% aqueous ammonia solution, If one chooses the drying air temperature in the spray shed into sheets and dried at 50 ° C in a circulating air dryer at about 145 ⁰ C, is obtained already superiors 5 cabinet. The 1 to 3 mm thick foamed polymer beads obtained in this way, which can be re-expanded, are granulated and can be foamed. If one selects the dry air by a 4 to 5-minute treatment in a hot temperature to about 19O ⁰ C, they may be already fully ascending air stream of 200 ⁰ C to a foam having a foamed polymer beads isolated. foam average density of 0.2.

IO

Example 4 η ·· ιο

^r Example 9

150 parts almost alternately constructed

Line anhydride-isobutylene copolymer with a 150 parts alternating isobutylene-maleic anhydride Ty value of 0.7 are suspended in about 1800 parts of dry copolymer in 500 parts of 20% strength aqueous toluenes. Then it is passed into the ethylamine solution dissolved. Then one sheds too. Connected vessel 33 parts of methyl amine gas and the plates and approximately 2 thick is dried at 70 ⁰ C. mm stirred for 10 hours at 6O ⁰ C to give the half amide polymer plates are then granulated forms the Maleinanhydridcopolymerisat. Then, and can then be filtered off and dried at 8O ⁰ C for about 5 minutes long. Heating in a stream of hot air at 180 ⁰ C to a

The isolated polymer is added in a small vertruder Ex ao foam with an average density of 0.09, the foam a heating temperature of about who has in storage in hot air stream at 24O ⁰ C. ^{115 0} C remains dimensionally stable at the outlet nozzle of the extruder,
one strand of foamed material, the “. .

is fixed by cooling air. The foam has a B e 1 s ρ 1 e l lü

average density of 0.25 and when stored at 130 ° C is 95 150 parts of alternating isobutylene maleic anhydride form stability. Foam copolymer can be dissolved in slabs cut to 400 parts of dimethylformamide at temperatures above 150 ⁰ C and can be further processed with 100 Teithermoplastisch with a η value of 0.7 from the strand. len cyclohexylamine stirred at 5O ⁰ C. After 5 hours

160 parts of 20% strength aqueous methylamine Example 5 ₃₀ solution are added and the plates are poured into the thoroughly

The unfoamed polymerisation obtained in Example 4 were dried 8O ⁰ C in a circulating air oven. The approximately sat powder is dissolved in dimethylformamide and 2 to 4 mm thick polymer plates are cast on plates containing closing granulated at 8O ⁰ C in a circulating air oven. The granules obtained in this way can be dried thoroughly. The sheet materials can be foamed by heating for 5 minutes in the electroless Heißluftanschließend directly or in granulated form by 35 at about 190 ⁰ C to form a foam with a hot air treatment of about 5 minutes at 190 average density of 0.14,
to 210 ⁰ C are foamed. The resulting.

Foam has an average density of 0.2. Example ii

_ 100 parts of an approximately alternating B e 1 s ρ 1 e 1 6 ₄₀ ethylene-maleic anhydride copolymer with a

100 parts of polymaleic anhydride with a? J value of 7j value of 0.8 are dissolved in 400 parts of 20% methyl-0.22 amine solution in 500 parts of 20% methylamine solution. The solution is dissolved to form plates. The solution is then poured onto dry cast iron and dried at 80.degree. The thus obtained about sheets and the solvent is evaporated and exceeded 3 mm thick polymer plates are then schüssiges from amine at 8O ⁰ C. The resulting 45 granulated. The granules can be granulated th long heating in a hot air flow lines at about 200 ⁰ C for minutes by about 5 about 2.5 mm thick polymer plates. Heating the granules with a transit to a foam with an average density of diameter of 2.5 to 5 mm for 5 minutes in a hot air 0.18 lather which at 120 ⁰ C more dimensionally stable current at 210 ⁰ C, they foam to a brownish remains. Foam with an average density of 0.18. 5 «B eis ρ ie I 12

