CS248293B1 - Method of polyester production with small stress - Google Patents

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Cnocofi nojTjmeHHH cjioxhmx ποηη3Φηροβ c MajibíM HanpHJfceHneM 2522 £ I2_2E22222222_222SE2I £ 222i H3ofipeTeHne othochtch to cnoco6y nojiyneHHH cjiojkhux ποηη3Φηροβ c MajibíM hANP-xeHHeM, HME »MNX nmpoKHň TexHHnecKHH προφκηΒ πρΗΜβΗβΗΗΗ, oh Ballad HaňranpHMeHeHne b onranecKoň npoMbinineHHOc ™ b xaqecTBe οπτηηθοκη npo3panHbix no-JIHMepHblX φορΜΟΒΟΗΗΗΧ MaTepHajIOB, ΟΚ J J J J J J J J J py J py py py py py

XapaKTepHCTHKa H3BegTHbix_ TexHHyecKHX pgmeHHn: fliIH nOnyneHHH CJIOKHblX ΠΟΠΗ3φΗρθΒ (nojlH3CTepHblX 3φΗρθβ) H3BeCTHbI cnOCOfibl, OCHOBbIBK> meCH Ha n0jIHMepH3aiíHH ΟΠΗρΟΟρΤΟΒφκρΟΒ. OflHaKO HeflOCTaTKOM ΠρΗ3TOM aBjíaeTca to $ hto npHMeHeHHbie. οπΗροορτο3φπρω npe # CTaBjiHWT cofioň xpuc-TajijnmecKHe coegHHeHHH m noaTOMy hx mojkho nepepafioTaTb tojibko Bbíme tohkhnnaBJíeHHH. Ha βτογο b KaqecTBe flajibHeňmero HeflocTaTKa BbiTexaeT, ίτο neophyl-XOgHMO rtpH6aBJlHeMblň flJIH ΗΗΗΗΗΗρΟΒΗΗΗΗ nojMMepH3aUHH HHHUHaTOp ΠΡΗ 3THX ΤβΜ "nepaTypHbix ycjiOBHHX have πρΗΗΗΗΗβτ» CTafiHJiifHocTb NPN xpaHeHHH cMecn they may ΜβροΒ η τβΜ Cambio cjáiniKOM κοροτκΗβ BpeMeHa fljia TiepepafioTKH. flanbiue H3Bec-TeH cnocofi, npH κοτοροΜ TpHOKcaH HaxoflHT npHMeHeHne Kax coMonoMep h pacT-BopHTejifc fljia οήΗροορτο3φΗροΒ (naTeHT JP -65_3708; cp. h C.A. 63, 11732h {(1965)). OflnaKO Ηβηοοτβτοκ πρκ stom 3aKjnoHaeTCH b tom, ητο πρκ πομοπιη hc-nojibáoBaHHoró KaK KaTajra3aTop nojmMepH3anHH BFj-Et ^ O gocTHraeTCH jnmb bw-XOfl nojiHMepoB b 40%.

BnpóqeM b jiHTepaType H3BecTHbi flBa βπΗροορτοοφΗρβ cjiefly »me φορΜνπΗ:

