BE648787A - - Google Patents

Description

  

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 EMI1.1
 



  :. Po1.Jaa1n .. aromatic., And, 1eur.dhf ..... -,
 EMI1.2
 fc presents 1n'fent, in: .. the p; arat1OD po: \ aa1n .. armtîques and their * derivatives. EU * 4 = 0 * rnt aua.1; a ptrftôttonnl process of prpuaUoD, 4. products of = ld u4tiea mine aromat1./a1ct'bTd. and the pjcdaitt of con48111 &t1cn!; 'obtained. "The 1nTCt1on also relates to the improved polJ1.oc, anate.," MoaâHqM * derived from these aromatic PolTP1nl.



  Hit refers to the..1 1 of the polyols which comp1'llU184'1t

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 EMI2.1
 duiar4dadd, ttioa d-402yde dgalkylène on the MOM'- 1 polymers of the invention. IKle concerned in other the polymers produced from the aromatic polyans, xomatic polytio-cyanatta and / or polyols * according to X'ianat3oa ", Kilt also relates to the retint polydpoq, rdrs resulting from the reaction of polyipoxydtt with the polyamines - rom ticks muvent 11, nvsatioa. Wt.



  We oonnatt direrproodd6s of preparation of product Y, y of oonfienietion # by Mooplw of aniline and tomaldi.% Id ,,, By ruccwple, the amriasin patent nD 2,133,730 describes a process by which one reacts the innilinw and the fbraald4hjrd a ') pr4soice large amounts of hydrochloric acid at different temperatures. # 90 * C * One embodiment of the process described in this patent is the neotit4 to neutralize the pol-amines produced, to separate the aqueous layer, and to wash. and to release the polyamine before being able to use it.



  .We have discovered that at.3quss mines, for example, uai.tizs' and & Îddhydes, prefirtnct 3t. '7 tbrmsid8tqrdr "can be added to high ttmpératurses *, catalytic amounts of acid are present to daonwr tntiressantaes polyamines. Using amounts * aata3, rtiqtus detacidate ca removes asutralisatton, 3a # s and"' ' 1 <<< chg <of the coanus ..a outrt processes, 1 * following process - #; I # Iùvrtt: We give very different polyaslnta from those ommes and aoo * 4stbloo up to pjc3saat psr ex ple by the réllay partition of the bonds ortha tt ptra be the Cmuptit hisslène de liaison and the morals axed, ticked by the polytuints.



  The object of the invention is to provide a process for the production of palrsmiaes sttsat3, M, 'QUOI $ r4,' a novelty preceded by r1 rpa; Yi of product of conditioning tint armat4que / ald "yde rrxicn 1 high p4r4tures oa presence of oatalyt4queo quantities of égtalyçmr aa3, rv

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 '' a new process for the production of a pre-
 EMI3.1
 erotic amine / tJLdehyde ration presenting proportions' Inaccessible until now Hd'i * oaere <inaccessible until now) #]} new aromatic polyisocyanates from new aromatic polyisocyanates following the invention of polyols comprising, products oxide addition
 EMI3.2
 ds & Uwl4o on Aromatic polyamine Muselles according to 3 * Invention;

      compositions comprising the product of the reaction of organic polyisocyanates and aromatic polyamines according to the invention; polyurethanes comprising the product of the residue of the novel aromatic polyisocyanates according to the invention with one or more polyols;

   polyurethanes comprising the reaction product
 EMI3.3
 organic polyols and novel polyols according to the invention; vulcanizable and vulcanized compositions from
 EMI3.4
 aronastic polyamines according to the intention and of polypo3 <ydes., i tH '<Mt $ MC but $ do the invention poo 3mbtmb de 8 * description below.
 EMI3.5
 



  8uitant the process of the invention, reacting an aromatic amine with an aldehyde $ in proportions any that the molar ratio of amine t aldehyde is between 10 μl and 1 # µtl, in the presence of a catalytic amount of an acid catalyst. at a temperature and for a time sufficient to form an aromatic alder / aldibyde condensation product;

  , and this product is then separated from the mixture of riaotlom4. The aromatic amines used according to the invention
 EMI3.6
 only one mixed are W-al! <yl <tnilin <n <whose alkyl substituent does not contain more than 12 and preferably not more than 4 carbon atoms, and mono anilines.

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 EMI4.1
 4 'di, trigop and t4tra-C-substitudot' in which each.,. : ',; The substituent preferably contains no more than 9> '(other than hydrogen) and the total number of atoms of the 80 $ titwmts (other than hydrogen) does not exceed 24. On' ## ''. prefer that the substituents be characterized by the following 2k facts:
1.

   Substituent mask -) can be an alkyl radical,
 EMI4.2
 cyolo- * Dtyl <, alkenyl, cyeloalkenyl, MUcylt, allcoxy, ary3f fslkaryl, fyloxyt aryltbio ,, 4 alkylthlo, dl <UylMtiaOt <ti <tIy]. <.



  MinotHqrl allqrlsulfonyle # arylnlfonyle, <dkylMlfiayl <, Myltulfinylt, chloroo brooo, hydroxyl, amino, maaaa3.lqllamino "aeraapto, suitsm7.e, W-H! YlMlf * Nyle <or X, lt-dia3.lylsultaryle.



   2. A substituent may also have the form of a ring system linked to the aniline ring, as is the case for
 EMI4.3
 '1! A. or -yhtalear, or 1-sminaaat, braaa. "#}
3. In general, there are at least 2 hydrogen atoms in the reactivate positions of the aromatic ring, usually in the ortho or para position to the amino group. Part of a mixture of amines may not have only one atom
 EMI4.4
 dj'hydrojgbne in a reactive position of the nucleus .aramst36qua.

   In a high mixture, the wrong proportion of amines having only one hydrogen atom in a reactive position of the nucleus necessarily imposes a limitation on the maximum molecular weight of the polyamines which can be prepared by condensation of the polyamines. mixture of amines with formaldehyde. In function
 EMI4.5
 Depending on the end use of the aromatic polyamide, it may or may not be desirable to limit the maximum molecular weight in this manner.



   4. The aromatic amine / formaldehyde condensation products *
 EMI4.6
 dehyde can be used-mtmou as starting aromatic smines for a new condensation with the following formaldehyde; the method of the invention.
 EMI4.7
 Preferred aromatic aminos for the following prootaé

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 EMI5.1
 . nnvootion can be: repr4.ctl .. by the formula
 EMI5.2
 
 EMI5.3
 Ob e may be a hydrogen atom or aikylized radical and each] la "individually may be a hydrogen trump or a Resr as substituted constituents under 1 to 4 al-dsasus.



  Examples of aronic amines which p << uv <tnt itra used according to 1 # lnver-tion are 8 tnilin o-, a- and pt.oluid, nes, o-, a- and p-4t! ylanilines, 2,3-xylidine, lu 3,5-lidins, p-octylan, p-tert-butylanilina, o-, m- and p-xnisidiines, 0-8 bzz a- and p -phenêttdln% 2,3, -tx'iraethylaa.lias, 2-a <thoxy-5-aethylaniline., p-cyca.ohecylanilina, o-, m- and p.-bansyl.



  , anilines, o-, m- and p-bt, H-dnétyZaminomthyla3linos, p-pianoxyaa.lins, o-, m- and p-bT, t-diméttr3rZaainoiliusry m- it p-aminophênoloi m- and p-ph & iyl & nediunint lM 204-and 2,6-tolylèa diwaln s, benzidine, alpha-taphtyZaai.s, ot * "and p-chloroanlllnee, dPo- m- and p- 'cMtinophéQtylethyl sulfides, p- tminobenzenesulfonmide, 1 p- (oyclebex-2-Myl) anilin, p-aminophkwlétbyltultone, p-aminophicyl. phéayl.sui. '. ra and Mitons, o-, m-, and p..tasxc, aptosil3aes, 'Iw l-methyl-p-sminoberaenesu7, tanamide, NN-diatethyl-p-taim- bonzèneaultonam: Lde ,, les o-, a- et p broaiosaili.neg les o, net P-audophkylitmatoxyeet et les oq) va- and p-aminophinylphinyla4toxides.



  Particular substituents are preferred depending on the use of the aromatic ualae /, odéirde condensation product. For many uses (where, usually, the polyamine must be trot oto = d *, in rolyisecymat4

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 EMI6.1
 We prefer to use the sullint 11-tM. The orthohloroanillnt eonvitat for the preparation of particularly interesting compositions in the 'ilagUmbres ixooyatate / aaint. In many applications, toluidines and xylidins are preferred. The products of aoadaasatian part-dod4cylaniline / fontaldehyde can be converted into useful tenaloactants by addition of dbithylbene oxide. A general, however, law produced e oondentation the most interesting are obtained from 4lvuiints, cuoroanlline and tUtyl- ose \ '<s.



  According to the process of the invention, aroast3que laaaine, is bending with forzalddhyde, you forcmld <hyd <can be in aqueous solution (for example the 37% solution of #trot known as tormalins) or = solution -in an organic solvent coamt msthanol. The paratorma.di hyd or the trioxant can be used as an id6hydeanie and if desired, the IbrmaddkWde can be added as daniriroic; id6hydeanie.

   Other ald & Vdon and eitoaes are not & 4niraimeni ', not preferred for various reasons $ notu, weoat their low reactivity or the possibility that they offer to give rise to side reactions (for example, when * # acts do ehloral). The proportions of $ 4m ± ne and of forMld <hydw are aom- prized between the soften ** aaint-foraaldehydt ratios of 1.5il to 10 çlle The int rv <13. <<narrow molar ratios preferred for a so-called use; mindo of the polyaoint is not a function of this use) Mi <also of the nature of the substituents present on the aroaatiqut nucleus and of the conditions used for the condeasation reaction, such as the reaction t "p4r * ture and the nature of the catalyst.

   For example, when polyMiM is used to produce polyisocyanates, the proportions pj: 414rés correspond to amlnttforaaldehyde ratios of 2 <1 t 7 <1 and preferably 3tl to 6sle <7, .. ', A particularity, ! taporttntw of the process following the in-

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 The invention is the use of catalytic amounts of acidic cacalyzer in the condensation mixture. The acids used as the catalyst are protonic acids and
 EMI7.1
 acid! of Levii which hydrolyzes you in water to give proton acids. (Lewis acids are studied, for example, in Adv & ncd Organic Chemistry Fuscm read Edition, pages 3H et seq.).

   The acid catalyst also preferably has a pKa in water not exceeding 3. (The pKa is the log10 of the inverse of the dissociation constant
 EMI7.2
 acid) Decided examples suitable as eatàlyseurt are hydrochloric acid, aryltulronic acids, benzenettulfonic and p-toluensuloxii.qus acids, alkanesulfuric acids such as methane acid sultoblqutov boron trifluoride and its complexes of 'addition with
 EMI7.3
 amines and ethers, as well as peroblort acid, 4u *, Polybasic protonic acids like sulfuric acid and phosphoric acid tend to form salts (with the aromatic amine)

   which are insoluble in the mixture of
 EMI7.4
 reaction. Therefore, it is preferred to use mono-basic tonic acids or Lewis acids which hydrolyze to give aon-basic protonic acids. As desired, the acid catalyst can be introduced as such of the aromatic amine. The acid catalyst is used in the condensation mixture in catalytic amounts. By.
 EMI7.5
 For example, a suitable arousal amine to acid catalyst molar ratio is between 20: 1 and 1000: 1. We prefer
 EMI7.6
 amine: acid catalyst molar ratios between $ 0: 1. and 200: 1 and better still between 100: 1 and 150: 1.