Example 7 The example! Obtained 3 geöocksae- at 8O ⁰ C

100 parts of an approximately alternating polymer bead are processed in a small ex-copolymer of styrene and maleic anhydride with a truder at a heating temperature of 245 ° C, a 17 value of 0.56 in 800 parts of 20% strength 55 from the nozzle of the extruder a strand of the methylamine solution dissolved. Then one dries the foamed material exits, which has a medium density solution at SO ⁰ C to sheets with a thickness of about 0.0K is almost colorless and at 140 ⁰ C 30 Mi-2 to 4 is now on. The panels are granulated and notes can be stored without collapsing after treatment for 3 to 5 minutes at 185 ^° C

foamy in the hot air. A colored example 13 results

thick foam with an average density

from 0Λ which remains dimensionally stable at 120 ° C. The granules obtained in Example 1 are 5 minutes

pre-peeled at 160 ^° C. in the hot air cabinet and then

Examples Pendants- hot in a heated to 180 ⁰ C Hattrapresse

300 parts of an alternating isobutylene-maleic 65 fill, wherein the material under a pressure of about

anhydride copolymers with a »/ value of 0.7 0.3 atmospheres minutes long. It resal-

are suspended in 1700 parts of benzene. Then advantage a foam plate which formstabfl at 130 ⁰ C by passing it 31 parts of methylamine, stirred remains.

Example 14

200 parts of an approximately alternating maleic anhydride-methylpentene copolymer (fa value 0.36) prepared by free radical polymerization in benzene from equimolar amounts of maleic anhydride and 2-methylpentene-1 are dissolved in 600 parts of 20% strength aqueous methylamine solution. Then, the solution is concentrated by distilling off the solvent to a solids content of 30% a, poured onto a drying tray and dried at 8O ⁰ C. The polymerizate obtained are granulated mm to an average grain diameter of 2.5. The granules can be foamed in a hot air stream at 170 ⁰ C to a foam with an average density of 0.2.

Example 15

400 parts of approximately alternating maleic anhydride-isobutylene copolymer (jj value 0.74) are dissolved in 800 parts of about 35% strength aqueous methylamine solution and 2000 parts of water. The solution is refluxed at normal pressure for 18 hours and then concentrated to a solids content of about 30 percent by weight, the initially clear solution becoming somewhat cloudy, which is probably due to the formation of very small amounts of imidation products. This solution is then ^{dried to opaque plates at 80 °} C. on drying trays. The plates are ground and sorted. The granulate content with a grain size between 4 and 2 mm is exposed to a stream of hot air at around 200 ° C. for 2.5 minutes, the material foaming into a pure white, very fine-pored foam with an average density of 0.047. If the same procedure is carried out with the granulate fraction with a grain diameter between 1 and 0.8 mm, a foam with an average density of 0.059 is obtained. The granule fraction having a grain diameter of 2 to 1 mm is closest to * 1 minute in Heißhiftstrom at about 200 ⁰ C prefoamed. After several hours of storage at room temperature, the pre-expanded material is again ^{exposed to a stream of hot air of about 200 °} C. for 2 minutes, during which it expands to form a foam with an average density of 0.042, which is pure white and does not collapse ^{after storage at 145 ° C. for 30 minutes} .

Example 16

100 parts of isobutylene-maleic anhydride copolymer with a "j-value of 1.1 is dissolved in a small kneader in 200 parts of an aqueous about 35% methyl amine solution and kneaded for 10 hours at 8O ⁰ C intensive. Then, one set at 25 ⁰ C a very small amount (about 0.3 g) Azodiisobutyrodiamidin (prepared from azodiisobutyronitrile and ammonia) is added, which will act essentially as a pore initiator. Then is prepared from the homogenized Miso research thin films forth, dried and heated for about 2 to 3 minutes at 200 ⁰ C. It is a very fine-pored flexible foamed sheet is formed.

Example 17

The procedure is as in Example 16. Only 10 parts of finely powdered talc or finely powdered activated charcoal are mixed in instead of the amidine. The mixture is dried at 80 ⁰ C and granulated the

holding boards. When the granulate is heated in a stream of air at 200 ^° C., a fine-pored foam is formed in each case.

In all foams produced by the processes described, the imide groups formed from the half-amide or half-amide salt structures can be detected by infrared spectrometry through the appearance of the characteristic double * band at 1670 to 1710 cm " ¹ and 1720 to 1790 cm" ¹ (cf. also W. 011 i η g, spectral assignment tables

the IR absorption bands, Springer Verlag [1962]).