Ch2 C / ° / c

CH 4 R 4 and R 1 R 4 H H b H CH 3 Cl CH; (iCH2 248293 2 KOTOpwe npH cHflapTHferx ycnoBHHX jkh / jkh (Liebigs Ann. Chem, 623, 183, (1959); J. Polytn. Sci., Polyro. Lett. 18, 1. 25, (1980)). 3φκρ and HMeeT Ηεοοετετοκ 'HTO oh upeaBbraaHHo γηγροοκοπηηημη, BcnencTBHeqero, KaK h3bectho, 3HawnTem> HO BO3MymaeTC «κητηοηηηη nojiHMepH33HHH c pac-KpbiTHeM UHKjia h tojibko bo3hhk3k> t nojiHMepbi HH3Koň MoneKynapHoň Maccw. CNHP-Ορτθ3φκρ b XOTH HBJIHeTCH npOCTO MaHHnyjIHpyeMblM, OflHaKO κβτηοηηηβ nOJlHMepH -3au HH c pacKpbiTHeM pHKjia co3flaeT npobjíeMbi ποτομυ, HTO BcjieflCTBne peaKTHB-hocth xjiopMerajihHoň rpynnbi npOHCXOflHT peaxuHH obpbiea neneft η περε3ετερΗφΗ-Kau, HH BCjieflCTBHe Nero Βθ3ΗΗΚ3ΐοτ tojibko ojmroMepbi, OKpameHHbie b xejiTbiňHBeT. ÍÍ3BGCTGH H ňajIBHeHinHH JKHflKHH εΠΗρθΟρτΟ3φπρ, nOJJHMGpH3yiMHHňca ΤερΜΗ-HGCKH- paflHajlBHblM Q ΚβΤΗΟΗΗΗΜ ΟΠΟΟΟβοΜ Η ΠρΗ KQTOpOM B BbllDG Η3 3Β3ΗΗθίί φθρ wash-R '/ R2 npaflCTaBjíeH rpynnoň -CH2 (JP πετεΗτ -121584-79; DE-OS No. 3,035,431) .OflHaKo b 3tom cjiynae cymecTBeHHMH HGflOCTaTok. AaKjnonaeTcn b that MTO NPE-BpaUIGHHG ΜΟΗΟΜερΟΒ ΠρΗ IIOJIHMepH3HnHH TOJIBKO ΟΗβΗΒ majli, T3K MTO HCnOjlh3O-BaHHG nojiyHBHHoro cjiojkhoio ποπΗ3φΗρ3 BQ3MOJKHO tojibko nocjie omhctkh nepe-ocaxneHHeM.

Bce H3BGCTHbie cnupoopTo3φκρω HMeiOT COBMeCTHbIH npH3Hax, MTO nOjmMGpHaaiJHHnpoHcxoflHTc ohghb MajibiMBbMHbM cxaTHGM (cyMMbi o6men ycaflKH C 0.5 flO M3KC <2%). BbI3BaH BblPIG OnHCHHHblMH H BbITBKaiOmHMH H3 φΗ3ΗΗεεΚΗΧ H XHMHMeCKHXCBoňcTB and Tara H3 ycnoBHň πρη ρεβκιρίΗ ΗεβοετετκεΜΗ, cymocTBeHHbiň Hefloc-T3TOK ypOBHft TGXHHKH 33KJH0HaeTCH Β TOM MTO Flo CHX ΠΟρ HGBO3MO3CHO 6bUIO TeXttHMeCKH HCnOJlb3OBaTb BaXHblň 3φφθΚΤ nOJIHM8pH3aiJHH C MajIblM OÓBGMHblM CMa-THGM ϋΠΗρθθρτθ3φΗρθΒ flJIH nOJiyHGHHH CJlOXHblX ΠΟίΙΗΒφΗρΟΒ C MajIblM XΠρίΒΚεΗΗεΜΗ HX ΠρΗΜβ ΗΘΗΗΗ B K3HGCTBG nOJJHMGpHblX φορΜΟΒΟΜΗΜΧ Ma TepnaJIOB HJIH KJIGGB. HGJIb H3OfípGTGHHH:

JlejIBlO, ηpe f3θ6ρεΤβΗΗΗ HBJIHeTCH npeOflOJieHHe HOflOCTaTKOB ypOBHS TeXHHKH.