   According to a preferred embodiment of the process of
 EMI7.7
 1 ": The invention, the aromatic amine and the catalyst are introduced into a reaction vessel and the amine / catalyst mixture is then heated to a predetermined reaction temperature.

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 EMI8.1
 



  8oQo quote, we add the to: rma1ddh, 48 to the reaction mixture preferably under its ourfacep at a predetermined rate Short of the & 4I11Uon, the water of condensation and the water or the II .1 ..



  , solvent optionally introduced with formaldehyde, are,; preferably distilled from the reaction mixture. After the addition of the tormald'h1d., The reaction mixture is maintained at the reaction temperature for a predetermined period of time after which the condensation product is collected. Preferably, on ra
 EMI8.2
 - Tools the product by reducing the pressure in the reaction r, .1p1I11t., to separate the amine 'aromatic unchanged tt all water 1',. 1c1u.U. or the optional solvent.



   An important feature of the invention is that, when the new process is carried out at temperatures of at idle 105 ° C., the proportions of ortho and para bonds of the poly-,
 EMI8.3
 amines produced are very different from those of the polyamines known or available heretofore. This difference increases
 EMI8.4
 1.4, with the reaction temperature * The exact upper bound, @ the reaction temperature is not necessarily critical but generally does not exceed the boiling point of the amine
 EMI8.5
 aroaatiqua under the particular reaction pressure used.



  Its reaction ttapdrature, the appoi * 1i mas, a3, re UI1ft., ToN & 14èr4. and the content of catalyst are selected to give a product having the desired isomer ratio and average molecular weight. Laboratory-scale tests will suffice to determine
 EMI8.6
 complete the reaction temperature, 1. ratio r'aot1t..t the concentration of catalyst required to give a particular polyamine desired, but the reaction temperature is at
 EMI8.7
 mine 10500 and preferably from 125 to 20C.



   The exact reaction time * used is a function of several variables *, for example the concentration of catalyst, the nature and proportions of the reactants, the reaction temperature, and it therefore varies over a wide range. For example, the du-

 <Desc / Clms Page number 9>

 
 EMI9.1
 :!. "4.tOft" Û toi'lliald'h14. may vary from 4 1 10 T '' 1 t knocks, preferably 4. 0.5 beur '., and << ieux e8 I * 1 * to 4 knocks. The subsequent reaction time can read (10 minutes to 4 hours, and preferably from 0.5 to 2 hours, preferably the reaction is carried out in 11 minutes.
 EMI9.2
 diluted.

   If desired, however, a solvent can be used.
 EMI9.3
 inert organic like toluene, xylene, ehlorobenslras or Q-c1ioblroben & àn .. he praoddi is usually performed under "'' 10A
 EMI9.4
 
 EMI9.5
 atmospheric during the aldehyde intake and reaction but higher pressures can be used. L461S11 ". If the reaction rates are used. higher than the temperature of the release of the erotic amine, it is a6aile to use pressures greater than the etiosphlrify pressure. to collect the condensation product at the level of the I6a4. , it is preferred to heat the reaction mixture under pressure (reduced for ohaistr 1 "& 1.1, the optional solvent <t 1. iaehtn-
 EMI9.6
 
 EMI9.7
 fairy.

   During the separation, the temperature is preferably 1} \ f8 & 1tained, equal to or greater than the temperature of JII ".Ot1on for a period of up to 1 hour after the separation.
 EMI9.8
 
 EMI9.9
 DUt1.0A of pressure up to 10 mm of mercury or anion. ii The apparatus used for the reaction can draw a conventional reaction vessel i, .4. provided with a stirrer, a device 4.



  H, 141.t111atf: on and a conventional heat transfer device *,: r, '. Pp.re1 \ in contact with the reaction mixture can be formed. truit in materials such as mild steel, Snox steel, yc1abl., l. glass or Saatelloy following 1.1 nature of the acid catalyst utility. ït'exeaple f .. '\ - apr1 illustrates the process according to the invention.



  . rt Production of aromstlqueg polyaaines In a 4. reaction flask in "Pyrex" with a capacity 4. 12 liters equipped with a stirrer, a thermometer, a column -

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 EMI10.1
 do dH'tj # iâf.on.d'uBKdMKm 4 '* Mt,; Tdalièio <U} $ ', h, fonaalint and a mmtetu ,, ohautt4att Introduced <9 <M i (96 # 5 molto) of aniline and 55.5 oat3 about 0 ,? mole of a *. , E, 37% aqueous hydrochloric acid solution. The reaction flask is heated to 135100.

   Fo = ald4hyde (1956 gt V i '., 1 aol) under the surface of the stirred reaction mixture was added 5 hours 43% under the surface of the stirred reaction mixture. addition, CM avaintie ;; the reaction rate is distilled off 10, water and other volatile compounds ** A * low
 EMI10.2
 'he
 EMI10.3
 Amount of anilint diitin in water and the distillate is "r" txwnpt of foraldehyde. After the addition, the reaction mixture is heated to 130-135 * 0 for 2 hours. O'dicLinue then will go. from * 11 4nt the pressure in 5 strokes to a minimum of approx.



  4 mon de marouroi during this texps, the teapératurt is maintained * 130-13'C. The minimum pressure = is maintained * for 30 ni-outos * Cu then introduced from Itasote into the riaatim flask, F. for ra 4n * r the pr <mion to the atmospheric value. the yield is 4169> s of residual product. The polya2ine obtained has an aoetylation equivalent weight of 10108 ##. ,, and an equivalent weight of active hydrog of 50.55 (after corroom - tar for HCl). The average sbléoulairt weight $, mt = xuri by 1 <;, s 'method' 'Th <r <KM) t <triqu <' 4n solution in 1 a.aitar., Is 267 ..
 EMI10.4
 
 EMI10.5
 



  The water content of the product is 0.077% your weight,: Ammatic polyalines obtained by 10 proo4id suix., X before the invention are characterized, by the prison, ** of aniline rings (or their substituted derivatives) linked by te, methylene groups. Polyamines are * blends of 41 * xln $ of tri-alents and superior polyaaints.

   It is clear that the POr mines are o = ples mixtures of compounds which M all characterize otjtndtnt by the. Presenct of at least two aniline nuclei (ea of their derivatives) linked by a mtbylëns.I group: it is obvious 'also WHO' = * polyamize with JI nuclei <dwarf <nrom-tic = Gate 4a ..

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 EMI11.1
 approximately A-1 n6tt "l.s groups * (When 10 * ilu & 4 omtiont certain cyclic polyaers, these po3: neatas Yoycli) L <ïU include an equal number of mine rings and methylene groups)
The process of the invention leads to a surprising and unexpected result:

   polyamines contain a proportion
 EMI11.2
 #exceptionally high ortho bonds, ie the methylene groups which connect the substituted aniline or aniline rings are attached in an unusually high proportion in ortho positions to the amino groups of that ring. The following example illustrates this unexpected feature.
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  , of the inv ition ..! A polyamine (tPolyamine 19) is prepared by the procedure described in US Pat. No. 2,683,730 and four polyamines.
 EMI11.4
 (s9, eCs ,; sDs and * Bu) by the method according to the invention of Despite analogous to o3lle described in 1 # exemplel. The diajaine fraction of each pclyanine (i.e. methylenediani line) is separated of the rest of the polyaine using a conventional laboratory distillation column. Each diamine fraction
 EMI11.5
 is then required for a chr <Maato <r <tphique 4a vapor phase analysis to determine the proportion of isomers 484 #, 4 'and ej, 20 ,, A chromatograph y and M, bI 500 with temperature program t comprising - a column of aluminum of 2? x 6,

  g35 Ma filled with Chroaosorb We from Johns-.ianville having a particle size of 0.177 to i1.50 ma and containing 2% by weight of Corning 710 pow silicone oil. The table below shows the solar ratios aniline! fojmaldehyde, the molar ratios of aniline: catalyst MI the reaction temperaturea, the molecular weight aoya, the percentages by weight of dioxin and the ratios of orthot bonds, para bonds of the diamines, for Polyamine A (obtained by the assigned pros described in the American patent n * 2,683,730) and for the polyamines B, C, D and E obtained by the process according to the invention.

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 EMI12.1
 



    TABLE 1 fI.RISIUN ilE PDLÏ1IN. "Fi ..
 EMI12.2
 



  Polyezine Aniline: Anilines increase in weight.



  Polyamine Aniline: .An1l1ne: of ri-action, means of diamime Analysis <your doins? in J) o1ds ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ * 0¯¯¯¯ .. isomer 2.2 'isomer 2.4 isomer 4.4 1.. 1 '1.67 il 80 ... M. * -, as "l. <. ,, 0 96> o 6,1, 1 US 233 70 8,5,' :. f 37 6 M, 9 '145 155 246 - '-' -1, '; -,' /; - - "', 7 ####. # *. '!; . 17S '"2n 34 .1 ,,. 245 1 261 47iq" 24 -: "," 20.7;:,'. ,. 71.0 '",.

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 EMI13.1
 



  XI spring 4 * f given * el * & * ff9 * * ji # Sa *** # <** # 4 # a, a polytots b'tranuraf by p 4m4 milms tMwM'tW contains a soniblmunt Pl A éo proportion of zip ndtbylène liea in ortto position by rappffl Mac gmqw soi des Moyaux amint aroa & tMP # qlte 00110 <5ti 6µs * summerH ** I PaYa, mine # oonnuti.



  There is no Boy <ad, * ef ± 4otu # r 1 * siM iM <MM '<M <M <M M- tat4, see for the proportions 4,9 &. "Res <! Lu trt-pouamm os polyamines greater than asula of $ poootb $ Utio% M4té 440 apporetlu 4 # analysis sQtta9.3buxrticis, '<M3Ly a 3' am, be that the p olytatats obtained # by the prooi44 4v t fjboiRMdMa <&# 4at4 = have more bonds en ortbo qu! # * jpJoaMta ommffl ,, 109 omple mlymt tlluwtre this pwrtieulayiti 4 X'iftir4i tUMU | i jasssffiitEii U -ta polyamine y is prepared by im proaioi mffinygnuff at samit described in ep7.a 1, using eoomi <M.te9LyMM 4 * JL # * - ',;' old 4tâ = osulton: Lque.The molar ratio mllAn * ttdxaâlAâhgr4 *, is) tl; the molar ratio an.l.ns:, said ** f * w1 fffltiflptir is 1f "5: 1 the average molecular weight of the polyjMJbK y jMdNit; sat;, 325;

   1 <equivalent weight of active hydrogen is 106.0 and the weight, qoivnlarity of active hydrogen is 4.7.
 EMI13.2
 



  '
 EMI13.3
 The polyamine A (described above in 1'ax..s 2) ot U poyamine F are analyzed in llinfrarougota FIS.1 taking * 3jt infrared spectrum of polyajiine 1 and Fig.2 that of pay-) faiM? establishes with a prize of Nall.



