SG187335A1

SG187335A1 - Method for preparing amino-terminated polyether

Info

Publication number: SG187335A1
Application number: SG2012050605A
Authority: SG
Inventors: Zheng Chu; Junxiu Yuan; Dongmei Xu; Kang Wang; Gang Jin
Original assignee: China Petrochemical Corp; Nanjing Chem Ind Co Res Inst
Priority date: 2011-07-07
Filing date: 2012-07-06
Publication date: 2013-02-28
Also published as: CN102408559A

Description

Co LE EB we RR EE See Ly Lo CL Tins Ti ee Tn

LL CL Soe LT "Method for Preparing Amino-Terminated Polyether ST he

Coe Field of thie Invention CL en Ded TT Tan TE

Co 0 Ln NU The:present invention’ pertains to. macromolecular material field, and relatestoa oo. N eS Els "method for preparing arhjno-teiminated polyether. | Se COR . sn E Go “wo _-is.. Background of theInvention: ~. Loti fcc 0 ee

SoLnER TE Amino-terminated polyether is a sort of. polymers with flexible polyether skeleton i 7 371 and terminated with amiiio; most of which are obtained from relevant polyether glycols 0

EP 10 - through chemical treatmeént-of terminal hydroxyl.” . Amiino-terminated-polyether-can be Cire Ta

Pel7 hu categorizéd into aromatic polyether and aliphatic polyether. depending onithie structure oT vi of hydrocarbyl bonded to the termifial amino... At present, amino-terminated polyether + = - an SL Lis mainly used as curing agent of epoxy, resin, and a'raw material for adhesive, il Le Geel

LT Ln “2:2, polyurethane; and spray polyurea elastomer, (SPUA), and’is' widely applied in corrosion Cae

CT 1s Se protection; pipeline; building. ship, water. conservancy, transportation, mechinery; ee oo - ~ Le mining industries and wearing field. } "Up'to now. there are'mainly three methods for cio. oo

LT CL LL - synthesizing amin6-terminated polyether, i.e i catalytic reductive amination method, ss LT oo leo The catalytic reductive amination method deals withthe terminal hydroxylof, . <i Tl

Lend “i920 * - polyether glycol, and replaces the terminal hydroxyl. with amino by-ammionolysis. “Thee. no

LoL sr co ‘catalytic feductive amination method should be performed at high temperature and high i een

CC - 3 i» ~ T pressure: the equipment investment and operating cost is'High, and the catalyst EE TEI o hn - EA preparation procedure is complex. A high pressure reduction amination‘miethod is UE

Co no a _ mainly. used in industrial production in foreign countries... EEE FEE :

LT cleaving grow mefod mainly comprises phosgen method: salon chloride

TLC method, and halogenation method, etc. A'drawback of amit terminated polyether, © Se ce x g : a : | synthesized by, leaving group method is that the rai material can ot be ayailable easily : : | see rE "tis". during reaction. in the post-trsatiment of ihe product, a large amount of alkali sn -

CU ried weal the acid benrated fn he action. and gran del of morgane al will be genefated and Raid 6 sepa, asa tren moto polar hel and then ns amg terminated postr fresh ©

TT appropriate weatment, This thethod Hasa sible pidegss route, but there are many side: ©

BT veacions in th proces of rection béwasn poly ter hol and arson nC en - : ; . addition, acrylonitrile teids fo elf-polymerize; and thereby has stringent requirement - ; ~ : Se - i : 15 for the reaction conditions. Therefore, cyanogen alkylation method is difficult to oo 2 ; ) a = $7 = RR ) " Hereinafter some references involving Syiniiesis of amino-terminated polyether. wil ne - . ert 36 widfanctionial polyether with a molecular mass of 5,000 of bicfuntional polyether witha ©.

B en wl ) molecular mass of 2.000 iri the presence of hydrogetr. _. The catalyst.used ir the method : 3 a J oo Se

SE 2 . * pon-erystiling diloy catalysts” The non-crystalline alloy Gatdlyst used in the meihiod nL Se ny comprises Nin content of 40-50% AL ng conten of 40-50%, snd canst - : | ; - - - - | promoter element M no mors than10% tops whéréin Mis one or more selected” : “ . : - ~ ~ -

Jn - y : : i is rom Mo, La; Cr, and Mn” a - 7 I ) ) Sl ~ i BE = rn — no ; E -

STE In this method, chorine-termirated adduct iS produced by first reacting a oligomer of

LE oo - - hydroxy! compound (with a molecu thas of no Ks than 92) with epichlorohydrir, Cd y i 0 and ther the polyetheraminie is obtained by reacting the resulted chloriné-trminated © © 1.

SE CNIO1S22607A disclosed a method for preparing polyeineramine with a formula of +“ “i i oo i : RUNRR), wherein A is a iteger in aang of 120. Ry i an organic group having - . - . - ; o ; o Lh - - 2-600 oxy-alkylene groups: Riad R can be identical or differént, representing al 5 KE Lo : . ES, Ey ON1019213924 disclosed a method for preparing poiyetheraming, in whick, Ln rE rn : Cl - polyether with different Hioecular mass is polymerized from cthylere oxide, propylene Lo y ~ : - 5 Lo “oxide. of mixture of then; sexe, polyether nitrile is Obtained by reacting the polyethers 3 C ol : E wo : n USA618717 disclosed amethod for preparing privy afi hm oxyethylene” o - - : Ea

LT iyo monoalkyl ether The catalyst used ithe method comprises S090wtof Ni i . , - IE | - } * chromium oxide, ro xi, tai oxide, efeprium oxide. thoriuin oxide - : - p = - ) i N a : | . } A p - olyosyalkylene aldafiolor polio faving a molécular mass of 230-5000 and ammonia : a ; - oo

Cs inthe presence of hidvogen: The catalyst used n the method isa supporied catalyst, © © OseiikMo supporied on the support wherein th ft ore volute of he alumina on Eo ~ measured by nitrogen desorption method 7021 10A; the total active metals supported” al i " a0. onthe supp account for 10-40% GF the catalyst and the -aumina aeons forat + coming comac dry mind plete ings molecular mass foes + - - . ils, catalyst in the condition of free of water The catalyst comp ses 60-75% TN and a 7 - a0 of metalic duminum, The escion is performed acd emperatareof TC ; - = i . ~ . - - F US3003107 discldsed a method for preparing poly(oxytetramethyléie) diamine by oo ~ i | vo | ~

CL reing ammoniation rein of poly (xsueraetylene) glycol nthe presence Of amine tt sltn mosmaoh gong etn and Mo contained nan oxyeen- fre support. wherein, the coment of Ni fs T0Twsh: : ns ol . Ra wits: The reaction is performed at at mperature of 150~220°C an i ap roti cof ov : - } - ) oo : - oe : a 00~10.000psie tie ratio berieer amonia and polyether alcohol is 10-15071 nd the Ge . -

Soe Bn Son sete ae

} . PASS “ratio between hydroien and polyethicr Alcohol is 05:80:15 he resultant mixtire po the” - Lo Lo . - oo : EE 3 " renition; a separsted by, fractionation. “Polytetrahydrofuran haying amolecili mass of i B ’

TT 1000 or 2000 inated n'a continous tbl redio. he conversion ca be 91-96%: bata Vo str mesa 00 itn ahs = 2 ©

Te retort gorgrson iemly Te. TE Le

SUT Uses disclosed a method for preparing polyetieramine by ammonalysis of

Lh polvethdraiyeol inthe presence of Raney nickel cada in anhydrous ethaiol or

ST conversion of polvether glycol is 4006. rah TL Tl TT

ET Goings bilan actor with Cielohéate as thé solvent. The catalyst used in the. ~~ 0, <1

SE Co : is ethod is prepared with coprecipitation mefhod: and comprises 75wi%% of Ni, 331% : En - 8 | Lo ax i ou eo 210 ke Ga his : : so ee . i la i | . oo vo Cn] » ; oS oo TY - DE1643436 discidsed a method for preparii polyoxyalkylend amine from the “ - Se

TUT omespbnding alcohol i ihe preseiice of Ni-Cu-Cr catalyit. The catalyit used inthe © ( -.

La method Compras GOES mak of NE 14-37 of Ci snd Smoltar Cy = Lo “corresponding aldo in the preséice of Ni-AlMo catalyst “The catalyst used in he a . oo

TS TR Te a ES rE

LT DRsaN00 discos a method fr preparing amie fo th comesponding alcorol.

LT Caloutaied by oxide: th epalystused inthe method comprises 20-85% of Zr, 150% of, | ©

TL Cu3070% FN 01-5% or MO and 0:10% of Alor Mn. Le

LT ne DEI953263 disclosed a method for preparing amine fro the corresponding alcohol...