B naCTHOCTH OHGHB MajlOe OfiBBMHOe CXaTOe ΠρΗ nOJIHMBpH3apHH εΠΗρΟΟρΤΟΒφΗρΟΒCJÍGflyGT TéXHHHGCKH HCHOJlB3OBaTB flJIH nOJiyHeHHH CJIOSKHBIX ΠΟΠΗ3φΗρθΒ C MajIblM • HanpHWeHHGM, npHHGM OflHOBpGMGHHO C.JIGflyGT 06eCneMHTb 6OJIbHiyi0 CTaSHJIBHOCTBnpH ΧρΗΗβΗΗΗ HCXOflHOH CMGCH MOHOM6pOB FLO HeKOTOpbIX HěflejIB H BO3MO3KHyM TBX B "HOjIOTHHeCKOM OTHOIUGHHH flOjiryW 3CH3H8CnOCO6H0CTB FIO 3 flHéň. KpOMG HT ΠρΗΧΟ “flHTca ycTpaHHTB floροεκοπΗΗΗοετΒ εηΗροορτθ3φΗρθΒ h flocTHHB nojiHoro npeBpa-meHHH MOHOMGpOB ΠρΗ OflHOBpGMBHHO BblCOKHX MOJTeKyjIHpHbtX MaCC3X. B COOTBGTCT “BHH C nejlbio nOJiynaeMblG CJlOMHbie Π0ΠΗ3φΗρΜ flOJDXHbl 6bITB nOjníOCTBIO 6ecyBeTHbIMHη οπτΗπεεκΗ npO3paMHHMH. H3JlO »GHHe CymHOCTH_H3O6gGTGHMH2 fljiH pGajiH3au; HH NEJM 3anaMa naHHoro Η3ο6ρετεΗΗ« - yKaeaTB cnocoC, πρ «πομο- íihh KOToporo BO3MOOTO noflBepraTB nojiHMGpH3aHHH npocTO MaKHnyjiHpyeMbie, CTa- 1ÓHjibHbie h jierKo nojryMaeMbie επκροορτοΒφΗρΜ o6pa3ya cjioxhmg ποβηβΦηρμ MajibíMHanpaweHHGM C.

CornacHO Η3θ6ρετεΗΗΚ »aaflaqa pemaeTCH cboco6óm nojiyneHHH cjioambix ποιπϊβΦηροβC MajIblM HanpHXeHHeM H3 εΠΗρθθρΤΟ3φκρθΒ, OTJTHHaiOnpiMCH TGM MTO SyTHpOJiaKTOHH H3O6yTHΙΙΓJIHUHnOBblfí 3φΗΡ B MOJIBHOM COOTHOmGHHH 1 S 1 Flo 2f 1 B TBTpaXJTOpMGTa" hg b KanecTBe pacTBopHTGna πρκ 30eC Β τεπβΗΗβ 5 qacoB b npHcyTCTBHH BFyEt ^ ble KanecTBe KaTajra3aTopa npGBpa®a »T επκροορτο3φΗρ 2-H3o6yTHJioKCHMGTHn - 1.4.6-TpHOKca-cnHpo- [4.4] -HOHaH. llojiytieHHblft TaKHM O6pa3OM 2-H3O6YTHJIOKCH “MGTHJI-1 .4.6-TpHOKca-cnHpo- [4.4] - HOHaH flajiBine cornacHO θ3θ6ρετεκΗΐο ποηΗΜερκ-syeTca WPC 08G / 234816-5 2,2-6hc- (1,4,6-TpnoKca-cnnpo- [4.AJ-h-HaH-2-β-bicyclic) -nponaHa b npucyrcTBHH Et} O + SbCl-b KOjinnecTBe c 1 Bec. % P; 3 Bec.% othochtgjibho KojnmecTBa cnupoopTOBíJiHpa npn 80 π, ο 100 DEG C. b Te4e-HHE 6 no 8 qacoB, linden one hundred meters cnoco6e cornacno n3o6peTeHwo fiocraraeTCH CTA-BHJIhHOCTh NPN ΧρβΗβΗΚΗ HCXOflHOň CMeCH MOHOMepOB, COCTaBJIHHMuaH ΗβΚΟ TOpbieHeflenu, 6ea toro , uTGM BCTpenajmcb BbineneHHH KpHCTannoB hih flpyrne noMyT-HeHHHj JxxoflHbie MOHOMepbi h cMecn MOHOMepOB He rnrpocKonnHHbi. Wn3Hecnoco6-HocTb HcxoflHOň CMeCH nojinMepn3aijnH cocTaBJíaeT Gojihwe 72 nacoB, BpeMH rene-o6pa3OBaHH «NPH 100G BCE EME okojio 1 qaca, IIojiHMepH3 aipin προΗοχορ, ΗΤ npnnOJIHOM npeBpaníGHHH MOHOMepOB Η ΠρΗΒΟβΗΤ K BblCOKHM MQneRynHpHbtM MaccaMCJ10» HbIX Π0ΠΗ3φΗρ0Β, KOTOpbie ΚρΟΜβ ΤΟΓΟ nojIHOCThlO GeCUBeTHbl Η ΟΠΤΜΗβΟΚΗnpo3paHHM . OG ^ ee o6f> eMHoe CXAM Bo apeMH rejieo6pa30BaHHH η οπιηβθηηη 3a-b BHCtoMOCTH OT COOTHOmeHHň ΚΟΜΠΟΗβΗΤΟΒ CMeCH MOHOMepOB COCTaBJIHeT 1 Flo 1.6% nonyneHHbie thkhm ofípaaoM cnoatHbie ποπηβΦηρμ ημθιοτ Mano HanpaaceHHe h ohhthGkh b nmpoKoň oGnacra TeMnepaTyp. Ohh HenyBCTBHTenbHb κ o6pa30BaHHio mhk-pOTpemHH h ycToňnHBbi κ pe3KOMy H3MeHeHHro TeMnepaTypbi, Hanp, b oGnacra c-40 ° G o + 80 ° C