  The maxima appearing at about 12.3 microns are e * r * 6t4¯ '1ltquss, dhna substitution in para, and the maxima appearing at about 13-23,, 3 * lirons are characterized by a substitution in ortho. Comparing Figs. 1 and 2, we see that the po3r A has a much higher absorption at 12.3 will make qat'l .3i1 microns, while the polyamine Y has aaxiaa 22,, 3 microns and 13.3 aicrona of approximately equal absorption, It can be seen from these data that the ratio of liaixone ortha

 <Desc / Clms Page number 14>

 
 EMI14.1
 libleme pt 94% bumetup plus tromd pour 14 r 'y pow la ## Le & v4r & 4bles dt la!' 4Mti <m can be obotated 4 <t, obtaining a poU "* tytat a d0 oofflsltice rather than an autee.

   us and Mpoz% t # of the t odrab4res of r4aetton plus flrv3ts 4aaa <! at m produces a greater percentage of 410vi of ortho C * t 40 bonds illustrated by the do = 463, from Ubleau 1 above. For a 4y $ M'w ritot4 = ptyUeu3LiMt'M <"<'' tat4cm rap = t as 4aillnettor ld4byde entratue a riduc- Utloa of the aolU report.? Ixi2.in il1orBuad4hydê ntrtS & t a * rduc-
 EMI14.2
 tion 6t. \ weight aol.oula12 :. d. polyamine.Ceoi twl illustrated by In OD1ÇartJ.aoa weights t4ieu, s, irss and ratios $ anilines tor: u14'hld .. of the polyamine obtained in 3.'ex <Mp3. 1 and 11am1n.

   B described in exap1. 2, The molecular weight also increases ## e the reaction t4ap4r & tur4 (see, for example tableati 1) loodt t'e, iqus part by a slight increase in the amount "Ju.1n. Qut d.11t111. Du müs, i reaction and do * es leaked by the r'4uot1 # of the molar ratio an1l1n..tormald'hyd ..



  Some ## laboratory tests p <) * amtt <to determine the condition * risc.anaslias act4a which gives a particular polyamine de- µir4. In general, useful polyamines obtained by the process of Iginienti contain from 1 85%, preferably 25 to 1%, greater than 40 to 70 and more,%. 49 to ± 0 by weight of diamine, these percentages * 'both calculated on the basis of the total weight 6e la:. pol1u1n .. The proportion 4'a: a1n-, used. reactive coma ut 0b01I1 its anointing of the app) .1o., contemplated t1on of the polyamine, The po17u1ne, 'obtained by the method 4. the praying s.a81Uoa. are xtaçsioent interesting products.

   For example, sllss can be used to crosslink ilattambers which contain cbl01'O groups, such as those obtained by pol1m'rlsant m41aq. of butylene oxide and 4 "plcblor¯4r1nI.W .. paa can be used as vulcanizing agents of 4la.toQr .. de poljuritha = 4 and eoaat curing agents of po17'poQ- des. po17am1n .. can ttrt phosgenées in po111IOqanat ..

 <Desc / Clms Page number 15>

 
 EMI15.1
 which Mat Interesting, by Pl, $, VPoar the preparation w polyurethane fetinea They react with <pexyd <Vidin t4s' trio of IP03Wde of propylene to form polyols which are utilo j Pàr exeapla for the preparation of polyurethane resins or plasticizers.

   in addition, they can be used as a reaction element in processes which use primary or secondary aromatic amines as the starting compound.



   The examples below illustrate the process of the invention and loir new polyamines obtained.



   Polyamine G is prepared using the apparatus and method described in Example 1, but with the following modifications ** -: tions}
 EMI15.2
 2, b-dimbthylanilirre (194 g, 1.60 mol) containing 0 # 0114 Noie resolves hydrochloric acid is heated to 13 ° C. 33 ° C. in a 500 ca 3 "Pyrex" flask. Formaldehyde (0.400 aolt O 37% aqueous solution) is introduced into the flask below the level of the liquid over 2.5 hours while the water formed is distilled off through a gooseneck. The reaction mixture is maintained at 130 -135 * C. during the addition of the reagent and then for 5 hours.

   Pressure
 EMI15.3
 au% then slowly reduced to 1 am of mercury while maintaining the reaction mixture at 135 ° C. to distill off the residual water and unchanged 2, b-ciéthy.aniltna. The average molecular weight of the product, polyamine 8, is 256; the equivalent weight of acetyla-! tion is 130.6; and the equivalent weight of active hydrogen is
 EMI15.4
 àw.

   Analysis by vapor phase chromatography indicates that the polyamine fez consists of substantially pure 2, b, 2'b'-tdtxanathrl ,, il, 'ethylenedianiline. ffCEHPLE 5. -
Polyamine H is prepared using the apparatus and procedure described in Example 4 but with the modifications.
 EMI15.5
 following tions:

   formaldehyde (0.500 sheet of 37% aqueous solution j) is reacted with N-rthylanüine (2.00 moles)

 <Desc / Clms Page number 16>

 
 EMI16.1
 containing 0.0143 mol of cIdorhydyiqM acid.It edition * of introduction of the reagent, heating and distillation are the same as those of Example 4.'U average molecular weight, the equivalent yeida of acetylatton and the weight equivalent of active hydrogen of polyamine a are respectively 268,115,

  1 and 108829 The va * = low of the equivalent weight of active hydrogen shows that there is partial migration of the methyl groups from the asot atone towards the nucleus * analysis by phase chromatography will show that the Polyamine 9 contains three isomeric diamines,
 EMI16.2
 1 lt, Idtmethyl2,2nétbylènsdiul.line, H, N -dtaethyl-2,4'aétirlrediani.line and VtS 'diaethyl- * 4t4 * Haétliylenedianillne. in the approximate ratio of Î # 2821jls .7587 ± = * LE 6.



   To further clarify the differences between
 EMI16.3
 polyaz4nos follow! #invention and those known and accessible Up to now, the fraction of -tlamine and all of the polyaactnes A etc. are subjected to infrared analysis. These sound are described in Example 2, the polyamine β being prepared by the method described in US Pat. No. 2,683,730 and the polyamine C by the method of the present invention.
 EMI16.4
 are raised in 1% solution of Ipamine in the t, 1-dimdtt, tbraa greedy.

   This solvent is suitable for establishing infrared spectra in the doMiM <of the following wavelengths 2 # 3-alorms 2.8-5.7 nierons 10-11.2 microns 1 and 11 # 7-14j, $ microns . The table below provides details concerning
 EMI16.5
 Ilge. 3 to 6. TABLE II
 EMI16.6
 ! & lasts - P211raalme
 EMI16.7
 
<tb>
<tb> 3 <SEP> Polyamine <SEP> to
<tb>
 
 EMI16.8
 4 polyamine C 5 41 amine fraction of polla # 1n. J.



  6 l: raot1on of d1am.1n & pol1am148 C

 <Desc / Clms Page number 17>

 
 EMI17.1
 1 Ce = * on 1 "saw in example 2, the mmitte which bait- are about 12.3 will be characteristic of the para eabetiturion and the 1,2,4 substitution on an aroajatic nucleus where the Mximt which appear at about 13-13.3 talorons are characteristic * of the ortho substitution on an aromatic ring. The spectra * represented by the Mt <. 36 very clearly that the amines according to the present invention (polyaalnt C) have a higher ortho t para substitution ratio than that of the polyamines obtained so far (polyMint
 EMI17.2
 AT).
 EMI17.3
 



  The lnt4r2t of ammauque polyamines according to 1, nvratiax is not yet increased by the fact that they have
 EMI17.4
 
 EMI17.5
 | i high melting and lower viscosities than poly-law 3, arboatiquas rtes of comparable molecular weight, obtained by previous processes. For example, 4,4. <- diattlr & -3,3 - <llchloro '' diphinir7.métha; xne is a comaerce compound suitable for the retiottution of polyurethane elastomers.

   However, it suffers from the disadvantage of being solid at room temperature ïh, forming part of the present invention, portho-ohloroaniline and formaldehyde, mixtures of polyamines which are hitherto unavailable are obtained. This resumes an important proportion il * x, r'-damino-3,3'-diahlorodiphényLaéth $ aae. These mixtures * have somewhat higher melting intervals than the known isomer, 3rd En outrovltamiet con. holding a significant proportion of 2-di & mino-3.3 '<- dichlpro MphenylJBethene, heat to melting temperature, and cooled
 EMI17.6
 1 at room temperature or at a lower temperature liquid annuity for several days before slowly crystallizing.



  This new property constitutes a significant advantage for the preparation of reactive resin mixtures, as these mixtures can be processed at substantially elevated temperatures and therefore have a great flat shelf life. The preparation
 EMI17.7
 o-chlorunilin / formaldebbyde condensation product of this il-

 <Desc / Clms Page number 18>

 
 EMI18.1
 lustered by the auiyàîmtp free which also shows 10: 9at4r & t.



  JSXEbE
 EMI18.2
 The preparation process is similar to that described
 EMI18.3
 dano Example 1. Into a flask with a capacity of 22 litxes, aa introduced 13.1? Oad (117.5 moles) of oohloxaailias, st 3a3 (o # 9o5 Mlw) of a mixed alkarylphonic acid of a weight of 9 slow of 103.3. The acid aminticatalyst molar ratio is therefore .30s1. The mixture was heated to 130 ° C. and added 2413 t (29;, 75 moles) of aqueous motion to 37 of tormau4byde. batch anainsstormaldehyde molar ratio is rowing 4it is done. react the polyamine and the product is isolated as described in lb mplo 2; 7420 of polyamine I.

   This is * sent to a 4th ion exchange * to separate the catalyst if the product has the following properties t Equivalent weight of laprdrô, active gene 68.3 Weight Bolésulaire 3M 3% PB Tmour in dlem: tno ,,% in weight 74 # 2 The analysis by caromatography in raper phase shows that * the diamine fraction includes the tiombres and-after in the i.rdiqu6ess proportions 2.2'-diMtino-3.3'-dichlorodiph <nylatn & n <- # 2,3 . & 4'diamino-3,3'd.GhlorodiphlnltJ.mdthans 3,3, # '*', 4'-diMino-3,3'-dieM.orodiph & Txln <th & n <- 726% U polyamine 1 is used to crosslink a polyurethane Haatojoere Û9.

