DE2012723A1 - Hard foams - Google Patents

Description

The invention relates to new rigid foams which consist of new thermosetting hydrocarbon resins.

The rigid foams of the present invention are prepared by reacting a foaming agent in a liquid * -poly -'- interfered mergemisch the polyfunctional Pblydien, a polyfunctional organic chain extender and a radl * --earth Peroxydlnitlator enthillto Polymergeinisch The liquid is warmed slightly by _s vepanlassen to a chain extension of the polybutadienes and initiation of sudsing _s creating a elastometer foam formed wirdo When the foam for the end · "stage _s is ready then heat is applied" so the Elasto = · wan? in © inen hard. heat-fixed rigid foam is hardened c

009839/2133

BATH ORIGINAL

The; own new xig m Haraschaurastoffe the present invent the pre -ell that _a soft elastomeric Schaumgegenstä de can weräen * ^ cut which is then converted into the desired form and can be finally gehörtet .in a heat-set hard foam. The heat-curing, cross-linked, cyelized polydiene resins which can be used for the foams according to the invention belong to the family of resins which are characterized by cross-linked, linearly elongated chains of condensed cyeloallphatic groups, as described in German patent applications P 16 k5 503.1, P 17 20 177 · 3 »P described 17 20 178.4 and P 16 $ 5 523.5, Ee is pointed out that the ^ Polyäthermischpolyraeren ,, the Kohlenwasserstoffmiachpolymeran and forms internally plasticized described _it the ia these applications, can be used just as well »as the chain extenders and radical initiators listed there. In this German patent applications hereby reference is made ₀

The erfindungagemäßen resin foams are prepared by a that sin blowing agent or a foaming agent, a liquid powder mixture is added _p the polyfunktioneile prepolymers, of which at least one of a polyfunctional PoIydienvorpolyme ^ ¹ predominantly dependent ligand Viny groups! IAFE on alternating carbon atoms of an elongated carbon backbone chain, and a polyfunktioneilen chain which can react with the functional groups of the polydiene, as well as a free radical peroxide initiator, which can cause the cyclization of the remaining vinyl groups and the crosslinking of attached chains.

The Polydienvorpolymeren used in the preparation of the thermosetting resin foams of the present invention should übeswieeend abhängende Vliiylgruppen on alternating carbon "atoms of Kohlenstoffp ^ axüstkette contained _s which preferably at least 80% of the olefinic ünsättigung contribute, and they should varzugsweisa" in molecular weight of approximately 500

009839/2133

ORIGINAL BATHROOM

feeaitsen to about 3000 can "although higher molecular weights ver" applies, if the viscosity is not a problem, "The preferred polydiene is i _a 2 ~ _s polybutadiene although 3J ¹ J -polyisoprene is well suited" Difunktioneile connections ^ a terminal substitution and are preferably _ε however, other are polyf oint ioneile prepolymers ^ where funktiohellen groups at the "entgegengesetsten ends of the molecule but not present in the end positions are used. ₈ Dihydroxy-substituted prepolymers are also generally preferred, and are because of ease of reaction, but aicarboxy-substituted compounds or other poly-diene prepolymers that have chemically functional groups that preferably terminate _{with a s} can also be satisfactory preferably _a can, however, production conditions are adjusted _so-B that in general, all polymers having a goose PunktionalStat of more than 1 use känn "

The selection of a suitable organic chain extender depends on the functional groups on the prepolymers from, if the functional groups are groups of the prepolymer hydroxyl ", then ■ KettenverlängererDiisocyanate should _c Disäurehalogenidei, Dlafiuran or Diester 'be." tienn the func "tional groups <! s prepolymer carboxyl groups are then _s should Ke t th Extender diepoxides ,, diamines, diols or -Diaziridine be. If the funktloneIlen groups on the prepolymer amino Bind _s then the chain diisopropyl "should oyanate, Anliyöridej dianhydrides _9th Dicarboxylic acids “diacid” halides ₉ diesters or “diepoxides 3ein _a The aliphatic or aromatic organic chain extenders are preferably difunctionalXl ₉ but they can also contain more than two functional groups

Are typical Prlisocyanatverb _s indungen the longer chain than River f..icn when erfir.clungr.5Pir ₁ method are used könnan _ß;

00 9 839/2 13 3

Table I.