B = ; - Si, The catalyst used in the method comprises 70-95% of Co and Ni, 5:30% of Cit. wheéit, * ~ ) Sn ) ’ - Zl | : ah ol the weight ratio 5 Co anid Ni is from 4:1 10 Ta 2 i iy : : ; ; fi i Se : a . -

CEL DEIORIID disclosed a miethod for preparing amine fri alcolistor aldehyde. ©, LL

J - Pa “ ve «The catalystused in the néthod is composed GNI. Cu. antl Sn ¢alkulated by oxide; the - or ; = . . pr : ger i cdient of zrs 22:40% the coriert of Cu i$ 1 30%: the content OENi i] 5.50%. and” Et - Pp : } T ~ a a i 10° : “th et ontent of Co 1s: 30% A 33 & g S < cE nL : . ~ ; i“ . ; 3 - “ ~ : . ; . . - Jf - Summary of th fiver ie a ie ’ i 2 - Ba : 3 ; : al = g =

TTT he hed of the present invention is 1 provide d netfiod for preparing <r

CET ing terminated polyether by catalytic reductive amination method; 1 v0 sn he present invention provides a method for preparing amino-terminated polyether 1

EE 3 - 2 : SE by. catalytic reductive amination of polyether glycol in the présence of hydrogen, at least: Co Lo

IE Ee tt ina peat sito apni " = ES Co - sistigeaig tie fog isturs, rémoving water, resid li pen, Woe oo - oo

EEL ~ : oe oF low-bailing by-products from the reaction mixture by reduced pressure distillation, so as El : o =

CH whersithe amount of the Rinéy ick cays is 2-150 of the amount ofthe 7

EET gigeol by moe and the amount of hydroge is 04-1 tines of the aiount of hydrésyd 1

CE mse ena bm ps ncn

Ser conducted at a femperaiuré is. 120-250°C and a pressure of 8-35MPa (preferably FCT

LE Lo . — 820MPa) tor pe od uration of | sis ¥ = | i Ce 7 Lo : pe ov E i he ihe Raney riokel catalyst comprises NivAl and eal Mi: based.on the foal weight.

CL ofthecaalystand calculi belt th cortent of Nis in’ range of 09504, . : - 0 L the cantent of Als im range'of 5-20wi%. dnd the content of meal Mis W ; range of : x EE

Co 0.5% and the metal M is one, two; o thre selected from Cr, Fe, Cu and Zn © + C

TA onder to rther improve the conversion Of rw mserial the metal M preferably ©. LT in ai Ba = : Comprises Zn aid one or tw Selected rom Cr, Fe, and Cu . More reierabiy: based i 2 w co - i - a a - ihe total weight ofthe metal Vind dleulated by element, the conte of Ziising Le | Lo - ¥ : - } a i : : ane at 000% and the for al content of Cr. Fe and Ca i ; in a rage 0 ; 30- 7 ov 7 3 i : : - | A ell morrefeably, based on th fol eghtof the metal M and clclaedby

TT cmon 2 i ge $5000, te end

CG sina mange of 30Sbwine: Tt LT

CTT Usually; the Raney nickel catalyst in the preset invention may be prepared by the ©" gh 20 method Comprising hedfllo ing. stop < : | Si Ee 5 i TE = 3 4 ) ig ; © ing ar tempers of 45-100°C fora period drain of 055h, dis ©

LT eal onde hing rege S100 dpe aion

Se br TF ee Te a Cat, ST BL ra al Se Ta LL TRIAGE um a Lh aT TL te Ee RETR AT Rae Cm TL BR > vel DFE fii ED PT Tr ge GL Ta ETE Sah. CATE Ma SE

Ce IR LT aE eT TR ere 0 a Tp LTTE a TY eT ta i Te ne TI TT Te Ee IA

CE nell ET TT I ET Te Ln TE LT UE ET LETT ee LT i he TE pA i eT SR a an Dl AT ILE ne le NT MET a TT ns nT ee an

Arnab DAR SEE i BR De RA, ET a0 ee Ee

Ege ALI nT pe TE RRR RR te i A I De anh

LT Ee eT Le TL ES EE TE Te Ge Be ee pT Tl SE a WERE SRE Ge Te

Sage Lenleael 907 Lr 0f0:525h to activate: wherein the: Concentration of sodiim hydroXide is 0=40wt%, > a 7nd #557

CNTR Te TO nN Ee IT RT se ee TEE Tn Te Ts eT

Ema TT es the amount of sodiumthydroxide: is 123 times of the weight of the-alloy powder: ».3. 5 27min

Pepe pT BN La ag a a te EE LT ah Te ET BT Sed J Ee en

Een Tb) standing the mixture obtained by step (1) to separat€ theisupernatant white 50H au EeE Da coer ne oe flocculate iwashing black precipitate with warm water for several times £07. en TE 0th

Gn Te eT TL pe Van Ne Te LT LT pa TRE TI ey a Te

SA SSE neutrality, and then: washing with anhydrous ethanol: for 2-5 times:to obtain Raney. ELT pe TN VL SI RR I Se ae

SER hes Be oe i niCkel-catalyst: next storing the Raney: nickel, catalystin-anhydrous ethanol.x. «7c bes 00s

ST Ee TD Ee Ly TT ee SR Le ET a SE ee eT sh ene a

JE eee Banani te # The alloy powder comprises Ni, Aland metal M. “wherein: the-metal.M: is:0n€, two = 5 il

Coase Ee ee TL A rE EY Et a TE ED TA Arete ey CE ee an eh Te en TS RT Te eB Te Se IT LL EE ET

AR LE AA nd TR TR a gt TE i RE tbe etn DT

CU nT of thie seléeted from CF: FerCuand Zn. % Preferably; the. metal M.cofmprises Znand' “+ = 500 - ae Ia LE PA Wt A y i Ea H : i IK hy ta = SE JRE 2 EE En Te #5 Ta - = o : aE ern Ct . al Hh : To at i

PRE LT TA EL eR a Ree aly RT TT MR Re eT DE i Tl ne “ana RA Toner two selected from. CriFe..and Cu, The composition of the alloy powder canbe; - © ii Tem

HI RR I SD ee a on EE TE ey

Cig + 105 So determined:as-appropridte according:to'the composition‘of the Ranéy.nickel catalyst as. =. = wo 20,

Ta hentioned above,” A persbriskilledif the art Gan select dnd control the composition of, x, «1

Shp te eethielalloy powder with the common knowledge'in the-artito ensure the finally. obtained." FE nn

SU Een. a Raney nickel catalyst comply. with thelcomposition mentioned above. - erat rs Dn a a aT

Se ETL EU pet IT eT a el Tp Se he Tn ne Ta Te a TTT ae TT RE a eT

DETR ET SE Sen Te i Rel LL Eh ay ee Se se ST en Te a TE ae Da Tee

Lage omega dn the'method according to the presentiinvention: the poly@thier glycol'has the = 177 n gs wr 08

San ae Dy se el Se AE A eR

Shel eee 5: following general structural formula (a)-ori(b): sR sR0 ET sla eR a8 Natale sts eT pn AE TT ee SD AE rg pe REE BI LB Rh ee Tn

Em NET Le al pi peg ee CSET ET TE ol Se I en eS re a Ty

Sp een ET CR ep ES SL LT SS ay Sg Tas Te Le Te SE

SET ee a Tes PR Th SEIT RRR Se ae pI TU en RR i nO em Re

Sl Tale, Le Ein formula (a)RieRirand Ri are, independently:selected from linear or branched. - ne 0

CRE a ey Le TT Nn ST TT TY RE TE pn ERTS CR A Dn IR ET SR BT AY “lL Fesegs divalent aliphatic groups with. 2:4; carbon-atoms;(¢-g:: linear of branched alkylene: ivi em = 7 nl

LF RE groups with 224 carbon atoms) mis 0:11 57 preferably 2990: n is,0- 115; preferably 2-90: 5.5, 5 TRS

Ee eA an en RT ae HR IE ET Tre a VE ah nT a Tn Ben Fe

Lass F720 =: and the sumfofim and:n is J=1 155 preferably. 2-90 =x". Lg. Zr Fea sn tama er Tene Tap TS TE

CLUE sn Lag Ge SE i Ce TL her Se Se pi er DR RD

SE IE a Se Tp BAS EE A re fg ER eT Ee LT nn

PTT nt LT TE Se GE Te Re AY A TAT RR TR Le

SIRI lrg SVT SETS ens a CAH eR SE TT pe LE sen Tae en TE eT Pe

CLT ETRE NE TT EA Se BO eT TE ee JT TR Ie nee TI en es RT lA LT A snr BR nT en NE SE Np te Ta aT Te de TE ge rE ET RR I ee Re Nn TT AE TL TE ee

BE LE aL nT Ta TRI es TN a Ee TTR RI TER DT ST Sa ee Tg Ne St Sed

CEL EEN DO en TY EE ARSE RE eB I en TR a TT ae

Ce SEI Tat TR TIT TT hy a TT er Sg TD ATR Th Te Td Ea Se a FAR BE a Te Ae ey

A Ln TL Ta TT ER Tn Te TR, Se nea TI Ts ER Tr La A Te a

Tig Ta nl ren ee CR RT A ET TF ER LR ee TR

Fede my en a, EE tp Mg Le Re TE RT pn 0s ee De TR a

CR UTR TD EE et nF TT I SU TTT a ae Pan Er mp ETI On Tan nT ul pt mee TI Te ng SLES a