OriTHHecKHe fleTaroi H3 cTexna, cKneeHHbie πρκ noMonpt cnocoGa cornacHO H3o6pe-TeHHto, Ka * k jihh3H, nnocKHe nnacTHHbi h nonoGHbie onranecKHe fleTajiH npH com-HaTHoft TeMnepaType MexaHHUecKH HepashteMHbi. B cnynae HeoGxonHMoera hx mojkhopa3fceflHHHTh HarpeBaHHeM n ° 150 C b TeneHHe HecKOjibKHX MHHyT ηπη oGpaGoTKOHΚΗΠΗΒΙΗΜ ΧίΙΟροφορΜΟΜ. ”IIpUMepM KOHKpeTHOrO BbinonHeHHH1

HaoGpeTeHHe nonpoGnee noncHneTCH πρκ πομοπιη cnenywmHX npHMepoa κοΗκρετΗο-ΓΟ BbinOJTHeHHH. ΠρΗΜβρ 1. 172 r (2 mojih) GyraponaKTOH pacTBOpniOT b 600 mji TeTpaxnopMeTaH cMenm-BawT c 6 mji BF? Et40. ΠρΗ nepeMemHsaHHH floSaBnaioT well xanjiHM 260 r (2 Monbat) H306yTHJirjIHlWJ0B0r0 θφκρβ ΠρΗ B 30 C 2 ΤβΗβΗΗβ Hacoba, 3βΤβΜ flaiOT BO3MOJK "HocTb flonojiHHTenbHoň peaKUHH b TeueHHe 3 uacoB CMemHBaiOT c h np 300 10% NaOH -nor ívih τογο, htoGm pa3pymHTb xaTajiH3aTop,

OpraHHMecKyw φββγ οτηβΠΗίοτ, cymaT c K2G03 h flHCTHJumpyioT. CHanana ynanaioTpacTBopHTejib, ποτομ ocTaTOK φpaκ ^ HOHHpywτ b BaxyyMe. nonynawT 250 r cnnpo-ορτθ3φπρβ 2-H3o6yTHjiOKCHMeTHji-1,4,6-TpHOKca-cnHpo- [4.4] -HOHaH b xanecTBenpo3paqn xhakocth. 72 ° C 74 ° C / 33 ° C = 1.4438; p10 = c 1.0383 r · cm cm5 C «H20O () 4BbWHcjieHo: C 61.09% H 9.32% (216.24) Hanone: C 60.93% H 9.39%

