I HC QUC GIA THNH PH H CH MINH TRNG I HC KHOA HC T NHIN KHOA KHOA HC VT LIU B MN: VT LIU POLYMER&COMPOSITE

SEMILAR L THUYT

PU NANOCOMPOSITE CHNG CHY

GVHD: TS HONG TH NG QU SVTH: V VN K - MSSV: 1019076

TP. H Ch Minh, thng 12 nm 2013.

M C L C A. TNG QUAN V VT LIU POLYURETHANE ..................................................... 4 I. S lc v vt liu polyurethane. ................................................................................. 4 1) Gii thiu v vt liu Polyurethane. ......................................................................... 4 2) Cc tnh cht ca vt liu Polyurethane. .................................................................. 4 II. Phn loi polyurethane. ............................................................................................... 5 1) PU mng. .................................................................................................................. 5 2) PU Xp. .................................................................................................................... 5 3) Polyurethane nhit do (TPU).................................................................................. 7 III. Nguyn liu trong tng hp Polyurethane. ................................................................ 9 1) Polyol. ...................................................................................................................... 9 2) Isocyanate. .............................................................................................................. 10 3) Cht ko di mch. ................................................................................................. 11 4) Cht xc tc. ........................................................................................................... 12 5) Cht hot ng b mt. .......................................................................................... 13 IV. Phn ng tng hp Polyurethane............................................................................. 13 1) Phn ng tng hp PU. .......................................................................................... 13 2) Cc phn ng ph c th xy ra trong qu trnh tng hp PU. .............................. 14 V. Cc phng php tng hp Polyurethane. ................................................................ 18 1) Phng php c dung mi. .................................................................................... 18 VI. Khong st Montmorillonite.................................................................................... 20 1) S lc v khong st Montmorillonite. ................................................................ 20 2) Cu trc ca Montmorillonite. ............................................................................... 21 VII. ng dng ca PU. .................................................................................................. 22 B. NANOCOMPOSITE CHNG CHY. ....................................................................... 22 I) Qu trnh chy ca polymer. ...................................................................................... 22 II) C ch chng chy ca ph gia. ............................................................................... 24

1) c ch vt l. .......................................................................................................... 24 2) C ch ha hc. ...................................................................................................... 24 III) C ch chng chy ca Nanocomposite. ................................................................. 25 IV) Mt s phng php kim tra kh nng chng chy ca vt liu. .......................... 26 1) Phng php o ch s gii hn oxy (LOI). .......................................................... 26 2) Phng php UL-94. .............................................................................................. 27 3) Phng php nhit lng hnh nn. ....................................................................... 29 C. MT S NGHIN CU V PU NANOCOMPOSITE CHNG CHY. ................. 30 D. KT LUN. ................................................................................................................. 56 E. TI LIU THAM KHO. ........................................................................................... 57

A. TNG QUAN V VT LIU POLYURETHANE I. S lc v vt liu polyurethane[1]. 1) Gii thiu v vt liu Polyurethane. Polyurethane(PU) l mt loi vt liu a nng c s dng rng ri trong nhiu lnh vc nh sn ph, cch m, cch nhit, cc vt liu xy dng, nm mt, m cy ghp y sinh Phn ng to PU u tin c thc hin vo nm 1937 bi gio s Otto Bayer sau c pht trin bi cc nh ha hc ti DuPont v ICI. Thnh phn chnh to nn PU l isocyante v polyol. PU thng c to thnh t phn ng trng hp bc gia polyol v diisocyanate. Phn ng xy ra gia nhm isocyanate vi H linh ng ca polyol to thnh lin kt urethane.

Hnh 1: phn ng to lin kt urethane 2) Cc tnh cht ca vt liu Polyurethane. Ty thuc vo tng trng hp m PU th hin cc tnh cht khc nhau. Mt s tnh cht c trng nh: - Kh nng chng mi mn cao. - n hi ln v khong nhit ng dng rng. - C kh nng khng du m v nhiu loi dung mi khc nhau. - C kh nng chu ng thi tit khc nghit v chu ng c cc tia bc x t nh sng mt tri. - Kh nng dn di v bn c hc cao.