~ . i J ) : et i Cy vo Lo : ; Ra > : Co - = BR i. : - . ne : oi . : - in formula (b). R is selected from hydrogef and linear or branched aliphatic groups - . - i y . tmnt 1 hoon sm ott aa . | E . 5 : | R; and R; ars rdeendéntly selesiei rou fnegr or petit dbvalgar lpi groups ~ : ; Si =: - . - 7 : Sr se Raving 2-4 carbon toms (e.&, fnéar or brarichied alkylene groups having 24 carbén : : - : : - i

CT TE tone mis 0.40, preferably 1-30: 1 is 0-40; preferably 1-30; and the sumiofin dad nis «Ho

Ll ne metho according to he present invenion, the tained sminosermimaed on = N ~ Ea polyether has the following gerieral sitiral formula (¢) or (d): To Fo a

I mt ee ip he bi } . oe 25 {groups with 224 casbon ngs); Ri and RG are identical of different and are . Co 5 } B ol }

Ce independent selected fom hydrogen and liner or branched alpha groups having © ie on aris it pi ts seen os 1

ET TEE i i ei atm ot

- ; ns Ce : : : - | | oo te - ) 1 ri . vl i - wi - > SE : or i

Cle a pretend SSR a ee DE

Cae eT le RE ee Le

A rs—forgfordn Ce ET se TI

Ce | ord BARGE Te pe en = oo - . wl ) in formula () R'is selected from hydrogen and lincar or branched aliphatic groups . St 5

CU Re an dependents sold on inst obra gilnalphic rps

TS having 2:4 carbon atts e.g. Tinear or branched alkylene giotips having 2:4 carbon + ©1111 wR ol aid re ly led

Ln drogen and linear or branched aliphatic groups having 1-6 carbon atoms (e.g Jinear - ‘ oo : ¥ 3 : or branched alkyl groups having 1:6 carbon ators): in 50-40, preferably 1-30: 0 is. ” :

Lo | ) - ¥ 0, - In the method according 60 the present invention; the amiiating agent can be any oT Lo : - ) :

CA ondary aang agen the ar. fof Sample, the aminati agent can be selected

C0 mom ammonia Gach as moni gs indir ammonia ur) aliphatic amine and “7 >, Cn < 1 “alicyclic imine. Preferably, the anirading agént is selected from ammonia ws ! : wd 7” Ce aliphatic amie (such as aliphatic arine faving. 1-10 carbon ators) and alicyclic —— = Cel ti : ‘ - Tie he selected from methy amie, diricthylamine, éth3 mine, diethylamine, i on - = to - E *n-propylamine, dip-propylaminé, sdpropylamine, diisopropylamine. hexylarmine (such I wl -

UL seine dn The catalyte redive amination reaction can also conducted ina

Co SIRE ne EE ET en ETT

AT Gondifion of absent from a solvent. view of simplicity, catalytic reductive amination, © 7 1." eons pel conti i cndion of sb foment

ST hydrogen added to the reactor Gan be controlled by-regulating the pressure of hydrogen + ©

Ee RI Se

Mba ne

Lo pressure distillation may be 100-120°C and the vacuim degre may boinarangeof | 0 co mesa tide CS Te

C0 nthe mtd according fo he présent inyention: te reactor cin b'ang corninon ©

TUT elon nthe ar, Preferably. the réctor fs a simed reactor + wooo he method sccdin to ths pisent invention. the Rey nickel catalyst andthe 1 © inating agent in be recycled and reused after uation: furthemord, the method ++ op To according fo he present inventory achieve advantages oF high product selectivity, high 1k conversion of aw material asy postirebmens; and loser environmental polltion. ©

EL hh - Hereinafter the method accordife to the present invention will be described in detail Go -

CT in combination wit the examples. 1, <i an Lp Elli oo : - 20 i . inthe following examples and comparative examples, the number-average : Co i: 3.7 Lo LC Cl oe “ “ > - - Ee molecular weight of the polymer. is medsiired by an ALLIANCE 2690 gel permeation Ce

SE i . a chromatograph purchased from WATERS (USA) CO? equipped iith.a PLeel Mixed-C } ’

I chromatic solu poured ford Agent Cats temperature 25°C, wherein = me Se pT et

Bi . - : : ttrabydofurdn is used 5446 mobile phase, and slemlg dite polysiyrene is - . : - CL

ETE hylroxyl-tenminated polyether is measured ascording fo the method described fn a3 Chinen GBI20083-85 the foal amine valu. primary sine coment,

I oniaiy amit oonjet, ard tery mine Gontént in ainonerminated polyether are 10 7 ; = “ik : | h : of : prepared Raney hickel catalyst is measiired with inductively coupled plasia atomic, i Sh : 2 i co CES Preparation Bxample 1 ST i ET ne ce - . - ny E © Kater solution of NOH with'a coricéniration Gf 40wi% is prepared by dissolving E Ga

Cu water The water slutoh BF NOH i added into a stainless tee three neck flask" ’ . ra is: | cule ith a thermometer an : Co wo w oc, By with vi gorous agitation, = . | bo i = -

CL NEALFECr ally poder (based onthe total weight STs alloy powder and messired 1", + - RK . BR _ Cr : by clement the conteri of Ni is 64%, the content of Al i$ 31 W%, the conter GiFeis ; ) 5 oo

CS Sd and the content Of Cris 2.56) i ddded into, threes neck flask fn baiches ©

AR add 24g ineach batch) within 25s. By regulating the addition rat of the alloy = - o ? : E - : ; ‘20 © powder; the féimperature of Solutio in the thregneck fask'is Kept i appro. 50°C. So -

CT Aion th solution inthe thse. mck asst a spp. 80°C or approx,

Ch o - LL ormin, + Afer he hydrogen gas is released completely; the superiatint hits Nocoulate Loa ci parte, ath back rsp sri t's beaker and swash with ware, © - Lk Ea “til the washing liquid is neutral against Him Solution, then wash 2-3 times with 3 Sv : co

. . g a . : LL catalyst iS stored ia pluged container with anhydrous ethanol.” By analyzing, iris fy ~ Sr . -

LT determined that i the prepared catalyst, the content of Ni is 84:8wt%. the content of Al - - - - Lo a ‘ “NaOH with a weight equal 103 fimes of the weight SF NALCr-Ca alloy powder ii. = CE - - BS 0 quipped with a thefmormeler, and is cool 0 30°C. With vigorous agitation; + cL

CT NALCrCu ally powder (baséd on the oil weight of the alloy powder and measured +

Tt, andahe content of Cu is 2196) ded no he treeneck fakin aches (add

Se aaah bach) thin Simin, By regulating the addition fe Of he alo powder, © co . : ss the temperature of Softion in the thrce-neck Mask i kept at approx: 50°C. . Afr HC B EN ES

Ce ET ition, the solution i ie thrée-neck flask is timed at appro: 90°C for approx. 80min, ©

CL eran drogen’ released comple: th Supertatant whie floceulate s+ ea ES ied, and the black precipite st : es is wash with water, dil Cn

LT Lo Life washing liquid is néura against litmus Solution: then wash 2-3 times with O3with Ce a

Ca ethanol and anhydrous dono 0 ota Raney nickel catalyst the obtained catalysis

STE i ie prepared ial the content of Ni 5 89.9w, fhe corent of ALs 7.60wt% + 5

Gar ng Ae NT TL TT ey ld nT en ET RT RR Ret TE

RT RAST nn eT re eT AT pa et Te nig LE

EE ENTRAR ER TIE Ta Me Te te Ue Tn Te ee TENE La ee Tes

Te ane Ll SET al Se a TT ae te rE ht dn Te, TEL TT LT ie ey oA a RRL ee ALL Le TT Te eT TE a EGTA ETT Tae nT en a TT rE are NEL TE Te En Be EE aT IE EA IRL at en GTR eer TT eg a RTE Ta a

CERES EE Tet AT DL RT a Te TL Te

Cea a UR pe TD aT AE TR en Ee LE Te TT TR a Be i 4 TR Tn TE Te I eT ct RAL Ren aT ITT TL gl Re Sma J ty vi SU a TE Te on ne EN gene LT Le TT TE eT TE eT ee El dg eT

Fels sien fv Preparation Example 3-0 0 se TR UNA an pin TE Hn a een BE a

Dorp RERET RT se rT aD Te ET Be Ten TT se TT TA en Sy aly Er Dh A water solution. off NaOH: withia concentration Of 33wt%is prepared by dissolving: +2100

A cp Re ee eT Ty TE ee TT AAT mele Ry et Sn Ta ete : Cae = 7 Ee Ce “=N aOH witha: we ight equal t6,2.5 tiinies Of the, weight 6f Ni -Al:€ u-Zn alloy’ powder in: He diy 50h

Gr RT Sn Tr Ras wn LE © 2 Bn eng en ee Era Ek CoE hla STL BA FA owt To sel Tee water. [The water solution-of WaOH:is added:into:a stainless steel three-neck flask’ 7: woe Fra He ate eT TO Ty he RL SE a a Ye Se TT Te ST ” CERTEY a