   The process is as follows. A so-called prepolymer prepared by containing 3 $ 4% of taylene 'dilsocymate (a 60/20 mixture of 2,4- and 2, 6 -toly ditio- cymatte in 1294% of polypropylene glycol hydrochloride having a molecular weight of 1225 and an Indian dtbrdz4ille of 19.3. The mixture obtained is stirred for 3 bmers at 14.0 in an atmosphere of nitrogen and then cooled. The prepo3.ymers obtained has an equivalent weight of 674 and a content in gîtupea -UCO free of 6.23%. this prepolymer (148.3 is heated to 65C and subjected to J '

 <Desc / Clms Page number 19>

 
 EMI19.1
 a vacuum of 2 aa of air to degtiter. The system if the kit in an atmosphere afasatei t7 s of liquid polyawlti * 2 (at ordinary temperature or about 25 ° C) is added * and the mixture is stirred * The mixture obtained has a time of t & UUatî = substantially exceeding 5 minutes.

   The compound known as' .dias3ào-.



  3,31-dieblorodiphiylmethane, must be heated beforehand to 100-105 * C to liquefy it and, with this time thins and << lification of the prepo13na8re / amine resin mixture is about 4 limits.



  The mixture prpolymr $ / polyam.ne 1 is poured into 'des'. cups. made of aluminum and in a chrome cup of 1 $ 2 x 2zfjào3 and vulcanized 'for 20 hours' ltt7. The eleatomer has the following properties d. '. = ".



  Shore A hardness 93.



  Shore D hardness "* '', '#. * 5 Tensile strength' 131! Cg / cc $ Elongated 200% B4s tearing strength '4J # f kg / ea Modulus at 1û0 elongation sa icg% c2 Remanent compression (22 hours; p ..., at 70 * C une coxpr * 48î = de ;; ï in
 EMI19.2
 Z6 polyamine 1 was used for: r'Ucu1. "-" lyateret having a brooding free group - $ Co content of up to 4dM M, 4%. With the known iachlorodiphenyletÏMne and in the mines working conditions (namely .riI1 '.



  11a mua) the content of srou, ..... 00 of the prepolymeM ett 11Jd.tl. at about 8X. The use of polyamines of the present * inien. The present invention also provides polyurethanes that are more retimulated and 464 in the form of harder and stronger castings. The present invention also provides derivative aromatic polyieocyanates. of certain $ dei

 <Desc / Clms Page number 20>

   aromatic polyamines according to the invention. polyamine lees used
 EMI20.1
 at the end of August those in which reactive aciino groups (ie with aminated hydrogen atoms) are excluded *, 6% vezent primary amino groups.

   In addition, these polyalkanates cannot contain other groups with active hydrogen atoms (for example hydro, tultamyl, H-alkylsulfamyl groups) # <i Aromatic polyisqcyanates have obtained by 1 het & mtiMt 'new * aromatic polyamines The reaction of pbaal4a.oxr is well known and is illustrated by the following example. z EXfKPLE 8. ¯ - # Preparation of an aromatic oolvieooyanate In a 2 liter round-bottomed, four-cola flask, fitted with a stirrer, a condenser, a thermometer, a gas inlet for the 'introduction of phosgene and a bromine funnel surrounded by a vapor circulation jacket for the addition of the polyamine, ion introduced 1175 g of ortbo-
 EMI20.2
 , d;

  Lohlozobtinzene as a vehicle for rac-.ian.Is contents of the flask are cooled to 0 ° C by a cooling bath. Liquid phosgene (396 four times the theoretical amount) is introduced into the flask. In 1 hour, 102 g of the polyamine of Example 1 are '
 EMI20.3
 adals in the flask while maintaining the temperature at 000., Gaseous phosgene is introduced throughout the operation under
 EMI20.4
 14 aurfaca of the reaction mixture at a rate of 0.8 liters per;

   Time (under normal temperature and pressure conditions)
 EMI20.5
 4th so as to maintain a large excess of pl3ossne and to minimize side reactions. at the end of the addition, the temperature is gradually raised to 145 ° C and maintained at this value for (. hours.

   The mixture is cooled to 30 C, filtered
 EMI20.6
 , to separate a trace of solids and Iborthodichlorobmibut is. driven by fractional distillation. ruz The residual product weighs 125, e had in. an e44a 4 which is equivalent to itocyanate of 135.1, determined by titration with m-

 <Desc / Clms Page number 21>

 
 EMI21.1
 butylanine according to the A8B process! D1638-61T. The product * has a toleoular weight of 335 determined by the `` theraétriqMe * method in solution in chloroform. The product is then subjected to
 EMI21.2
 fractional distillation in a molecular distillation column. The distillate represents 62.35% by weight of the product and has an average molecular weight of 260.

   The average molecular weight of the residue is 772. Assuming that the distillate
 EMI21.3
 consists entirely of di- and triisocyanstes, the polyliocyanate contains 35.4% by weight of dU ocymate ,,. Preferred aromatic polyloolers are those which derive from 1-Oanillme pdes alkylanillnes in which the rests} a; 3cyls аe contain no more than 4 carbon atoms, and chloroilinto. (The aromatic amines are first condensed with fluormaldehyde according to the method of the present invention! And the resulting polyamine is subjected to the formulation of the polyamide).



  -An interesting and unexpected feature of the invenlotion is. , to allow the preparation of a bis (isocyanatophenyl) -fmethant which is liquid at room temperature, This compote #st actup3.lea, t available commercially as isumber 4448-bit (isocyanotophenyl) methane which is solid at ...! - room temperature. It is often much more convenient
 EMI21.4
 to use liquids rather than solids.
This unexpected feature of the invention is due to the fact that the new process of the invention leads to poly-
 EMI21.5
 methylene polyarylamines which comprise much greater proportions of ortho bonds than the corresponding compounds available heretofore.

   In conspiracy - **, the polyiocoyma. your products from the polyamines prepared according to the process of the present invention are mixtures which have a content
 EMI21.6
 high on the ortho links. These mixtures have melting points

 <Desc / Clms Page number 22>

 
 EMI22.1
 musty high * as available co. | O8ttion pray including less lit.i $ ona ertho. j1 * '' Taking into account this interesting peculiarity of the intention, it * st therefore desirable to Pr d'ebard poly- '* .. *' aaip # i rizheig in methylene dianilines. 7-1- A high amintitoz-kalddhyde molar ratio is used, for example up to 10: 1.

   After iialeoent of the polyaminejodou variants can be used, * methylene df.an..l.3.nrs can * be - 1801Î * 4 of the polyamin * raa fractional distillation under reduced pressure then ph sgàt4ëà 'to give the bis (isocyanatophenyl ) methane $ or the poly = îno can be subjected to the action of phossene and the polylisceyanato-thus obtained can be subjected to a
 EMI22.2
 fractional distillation under reduced pressure to isolate
 EMI22.3
 bit (isocyanatopblnyl) mdthant.

   This last process is general * -
 EMI22.4
 preferred, particularly when trying to obtain
 EMI22.5
 a very pure diisoeyenate, since the phosienation reaction can
 EMI22.6
 drag some polymerization into higher polymers,
 EMI22.7
 The diliocyanates thus obtained are interesting because of their
 EMI22.8
 liquid character are suitable intermediates for
 EMI22.9
 the known processes which use diisocyanates. '*' rt- The principle which has just been laid down is generally applicable to pol.yisaayanatsaYaroraat..qt, as of the invention which have lower melting points and * v3s ..

   Lower cosities than the comparable cultured weight aromatic polyisocyanates obtained by the prior methods In many applications this lower viscosity and lower melting point is an advantage if wheat is used. The reaction of new polyisocyanates with polysols for tbrms 4as. Useful polyurethanes Co = * ilestomers are of great interest, polyttocygnatte ions are also valuable intermediates for the preparation of polyttocygnate coapositites. ',

 <Desc / Clms Page number 23>

 
 EMI23.1
 - In this compares various characteristics of the aromatic polyisocyanates of the invention with those of
 EMI23.2
 aromatic polyisocyanates available so far.



  . Polyisocyanate A is obtained by a process similar to that described in Example 8 above. Polytsocyan, ate B is a commercial product obtained by the process described in US Pat. No. 2,68,730.% Analysis by vapor phase chromatography indicates the following distribution of isomers in the diisocyanate fraction of ei-deesus polyisooranates! III
 EMI23.3
 Distribution of diisocyanate isomers
 EMI23.4
 'Q1Y'OCYJma, $ in di1socysnate <by weight of 1' 1 .. & '.LA' \ Â & Á!



  AT ; l '47.4 6.34 36.71 56.9' 39.4 l, e 98.2
 EMI23.5
 These polyiaocyanates are also subjected to wireless "\ 4" by infrared spectrography in solution at Al (nn Weight) in, -c11m & tbyltormam14e. Figure 7 shows the spectrum of polyloocyanate B and yi.B that of poly-11oo1anate A.

   By comparing the intensity of the maxima at rowing 12.3 and about 13.2 microns, it is seen that polyisoayanate A has a higher orthouub.titut1on para sonsiblommt substitution ratio than polylooayanate B.

 <Desc / Clms Page number 24>

   EXAMPLE 10.-
 EMI24.1
 Polyurethane 6: Lastomkres are prepared from #> polylsooy = ate -U (a known palyisoaysaets described in Example 9) and from polyloocyanate C. The polyiaocyanate 0 is a mixture of various O polyiMcyantM prepared by the process of the present invention 0 = described in Example 8.

   The polyiMcyent.te C has an equivalent weight of 140 and a content of -NCO groups of
 EMI24.2
 30x, found that the polysooyenate B has an equivalent weight, 135.6.
 EMI24.3
 -Elastomers are prepared by the tmpi process from the following compositions:
 EMI24.4
 fiimnfflf.L'ît: PT> t- .. ## ... Elastomèra B lastoaère PelyiMoyMmt 32 Polyloocyanste C # # 36 # 3 polyol (1) 100 100 1, Ball * * white-red * 94 - '.' # "94 f. D3.iae saab-.owsia.

   Hw, (1) A mixture of trilsopropanolazine and pplypropylem glycol have a molecular polae of 1..25, with the me3.ngo having an Index
 EMI24.5
 
<tb>
<tb> Hydroxyl <SEP> of <SEP> 121.26. <SEP>
<tb>
 
 EMI24.6
 The method of preparation of the melater is the su3 worth
The polyol and the charges are mixed and heated to
 EMI24.7
 . 138 under a pressure of 2 sm of mercury for 3 days, 5 hours in order to drive off the humidity. The mixture is cooled to 60 C and
 EMI24.8
 put under reduced pressure in a nitrogen atmosphere. The polyisoyanate is added, the mixture is boaageneiaé and heated at 12000 for approx = 1/2 hour.

   It is then cast and vulcanized at 120 ° C for 20 hours,
The characteristic properties of doua elastomers are,
 EMI24.9
 yetKmeea in Table IV below t

 <Desc / Clms Page number 25>

   TABLE IV Properties of the 3lastomers.
 EMI25.1
 



  Shore hardness at 91 89 aéistar in traction, kslom2 123 f 1 6siteace in tearing, 4 / ca 27
 EMI25.2
 
<tb>
<tb> Elongation, <SEP> * <SEP> 50
<tb>
 
 EMI25.3
 The table showed that the elast = èr3 C obtained ja part of the polyisocyanate of the invention plant has resistance $? '. *
 EMI25.4
 ,, the tensile significantly higher than the ptipgrj, lastoasi ,, from the known polyisocyanate. ,
 EMI25.5
 The invention also provides polyurethane compositior which comprise the reaction product of the novel,; i aromatic polyisocyates of the invention and one or more polyol. Many polyols can be used for this purpose, for example one or more selected from the following.