Io 2j, l | -Toluene diisocyanate

2 ο hexamethylene diisocyanate

3 «2.6 ~ toluene diisocyanate

kο dianlsidine diisocyanate

5 * 2,4-benzene diisocyanate

S ο ρ, ρ'-diisocyanatodlphenylmethane

7 ο l-chlorophenyl-2,4-diisocyanate

8 ο trlraethylene diisocyanate

9 pentamethylene diisocyanate 10c butylene "=" l ₈ 2 -dilsocyanate 11 "butylene-le ^ -dllsocyanat 12o xylene diisocyanate 13c 2,4-cyclohex ^ lendllsocyanate II. 1,1-dibutyl ether diisocyanate 15 »ljß-cyclopentane diisocyanate l6 ο 2 _v 5-indene diisocyanate 17ο diphenylmethane diisocyanate 18 ο 1,5-naphthalene diisocyanate 19 · tryphenylraethane diisocyanate o

Typical acid and anhydride chain extenders ₈ that can be used according to the invention ₉ are:

Tabel Adipic acid II Io Fumaric acid 2. 1, Ί »CyclGtiGxaiidlcarbonsä 3. Terephthalic acid ure _no Malonic acid 5. Trimer acid (Emery 316 2 6o Dlmeric acid (Empol 102 2 c = D) 7c Emery Industriee)) _o and 1016 (Empol dimer acids from Azelaic acid 8 _e

009839/2133

BADORfGINAL

9o sea azic acid 10 _β isophthalic acid 11ο endo-cis-blcyclo · »(2" 2 "i)" 5-hepten-2 _s 3 "= dicarboxylic acid planhydride 12, succinic anhydride 13" dödeceny!

16. Maleic anhydride 17 “Phthalic anhydride 18ο glutaric anhydride

19 ο 1 _S 4,5, β »7 ₉ 7 ° He3iaehl © rob icy clo» | p. 2 »l]» S-hepten'-a „3 ° dicarbon =

Acid anhydride 2Oo tetrachlorophthalic acid anhydrido

Suitable dianhydrides and Folyanhydridkeitemrerlängerersind the following ι ".. ■

Table IiI

1 ο 3 $ 3 ^B 9 ^ j, ^ * "Benzophsnontetraearboxylic acid planhydride

20 Polyaselaic acid polyanhydride 3ο pyromellitic dianhydride H «, pyromellitic dianhydride / glycol» adducts 5o is. ^ SsSa ^

Suitable © diepoxy chain extenders are as follows

Table IV

I. Epoxy »HoyaIcke 2 ο Up ~ epoxydicyclopent% LAETHER of ethylene glycol 3 ο compounds of EpiGhlorhydrin / bisphenol ^ Ä ^ Type

5 ο Dlcyelopentadlendloxyd

6 c Lteonendloxycl

7 o bis «= C 2 _s 2-epoxyp3? Oposy) 8, vinylcyclohexanedloxide.

009839/2133

BAD ORIGINAL < , ^ , ..

9. 3f ^

cyclohexane carboxylate

10. Zeafcanthine diepoxide

Ho 9 "13-epoxy-i2-hydroxyoctadecanoic acid"> triester with glycerine

Suitable diiniin «*, DiImId = and trilinide chain extenders are the following :

Table V

1.!, E
fc 2.1,6-hexane-N, N * -dlpropylenimine

3rd!, T

4. ijT

5. l, 8-0ctane _s N, N ^f -diethylenimine

6. l _s 8-octane _i) N _J , N ^l -dlpropyleniinine

7 c i, 3-Dl-C carboxy-N-propylene ImM) -benzene

8 ", 1 _s 3 _s 5 _s -Tri- (carboxy-N-propylenimld) -benzene

9. l ₉ 3 _s 5-Di- (ethylene-Nl, 2-butyl-ml) -benzolo

By reacting the liquid polydienes with the chain extenders an elastomeric material with a higher molecular weight can be achieved. The chain extension » The reaction is carried out at room temperature or at a slightly elevated temperature. »The reductions carried out within a short tent« temperature and the reaction times depend on the chain extenders used. Besides, it goes without saying j that the presence or absence of a catalyst for the chain extension reaction has an influence on the Reaction conditions o