SE st equipped with o thermometer: and is cdol to OSC! With vigorous agitation, “==. re

TE I Re rn DERE LT ne eT re TE Be EE ET ee re LT Te

ETE NIAC Za alloy powder (based on'the total weight of the alloy powder and measured = 5A eT TEE TAT Fe Ty Ae Ey Te TR ed a a a en I hn a le Eh eT

CRE The es TT ey a eT Rh TE Th eal on a TR LT eT my TT TE ne rT Re

SE CT by element the contentof Ni is 69wt%. the-contentof Al is 27wt%e; the ‘content. of Cus zw 127 ov

Fel ek Swid: and the content of Zn is 25 wi%)is addéd:into the three-ieck flask in batehes 2

I UT A a i BT en Th Le TT

NTE (Add 2:4 in each bah) within 25min: By egilating the addition fate Of the alloy iL

UE te TL Te En EA ly EE Ba Se TL a Sr Belle hs Ba Ey Te

Le ER TI La Se I Ree | ae tage Cp ETE eB eT eR oT ef soa ale 10 powder. the témiperatire;of solution‘in-the: three-neck flask.isikeptat approx: 50°C... eit 277,

Tl Ce ET Ee al Re ER nT BE ee PT ee ed ne Te Sn Th TTR Se etogte iin <5 A frer addition, the isolutionin the. threecrieck flask is stirfed at approx. :85°C for. approxs=s: ut tnt

IR Cr pi Dee I TT EE TT EUR eT Ee LT Pt, Ta TR Te RT eee ee LT ge A

TEST i 90min After the hydrogen gastisireleaséd completely. the supernatant white: flocculate 7 x7 £0 ne iS separated. and the black precipitate: is transferred toa beaker. and isiwash with water, 2 £5 TT

Cala ede ABE rillthe washing ligiid is‘neutral-against litmus:solution; then wash 223 timesiwith,” 5 “beim s 0 mm Te TT TR ET Te Te UT TEE ae Th nT eR Ee, a cal we C51 95wi% ethanol and anhydroustethanol ‘to obtain ‘Raney nickel:catalyst: the;obtainéd "+ pe Ce EST

Sy ee ET Te ER A nn eee LE Te TT ee TS Md le Ee pes AEE ah ts EL I ay BR TET Re Ta ae TT ET eT eT Fa nal con ie ei eatalystis stored in-a-plugged:containgr with.anhydrous ethanol. By-analyzing itis: sud

EAT LT a sn EE No een a ee Can Te rE A Ta LT Ten i he LE A

SU en Mein determined thatiin théiprepared catalyst. the content-of Ni is 86.4wt%:the content of Al io fo 87 ir’

ET eR eT i we Te ee PE ee RE ee eT CR RT LE TE Ee RE ah

Cagle nT as 10.2wt%. thescontent of Cu is 1 2wt%: and the content of Zn is 2. 2Wt%5 fu. Ci pe ei

SE IE mE an Te RE Ra I Se ad ete LT Ee ie

PRE ea RT BT Se Bn pe LS IT es el De ET Be Tn TIL Te ETT A mn Te lg AT Te

Joe Th LF -F Lo - Tess co ST = Se TE iy a Cel ERE vu = Re Tait Ss ir BE = Fo = ana “5 = Fo Pe © x Ea Lae LT ERO ES Re ; Te

Ce nS Me a Se Gem ee GETS ER a Te TT A Te Le De eT re EL Te ee

Shrine 00 2 Preparation Exampled:: sini ie Loci nt 0 re ann SA ie fern TE an Te Tg

PSE BL Te hy RT LA Fy Fa An aE Tr ee I TAT Ce EE Tn my ET

LES mE TR ee EE eg Ty TE PAT al Tn TE Tenn EI Ren Te ie

BL rte ne HY A water solution’ ofiNaOH-withia concentration’ of. 40wt%, is preparéd by dissolving -ii = ste irs Ta NaOH witha Weight'equal 102 times: ofthe, weight of Ni-Al-CusFealloy powderin-=s 5 «0 Belin

SR Ti ates Fhe water soliition of NaOH'is added into’a’stainless steél three-fleck flask + FT 0

Ta EE ee RI STITT Bn Sn te EE ee ee Tm Te en

CTT ewe sn ee a TT DRL Ee eg RE Sep Dn TE TR TI ETL Tay te gin ST eae EE HE Tequipped. with a thermometer-and:is cool to 50%CT TWith Vigorous agitation. iis je EE

Pe Se Tree RI TE Te ee IA FE gr TE SR Te sn DT RD Le Tel Fn rp mR ey UE Te Tel TT LE

CN Se ET I Cee Ee eS eT aT Te Te EE ng Te a . } Ra Sh i Gene - : n la “i =, : pr ¥ oi -. Aa GE 3 7 J gp Ee we Tr ee REA Ea o ur TE - or a : . w Se ; : oe Sa : i 2 TE : Fora pS i

En Ee TT Te en TR Tt OU a TR LE LT Le er Te

I I

Pe Le IN I a A eh a Ba A TT TTR Th A TR es SE Ta ee wr 1. = Se ES Ta 0 v ee Ta rT Ti A Tr Ry wi = Veen : LER LE . LE Et a TE pi i: a ha a Cel a

Ean al TR ST Te PE IE en ae Se el Be UE

JE ee RTT eT TB See a Te i Pe al aS Te I a RR Te

Li i fri ye 5 Ni-AlCu:Fe dlloy. powder (based: on the total: weight of the.alloy powder-and measured. "75 Te ee GATE AR fF BT A TE Re eT en eh ee En a

DERRY se by ‘element; the content’ of Ni is:65wt%. the Coritent of Al'iS 29wt%. the-content of Curis wii in oo) 77

Fle LE ee EE ye Ee a Be 0 3 TR nd et Te TUT Le rg RE 0 3wt%, and the contentof Fetis 3wt%) is added into the three-neckiflask:in batches (add - =". i: Vs 7 70

Taal nh 0 0ho 0.7244 ineach batch) within 25min’, :By'regulating; the addition rate of the alloy powders ©.) LES nil dE SU TE FLT Te ama ee AT TT FL Ter Te TT et RT eT Be TET ee Ts mel ee

Ce TE a Ee TE TR i ee Sel nel ey I Te ee

Tels TTS he temperature of solution-in the threeneck flask is kept atapprox, 50°C. After iv Lr Ln

Sl Sele ag TIE ST I i TT TR TRE Tole Te ee ne TES em Te Tae aT

Sonn nT CT Tn addition: thessolutionin the three-neck flaskeis stirred at approx. 90°C for approx. 60min.» El

Cnn Tea ATT Te ns a RE Ee Cn RE TET ah TE Lane Tes By Te eT A nets VTL tL Afteritheshydrogen gas is released completely. the supernatant white flocculate is’ |, wn Ll

Poet ePE Te at A ST LEE Tae LUN aE eT Tea Les TL aT ee ara 00 Ulli ESA oT

CWE EL ee UT Gg YD Ee Re he Te Tae nF eA RT Tn At eS Lae Cee Ee eT EE

LENT separated. and the black precipitate is'transferred t0,a beaker: and"is wash with water. til "a0 op ph RET en EER agg al I AE eT i LT Tn LT TE wa DIE iheiwashiig liquid is heéutralagainst litmus Solution, then Wash 2-3 times with 95wi% wR

CN SE TD Tn ne IRR TL RETR TT ST Rn ea ee me Tn TE er

Lott Seto ]0: cethianol and anhydrous ethanol to obtain: Raney nickel catalyst: the-obtained catalyst.is | <3 502 =e ee a bred ha plugged container with anhydrous ethafol: « By afalyzing. itis determined ix 5

CEE IR Tr em a Ee EE CR ST RR LE ee

FEU TD 2h dthatiin the prepared: Catalyst. the content Of Nitis 79.5wt%. the content of Al is. 15:3; = "vis

Cee TE en eT RD ene RT RT en RB Ty

LETS thercontent’of Cu'is 2 48wi%t and theicontent of Fess 2 72wt%. wk ee DUTT a Tn Ee a Te I a Tae ae eR Lg RT fe

CPE hielo 185 Preparation Example 57 i ih nf Looe Tule mh TL ae BLS ee SO

CSL TET a Awater sOlution of NaOH with a‘concentration of 25Wt% is prepared by dissolving vet

Fe TE ER Ie FE Te Se pT Se Sn rh Ta Ne Ig en Teh Ts len Ee

SLT NaOHewith'a weight equalt 4 times: of the Weight of NizAI-Cu alloy powder.in Water.” “1. 0 2 + pA Te Re Te tm Tn i ER Te et BE Ln Sn TU TT ag EL Ln “gE The water solliion of NaOFHis addéd into a’stainTess stech three-neck flask equipped = 7 20

Ce ER SL Tl he ET EE TT i Ba Ce RR en TT Te TT en el

Lek ons tL with a thermometer. ‘and is’ 001 10:50°C. “+ With-vigorous agitation. Ni-Al-Cu alloy. «= 77: mmo