  (a) polyesters and polyester-ethers terminated by a hydroxyl function;
 EMI25.6
 1. (b) polyhydroxyalkanes and adducts thereof A 1f with alkylene oxides; (c) trialkanolamines and their adducts thereof with alkylene oxides; alcohols derived from mono- and polyamines by addition of alkylene oxide;

   (a) non-reducing sugars and derivatives of sweat * and their adducts with alkylene oxides;
 EMI25.7
 (t) the adducts of alkylene oxides on the ternary aromatic amine / phenol / aldehyde condensates;
 EMI25.8
 (, g) the adducts of alkylene oxides on the acids of phosphorus, and on various phosphates * and phosphites ending in a hydroxyl function;

   

 <Desc / Clms Page number 26>

 
 EMI26.1
 (h) the products * ds4dalg <ln the oxides of ethyltoe on the po3, .. nclsj '101 #) - \ v (1) the Polytetramethylbuf 4 .Yaols K Examples of polyesters end with a hydroxyl function have the polyotterd which are prepared> ar polymerization of a l <tot <me (preferably a tpsUon-caprolectoae) in the presence.



  '"ua, active hydrogen initiator, as described in African Patent No. 9, t..b. Ï4X polyesters obtained from muplic acid and dlola oo = vli -Oithylene glycol, propylene glycolp [: the diethyltoe glycol, etpropylene glycol and the triulah ooame 1 # 1 # 1-trimétbylolprop ntij, .2.6-boxanotr: iol and glyod- .1 are interesting ig4l * meat ig4l * ies oopolymers of laetones and '. <d' allcyleae oxides can also be used with good
 EMI26.2
 results@
 EMI26.3
 Suitable polYhYdroxya7, aaats are, for example, dtbylene glycol, propylene glycol, l, 3'-dJLhydyojprcp <tne le.-Dill'drOxytbltti3la l, 4-ttihyaroxybut ne, 1,4- , 1 * 5- and the.% 1 # 21- 1 <3'- 1.5-j 1.6. and l ,, d-d3yàra.



  3wootanes # 1,10dibyàrQxydaane, glycerol,., 3,3trih, rdra.



  31 Dutane # le i, 26triyaroxxhexaae, le l ,, l, l-.tarimétty3a.6ttue, le.,., L.trislétt110ljïrOpane "pentaerythritah to, e rxy? .3, to ,, arbitol, sorbitol and mahnitol The products 4 # addit4 = ¯ of oxidizing d # -Ielene on these, pol3 to hydroxyalkanea can be used, preferably the adducts with 4 # dtbyle4o oxide, p propyltw & 4 oxide and .'epw4. "butane or their melengee.



  Another class of polyols which are suitable for use with trialkylemines and their adducts with oxides,; .. dfalkylkm. Suitable trieleanols are, for example, tac3itbaaolsmlae 1 triiM'prcpanol) Mine and trtbutanolminte. Suitable <U <ylene oxide editor * are preferably those in which the oxytU <ylene moiety contains 2 to 4 carbbae atoms:

   

 <Desc / Clms Page number 27>

 Another interesting class of suitable polyols are the adducts of alkene oxides to mono- and polyamines. Mono- and polyamines are pre- treated
 EMI27.1
 tdre = e avde alkylene oxides having 2 to 4 carbon atoms, for example 1- * ethylene oxide, 1,2-epoxypropane, 4poxy- ¯. ¯ butanes and mixtures thereof. The mono- and polyamtues which are suitable for the reaction with the alkylene oxides are, among others, Bethylaalne, l'stYylamine, loisopropylamne, butylamlue la bonsylaulnej, ljlfnillnep the toluidineso the napbtylamines, ljldtbylè-diethylamine, ethylamine, ethylamine triethylenetetramine, 183-tutue4audnto 1, -propanediamine, la. 1,4-.butanediamine, 1m.



  1 # 2- # 1 # 3-j 1 # 4- # lp5- and 1.6-hexanediamine, phenylenediaminus, toluenediamine and compounds of the above class which are of particular interest are listed '
 EMI27.2
 notably Dt, à, bt, t..tetrakis (2-hydroxythyl, th, y3.ëaediana, - la DI, t, f, 119-tetrakis (z-bydrocypxopYl) t'lt: ediami, ne, lat Y # X.tgp on #tu% -, pentakis (2-bydroxypropyl) clié thylbuotriamlnep phecyldiisopropanelamine and the adducts of higher alkglena oxides with aniline.

   Other compounds that deserve one. of particular mention are the adducts of alkylem oxides with aniline and the aniline substituted condensation products.
 EMI27.3
 tu6a / i oraalâëb; yde, particularly the condensation products contemplated in the present invention.



   Another class of suitable polyols includes non-reducing sugars, their derivatives and preferably their adducts with alkylene oxides in which the alkylene oxide residues contain 2 to 4 carbon atoms * Among non-reducing sugars and their derivatives, we can mention
 EMI27.4
 sucrose, aluylgluaos3das such as methylglucoside, ethyl. glucoside, etc ..., glucoside polyols such as ethylene glycol glucoside, propylene glycol glucosiaer, g3rc3 g .uèo- ld * - # 'fi:

   fez
 EMI27.5
 and ly2., 6-hexmotriol Slucolde.

 <Desc / Clms Page number 28>

   Another * interesting * class of polyols contains the pro-
 EMI28.1
 & D <yinw oxide adducts on polyphenols, wherein the alkylene oxides have 2 to 4 carbon atoms. Among the polyphenols which are suitable, mention may be made, for example, of
 EMI28.2
 bisphinol As, the & i <ph4no F,! # product of codouatIO4 of phenol 'and foroaldehyde, more particularly the Xovolnues resins, the condensation product of cuver,% phenolic compound with acrolein,

   the simplest members of this class being the
 EMI28.3
 lalj, 3-tria (hydmxyphenyl) propane ## the condensation products of various compounds, $ phenols with tlyoxai, glutaraldsbhyde and other dialdebydouo the simpler members of this clause being 112,2'-tetrakia (hydyoxyph & tyl) ethanee.

   Another interesting class of de-polyol, $ includes the
 EMI28.4
 addition product of alkylene oxide *, preferably oxides; #; ! ir, bal 4e 12-pocypxapans 4 '.' poxybutane and mixtures thereof, s ternary condensation product aroaatiqu./pbéno1/: di \ 1f4 .. v La's products of cdensa #, aa ternary are prepared by stringing a lead aromatic, for example aniline or tolu-
 EMI28.5
 d; neo an eh4pl like the pnsol proper had the cresol and a '3sr "bzz preferably 1 aral, drrte 168 tmpd tffla dlov4tok #de èo to 1f $ O. The condensation product is then isolated and' 1 '" t. | éa | i | "avei l, 1oq4. of allcylne, using a catalyst tlla ai - (J. ':' '4-1'., in order to tom" r the polyols.

   The products * 4ÍfUiQJ) (t, 9xy9 - "J 4. p-Qp) '1ce and mixed addition oxides of PlÓ.PI1.d. c &. 't. "9'lD on batch ternary condensation products 8D1J1u / pWnol / tftru.ld.'byo .. deserve a special lie *.



   Another interesting class of polyol is the adducts of alkylene oxides to phosphorus acids.
 EMI28.6
 tV, 4 "tf". \ "1, a-POJ7Pn an81 the 4.1 and the ',, yr' 's paa have the oxides of aïjçylin * preferred.' i, y, .. gy 14 * oicto pwpphor =. 168 pgkpbos' i P5 | 81 * iëf # lfôide plwjspàorous acids, p: bo ... 1: J

 <Desc / Clms Page number 29>

 
 EMI29.1
 , phoriquee, ccame lsaalda tripolypi4oophoriquel.convimüont well ..



  Phorphites or = * tris (alpropylene glyool) phosphite and photphonate which can be obtained from the latter by the presence of an alkyl halide, rather than butyl bromide, are also suitable.
Another interesting class of polyols includes
 EMI29.2
 polytetranethylene glycolt which are prepared by polymerizing titrahydrotturaane in the presence of an acid catalyst * The polyol or mixture of polyols used may have a hydroxyl number which varies between wide limits *. In general,

     
 EMI29.3
 the hydroxyl number of the polyols used here can vary between <! 0 tc, 100 # preferably between 30 and 00, and more special <4 * Bt between 35 and 430. The hydroxyl number is defined by noe: 4th mg of potassium hydroxide needed to make the 4th. Complete lization of the hydrolysis product of the fully asethylated compound prepared from 1 g of polyol. The hydroxyl number
 EMI29.4
 it is also defined by relations
 EMI29.5
 56.1 x 100 xf Q8 on OH = Hydroxyl number of the polyol
 EMI29.6
 ; f a functionality, i.e. the average number of hydroxyl groups per molecule of the polyol
M = molecular weight of the polyol.



   The exact nature of the polyol used depends on the use for which the polyurethane is intended. For example, when it is desired to prepare foams, the molecular weight of the hydroxyl number is omitted so as to give flexible, semi-flexible or rigid foams. The above polyols preferably have a Hydroxyl Number of between 200 and 1000 when holding
 EMI29.7
 to prepare rigid mousse, between 50 and 250 when.

   are used to prepare these semi-flexible foams and between 20 and 70

 <Desc / Clms Page number 30>

 
 EMI30.1
 f 5 '/ i. or rather, when they have For 3-4 preparation of flexible Ugges. These restrictive * n'oat p * <values and #are given only to illustrate the large number of possible ooabineiawi of * ci-doasus polyols. In some cases, it may be necessary to use one or more organic olyisooyanates supplemented with the polyisooyanates armatiquiii of the present invention to prepare a polyurethane conferred on .os.tls.ai. Many organic saayanates and polgothiocyanates are available at fine temperature.

   For example, # preferred laocyanataa are polylsoeyimateis and polylsothioayanates. forswla géaéralot where 0 is an asset, oxygen or jump're, x is an integer equal to or greater than 2 and R is an aikylèae radical, substituted alkylene # arylene or amylene subatitud ,, a hydrooarbon radical or a hydrocarbon radical substituted eoapr <Mttnt 'one or more ry3.a -UCO bonds and one * or more alkyl bond -tCG ..