For the hardening stages of the process it is important that radical aliphatic or aromatic peroxydinitators are present ο dles <? rerOxydinitiatoren are for the cyclization of the pendent vinyl groups of the polydiene and the bond adjacent chains essential The Psr-osydiinitiator is In the starting point, what the polydiene polymer and the

009 839/2133

BAD ORfGINAt

organic chain extender containing, introduced _t . - he being a molecule; τ is distributed by the resulting elastomeric polymer and practically no reaction takes place o When heat is applied in the final stage, the peroxide initiator decomposes and supplies free radicals, which force the hanging vinyl groups to form a connection, so that crosslinked / condensed cycloaliphatic chains are formed.

The amount of peroxide initiator used in the resins is determined depending on the peroxide initiator used and the one used Polydiene. In general, the amount of peroxide used is between about 0.5 and 10 Uew.- £ and especially in Range from about 2 to about 6 parts by weight based on that Prepolymer · Examples of typical organic peroxides that can be used in this process are shown in the following » listed in the table:

Table VI

Ι "Di-t" * butyl peroxide

2ο 2,5-dimethyl-2,5-bis- (tert-butylperoxy) hexane

3e n «butyl- ^{i Jp i} } bis (tert-butoxy peroxy) valerate

Uo 2,5-dimethyl-2,5 = 'bis- (tert-butylperoxy) -hexyne-3

5 · tert-butyl perbenzoate

6. Dicumyl peroxide

7. Methyl ethyl ketone peroxide.

8. Cumene hydroperoxide

9β Di-H-methyl-t-butyl percarbamate

10. Lauroyl peroxide

ile acetyl peroxide

12. Decanoyl peroxide

13o t-butyl peracetate

I ^. t-butylperoxyisobutyrato

For the production of these resins it is preferred to use the poly functional diene with the polyfunctional organic chain extender in approximately stoichiometric proportions

009839/2133

BATH

mix, However _it's hingewlesen that the purpose of using las tomers increase of liettenverlängarers _s lies in the molecular weight of the intermediates au * and if so, "read molecular weight of the Ausgangspolydiens is increased, then the amount of polyfunktioneilen organic chain extender can be reduced accordingly = Approximately stoichiometric numbers of polydiene and chain extenders are preferred when the polydiene used has a molecular weight between 500 and 3000 _s and smaller amounts of the organic chain extender can be used when using polydienes with a higher molecular weight, for example 15,000 and upwards. Furthermore, the amount of Kectenverlängersr used also depends on the functionality of the polydiene used. So you need for a polydiene having a functionality of two more chain than with a polydiene having a functionality! "5" Other ratios may be necessary if other-e, κΙθ a "B _e copolymers or inwardness plasticizer _s use ingredients"

Pae foam material is prepared by adding a blowing agent or foaming agent SSMA liquid AuEgangspolymergemisch formed propellant and blowing agent, one of which was found to rX ".h suitable, ALND Wasserj nledrigmolekulare liquid hydrocarbons, such zobo propane, butane and pentane liquid * Pluorkohlenstcffe as e" B _e trichlorofluoromethane, dichlorodifluoromethane, l ^ -dichlorotetrafluoroethane and 1,1-difluoroi-chloroethane; and chemically decomposing agents such as Z ₀ B ₀ dinitroBopentamethylenetetramln _s OxyblButyamid- (benzolBUlfilobisyl '2 ~), ammonium carbonate-azilobisylodicronamidium and ammonium carbonate- _8-hydrazide -nari'-dimethyl-N ^ N'-nitrosoterephthalamid. a silicone oils such as ζ ^ B ₀ is a dimethylsiloxane polymer, can be described as surfactant _s use, the size of the gas bubbles to steuerno When the liquid Polymergeraisch a reaction temperature in the range 23-90 ^c C is subjected, then the blowing agent or foaming agent is activated while _s dan elaotomex »e material formed