Claims (5)

saturated dicarboxylic acids or their half or full claims: esters are reacted with amines. Preferably, using ma- 1. Process for the production of foams, polymer produced with linseed anhydride «with amines characterized in that homo- 5 reacted, which are to be used according to the invention or copolymers of predominantly semi-polymeric semi-amides or their salts in almost amide present α, / 3-unsaturated dicarbon quantitative yield arise. acidic or amine salts of these polymeric semi-preferred are predominantly alternating amide maleic anhydride copolymers built up to temperatures between 120 and 250 ^{0 C are used,} be heated. 10 although not alternating painting 2. The method according to claim 1, characterized in that anhydride copolymers are in principle suitable. the draws that polymeric hemiamides or amine salts manufacture such maleic anhydride copol> Polymeric half-amides are used, which is done according to conventional ionic, mixed by reacting predominantly alternating ionic-radical or preferably radical initiation structures Copolymers of the maleic anhydride polymerisation process in emulsion, solution, drids can be obtained with amines. as bulk or suspension polymerization; at- 3. The method according to claim 1 and 2, characterized for example in acetone or aromatics such as benzene, characterized in that reaction products of toluene or xylene, in halogenated hydrocarbons, such as primary amines with maleic anhydride-isobutylene-chloroform, methylene chloride and methyl chloride or Copolymers are used. aliphatics, such as gasoline fractions as suspension 4. The method according to claim 1 to 3, characterized thereby. indicates that methylamine is used as the primary amine. is used. anhydride copolymers are in principle all with 5. The method according to claim 1, characterized marked maleic anhydride copolymerizable monomers drawn, that the polymeric hemiamides or their 25 are suitable, but preferred are those which are pre-amine salts before the foaming process by alternating maleic anhydride-copoly conversion deliver in a solution and subsequent merisate, such as B. styrene, core or side insulation from the solution into a compact form chain-alkylated styrenes, such as * - or p-methylstyrene, be convicted. halogenated styrenes, such as. B. p-chlorostyrene, vinyl 30 esters such as vinyl acetate or propionate or benzoate, Vinyl ethers such as vinyl methyl ether, vinyl isopropyl or -isobutyl ether. Vinyl halides such as vinyl fluorine d, -chlo- rid, bromide or vinyl amides such as vinyl pyrrolidone, Vinyl acetamide or (meth) acrylonitrile or (meth) - 35 acrylic acid and its derivatives such as esters or amides; The subject matter of the present process is that the unsaturated hydrocarbon positions are also well suited of foams, characterized in that substances such as indene, diisobutylene, cycloenes that homo- or copolymers of predominantly as such as cyclobutene, cyclopentene or olefins such as ethylene, Half-amides present «, / 9-unsaturated dicarbon propylene, butene-1,2-methylbutene-1,2-methylpentene-1, acids or amine salts of these polymeric hemiamides 40 or isobutylene. It is also possible to be polyfunctional »Can be heated to temperatures of over 120 ° C. Comonomers such as B. butadiene, isoprene, divinylben- The advantage of the present process zol, glycol dimethacrylate or cyclooctatetraene or Suitable foams lies in the fact that they also use a divinyl ether, albeit too strong on the one hand not networked, d. H. still thermoplastically processed crosslinked polymers as starting materials for the are bar, but on the other hand, a very cheap 45 process-based foam production is less good have thermal stability and are suitable at temperatures. Of course, the Comono- twischea 120 and 150 ⁰ C are not used to coincide meren also in a mixture with one another as is the case with polystyrene foams, where mixed polymers of maleic anhydride the case is. stand. Although the invention for the production of 50 It has been shown that in addition to vinyl aromatics such as Foams used polymers such as styrene or olefins such as ethylene the use of known in principle, but it has not yet been possible to prefer isobutylene as a comonomer for the manufacture To convert it into foams, so that it can be used as a substitution of the predominantly alternating structure, What is surprising is that such poly- preferably as a preliminary stage for the starting material the- merisate, without the addition of blowing agents, such as lowering maleic anhydride copolymers, is suitable, Rigid-boiling hydrocarbons or fluorocarbons in order to produce particularly high-quality products according to the process Hydrogen, are required to get under the process foams. conditions can be converted into foams, the implementation of this maleic anhydride copoly excellent thermal stability. 60 fan out ways to the invention for the manufacturing The homo- or copolymers of polymers to be used as hemamides treatment of foams present «, / J-unsaturated dicarboxylic acids or hemiamides or their salts, their salts are known in principle. They are obtained. Although, as described at the beginning, the homo- z. B. by homo- or copolymerization of semi- or copolymers of hemiamides «, / J-unsaturated- amides «, / ϊ-unsaturated dicarboxylic acids, ζ. B. Fu- 65 ter dicarboxylic acids or their salts on others maric or maleic acid or their salts. Better ways are accessible, the implementation of Malein- If the preparation of the polymers or the salts, anhydride copolymers with amines is preferred .ndem homo- or copolymers of α, / 3-unge mode of representation.