OflHHaKOBbie pe3yjibTaTbi nojiynaioTca h npn Hcnonb3OBaHHH 130 r (1 mojib) hso-GyTHJirjlHUHnOBOrO 3φΗρΒ,

B 10 r 2 -H 6 O 6 Y thiOCHCH 2 MeHi 1 -1.4.6-TpHOKca-cHpo- [4,4j-HOHaHa npH 40 ρ, 50 50 ° CnpH nepeMeiuHBaHHH pacTBopaioT. 0.1 EtjO r 'sbcl, 3τβ roTOBaa κ ynoTpeGneHHioHcxo / Jhana cMecb nojiHMepH3an HH b 3axpbiTOM cocyne cnocoGHa κ πρημθηθηημ 3 ηΗΗh nojiHMepMsyeTCH NPRI 100C TeneHHe b 8 b nacóB 33κρητομ Φορμοβοηηομ cocynehjih KHK KJieeBoíí cNon = Me »NY onrayecKHMH fleTajwMH o6pa3yn GeciíBerabiň, onra-MecKH npo3panHbi cnoxHbiň ποηποφηρ c HanpnweHHeM oGmeň φopMyπbI (-CHj-CH 1 -CH 3 -CH-CH-CH 3 -O) - / 0 CH, O-CH 3 -CH 2 CH 2, * * 248293 4 rp, en = 10 after 15 h ofimaa oGbeMHaa and yca1a cocTaBaiaeT 1.6%.

CTeKjioBaHHH (T8) cnoiHor.o nojin9 <i> npa cocTaBJiaeT -35 C, ero πηττακτbβ - p2 ° = 1.055 r · cm.. ngHMeg_2

PacŤBop 20.506 r (0.04 Mojib) 2.2-6hc- (1 .4.6-TpnoKca-cnnpo- [4.4] -ηοη8η-2 - MeTHjioKCH (beHHJi) -nponaHa - nonyneHHoro no DD-WP C 08G / 234816- 5 - b 25,95 r (0,12 MOjib) 2-H3o6yTHJioKCHMeTHJi-1 .4.6-TpHOKca-cnnpo- [4.4] -HOHaHa - nonyneH * Horo KaK yKaaaHo b npHMepe 1 - CMeraHBaioT c 0,75 r Et} . íÍHHixuaToppacTBopaioT NPH 40.flo 50 ° C h h nepeMeniHBaHHH HcxoflHaH cMecb nonHMepH3auHHJOKpaiueHHaa b ^ η ejiTbiň, Ββτ, KOTopaa πρκ κομη3τηοη teMnepaType b 3εκρ «τοΜ what e-tsa # coxpaMeT cnocofíHocrb κ npuMeHeHHW b Tenemie HecKonbKHX flHeň, 3aTeMnonnMepH3yeTCH NPH 100C b Tepejme 6 nacOB b 33κρμτομ φορΜΟΒΟΗΗΟΜ Coca-eHnu Kax KJieeBOň cNon = MexKfly οπτΗηεοκκΜΗ fleraňaMH. Bo3HHKHyTbiň cnoacHbiň nojiH-ΟφΗρ - fíeCUBeTHbIH Η OnTHHéCKH npO3paHHbIH. IljIOTHOCTb COCTaBJÍHeT p10 = 1.117 r · cm-i. O6ntaa oSbeMHaa YCA ^ Ka bo BpeMH npouecca nonHMepH3anHH coc -TaBJíaeT 0K0.n0 1%. $ OpMyna_H3o6geTeHHa