009839/2133

BATHROOM LOCAL GINAL

The Ket ^ gnverläng'ö ^ iüigörsaktioB takes place at or mo iig e-riiöljten aei: upöx-ct'üiir ₉ where söliEiKßte e '"astomeric Zid.scheüprödwlcfcaietarialien sisrden PexOK ^ ainitiaiw throughout Ha3? Zmoiefculü3? dispes »giept contain« dia ket ternary «storage ^ ealitlon can catalyze - turn _a mn. 'reduce au ^ by fcatalytisehe means incorporating _t in the Teshnik to see known sinä _s "/ or-ausgesetsst ^ that si © niclit the -siachfolgenö © Cyelisiss'ung and ^' reactions temperature or ^1, the reaction time · interfere ernetKims- «" -Viähresiä das.pQlymer is in the elaotOBisren 2stand _s . kami-it was easy to handle nnü. processed ■ Ferdeiu The ve ^ ultl & renäe product is an eiasto = '|

me'rex ¹ foam with similar HandhabirngssigiiSiaeliaften as ein'GuDsaiiäcfcaiyHS-toff "-If OCE finished oegensataiia is vjorden made ₃ dt, on wi ^ d this -.güa.jmiax" Taege ^ iiisshssaprooukt on alma TemperetEF in-Bsi'eiöh you $ 5 to 205 ⁹ G erhitsstg whereby a C ^ elisierung and Ysrnstssung takes place _s aid a ä & e _a hard ^ transparent has ss;? Jatri :: ₀ is formed, the -a Bareol "■ hardness of minösstiesifä approximately 25 _sec and a good chemical resistance to · Stielest of fteti * © xyd _s saltpeter? "- SaU ^ e ₈ konsentr-ated Sch" tiefelsSu2 © _s KatTiurah ^ dro7iyällÖEung ₃ acetic acid, halogenated ''hydrocarbons;, Äeeton and coals "liEsaerstofflösungsmittel has _o If gexiünsöht _s can · the th "3m © ffixie2? Fc'e Ha:!? Sä schr.iell by rapid ez'hitsen of the reaction« = · 'j

participant · formed on eiviöhte temperatures tj @ s? iSen _s whereby "

zve ± reactions are the same. '

The Sahaiffiidicht nml the strength depend largely on the veaniende'tön Ma «g @ fecllusitt ©! · & Ά®3? SöhSüSiaaittel- afc-o Dis 3c: hatsmdiöMie -und the firmness oind ass · amount of propellant used =, means © the SsGhavimltu® '! ^ Siigeketot .proportional »The specific case of the Sehsamm came '., Iiii area \? Öii migefälir O ₀ 2 Ms i _a 00« =

I ₁ , 09 liögea _a währ-änä. .'d £ © ^ esfcigkeii In the area of. A5.0 kg / em ^{2 to} about 210- - 3500-kg / cm ² can be, Andes »® physical dep HarKmafceriale are influenced by the mixed amount ttslE in pixmmc-tton & lsw manner

Β'β39ν 2 1 33

BATH

The inventions hold foams can di-; r: various V ^ ri-.inuungen v / ground, such as aJU building materials !, Sehwinniat.erialian or .TsoXier-maGoria.Uen, Diaso Süha'iinstoiVü «r ^ tu ^ n a tforzUgii'jheo Bav.mata '.-' iaX, da elastomore Plüfetsn da :: ⁵ tiiewünsjh'ien thickness: ln a r. -mtralyn! Produktlonßiinlaye hergs ^ teXlb ^ vex'paakt and sent for further processing v / erdsn lc? 5nnen _e After they have been cut or processed i-rorden Bln-; i _s can the olautomersi. » S-; hauiiiov.offi; by using WäiTns i ^ hilrtet werdiiiij, iun d- ^a B eud - KÜltige Produkt- hsi'bestü ^ ltjn ·. .For example, d.;. 2 foams are particularly suitable for vox \ ". Lying Fpi'iniiuriB ^: > _: $ i <nb _s where thermal or akia ^ uiaehe insulation is used for panels; ünsöhi; leb * Bfeiopielriwtiilse kcnii one foamsUea i'lüsaigea Har?. in the Haum zxr .-. jjh & n (vie Flatten oincisÄ ^ n. But you can also use a plate au Schnsiden, attach to the wall and harden through the «Anvendmi's» on heat into a hard ον.νϋ & ηύ , swim.:ü'tiiper * »: .-; ■! -« the £ in: 'aeh öaduroh her ^ udtellt "that one entwadei · dan fcllasfeoii.ereii foam-formed and an-i-shließönd application of heat hai -.. .3t _Λ or that tovmt the finished rigid foam entspreshend *