  R can also have ci * $ radicals such as -R2H- OtL Z can #; be a bivalent bond group ce = * -0-8 -0--0, -CO- ### '.; / -CC2- # -8-8 -t3-tS- -i0 "etc. Among these eoapos4s there may be mentioned $ JL'hMMa <thyl6n <MLiiMcyMMtt <, lM.3tylyltn diitocy <MMLtw <'; r.,' (0C CB2Cfa2Cii20CH2) 2, 1 <l <thyt-, 4-diiMey <natooyclohMMM,; z, 1;

   phenylanedlisocyanate, 4 "and Z, 6-tolylnsd.i.isocyaata" 'cûlorophénylànedliaocyanatea, dlphenylaethane-4,4 * -dilaocyapatej, 14 tyipMnylm <MMm <', 4 '' - t <riiMcyMMqttline * tl a, a-dl, isotb, toayanata and iaopropylbensfc # ne-a, -4-dilaocyanate, #. '#. # -, Also included in this group are the diaerea and trlzers of isocyanates and diloooyanates and dM dilsocyana- # 't. you polymers of general formulas

 <Desc / Clms Page number 31>

        or ?!; and y are 2 or more, as well as compounds of formula%
 EMI31.1
 general ## M (HCO) X where x is 2 or more, and m is an atom or a troop anotona33o ', ne! or pol, rtona't, totual. Examples of compounds of this type.



  Are diisoeyanâte t, ypbob4qu8 (G2g3P (0) (rço2f 1 dlisocyaaate pbénylpho s phonique, C6H5P (NCO) Z; cON) OBis which include a -8i-aC3 group and isocyanates which derive from sultonatCOides (t! .



  Other useful polyloocyanates are described in an article by 8létkea, Innalen 562 # pages 122-135 (1949). The polyurethanes obtained according to the present invention may take the form of foams, elastomers, coatings or moldings. Foams can be obtained, for example, by the one-step process in which all of the reactants are mixed at the same time as the foam is formed. Alternatively, foams can be obtained by the quasi-prepolymer process.

   In this process, the isocyanate is first treated with a portion of the polyol to give a compound containing a high percentage of free -NCO groups (eg, 20-50%) and this compound is then expaused by reacting it. with polyol and a blow molding. To form elastomers, the prepolymer process is of interest, In this process, the isocyanates are treated with an amount slightly less than the amount
 EMI31.2
 atoschionetrics of a polyol in order to rorinsr:

  .ua prepolyxèm containing a small percentage (for example 1 10%) of free -NCO groups * The prepolymer is then converted into an elastomer by reacting it with a crosslinking agent containing hydrogen atoms.
 EMI31.3
 active agents such as a diamine, for example a bis (1-aminochlorophenyl) mdthanoi. To produce coatings, various pMedas

 <Desc / Clms Page number 32>

 
 EMI32.1
 known are suitable, by G8IPlol 1 '; i #' '"; (1) the use of a pr'po1Javt containing a t4lble percentage' '., 6' free -tfCO groups, which and hardened by 1ct1t4 atlio.p" '- 1.



  "riqutj ;; r: riquef ::.



  - 1: f (2) the use of a binary system in which a prpelymM is JÚ1..m 'with a juit polyol * before the.p1) 11.l.t10111 || (3) the use of a * aba1la system. unique, which coup don ii .. '. constituents and requires heat treatment, One of ifë,% ik.



  / constituents is a P01711007 $ 1 & prepo3yaèrs in which the -, '-, 1. Free -NCO groups were blocked (by 8xeap18 by a phenol) '<in order to render them inactive until they were unblocked by Oblut.tQ8. The second component is a polyol * (4) the use of a single component '1I "" which does not contain free 11001 ... te groups :.



  Unsaturated iras acid diglycerides are 1; 1; 1, 1, 80, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 3, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 001, for the ester chains.



  .. \ 8 4uro1l.ement .. carried out by drying, the usual oxidatit of fatty acid ires * Polyurethanes capable of being .pu3, és are exhausted by prooddis-saiblableo to those that are: "1111 'to produce the' la.to1Iltl "eÍ. All the processes which have to be cited are well known * ZI * = still arises from the fact that the utility of the polyamines and of the following polyurethanes in the production of polyurethanes is IJ'4e 'tr. , 1; 1OA d.aI production viscosities Interior to J! F8,,, you at n.co.1t4. :

  l.nt4r1eur, u f '' / .. '' l '.' 4aQ. which could be obtained q u illà prlses3t '$, from a poiytinw and a po41400ya = te molecular weight aomplracab.s. - The amount of polyloocymate utility * varies widely depending on the nature of the polyurethane. In general, the ratio 'which-' ... / ... 1 "total of, MCOuiqU1Val¯t) tÓta1. active (groups "'Pro .. rather possible water must be from 0.8 to 1; 281.0 and from
 EMI32.2
 t

 <Desc / Clms Page number 33>

   preferably 1.0 1.1: 1.



   Afraid of preparing mousse $$!). ' expansion can be achieved = using a small amount of water in the reaction burst (e.g. 0.5 to 5% by weight of water based on the total weight of the reaction mixture)

   or blowing agents which are vaporized by the heat of the reaction of the isocyanate with the active hydrogen compound or water and rota * These well known scat expansion methods * Blowing agents * preferred are water and certain halogenated aliphatic hydrocarbons the boiling points of which are between -40 C and 70 C,

   and which vaporize at a temperature equal to or less than that of the mixture which is to be processed tançasse, Another clinker of blowing agents includes ther-
 EMI33.1
 V4'ti, uly unstable which liberate closed gases on heating, omm la, M, M'-dimethyl.-dinitrotot <rpht & lamide.



   The amount of blowing agent used varies with the desired density of the foam. In general, we use for 100 g
 EMI33.2
 of reaction mixture having an average tiocyanate / by = active gas ratio of 1: 1, from 0.005 to 0.3 moles of gas to obtain foams with specific gravities ranging from 480 to 16 g / cm3.



   Of. catalysts can be used in the reaction mixture to accelerate the reaction * of the isocyanate with the
 EMI33.3
 active hydrogen compound. Numerous compounds, conrienaent coaate catalysts be, for example: (a) tertiary amines 1}] 1; ...

   (b) tertiary phosphines $
 EMI33.4
 (0) strong bases such as hydroxides, alcoholates and laaphenolates of metal alkalies and of m6t & fv, alkaline earth; (d) the acidic ones of strong acids such as ferric chloride, atannic chloride, stannexix chloride, antiaony triobloruya, bismuth nitrate and bitmuth chloride;

   

 <Desc / Clms Page number 34>

 
 EMI34.1
 % r - (0) lolî ebélatts from various ogme the 0 bust * that can be obtained * from dawjiy.tsa are from baasaylaoaitona, from
 EMI34.2
 
 EMI34.3
 trifluoroMtylâctoM degoitoacitate d # 4thylej de sai, ayi ... aldebyat, de ayolopentanarat - aarbQxylabe ,, .dacâCylaaétcuaata * ina ,, de b3, s-acéylaaétonealxyl3imiaes, dt saliaimina! # Cdp Pb, Ti # Zr, On # As,, ... 8S, or # moi Ma, 7 * 0 Co $ Nlj, ou'des long oonat Mo02'H ', UOi # (X) the aloool (| tta 0, the ph6:

  7.s # s da divors m <t <mt come Tl (0R) 4, 8 (OR) 8n (ORA] L (<), where R is an alicy- or aryl radical, and the reaction products of the alcoholates with carboxylic acidsj, #tes btta-dicitonts, and 2- (Ujjk- d & UWlu4r-o) aloanolop for example the well-known chelates of the tltant obtained by these processes or of the progidds tqulvaltntaj (g) the atla d # aoidos orgtniquM with various CMOM metals alkaline earth alkalis, alumlûlua, 1 # tainp lead, # '#' "luat3soina ,, 160 mganeseo cobalt, nickel and copper (b) dlrlvéa cr <tne) t <JJLlqu < d 1 étala tetravaltnt, larsani, c 1 antiaafka * and du'blaouth trivalent tt t4traTa-? 14utto and the d <yiv <w oarb = yléî of: gold and cobalt. '"' 'MdM <teetitires can Itrrr utuision eoaat aut.atirsaurs prima & res to speed up the reaction of the coapoai to #: '":

  - "tardrogttMt active with 1jiso0yaute or conat catalysts oeoond $ 4r * s # ixvr * 9 one or more of the catalysts, adtaluques cited * ai-dasstu., 1 bottom 9tt) tly * eur * si7.liuas or 1s combinations of oatalyatura # étalUquts can also be used 4, to accelerate the bzz '", tani 4ter reaction associated with data * Cttftly << ur <t #, .-' # - # lodt & M are the preferred aKtIliquM catalyst. The aatalrsaurs are used in a small amount, for example 0 # 001 to i $ 9, based on the weight of the reaction mixture. bzz

 <Desc / Clms Page number 35>

 
To prepare the mousse $, it is also part of the process of the present invention to use small amounts *,.
 EMI35.1
 



  "eg 0.001 to 5% by weight based on the total reaction mixture of an emulsifying agent such as a polysiloxane-polyoxyalkylene block copolymer containing 10 to 84 by weight of silomune polymer and 90 to 90% by weight of silomune polymer. by weight of alkylene oxide polymer, for example the block copolymers described in US Pat. Nos. 2,834,748 and 2,91,9,480. Another class of useful sulfifiers include the block copolymers o3., s3loae. non-hydrolyzable polyozyalkylene ". These compounds do not differ from the previous ones in that the polysiloxane part is linked to the polyoxyalHylene part not by aartons-oxyna..sili elun bonds but by direct carbon-silicioa bonds. generally, 'this aopolyoèrss contain 5 to 95% and preferably $ to 50%
 EMI35.2
 by weight of the polysiloxane, the remainder being PGl1OXTa1k11me.

   These copolymers can be prepared, for example, by heating
 EMI35.3
 a mixture (a) of a polymeric polyethylene containing a hydrocarbon group == valent substituted by a halogen atom bonded "to a silicon atom, and (drunk from an aloalia salt of a polymeric JKt1Ioqaïkylene at a temperature sufficient for that the polyoiloxmo and polyoxyalkylene sol form a block copolymer * Other useful emulsifiers include products such as
 EMI35.4
 polyithoxylated vegetable oils. Although the use of 4'a. emulsifying agent is desirable to affect the character of the foam; foams of the present invention can be prepared in some cases without emulsifying agents.



   Polyurethanes according to the present invention are very useful compositions. Thus, foams can be used for isolation, padding and coma * cushions. The
 EMI35.5
 'la.tomr.8 can be used / as 4tanQh4lt4 materials, \ eg for clay pipes. Coatings can; be used to cover objects made of metal, wood or glass. Castable polyurethanes can be used to coat electrical elements and to manufacture molded objects

 <Desc / Clms Page number 36>

 
 EMI36.1
 The oMapI * which autt WUIUt the formation of a moussa 4.



  .-T "pi 17 \ lrlthanne from a riouirtau po11110018D & t." R aroraat1que 4th the iavntion. j ".... '. 8'1 \ rR 1.) ..- H.,.' 1t 'i Un. moussa 4.- po17 \ lr'tbann. is obtained. by the Pl'0044d' to a t api from oompol1t1oD l \ I1yante. pitunt, arti "8ft J> 03-d.'o \ 'j, l Po1111OC1anate 4. ex.pl ..:" 80.4: Polyol (1). , 1j Vo '7'. .. ,, '} 100,0 HonOnuorotr1ch1oroa't1uAe' '5,0 Dllaurat. 4th 4ibat)' l'ta1D;>; 0 * 6. \ WW '' - trM <thyl-9 -tMt <n <diMi! # '0,3 .. tw.', lmui ifiant A25 1 # *, \ C (1) adduct mixed <of oxides 4 "tbJJ, tD..t 4'0x ; y4. dt proP11.ne (20/80 8D weight) on a product of OOD4GD.a U. tarnaisa? aD111ne! phmol / to: aal4Ih7d .., ant a 1n410, h1ell'Ole d 3U '.. and a tonoUonnal1tl 4.5, *. L. product 4. OOIi4.utioD 1DUir &.