Tm Sete Ie AT er TT an i a ee hed DIR I Wh eT Tne BT TA FR TR Lae a Ta TT a

CBee EE TA aan te Ln Te TR Le Pe MR

TE RENT 20 Cf “powder (based: onthe total weight ofithe alloy: powder:and measured by €lement. the © a 0 TEE ea Ee tT Ee he ATEN Tite a RI BT TE RT Tad pT a LTA ee

CoP hE FE donitentof NTFS 78 wWt%: thercontént of ATs 1:8:5Wt%; the content.of Cu is 3.5Wt%) Isr, ix Fre nh i ve dee F EES 00 added:into the thréeineck flask in:batches (add 2-4g. in‘éaéh-batch) within 25min, "BY. or ws W540

Pm EIT ear a Gs ne pe Ce teh S ee A ST TT eng a ET Te TT

Sen i man AT Rg eh TE TT ee Re Se TT Te LL Ee Te SL a

Loewe soko oregulating theiaddition rate. of the alloy powder! the temperaturelof solution in. the= zi 50 #8 ve TE ene Te TT Ld ap A EE en Te eh aig i A TR ne Te TR ey nn ren ST BT en TE Tn en te Ty en eT RE Re rT

Cul EEA Leo Ea thieerneck flaskids kept atapprox. 50°C: ‘After addition, the solution in-the:thtee-neck. i =.

CET TT Tr TE meg FT Se BO a ren Pd ERG LS ed EE a i Te ae BD en ee NET TT Ee SU Ee CR Dh me Ee TE Te CT Te Te te Te

CLR Ses a Pa Ll it Le LE LTE ane Lope wo ard . LotR CL TT Soe ur el RE iid aE aL ET nT SE Ee RE pm AT A I Te PR TE I eT aT # ATA La A Ee TT re en SE NE A Ra AE SEE TR te i eT Re TR TT Ee TT es

IR I Te RT LE a DL TT Re a i BA

DIRT oT en TE ee ST TE a en Te He IE LT Te I en tT I ET A es

CEE ar le mL ET Te IRA a eR Te TER TT Be ade le a RTE rE SE fk stirred at approx. 90°C for approx. 10min. Aflerahe hydrogen gas i lead ©

Ct completely. the supernaiant white locsulats is separated, and the black precipitates © © : ; = So . . - transferred to a Beaker. and fs wash with water tl] the washing liquid is neutral against - n . i - ims solution, ther wash 25 ines with 95Wi% éihanol aid anhydrous ethanol to ta : i 2 u Sl Preparation Exainple's re - . oy - = i oe Ee : : - - : i ge 10 CA water Soliion 6f NaOH with a concentration of 30wi% is prepared by dissolving, on ol ; . fe A NaOH with a weight Gqual (2 ines of the weight of Ni-Al-Cr alloy powder in water. oe Lo = : : . The water solution of NaOH is added into stainless seel thiee-neck flask equipped t ) or . | . ) oo i. “With a thermorneser, and fs ool 50°C. With vigorous agitation; Ni-ALC alloy ’ Lo w= .

Cn powder oss cn th al weigh of theo poder and measired by lems the ©

ES Conia of Nis Thwioh, the Gane of Abs 20-5wi%, thé content of Cris 3 5we) is 1 tC

Ce : : : : Ea B +: hree-neck flask i kept at appro. 30°C. * Afér addition, the solution if the threc-reck =: = - - : > Boel . TO flask iw stiied at appro. 80°C for approx. | 00min. Afiér the hydrogen gas released Cl .

Sa completely, the supematint whit occult is separated and th black pecipie is

FIT Firanstermedto a baked, and is Wash with water, tll the washing uid fs neural against © ©. +

J mus solutions then wash 353 ims with 95wt% efanol and anhydigus efanol 7S . oe Tn : obtain Raney'n kel catalyst, the obtained catalyst is stored a plied Comins With 7 Bh a

TRATES Ae TE i

RE EE ey el i Te

CR LL en ne MT ET eR

Cong a gE Tn Le BARR re

CE hydrous ethane: By halyzing it s determined that i the prepared caalysh the ©,

Le coment of Nis 90.8wth, the Content of AL 8.01 wit théconent of Cris Lows. 7

Clay EEE TRE TLE HET SB : - Ee CE preparation Example 7: i i : 3 oo ae Ri . Le Le - 2 : 5 -

LT Ts Aer soliion of NaOH with a Concentration of 35wt% is prepared by dissolving. co = © NaOH with a Weight eqidl to 2.5 time of the weighi of Ni-Al-Fe-Zi alloy powder in’ ~~ In co - ) } - tl 5 ] Water. The water Solution of NAOH is:added into:a stainless steel three-neck flask Es 2 Lo ; =

CTE hag in each batch) within min: By regulating the addition fate of the alloy powder,

LEE he temperature of solutionin the three neck flask is kept at approx. 50°C, After ©

CE addition, fhe solution in he threg-neck Task is sired a approx. 80°C forapprox. <1 TE

Cis, ro0min. Afer'he hydrogen gas i released completely. the supematant vihite 7 17 t

CE ith wate, he wasting iid i ntl against ims slut, ther ash 2-3 times

CTT ith 95k cthanol and andr edhanol © obtain Rey ike catalyst, he bined +

Cb casi ed na puget container wil any drous ing. By anazing is LL

N } Ce | - pray is 241%) the content gE Fe 192. 1wi%%. the coment of Zn i 2.2w%. | : So oo ; - : - - g

TET Comparative Preparation Examplg 1751 nw Fon ee

ET HT TL a LTT ad Te Se a a Hen TT En Re » i - a A whi Solition of NaOH with a concentration of 201% is pisared bf digetvint s, Lo te

NaOH With aweight equal to 4 times Of the weight oF Ni-Al alloy powder in water, ©.

RN ah on “The wate Solution of NaOH fs addédiinto-a stainless sieél threé‘neck flask equipped. k a a iT Ls basedion the tal weight of th alloy powder and measured by element the contentof ©

Ee Nis 6swite the content of Al is 35wi%) is.added ino the thréc-neck flask in batches: Co

LP (add 2g ah bath) within 25min “By relating the addition te of healloy + TL

CL 7 : n + After the addition. the solution i the three-neck flask is sired at approx. 80°C for i - RS

CE foceulares separated: and the, black precipitate is transferred to a beaker, and is wash ©

LE - . oo with water lf th washing liquid is neural against Tunis solution, then wash 2:3 times TL oo Co ki SE with 95wt96 cifianol and inhydrots thanol to obtain Raney hickel catalyst the obtained. . oe )

Ca castor in ped cer wi sno shan, By oo . Le CL 15> determined that in the prepared catalyst, the content of Ni is 89.5w1%. the content of AL | Ia ; E "7 . So LT is 10.5w% i ; i. - : oC SE : ) = AE . : a - : ns on Sa . } x . . ) wn . 100g bi-fuitional (ie. there are tivo hydroxyl grail in one molégule of Co ~ SA

Ls sirnylend str hyde emma plone trully DS

CL numblraverage molccular weight of 230.8 (procured from Polyethei Deparment of, | 15

TL Tianjin Pewochemical) and Sg Raney nickel catalyst prepared in preparation example 1. ©

Lb are addenda OSL high presi rector, The high pressure reactors purged with foot. ammonia gas (under standard condition) is addéd into the reactor with-agitation, and". como een 0 hydrogen is filled into the reactor by regulating the outlét-pressure of steel cylindér.of - + ov

CTE hydrogen to 2:5MPa (the folewatio of hydrogen t6 hydroxyl groups fi si toni

Atay ono 7S hydroxyl-terminated polyoxypropylene.ether is 1:2). The reactor is heated toa? ~> = . 7.0 "10

Lows en Sy 7 temperature at 200°C and maintained at the témperature-for 4h, and the maximum _".: © -

So ” ot Le Co . - . [PA In Ca tr EE EAR Su J Lt Ch . ar en Vo ! . nT ~ co . Le Te ont Cs EE os : J cL. Y.. +.-. .'pressure in the reactor is controlied at 15.5MPa. : Then, the-réactor is cooled.to 50°C... «i - =.

Coo iTe 5 The reactor is exhausted siowly and the gas is absorbed with water, and thefi the.” et SE

Cl rention mitre is diseharged. © LET nee Tn Tie

Ln wid oe The rection mixture is filtered in hot stateltoseparate the catalyst and liquid? eco

LTTE To mixture containing the product, the liquid mixture is transferred to a three-neck flask to:

Co... conduct reduced pressure distillation at 105°C and a.vacuum degree of -0.08MPa for 1h, =+- 7 7 7... iy .soasto obtain the product of amino-terminated polyether: ‘By analyzing, itis" =. - © i © esi. determined that the total amine value inthe obtained product is 7.25mmol/g, thew ©. © ~ Co

Sol conversion of polyether alcohol is 85.97wt%,.and the selectivity. of primary-amine is 7

CEs 1s T9797 W%%! na RE eet rE eT Tene ee

Lon. ComparativeExamplel oc TS Th LTT

LE ."." ‘Amino-tefrninated polyether is;prepared by the miethod-same’as the method ~~". ©) Tw described. in example 1 the differences thatthe Raney nickel catalyst is'prepared inthe ~~.