009839/2 133

BAi> ORlQfNAL

Claims (1)

P k TENT k NSPRÜ CH Ξ ■ Ιο / method for the production of a hard foam _s characterized by j, daö one a homogeneously Schäumungßmlttel In a Polymergemlseh incorporating ₀ which dicmgerüstkette from a polydiene having more hydroxyl · = ,, carboxyl or amino groups and having predominantly depend ligands Vlnylgruppen on alternating carbon atoms of the poly = ,. from a chain extender _s that can react with the functional groups of the polydiene _p and consists of a radical ferric oxide initiator " the Schüuniungsmlttel and the PolymergemlEch to react _s mti an e; c; schfiuniteß elastomer to produce resin ^ which contains the Fsr-or.yö- in unreacted form molecularly dispersed in itself _a and the Elastorae} * then cured herzustellerip. a foam consisting of a hard thernioflxier-th Hai = zmat2 ^r lx with a Barcol Hilrte of at least about 25 _o 2, Process according to claim: l _s gskennaelchnet characterized in that the polydiene polyfunktionelleB l _fl 2-polybutadiene or 3 ^ iI-PoIyisopren used wircu. 3ö "Method according to claim i _r fefii öem the chain extender for reaction with functional." Sin hydroxyl polydiene fiihig is .dadurch in _t that, as a chain extender a compound diisocyanatsubBtltulerte aliphatlsche ^ -a dlsäurehalogenidsubBtituierte allphatlsche connection. ₈ a di-acidic-halogenated aromatic compound _s a dicarboxylic acid-substituted aliphatic before the compound _s a di · = · cerbonic _{acid-substituted aromatic compound c} ■ a diester-substituted-a3.1phatic compound or a diester-substituted aromatic compound is used "- * - 009839/2 1 3 3 4. The method of claim 1, wherein the chain extender for reaction with functional carboxyl groups is on Capable of polydiene, characterized in that the chain extender is a diepoxy-substituted aliphatic compound, a diepoxy-substituted aromatic compound, a diamine-substituted aliphatic compound, a diamine-substituted aromatic compound, a dihydroxyl-substituted one aliphatic compound, a dihydroxyl-substituted aromatic compound, a diazlrldine-substituted aliphatic compound or a diazlidine substituted aromatic compound is used. 5. The method of claim 1, wherein the chain extender to react with the amino functional groups on Folydiene capable, characterized in that a diisocyanate-substituted aliphatic compound, a diisocyanate-substituted aromatic compound, an anhydride substituted aliphatic compound, an anhydride substituted aromatic compound, a dlanhydride substituted aliphatic compound, a dianhydride substituted aromatic compound, a dicarboxylic acid substituted aliphatic compound, a dicarboxylic acid-substituted aromatic compound, a disfiurehalide-substituted aromatic Compound, a diester-substituted aliphatic compound, a diester-substituted aromatic compound, a di-epoxy-substituted eliphatic compound or a di-epoxy-substituted aromatic compound is used. 6. The method according to claim 1, characterized in that one of the following is used as a solvent: water, propane, butane, pentane, trlchlorofluoromethane, dichlorodifluoromethane, 1,2-Dlchlorotetrafluoroäthan, 1,1-difluoro-l-clilorofithane, dinitrosopentamethylene tetrarain, ammonium carbonate , Azodicarbonamide, i, tl ^l- oxybis- (benzol8ulfonhydraaid), 2,2'-azobislsobutyronitrile and njn'-dimethyl-nn ^ nitrosoterephthalamld. 