  : ph4no1 / tonaalc14h1d8 from which 1. pol101 #a | pr4par <has a weight 4quJ.ft18Dt 4'It14J'O, 'a. aotif 4th é8, &.



  Ca) This copol1Ùre À b1001 POl1, J.1oxane-pol10Xlalk11.D8 4t formula 1,
 EMI36.2
 
 EMI36.3
 where does it represent
 EMI36.4
 
 EMI36.5
 The rigid foam thus obtained had an apiclflquo weight dw ^ 53 g / da-1 and comprised 892%. 0611ul; ec tfraéfs. I.w, p * of 74 or ..,. of a & ltmse forming the bush is 15 seconds, the togpa
 EMI36.6
 

 <Desc / Clms Page number 37>

 expansion is 75 seconds and the time the aos * remains sticky * is 75 seconds.



   , The invention also relates to a new class
 EMI37.1
 of pol; o11 which are obtained by adding oxides of ailcylene to the other poly8lOA "aJ'Out1qu .. of the invention. The oxide of ailpr?, lne envision $ are the <po9ty <tlcM vicinal which contain prefirsace cl 4, t more ffpeclaleaent 2 or 3 atoll. ' carbon, by 8Xempl ', Od' 4 "1n.,! <- <poxypropan 182-dpwqbutant, 2,3-epoxybutant, 1, x-ipo-el5thylpratans eC their .'8I11'1, etc . Alkylen oxides. are condensed with the novel aromatic polyamines of the invention by known methods.
Preferred polyamines for the preparation of polyols
 EMI37.2
 are those which derive from aniline or olJql8D1ltn ..

   (the alkyl residues preferably having no more than 12 carbon atoms) and formaldehyde according to the process of the invention.



  . The following example illustrates the preparation of a product
 EMI37.3
 lt of add.1tioD of alkyl oxide to one of the polyamines of the invention *
The polyamine used is obtained by a process analogous to that described in Example 1. The ratio: molar
 EMI37.4
 have of: 1; the molar ratio sui.ti.ast8Cl, is C * 9 140t1 and the temperature of the condensation reaction is' 13û135, C: The polyamine obtained has a molecular weight of 269.9 wn, equivalent weight of active hydrogen of 525 an equivalent weight of M <tyl <.tlOB of 103.2 * t an average functionality of 3s, tt.



  The above pplyelue (7700 bzz is Introduced * into a 22 liter flask. Potassium hydroxide is added and the contents are then heated to 150 ° C, then 9790 g of
 EMI37.5
 12- <pexyprop <o <are added $ with a flow ensuring a slight reflux, A part (3391 g) of the product contained in the flask
 EMI37.6
 Initially introduced into a 12 liter flask, and 10% of potassium hydroxide and an additional 3% of propylene oxide are added thereto.

 <Desc / Clms Page number 38>

 
 EMI38.1
 



  1 r The product contained in the 12 liter flask is re-cooled, diluted with isoprapyl3aue iâcoil and <successive * <6 <nt span of the columns of strong acid ion exchange resins and strong bû t. The tiopropyl alcohol is then distilled off to a final temperature of 18,500 under 2 Mt of ttorcurt. ¯v seraure The polyol aias .., bbteau y y - has an Acid number of. 06t. a said hydroxyl number of 9 and a PU of 7 # 2. The viscosity of the polyol is 0.000 c <aHpo 60 ° C. The polyol has an average polycsyptopylM chain length of 1.67 orypropylene units. By a method -similar to that of Example 128 d0; of the aromatic polysine described in 18 * x ple 12 are reacted with a bond of 1290 g of ethylene oxide and 7310 g of propylene oxide.

   The acid number of the polyol * thus obtained is OeO36 # 1 $ 1> iUce 4 $ hydroxyl is 359 # 5 # 'It * pU art of 7.2, the viscosity is 6300 cont4pois-ses at 60 ° C. and the nuclei chain length is 1.85 oxyalkyleate units. The polyols of Ibinient4on> may have an oy-4r <Mtyl <number which varies widely, for example from 20 to S50. The use = of the polyol d4t <Min <the particular value of 1, * Hydroxyl index '# -' # 'c The polyols $ of 111 = vent4on are very' nt3ler ccapositions: by folds 1U can be esteritated by acids
 EMI38.2
 of drying oils to give 'Interesting compositions of
 EMI38.3
 takes 40t. Useful tenltiaraat3ts compounds can be obtained from the adduct of dilâthylene oxides on the products of long cbab * dousatioft alkllail: Lne long cbab * (by reaceAp. Ea C $ â Ci / tormaid6hyde.

   The polyurethane has been used in CMMW durations for the intermediate polyurethane and horn resins: in the preparation of polyurothmes.



  The object of the iav <ntioo is the polyurethane compositions * which are obtained from the new polyois. eye.' 1'ies can take the form of 0OUI400 objects of ywv $ - 'ttaU, 484lastoibbres or #e flexible candles, scmi-flexiblcs or

 <Desc / Clms Page number 39>

 zigid. An interesting feature is that a lot of *
 EMI39.1
 # * rigid pods can be made self-extinguishing, cties.



  Polyurethanes are obtained by reacting the new polyols with one or more organic polylsocyanates.



  Catalysts, blowing agents, 4matitianttl agents and polyocyanates, as well as the various agents for forming foams have been discussed above in connection.
 EMI39.2
 polyurethanes obtained * from the new aromatic polyixooyanattet. The considerations which have been made also apply to the polyurethanes obtained from the polyols of the invention. The new polyols can be used * alone or in admixture with other polyols to form polyurethanes *.



   The following example illustrates the preparation of polyurethane foams from the novel polyols.



  EXAMPLE 14. Preparation of a polyurethane foam from a new
 EMI39.3
 LSi171ra1. ......:.



   A polyurethane foam is obtained by the one-time process from the composition, following
 EMI39.4
 Component Ooida POUU parts of example 12 100 ttonofluorotrichloronethane 26 4 Dilaurtte de * dibutyl4t & e 0 # 8 8sulsitiaat A 1 # 5 Tolylene diiaocyanate 54 tw
The creaming time is 14 seconds, the total expansion is ..50 seconds, and the time during which the foam remains sticky is 55 seconds. The specific weight (of the middle) of the rigid foam is 32 g / dm3 and the content of closed cells * is 91.4%.

   At 23 ° C, the compressive strength parallel to the expansion direction is 2.39 kg / cm2 and the compressive strength perpendicular to the expansion area is 0.95 kg / cm2.

 <Desc / Clms Page number 40>

 
 EMI40.1
 # * "a polyur <thtan <" nibble produced by the process, ',. a beat from the next composition
 EMI40.2
 f! nt1¯? '¯1h1lnt Part in 3'olroiIda l'ecempla s3 "#' # '### 100 #### <Monoiluorotrichloroulthânt #'>, .v 22 l, '' -; -> F, & Ml * ifiMtB., # - .., rl 3 ''.. ',', ..if '", m dihwrata' 1 da 'Aibu'ty J 0,0 * #' '' v, 1", you yléne ditzooymate, 6 # '-' # ... #; ::

   ##:, '#' '(1) Block copolyMre * polsilonpol, rox, ral4ln de fora -'
 EMI40.3
   we @ are a formula troop,
 EMI40.4
 The rigid foam thus obtained has the following properties!
 EMI40.5
 Teaps do * go 0 00 eik et a and 914 seconds Teaps dexpallâio7 ................. iv ........ ty seconds time during which the foam remains 00110 * -, 45 seconds .te Pold <specific ................. <. T ....... 32 1lda3 Percentage of closed cells 92.5, 1f, 1. tan08 at the oOJlple8s1on.



  Along with the direction of expansion ... 2. '
 EMI40.6
 
<tb>
<tb> * ion <SEP> 2.76 <SEP> kg / cm2
<tb>
 
 EMI40.7
 PerpeDd1cuJa1rem t to management
 EMI40.8
 
<tb>
<tb> expansion <SEP> 0.92 <SEP> kg / cm * <SEP>. <SEP>
<tb>
 



   A further subject of the invention is the curable compositions which comprise the novel aromatic polyamines and '. a polyepoxide. The polyepoxides envisaged are preferably those which contain 2 or 3 vicinal epoxy groups, such as Ya, following compositions *!

 <Desc / Clms Page number 41>

 
 EMI41.1
 ft bzz the p $ 3y <pcxyd <which e <mti EtOtot 2 or 3 ..thr 1 imiqertie- h 1 'it slt 9v t ac St u are' re P x3ssatt p::, t r a ', bl. Phone. que oeux qUi r'J "f.entl. pa1" f '' i '..
 EMI41.2
 
 EMI41.3
 i 0 (each R represents a 4'hy4ro atom, .ne or a hdi, 04'â, i, icyl.

   Lower cantwmnt 1 bzz 4 & tom * $ of carbon, e <M! A $ diz in patent ¯Inca1n n * 2,716,123;
 EMI41.4
 
 EMI41.5
 where each R represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, and R 'is a divalent hydrocarbon radical comprising 0 to 10 atoms of cardboard, e described in U.S. Patents Nos. 2,750,395 and 2.M3.MH
 EMI41.6
 
 EMI41.7
 #V! - (A, eht <ïtt $ <p: 6xraï an toa * 4'i11ANcèn. Ça Ma ft4t.oa1 aUrIl.



  1Jatlri8UJ 'containing l k A atoa .. of caxiboas, and the sit goes!

 <Desc / Clms Page number 42>

 
 EMI42.1
 ...... # # -. ## 7 't,' f: ### -y .'-.- '# .- # v, -v # -, ### .. # <radical bydroc * rbon <binent containing 2 MB a. " 4. " - #; #;,; carbon, As described in the patent. 'nca1n a * 2,745 8i7
 EMI42.2
 
 EMI42.3
 ois S * Mtva troop iiph U <iu 1îlv l xt et chaqn R srpxis .¯;:;: '.;: amber chosen in the group' con <tim <by the atom of horror: ..,;

   ', the radicals <t3JEy.w lntérimrs from 1 to cardboard trumps,' ocme described in the wiérlcain patent n ', .88, .t4dt'
 EMI42.4
 
 EMI42.5
 Uv # "### u # ..s *. #: .F" \ # ## .. '###; -> t- #; ##### ;; ###. and Each ', is chosen in by Illot4 0 * i 4'hJeSl'O'ù, and the r.dJ. = 8UJ. lower, obaquo X e.tcbo: l..1 'in the group consisting of etûM 4'b74ro & en., atm *, * of halogen and alkyl radicals Dt'I "ī: r ..' au ) Min <of the Xs.