- C kh nng phn hy sinh hc, kh nhy vi s tn cng ca vi khun v nm mc. II. Phn loi polyurethane. 1) PU mng. PU mng c ng dng nhiu trong lnh vc sn ph nh: lp ph kim loi, sn tu bin, sn ph cc phng tin, b tng, s dng trong y t[2]. to mng PU c th thc hin bng 3 phng php: - PU phun mt thnh phn: Hu ht cc trng hp da vo s khu mng din ra bi phn ng ca hi nc trong khng kh vi prepolyme hnh thnh polyme rn. Kh cacbon dioxit c to thnh trong sut phn ng ny c thot ra ngoi khng kh hoc c gi li bng cc cht n trong h thng phn ng. Loi ny c dng lm vt liu chng thm nc v sn PU mt lp ph. - Polyurethane phun xt hai thnh phn c s dng sn xut sn v lp ph chng ha cht. Polyurethane c th tan trong mt vi dung mi d dng trong qu trnh phun xt. Polyurethane ngy cng tr nn rt quan trng trong lnh vc ny ca th trng v vn tc kt mng ca chng rt nhanh. - Latex: Polyurethane kt mng hon ton c to thnh trong latex, v vic loi b mi trng huyn ph to thnh lp film. Loi ny c dng to nn nhng chi tit c ph mng nh cc vt ngn m v cc cht kt dnh. p lc bo v mi trng trong vic gim thiu hm lng hp cht hu c d bay hi (VoC) dn n s quan tm ngy cng ln trong lnh vc ny. 2) PU Xp[1]. PU xp c s dng nhiu nht trong cc loi PU(chim n 80% tng sn lng PU), v chng c n hi cao v nhiu tnh cht c l tt[1]. PU xp c th phn thnh hai loi chnh l: PU xp cng v PU xp mm. Di y l bng thnh phn ca xp cng v xp mm.

S khc bit c bn nht gia xp cng v xp mm l thnh phn isocyanate cu to nn xp. Trong khi xp cng thng c tng hp t MDI th xp mm li c tng hp t TDI chnh v s khc bit c bn dn ti cc ng dng khc nhau ca hai loi PU xp. Trong khi PU xp cng c s dng sn xut cc tm ngn trong cc cng trnh xy dng, lm cng ngh cch nhit trong t lnh, lm vt liu cch ly trn tng v trn nh, ngoi ra chng cng c ng dng trong mt s cc chi tit ca ngnh cng nghip sn xut t. Cn PU xp mm PU xp mm thng c dng lm gia dng nh nm, gi, tm lt thm C hai phng php tng hp PU xp: Phng php vt l: S dng cht to bt vt l (cht khng phn ng vi cc monome v c nhit si thp nh: propane, butane, pentane, fluorocarbon) vo phn ng, phn ng to lin kt urethane gia polyol v isocyanate l phn ng ta nhit v chnh qu trnh khuch tn ca lng nhit ny hnh thnh cc l xp trong lng polyme. Phng php ha hc: S dng cht to bt ha hc (cht phn ng vi monome isocyanate to thnh kh CO2 thng thng ngi ta hay s dng nc, ngoi ra cn c th dng cc axit hu c. Song song vi phn ng to kh CO2, phn ng polyme ha vn tip din, qu trnh to PU xp c m t thng qua hai phn ng sau:

Isocyanate + polyol Isocyanate + H2O

polyme (1) CO2 (2)

PU xp c tng hp trong qu trnh ny s c nhng tnh cht tt nu hai phn ng trn din ra cng mt tc .Nu phn ng polyme ha xy ra nhanh hn th polyme hnh thnh s c trng lng phn t cao, mc to xp thp.Cn nu phn ng th hai din ra nhanh hn, bt xp pht trin qu nhiu s dn n ph v cu trc vt liu.Chnh v vy qu trnh gia cng cn c kim sot khi qu trnh to bt kt thc th qu trnh polyme ha cng hon thnh. 3) Polyurethane nhit do (TPU). TPU l mt copolyme khi mch thng bao gm cc phn on cng v mm. Cc phn on cng l ni tp trung nhiu n v ti lp ca monomer isocyanate, chng to lin kt hydrogen vi nhau to nn tnhcng cho vt liu. Cn phn mm l nhng vng tp trung nhiu n v ti lp ca monomer polyol, chng c dng mch thng, mm do v linh ng, t gp phn to nn tnh mm do cho PU[1], [3], [4], [5].