009839/2133 BAD ORfGINAL 7o heat-curing Harsachauinzusamraensetsungg thereby marked ° draws »that it consists of the following s a foaming agent and a polymer mixture ,, the ^ a Bareol Hiirte can be gehörtet of about 25 _fl which s is a polydiene having a plurality of hydroxyl = · ^ carboxyl · = or amino * = * groups and predominantly depend ligands Vlnylgruppen on alternating carbon atoms of the following of the Polydlengerüsts _s a organic chain extender he j, which can react with the functional groups of the polydiene ₈ and a radical perosydlnitiatoro 8 ο composition according to claim 7 characterized in that the _{B £} poXyfunktlonelle polydiene 1 ₉ 2-Polybutadlen or 3 s ² I -polyisoprene is <, 9 ο Harss according to claim 7 _S characterized ₉ that the chain extender _{s is} capable of reacting with the functional hydroxyl groups on the polydiene Is _{s is selected} from one of the following compounds s diisocyanate-substituted aliphatic bleeding ₃ dlisoeyanate-substituted aromatic compounds "dlsäurehalogenldsubstituierfce" dlsäurehalogenldsubstituierfce decisions ₉ disSurehalogenldsubstltuIerte aromatic compounds _s dlearbonsäiiresMbstituierte aliphatic dicarboxylic © Verblndungen ₉ = "acid-substituted aromatic verb _s indungen diestersMisstituierte allphatlsche compounds and aromatic älestersufostitulerfce- Verbindungen.o 1oo ZusaramsEisetsting according to claim T ₈ characterized gekennseieh °> neta that-the sui "reaction with". The functional carboxyl groups is chosen from the following ¹ compounds at a polydiene capable chain extenders from a ⁵ sdiepoaryäsufosfcltuierte aliphatic "compounds _s dlepoxyclsiubstltuierte aromatic dlamlns'.ubstltuierte allphatlsche nnectivity _s "lerte- aromatlsöhe connections ₉ dihydroxy! substituted compounds tlsehe _s äihydrosy! © substituted romatiiöhe 009839/2 133 .. ■ BATH ORIGINARY ,,,, -Ik- bonds j diazlidine-substituted aliphatic compounds, and diaziridine substituted aromatic compounds = Ho composition according to claim 7, characterized in that _a de * "Kefcfcenvei'liiiifeerei'j, Uer sui? _S is reactive with the functional amino groups on the polydiene capable ^aut: one of the following compounds selected wlrds diisocyanatsubstitulerte aliphatic compounds diisocyanatsubstitu? = rte aromatic compounds anhydridsubstituierte aliphatiethe compounds anhydr-idßubstitulerte aromatic compounds, di "anhydridsubstituierte aliphatic compounds, aromatic compound to dianhydridsubstitulerte _s dicarbonsäur? .substituierte aliphatic ¥ arbindungen _s dicarbonsäuresubstituierte aromatic Verbindungenj dlsSurehalogenidsubstltuierte aliphatic compounds, aromatic compounds disäurahalosenidaubstituierte, öiestersubstltxjiarte aliphatischa connections !, this 'r-substituted aroiaatiEcha% ^r srbindungen _s dlepoxydsübstitulerto? aliphatic compounds ₅ i are the epoxy-substituted aromatic compounds. connections » . 12o composition of claim 7 characterized gsken _S = "> £ ₉ leans that the SchKui: imi'ctel elney from the following compounds from = · is selected j water Fropan _{s s} butane, pentane, Trichlorofluoro" methane _s Diehlorodifluor-omethan " i _i 2-Dichlorotetrafluoi-o8i; iian ₃ 1 j 1-Difluor-D «'.! .- = i; chloroethane _s Dinitrosop ^ ntamethylente r-amln _a Ammoniuracarbori-at _s Äao <iisarbonamid ₃ * ΐ ₆ % ^ν -oxybis «Cbenn ... see below nit r oaot er ephviiali-amid _o M.SNT ANVVXLTt i 8 3 9/2 i 3 3 BAD ORIGtINAt