  4 so always an atoa. 4'halob ,. 0088 '4'r1t in the brtytt!' Micna * 2.874.T. '#'; . ' r ... ..] * '' J? #: ±

 <Desc / Clms Page number 43>

 
 EMI43.1
 
 EMI43.2
 
 EMI43.3
 where CUo1 \. \ 'R, is an' a tom. of hydrogen or a croup aJ.k: 1'1.
 EMI43.4
 less than 1 to 4 carbon atoms. i De * particular examples of polyepoxydew of the classes
 EMI43.5
 represented by the general formulas above are
 EMI43.6
 ?, 4- <Spoxy-6-aethylcycloheaylaethyl, 4-epoxy6methylcyalohexxecarboxylatt, bis (3, -âpoxy-bm # tb, ylcyclohtylmithylo? ilether, 304-6poxycycloycycloycycloheaylaethyl9, zyxyxyl-6-aethylcycloheaylaethyl) isadipate (3,4-époqrcyaohr.

   2-ethyl-1,3-hexanediol carboxylate), 1,1,1-trimethylolpropane tris (3, i-epoxycycloliexanecarboxylate), tris3,46poxrcyalo-
 EMI43.7
 bumecorboxylate) 1.0 2.0 3 -propan-triol ,, 1-brono-3,, 4.



  'Yihee-atrborlste te J .... b: romo ...,, 4.'poX)' o; rolon.xuaMmethyls the bit bibagate (3.4-IPOX1-6-mlth11c7clohCXf1841.), And the bis (3, -xYcYalohexaneaarboxylate of et14th71.glycol.



  Another class includes polyepoxides with ither groups
 EMI43.8
 111c1q11qUt, 0 # 6 $ t i.e. groups of the type
 EMI43.9
 
 EMI43.10
 Specific sources of these polyopoxides are 1 # diglyctdyl ethor, 1 c11 (2, '- POX7C101optDtJ11qU8) jether, 19 cl14th8O diglycidyl from 2,2-bis (para-droqph4nrl) propt.n. and their upper condensation products and 6 "'thTl -' ,. 4-
 EMI43.11
 \
 EMI43.12
 i17C1 epoxycyclotexanocarboxylate.
 EMI43.13
 Other particularly interesting epoxies which little.
 EMI43.14
 to be used are in particular 9,10-epoxy-stearate of '3, -, pax3r..b¯mtby'cyclohexylmétyle, 9,10,11,12-di.épcxystésrts of, 1-epoxy-5methZrlcyc, ohexylmethylc, POX141 soybean oil, the

 <Desc / Clms Page number 44>

 
 EMI44.1
 J.-T1n11C7ClohexèD dioxide. and d1qclopentum dioxide.



  # '#> The proportions of POl) -IUI1n' and of po11'poX) '4th of No. 81l .. composition, * the selectable can vary between "A wide. $ Limits. In general, these components are used in proportions such that there is about 0.9 to 1.1 equivalents of Mine hindrance hydra per equivalent of epoxide. The present invention is contemplated. ge also the use of various fillers, pigments other
 EMI44.2
 imtiles or polyepoxides and epoxies known as curing catalysts in the usual amounts.

   The curable compositions can be made into resinous products. hard and infusible, for example by baking at 85 C for
2 hours, then at 150 C for 4 hours.



   The cures products are of interest * for the production of molded articles, coatings, laminates, cast articles, etc.



   <The following example illustrates the preparation of a hardened resinous product from an aromatic polyamine according to the invention and a polyepoxide, '-
 EMI44.3
 The pelyMiM used in this example is prepared by a process analogous to that described in Example 1, "the molar ratio 4n: Llînei fomaldehyde is 3il and 1 # bzz quant4 | é hydrochloric acid used oo = The catalyst is z 4 d <40 that which is used .. bzz f do equivalent dàlacdtylate: L = is that of active hydrogen. of ,, 1 "and the average molecular weight of 300 * The above pblyaaine (10., 22 s) and 24.995 s of Jv dioxide:

  'ylcyalohaxëae are mixed z, 4O-5O * C and introduced into four aluminum look-alikes. The compositions are cured at 100 ° C. for 3 hours, and mold No. 1 is removed from an oven,
 EMI44.4
 The trms <Mee Mussels are ÇbAuff4s at 160 * C for 3 hours and # &, 2,6 4; 9 # r. ' 2 is removed. The two remaining balls are, ### ,, heated to 200 ° C for 3 hours and mold # 3 is removed.

 <Desc / Clms Page number 45>

 
 EMI45.1
 
 EMI45.2
 



  't .. ", 4.ms..r ouït il ohautt' 1 2408C for 3 hours ... The down4.



  '. 8sscol, 93i-1) dt each 4 ..,. ohm t1llon ... t d'tera1ft ',. The. results are shown as c1-4..lIOu ...
 EMI45.3
 



  Sample, Duretd **.: # '57, &# ..' ## '' --53.

 

Claims (1)

EMI46.1 BI '1. DIe. & T 1 0. 8. EMI46.2 1.- Process for the preparation of aromatic polyamines, characterized in that an aldehyde is reacted with 1.5 to 10 moles. 4'un., Aromatic amine per mole of aldehyde at a temperature of at least 105 C in the presence of a protonic acid or an acid of EMI46.3 Lewis which .'bfdro1y .. in 18. *, To give an acid pl'Otcm1qu., The molar ratio of aromatic mine to proton1qu.4I acid or Lewis acid being between 20: 1 and 1000: 1. 2. A method according to claim 1, characterized 'in that the aromatic amine is aniline, chloroaniline or N- EMI46.4 rfthylanilin. #. - 3: - Method according to claim 1, characterized in EMI46.5 00 that the aromatic minine is an alkylated aniline in which the alkyl radical contains up to 12 carbon atoms. 4. A process according to either of the preceding claims', characterized in that the aldehyde is formalhyde. 5.- Process according to either of the claims * EMI46.6 ., juHta44eat * ea * aefcé> inl in that the acid has a j! (Ka equals 3adt''t-. riew to 3 in water .. \; EMI46.7 6 ..! ' Process according to one or the other of the preceding reverdiat 'characterized in that the atolar amine ratio aro MÎ EMI46.8 tiquetaldehyde is between 2: 1 and? si. \ 7. A method according to claim 6, characterized in that the molar ratio is between 3: 1 and 6: 1 8. A process according to either of the preceding claims, characterized in that the aromatic amine protonic acid or Lewis acid molar ratio is between 50 μl and EMI46.9 400810,. : x, "r 9.- Method according to claim 8, characterized i ;. EMI46.10 00 that the molar ratio is between 100 µl and 150 * 1. "'" #: - # 10.- A method according to either of the preceding claims' *', characterized in that the temperature is between 125 and 250 ° C. 3 "' <Desc / Clms Page number 47> EMI47.1 r J. 11. Process according to one or the other of the preceding claims, characterized in that the acid is hydrochloride- * Cjve or methane IUlton1QUe acid. 12.- Process for the preparation of aromatic polyamines, V c. COIIIII substance. described c1-4.sau. & "'0 y <f <y <oc <to one or the other of apl * 1 to 7.}, t' 13.- Aromatic polyamines, preysed by 1 procedure following one * or the other rtVtnd1at1ons 1 t 12. '"1'11: .. # 14.- Process for preparing polylOoy & nak' aro # aU" '! # "that, characterized in that a polyamine is reacted according to the method. claim 13, with phosgene. '## it 15.- Process according to claim 14. characterized in that the aromatic pulyamine is a condensation product of aniline or chlorotniline with formaldehyde. j.6.- Process for the preparation of aroalweed polyisocyanates, in substance as described above & "" 0 with reference to,! xeaple. 1 ....- 1: ": 19 .-. Aromatic poiyisoayaaates, prepared by 1 *: pa," ':: v & t1t either of claims 14. 16. -: #> -. r) :; 1 '; f e: 1'- ,,,,. '4 ...' 1 ".PJI4Ó" de ja <MMwe <teee! "e) t" sîftu'pifc r'u; r. a re'BMMique oJ.1 '* following the resell' Hi7 '> u least one ethylene oxide. :.,; ' ..., 1, - Prid according to 1 & claim 18, ... r..r1 "ta 1! '' 9''ty" '-a1kylQ, is 6i oxide,' 8Xt4. of propyli} 1 '9 i.1tpe .. iifT ,. S "'"' '.? ..t.!.? . , If '. 1Ó.14 'JIU'I8IIt la l' '' Gd1 ',, "18, characterized ta #F; t rl,% $ y4M al'OlI & U4u. Is a 4th cefxsoa t1d- product of & lIW1,! ,, 1U .n. with foraldehyde .. 1 (},;,; 51 "" "id $ of py4paraa of polyols, in S30stan.ee / | &# 4é5 | s | i | itB $ -4ef # u | é restrained auas exeanles 12 and 13. 1'tJi 4-ca ". ,,,. O t4'tne s 13. {" ft .6 ai1I! "). '1'41ôl., Pr ,, pa'é' * J! 71 1.; ' 1'0,44 'Itd, yut' "W1 '} ¯ &;' '>: * fe | l | 0! <? 4j * * in # cations 1 $ to. 'i' ... l 'r <Desc / Clms Page number 48> EMI48.1 qqm4 te 4 <Governed MttM # of fMttMM ca, 1WMA ..... \\\ '8 "l', CI '" \ 1ft aires a pali Aur ..... ) 6 "" \ \ IR polyol M'M'il perodi4adm pUt. \ .. '1 "" 4 \\ &'. ua peMeyasê tM **% Mt 4 ^. \., ". ,., .1 ". ' 1 & PQV dtia% 408 M, .., .. $ h "11. q X4 & ot4. .tttt "'4 ...? << ea 4'MW and / at- # ta $). . U ... "" fftM4. ' 4t 4 $$ MMea de rdii o de, .1.,. 1¯ .--, MM "" "t.QIlla ....". 1 \ '. I'I \ I 'IV ,. rsrss 1'- .. V.tH 4 '' ... <! e! <M t. 10. Ub 14 bed bed; 414,., 34% * 4 ta pripardes by 14 ".tMi 8d." \ * 1t. \ 1, "41 '' '.11 IR 1!: U ..' ftO.w. 48 4pa?% Ttea de pazyépowdnf and * ftlt r4ggir un po2.1'10114 .. ".... For .let <aMq 11i1vU \\ 1 & nvaeaea 3.). $ 4 ,. '100444 1,, 1 van t ia claim 1'1,' 1, .. fI ", II ru ei s .. '" "JOZ²'4t oonW-en' 2 or 3 trmes' lOar t1 ,,: ai. - P? <4 p'irit1on 4.? << iaw <po171 "J, M) & <<t9 * at 4fer" '\ o1-4.li \ lI rit4rente at "tX88," U. '39 .- a4 <M, o114pOqc1t1I, prepa, '., By the' J'ONU ....., 1 ... 3L'Mt? <Des ia 9 19.