TRE ne mn TT BRIE Te ee Te fn w.t 20. . comparative préparation example 1... By:analyzing; it:is. determined that the total amine "0 © vo Te valuetin the obtained product is 4.83mmol/g; the conversion of polyethet:alcohol-gs; LL Te } . Lo ce “ no : i i iw E : ; oe - ] he I ) : Ee } : To - ein i. - Ti - - i nL : or i :

Ise Toe 158.4wt%; and the selectivity of primary amine'is 98.9wt% un Teel een TL

EE LL ew FR .. Te CO Se and ed LD ye el : Cl .

: CL oo ay “100g bi-functional hydroxyl terminated polyoxypropylene thet with 0 : oo - . a re aviigh wat wa 3 30 loin om eign Bement t+ i - fr o Li | Tianin Petrochemical) and SgiRasiey nickél catalyst prépared in preparation example - Ts 5 : a added io 0 0.5L high presur etor. The igh prs resctor purged with

ETS irogsh and hydioget with a pressire oF 0.4MPa Tor 2:3 fimes. Approx. S$ LS. 2h “ ks 5 . - dirvethylimine (unde standard condition) is added inio the reactor with agitation, and. co ni Lo

CL nos led mg the sor by ng heute pres of est sft of. 7 hydrogen to .0MPa (the mole ato of hydrogen hydroxy groupsin. + v

Bg . BR . oC . hydroxyl-terminated polyoxypropylene ether is 151.3). “The reactor is heated to ao > : - oo - .

C0 empire 210°C and mainiained ath temperate or 4h, andthe maximum © 17

Y t . | pressure in the reactor is Coritrolled at 13 MPa. Then, the reactor is cooled to s0°c. So - EN Cf : ie Pa : The reactor is exhausted slowly and the gas’ absorbed with water and then the : : Ry 3 i ) - Ba - Co The reaction mixture is filtered in fot state to Separate the catalyst and liquid } - : a ) “ a - : B pe i tnixture coniditing the product, the liquid fixtrd is transferred fo a three-neck flask to - ey : ) } = > ; - 3 - no “conduct reduced pressure distillation-af 105°C and a vactiim degree of -0,08MPa for 2h, ) - 5 . ) © sousuobuinthe product of nino terminated polyether. By analvifg itis

SUT determined that the total amine vale in the obtained product is 7-S8minolg the © or “ro conversion of polyettier aicohol is §7.79wt%; andl the selectivity of tertiary amines +. 4

CL ae eam pn, I Ce ne

Col © Comparative Example? } CE he LL SE

UT esoribed in example 2; the difference ishat the Raney nickel catalyst is prepared in the ©

Cr TT alin phe obtained prodct is 3mmoli the conversion of polyether alofial is, + i, besos ig aS 1 © wa

CA ber avérage molecular weight of 230.8 (procured from Polyether Department of + <r. : - . Tianjin Petrocherical) and Se Raney nickel catalyst prépaied im preparation example 2 E : : i . . . Th 5 ; or are added into a 0.5L high pressure reactor, - The high pressure reactor is purged with E . ~ © 0.0 mitogen and hidrogen witha pressire Of 0:4MPa for 2:3 times, Approx. SOL SLE

ST lived lamine (under standin condiion) i added fu the reactor wit agvion, ant ©

SL hydrous filled ito te reactor by regulating fhe outlet pressure of steel cylinder of +

B Ge T= : E hydrogen to 4,0MPa (the mole.ratio of hydrogen 10 bydrosgtgrups in | } : ; Co : no - wr CL ) ii = i ) i “hydroxy lterminated polyoxypropylene éther is I: 13). The reactor » heated Gao Su . »

Rt =: ~ gre emperature at 220°C and mained at the temperature for 4h, and the maximum © . : ns . i Lr ’ Cu ; in inthe reactor is controlled 12 3MPa The A. the Fear is cooled 10 50°C. : no = g

Re 5 . "the rector is Sxlustelislowly and the'gad i absorbed with water, anil then the reaction Co v - :

Ce ol ; . : - n > : . - The reaction mixture is filferéd in hot State (6 separate the caialyst aid figuid i ng =o Co :

Fret 0 mikiure Containing the product the lguid mixture iS transferred to a hee-néck flask 5 i a Co - conduct reduced pressure distillation at 120°C and a vacuum ogre of -0.09MP for 1h: EU - :

Ea co “50.8 to obtain the prodiiéx of aminosterininated polyether. « By analyzing, its’ : ) = o . . ~ ; So Se . A determined that the tal anvine value in the obiained product is 7.32mmol/g, the °° - : . So

~ ; E : Th i - convetsion of polyether aléohol i 86.12w19%, and the selectivity of tertiary amine ” ) . co : N -

CLUE Amines poleiber is prepared by fhe metiod sme as he method

ET tems Sa dis hi Ros ike is ped ia © ’ ’ co el comparative preparation example 3. Wadia, it is Gerermined that the total amine - . 9B wise, and the selectivity of tertiary amine is 95.21wt%, © © Lo

ST naples © TS Te . | : : 3 Le - . 1008 bik unctional hdr sind ; poly ELL % n - : sr ; . - " 3 ~ Ss ‘are added infos 0:51 High pressure reactor, The high pressure réacior is purged with Rs - Ea

TT nivogenand hydrogen with pressure of (4MPa for 2-3 times, Appro30L ©

CL drm das (under standard condition) isadded into th reactor wiih agitation. and +

CR drogen is filled into the feactor by regulating the outlet pressure of steel évlinder of © © ©

CT nydrbgen to 2.5MPa (the ole aio of hydrogen to hydroxyl roups int. iLL

ET tania esses der 3 Trarencor oto FR 0 i C So . Co temperature at 200°C and; maintained at the temperature for 4h, anid the makimum - a oe "3 : Ll : . - Lo i = RG piéssiure i the reactor is corirolled at T1.8MPa. Then the redtor is cogled f060%C. ; gy : ; : : -

CET The rehotoris exhausted slows) and the gas i absorbed with water and hen the

TER EE I Ta Te a En ee i i gE we he reaction miiire i filered ir ho Seite 1 separate the catalyst ind liguid - ie .. wn : .

Ce hon Tha ay CL oe RENE a Se ra wo ES aL wT . RE : CL Fa

Co - mixture comaining the product, th liquid mixture is transferred to a three-neck flask fo. - = ~ LL : } oo o E i . conduct reduced pressure distillation at 105°C and a vacuum degiée of -0.08MPa for 2h, } a - :. So i

TL uso obtain the produc of amino-erminsed plete’ By anabzing tis Cl

CTS etermined that he total amine value in the obtained product is 1 89mmolig, the. | ++ L

Ci 0 Amin deminated polyether i prepared by he method same as the methad +, oo LT comparative preparation example 1. By analyzing, itis defermined that the total amine ) : - Th ) =o

A a i dahie in the obi product i°1,52mindi the coversion of polyether aleohdl is 7 Cm 5 . ie s.s2wth, and the selectivity. of primary amine is 96 4wt%. SE : ; So . ” i .

Ty eth EE LT a de

L100 bi funrionl hydro erminaied polyoxfpropylens ether with tin ad oy ik ign ions

CULT iogen and hydrogen With apréseie of 04M Pa for 33 times, Approx JIL + Te.

Co mytamine der sd condition added ns 5 esctor with sation. nd °C

CTE hyiosen 1 4 SMa Ghe mole of fydrogen to hydroxyl groupsin TL eR eR eT Te

LT nydrotieminated polyoxypropylene cher 35:1) The actor ishestedtos TL

LT pressure in the reactor is controlled’at 9.2MPa, Then, the reactor is Sooled ec. i

CETL RT conduct reduced pressure disillation at 103°C nd a vacuum déeree of -0.08MPa for 1h, 1

FLERE TG an Ghai the prod oF iimo- Ermine polyettier By andlyzing, itis ni TT

TL ind tm wi coer tm 5

STEEL Gonversion of poliether alcohol is 97.47%, aid the Selectivity of feriary amine’is | 1 . - il : % s - | 97 3wt%h.. . i n : : : nn Ci + : i nn : o “ > . : ) . g . . ) Fa Co =O . : . o as Us. + 100g bifunctional hydroxyl-terminated polyoxypropylene ether with SL he So

CT umbreenge mel igh of 983.0 Ground fo Pls Depmeiner

CE Timi Petrochemical and 24 Raby nickel Catalyst prepared in prepéiation example 1. +17 +

Co BU are add ino a 0 SL high pressure reactor. The high pressure reactor fs purged with © + a0 ciylamine in fom of guid i added 0 he recor with agaton, and hdrogents

SL asa meat of deen o ado] grou in drogyleinaed

Cr polvoyprodlene fe is 2): Therein heated 0a temperature at 200Cand +

Le ] SL IS “maintained at the temperatiire for dh. and the maimuin frostire in he reactor is Co i . To