Cnoco6 nonyneHHH cnoatHbix ποπΗ3φΗροΒ c MajibíM HanpnxceHHeM H3 οπκροορτο3φΗροΒ, OTnunaEiinHHCH τθμ, ητο npeepamaroT SyraponaKTOH h Η3ο6γτΗπΓΠΗφί # θΒΜΗ 3φκρ bMonbHOM cooTHomeHHH lil p; about 2: 1 b TeTpaxnopMeTane b KanecTBe pacTBOpuTenHπρκ 30 * 0 b TeneHne 5 ňacoB b npHcyTCTBHH BFJ / EtjO b KanecTBe KaTanH3aTOpah Tax nonyneHHbif 2n3o6yTH.noKCHMeTH.nl .4.6-TpnoKca-cnnpo- [4.4] -ηοηθη ποπη-MepH3yeTCH ηπη ο ^ ηη ηπη c. -TpHOKCa-cnHpO- [4.4 ^ -ΗΟΗ3Η-2-ΜβΤΗηθΚΟΗφβΗΗη] -PρθΠ3Η3 BnpHcyTCTBHH Et ^ O ^ SbClg b CoBe c 1 Bec.% By 3 Bec. nacOB,

AHHOTan, KH

Cnoco6 nonyneHHB cnoxHbix ποπηβΦηροβ c ManbiM HanpHaceHHeM. Uenb Η3θ6ρετεΗΗΗ -TexHHnecKH Hcnonb3OBaTb oneHb Mano oCteMKoe cxaTHe επΗροορτοοφΗροΒ flnanonyneHHn CNO «Hbix ποηΗ3φκροΒ c ManbW HanpH» ehhe H36eraa κεηοετετκοΒ πρκH3BecTHbJX FLO CHX ΠΟρ ΠΟΠΗΜερΗ33Ι (ΗΗΧ 0ΠΗρθθρΤΟ3φΗρθΒ. 3aflana - yKa3aTb cnoco6, NPH nomon κοτοροΓ.ο bO3mo®ho NO / jBepraTb nonHMepn-3auHH προοτο MaHHnynHpyeMbie, CTa6HnbHbie h sockeye nonynaeMbie οπΗροορτο3φΗρωo6pa3yn cnoxHbie ποηκΒφΗρΜ c ManbíM HanpaxeHHeM pemaeTca τβΜ, ητο 2-H3o6yTHn OKCHMeTHn-1,4.6-TprtOKca-criHpo- [4.4] -HOHaH, nonyneHHbiň H3 6yTHponaKTOHa hH3o6yTHnrnHu; HflOBoro Βφκρε, nonHMěpH3yeTCH ηπη ο «ηη ηπη, c floneň 30 μοπβ-HblX npOHeHTÓB 2,2-6hC- (1 .4.6-TpHOKCa-cnHpO- [4.4] -ΗΟΗέΗ-2-ΜβΤΗΠΟΚΟΗφβΗΗπ) -nponaHa b npHcyTCTBHH EtsO + SbClg. IIonyneHHbie cornacHO ΠρΗΜΘΗβΗΗβ B OIJTHHeCKOň Πρθ ΜΜΙΠΠ6ΗΗΟΟΤΗ B KaHeCTBeonranecKH npo3panHbix nojiHMepHbix φορΜΟΒΟΗΗΗΧ MaTepHHjiOB, npeuH3HOHHoro Kneaηπη b Boar Tne cTpyKTypHbix KneeB. IIpH3HaHO Η3θ6ρβΤβΗΗβΜ ΠΟ pe3ynhTaTaM 3KCnepTH3Wt OCymeCTBneHHOň BeflOMCTBOMno p; Enami Η3θ6ρβτεΗΗϋ naTeHTOB PFLP h. 248293

Claims (1)

SUMMARY OF THE INVENTION A process for producing low-tension spiroorto-ester polyesters by reacting butyro-lactone and isobutylglycide ester in a 1: 1 to 2: 1 molar ratio in carbon tetrachloride as the solvent at 30 ° C for 5 hours. hours in the presence of BP. Et 2 O as a catalyst, and the resulting 2-isobutyloximethyl-1,4,6-trioxa-spiro- (4,4) -nonane is polymerized either alone or with up to 30 mol% of the 2,2-bis- 1, 4,6-trioxa-spiro- (4,4) -nonane-2-methyloxiphenyl / propane in the presence of Et2 O + SbCl3 in an amount of 1% by weight. % to 3 wt. relative to spiroortester, at 80 to 100 ° C for 6 to 8 hours.