SLT aommolied i 10.3MPa. Then, th feactor iscooled to 60°C. The reactor is extausted Lr

Ch CV iowly and the gas is absorbed with aie. and then the réaction mixture is discharged: - AE

ET imiiure containing the product, he liquid mitre is transferred fo a threneck flask to 1

CET Conduct reduced pressund disilaton at 105°C and d vacuunidegree of 0.08MPa for 1h,

TL so sto Gbiain the product of amiroterminated polyether. BY analyzing, cis

SET getermined thatthe tral amine valug inthe obtained prodictis 17Imimolig, the + <n ¥ RT I 3) wits? E Sa i Tue ERT SET SL SE -

Ch amen TT SR en

LT desired i simple 3 th diffrec is thr the Raney nickel catalysis prepared the

Se on ol + on "preparation example 2. “By analyzing. i is determined tft the total amine valuein the ) oo . -

Ch Aminaminaed polveter i prepared by the method same as the method <n

C0 described in example 7. the difference s that the Raney nickel catalyst is prepared in the - oo

A penaraton example 3 By analing. its detmined tht th fol aminesalue nthe’

CL seleiviy bf seeondary gmine is 9724wi LL i ra le ge TE Le A

To RE : ‘Example 0 - LT Sor 5 Laat ; . or B : i Co L

EL TL pin mts iment biomed mad. - | - - ~ wr : . preparation ehaniple . : By analyzing, it 5 detbrpined thathé total amine valie in the : Lo : Eh

Lo LS obtained product is 1.91mmolg the conversion of polyether alcohol is 95.06wt%% and | 1

CT mame TL ee Le . - : 0 described in example 7, the difference is thatthe Raney nickel catalyst is prepared in the - i. - :

LT Le : j= preparation example 5. By anglizing; its determined that the Eta amine value in the oo so Lo . = — 4 ~ obtained padi is 1. 76miole. th e coriversion of polyether alcohol is 87.63 wie: i Le : HR

IE the selectivity of secondiiry amine 95.98wige. 1 i Toni

FU Amikosterminated polyether is prepared by the method same as the method 1 7 . E 2 - Ca © described in example 7, the difference is that the Raney nickeF catalyst is prepared in the’ . ) - Te )

UL preparation example, BY analyzing, 1s determined hat th orl amine valu she

SEE - “obtained product 1 82mmolig thé conversion of polyether alcohols 89.41% and - CO . Ll - _ - - ; : 20 - the selectivity of secondary amine i 93 28wi%:, i. - So i. : : oo so “ : - - . ol

CU mamplery 0 Te

B 2 | = i - : Amino-terminated polyether i prepared by the method same as the method = = ) : Co

Ce dcberibed in'cxample 7, th difference iS hat the Raney nickel cals is prepared in the + +

Ce ppararion example, By inalyzing, it is detemined hat th otal amine vale nthe +

CR Amino-femminated polyether is prep by the medhod same as the method: Va mon ass Ry lope i . A : } i : comparartive preparation example 1 By, sual zing, i is detetmined that the total. | - : } ., ; . : ; Lo 2 i : ) So amine valiein the obtained product 161.71 — the conversion of polyether alcohol i oi ise 3w0k aid the slestiviy of secondary amine is9821we, C0

Ce ; 2 Example 14" i ue : Le ~ be 3 nn, Es Sed 2h Rv BE - -

CT 00g bfuneronal hydroxyl ténminated polyosypropylee ether with to

CET dumber average molecular weight 6f 2000.0 (procured from Polyether Departmentof © Y. - Br g . ) . 5 . Tidnj in Petrochemical) ind 3.52 Raiéy.n kel catalyst prepared in preparation. example: Bn . cl ) BE - Ln dare added into a 01. high pressure reactor. The high pressure reactor is purged with = | oo a . ~

CEST agen and hydrogen with pressure of 04MPa for 2-3 times. + Approx. 201 + +110

CL bie er by ng Dt sors nt

TT Sa tn MP ml i gen os ams

CL dou beminatad plyoipropytne thers Sil) The reactors heaed fon © . = 5, - reiperature at 200°C and maintained at the femperatie for 3h, and the pe —— oY - ERs y

CUD presente enor is contol. SMP. The, the rectors cooled 0 60°C.

The eaduons sxbausted Howl and the-gas is absorbed with water, and her fhe’ 7 +o - To el ; 5- conduct feduced pressure distillation at 105°C and a vacuum degre: of -0.09MPa for 2h, . . - - } nT ous to obtain the product 6 aminosierminied polyether, By analyzing. itis <0 - FREES | detgimined thi the total amine'value in the obtained product is 0.97 mmole the + 2 ) Te . fo conversion of polyether alcohols 96.1%, and th selcivy of primary amines i . LE : - Amino-terminated polyether is prepared bythe method same as the method : - . g wl . . -

SEL described in'example 14, the difference i tha the Raney nickel catalysts prepared in. 1 y B ’ i LE the comparative preparation example 1: ~ BY analysing. i Js determined that the total. : Tin 8 5 : = ig Lr is amine vale in the Gbrained ploduct is 0 Tarolig: the cGvers ion of polyether alcoho [ - x - L :

CT Bamps LE ! - . . : oo Tianjin Petrochemical) and 3.5¢ Raney fickel catalyst prepared in Gardening oo | iv - ) raed ino 031 presario Th igh presi aor fs purged ith

CL edn th reactor by relating th oiler pres of sel cylinder of hydrogen ts +

LL polvonypropyleneither i 67:1). The react is heated 0d emperaturs at 200°C and

ER Le cE maiptainéd at the tempefatire for’ hand the maxi pressure in the redctor is” - i | SE a

Shes controlled 114MPa. Then, the eactor is Gooled 10.60°C. The reactor is exhausted + + 1%.

Te slowly andthe sais aborted Wilh aera then the redton mixtures discharged! : . - Lo Bh he reaction mixturé is, filtered irf hot sate to separate the catalyst and liquid: " i = co =

C10 So as to obtain the product ofariio-trinaied polyethér By andlyzing, itis> Sa or pe o . v py = . deierpineit thatthe total amine valle in the obfainéd product i§ 0:089minole the fo ; oe - Se © ur conversion of polyether alcohol fs 100wt%. and th selectivity offerary amine fs

La pr I ET ER JE TI a Ee Ty

A . = i. ul i Amino-terminated polyether is prepared by thie method same’as the method. oe : a o

CET described in exatple 15; the differénce is th ire Raney nickel catalyst is prépared in’ “= *.

Samim valus inthe obtained poder J 091ihole, the conversion of polvethr alohol + + ¢

Te murber average moleshlar weight of 2000.0 (procured foi Polyéther Department of.

Ln Ae Te a eT en

Ce min Peoshemica ind 3.5 Raney ikl catalyst prepare in preparation ample +.

TF Sard added into a 031 high pressure reacior: “The high pressure reactors pured with 1 © ++ rT nitrogen and hydrogen with a pressure of 04MPa for 2.3 times. ~ Approx 26L 0

Bh - » no 5. hydrogens filled the feactor by regulating the outlet pressure of steely inder of SEL . oo

CT ydrogento 45MPa (the mole ratio of hydrogen to hydroxyl groups in sia oo

CL cre a 200°C and mained st he persue or Shand the mason

CT presse inthe scion confaled a | AMP. ARE ompletion, he Tenors. c ; oo a lo" “cooled 10 60°C, the feactor is exhausted slowly and the gs is absorbed with water, and. CS : : ) i ) ; - : : i . he J the the reaction i ixtute is discharged . Cl o : 7 a Fir ok 3 % a

CSE Re reaction mfiture is filtered in hot state To separate the catalyst and liquid. F - i. - <r . LL miture ontaining the prod, the liquid mixture is ransfeired wa three-neck flaskto © . a 2 : ~

TL conduetredicsd pressure disilition at 105°C and a Vacuum degree of -0.09MPa for 2h, ~~ : : is ; so as to obtain thé product of afhiio-ferminated polyether: - By analyzing, itis LE ST B ~

So detdmind thé ial amine vali in the obtained products 0. Sgmmolgifhe 7 i oo a “7 : : i 3 z “coriversion of polyeiter alcool 95 2wt%, andthe selectivity of tertiary amine = + - . ~ i 1 es ._Exainple17. vi on FEA i BE Co : Sa Ce iS . =”

CT 00g icfuhetional ie, there are three hydroxyl groupin one molecule of

CET polyoxypropylene éthen) hydrox ierminated polyoxypropylene ether with; wo

So umberaverage molesalar weight of S000.0(procured from Pelvther Deparment of + © Tani etrochimica and Sg Raney nickel alt prepared npreparatioh ample 3 >

CTT ake added into 2 0.51 high presse readior, The high pressuré rector is pursed with *

RET hydrogen to 3.0MPa (iG mole ratio of Rydrogen t6 hydrayl groups in <TH Fen

CE emperaure a 200°C and mainained at th temperature for and the maximum

CH prlsure ithe reactor iS Gonirolled a 8. 3M Pa. Then, the reagtor is cooled 10 60°C. © +. 1 oe ine reer is exhausted slowly and thie gas is absorbed with water; and then the +. © =

C0 eon mire Wished LC nT nine containing the produc, the Tiguid mixture i transforréd 6 4 three-néck flask tg. 1

J conduct reduced préssare distllition a 105°C aid a vacuum degreg of 0:08MPa for 2° © n+ 2 2S determined thane total amine valid in the obtained prodct is 0.58molig, the’ a BE i ’ : conversion of polyetheralcoho Fis 98 33w1%, antl te selectiv i of prifdy amie is : % o oY % - oo . i 7 74 . img o - : : Ee wi | Te : = : we : : = : . i: 7 = : | i i : | hl

CLT 07 1004 frunctional hydroxy Teiminated polyoxypropylene biher ith ¥ 7 fat

CS ri Peocinicn and Se Raney hike cast repre in preparation example 3+

I 2 Ee drogen is filled fi the reacior by regulati the Gutte pressure of steetchlindef of os & So BR fT nydiosen 10 S0MPa (lie mole ratio of hydrogen to hydroxyl groups in:

CoE hydroxyiemiated polyoxypropylene ethers 10:1). The reactor is heated toa + i ET WC Ao wot ti LF

Ch The ear sexhasted sow nd gas sabre with vate and the the CC

Ce resstionmiviure is discharged, UTS es

CT to mis rd ot to ep te cw oo BE x “10 Fi ture contaiing the product, the liquid fixie i transferred to three-neck ask 10 5 : : £ on ’

Co . ui . i. a5 csi th . ” : i io {ming termined po eth eri By nalyzing. tis | oo ; To . Let . 2 - g ‘conversion of polyether alcool is 100wt%. and the selectivity of tertiary amine is © pn x : ) : - a ~ Example 19 - p rE i” PA v ~ } BE Lr = - Le : nl 5

CE dpe hy mtd nse : i PE - . described in exarnple 18, th difference is that the Raney nickel cifalyst is preparedin = « * Lal . Se | | ~ 0 : ‘the preparation example 2. By ahalyzing. it is determined dha the total amine value in : ) ~ - | } “Uo ihe obtained product is 0.54mmalg, the conversion of polyether aldofiol is 88 4wtte, © 3 ’ os | i “and the Selectivity of © i ary " in i597. wt ii wo Hy : B wr Sa LE : . ; -

3 . : a 7 2 described example 13, the differences ih the Raney nickel catalyst is previred in’; : ER : o } - - - J oh the preparation examplé 4. By analyzing, itis determined that the total amine value in ) ) Ce = - RE

CT te obtained product is 0.55mmol, the conversion of polyether alcohol is 92 24wt%,

Te Ts and the’ selectivity of tertiary ain 15-94 36w1%. ; ie RE = - 5 4 a ; = Ce nN Lr hy ; Exampie 21 ol i a - : Sh So co ; Co ) Lr - n LL = : . - :

ES Kino-terminated polyether is prepared by the method same as the method.

Che ammoniacal liquor: By analyzing, itis detommied tht th toal amine value infhe - Lo . ~ Co * obtainéd prodict i 0.62mmolle, the conversion of polyether alcohol is 100wi%, and the : : : So

SUE Salderivity of primary amines 9745wi%. SL AT eh : a oo he Li nT Above thi pestered Exainlos of the preint invensionar desorbed in details bi Co ol - ; } - o : . - Is : “the present invention is hot limited to the details of he foregoing Bxgnbtes.. Within ) Ny C - - Le :

Le wg ~ “the techhical conception of the présent inventior, the technical Solution of the presént - : vi oC i CE - invention fray Have various mcdifications within the protective scope of the prim, . Se Lo . : © : ; : | . - I¥ should b noted hat the Sorcrete technical characiefistics described in he. oo So a - } - SR ~ 20 foregoing examples can be combined in any appropriate way under the condition of no’ i - = } : : . Ch I. describ the. possible cibinations. pid ; cy . LE Ci . . - ) ) E : Lo Nn co . ol i

Ln vt... the.combinations do not disobey, the thought of the presentiinvention:.. They shall also “> ©... © ®t S707 bedeemed as the:content disclosed by the present.invention, © 0 cio ne a LT Tiel RI Sew el De as cl JF Tee Le 2 0 TT Cla Te Lt soe rT T.

ban TT Se eB eT

CL A method for preparing aming-erminaied polyether by catalytic reductive +

UL nd atalyt, the method comprises th ollwingsieps: 1+ TT Tin Te

CL Ue imine presence of -Raey catalyst, contacting polyether elyeol havinga: nL eT uinberaverage molecular Weight of no less than 10 with at lea one aninatiig agent

Lo - So . - doling down sbtairied reaction mikture 10 25-60'C removing unreacted gas.. i - oo B :

Lu i. = discharging the reaction mixture, and removing water, residual aminating agent and. on i -

LEE sp deh amin iad potfetens + “a Lo Seal

CI her the mon of the Raney nickel atalyst 52-15% of the amen ofthe + +

TT veer ive by weights tha amos of he aminating agonis F530 mes ofthe.

Co monk ofhydrony drous nth polyether dyed by mole. and the smoungof

TL tne mers sot dos rons ne peste heb

IN il the Catalytic reductive apminition reaction is condusied atd femperdwre of.

Ct ete Te Te

Claims

Ceo 0727 The method according to claim 1; wherein the polyether glycol has'the |... i Ee - “following. general structural formula (a) or (b): RR FT fo CE CA Co Lr Ee + winformula.(a), Ri, Ry and Rs:are independently selected from linear or branched: *. :% 2% ARE HL 50 divalent aliphatic groups with 2-4 carbon'atoms;m i50-115;n is 0-115; and the-sum of Cre " CT mand nis 1-115; Lee ce eT Te Le Lon Tei F 0 in formula (b), R'is selected from hydrogen and linear or branched aliphatic groups, © SLED TM having 156 carbon atoms: Ro and Ry are independently selected from linear or branched” | i PE $5 107% ‘divalent aliphatic groups haying 2:4 carbon atoms: mis 0:40; n-i§ 0:40; and the sum. of Cll TE mand is 1-115, Te DO a ee ne eT oo co - Co - oT A Cc The mettiod according to claim 1, wherein the amino-terminated polyether has Sr . Ce Rolling general srewural formula (6) of (ds: 7 Fh TTR Te Te CoE ed dS (0) EE er DE Te TT Tp Te fol in formula’ (€) R); Ry: anid RY are independently selected from linear or branched” “x <7 2% 20 ee divalent aliphatic groups with 2:4.carbon atoms: Rs and Rs are identical or different.v ~ = Lo J co . anid are independeitly selected from hydrogen and linear or branched aliphatic, groups Lee CCC 707 shaving 1-6-carbon atoms: mais 0-115: is:0-115; and the sum of m'and nis 11155. oT

0 having 1-6 Carbon ators: Reand Ri are independently. selected from finearor branched © + Cd dalentalptic groups having 2-4 cron stom: Rand Re ae dental or differen, © CTs and eindependently selected fom Hydrgen'and linear or branched aliphatic groups + having 1-6 carbon sos: mis 0:40: m i 040s and the sum of mand nis 11S TE 0 The method cording io claim I, wherein the Rainey mickel catalyst is preparsd by + FT - CT components nto water solution of sodium hydroxide under vigorous agitation and +: 11 CT ng mper oF 510C ors prod drsion of 1550, dive. © ERIS the amount of sodium hydroxide is 1:3 times of the weight of the alloy powder; © TEN nding the mitre abiiined by sep (1) to efarae the supdmatght wie 7 TTR occult; washing black precipitae with war water for several times 19 1 1 £1 co 4 ¥ 3 EY ; . + neirality, and then wishin gw th adhydrous ethanol for? 5 tim e S16 obtain Raney. : i ; "- = 3 LT reels net. sori the Riney nickel catalyst in anfiydrous ean CU ae wherein: the alloy powder comprises Ni, Al and thétal'M, wherein, the etal Mis.

Conese, ore selected fro Ceres Cand Zn Te ny

0... .% 57 {The.method according to claim “1; wherein the aminating agent is selected from: "= © = in CL LAL methylamine, dimethylamine, ethylamine; diéthylamine, n-propylamine;~ ©... oC wf = di-n-propylamine, iSopropylamine, diisopropylamine, hexylamine, and Ln ol coe Tris cL eyelohexylamine, cot at TT rr ee a TT sp sf hw 6t The method according to claim:l, wherein the-amount of hydrogen'is controlled by © = = “i i

©. oo. 0.0 + regulating the pressure of hydrogen filling into'the reactor inthé range of oT Lon Ca ULSS8MPa. i en, Ee eR re Te ee IE - Pa = 7. The method according to claim 1, wherein the reduced pressure distillationis. Tr, Co et Se nn ~.- * conducted ‘at a température of 100-120°C and a vacuum degree of from ~0.08MPa, "~~.

tt. 07, 15. + 8. The method according to claim 1, wherein the reactor is a stirred reactor: + LC ho Lc