Hnh 2: nhng phn ng xy ra trong tng hp TPU[1].

Hnh 3: cu trc ca TPU[3]. Ngoi ra tnh cht ca TPU cn b chi phi bi cc yu t nh: Cu trc ca polyol. Loi tc cht diisocyanate. Loi cht ko di mch. T l NCO/OH. Nng phn on mm. Trng lng phn t ca polyol. Cht n. Vic gn kt xen k cc phn on cng xen ln cc phn on mm to nn tnh cht n hi cho TPU. Khi tc dng lc ln TPU, mt phn nhng phn on mm linh ng b gii xon, ko cng ra v nhng phn on cng th nh hng thng hng theo hng ko. Cc phn on cng ngn chn dng chy nha t do ca cc phn on mm linh ng cao t to ra tnh c l cao cho TPU. Ngoi nhng c tnh ni bt nh kh nng n hi tt, trong sut cao, TPU cn c kh nng khng du, m v khng mi mn cao. Vi nhng tnh cht u vit nh th th TPU thng c ng dng lm trong cc vt liu bc cp, ng dn,

lp bc si dt, giy, cc chi tit t, ngoi ra TPU cn ng dng trong lnh vc y sinh Mt hn ch ca nha TPU l kh nng ht m rt cao trong qu trnh lu tr. Khi phn ng vi nc chng sinh ra kh cacbonic, to bt kh trong qu trnh gia cng. V th, cn phi sy tht k trc khi s dng v c cch bo qun tt th cht lng ca nha cng nh sn phm mi c m bo c tnh cht cao. III. Nguyn liu trong tng hp Polyurethane. Qu trnh tng hp PU i hi phi c ti thiu hai tc cht chnh l isocyanates v polyols, ngoi ra nhng c tnh ring ca sn phm PU cn c khng ch trong qu trnh gia cng bng cch thm vo cc cht ph gia khc nh cht xc tc, cht hot ng b mt, cht to xp, cht ni di mch, cht chng chy... 1) Polyol. c im chung ca polyol l chng c cc nhm u v cui mch l cc nhm alcohol OH, trng lng phn t ca polyol thng cao hn nhiu so vi trng lng phn t ca polyisocyanate v thng dao ng t 400 ti 7000[6]. Hu ht cc polyols c phn loi thnh hai dng ch yu l polyether polyols v polyester polyols[6]. c miu t trong bng sau:

Bng 3: Mt s polyol thng dng trong tng hp PU. Cc loi Polyol Kh nng khng Polyether polyol HO-(R-O)nR-OH thy phn cao, c kh nng chng gim cp bi cc vi sinh vt, nm mc. linh Polypropylen oxide (PPO) hot cao Polytetramethylen oxide (PTMO) Tnh cht Polyol thng dng Cu trc

Polyester polyol

c tnh cht c l cao, kh nng nhit, Polyethylen adipate (PEA)

HO-RCO-(O- khng R-CO)n-O-ROH

khng du tt, bn x cao. Tuy nhin d b thy phn Polytetramethylen adipate (PTMA)

2) Isocyanate. Isocyanate l hp cht quan trng nht trong sn xut PU. Chng l hp cht c trng bi nhm NCO, nhm ny c hot tnh mnh vi nhm OH. Mun sn xut PU th hp cht isocyanate phi c t nht hai nhm chc. Hai loi hp cht isocyanate c cu trc vng thm quan trng nht sn xut ra PU l toluene diisocyanate (TDI) v diphenylmethane diisocyanate

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(MDI). Tuy nhin TDI d bay hi nhit thng, c tnh cao, gy ra nhiu vn nhim cho mi trng nn hin nay MDI thng c s dng ph bin hn. Ngoi ra cn mt s isocyanate dng hp cht bo khc. Di y l mt s isocyanate thng dng trong tng hp PU. Bng 4: Mt s isocyanate thng dng trong tng hp PU[1], [6]. Loi Tn hp cht 2,6-, 2,4-toluen diisocyanate (TDI) Dng vng thm 4,4-methylendiphenyl diisocyante (MDI) 1,6-hexamethylen diisocyante (HDI) Dng hp cht bo 4,4-dicyclohexylmethane diisocyanate (HMDI) Cu trc

3) Cht ko di mch. L cht c trng lng phn t lng thp bao gm hai nhm chnh l cc hp cht hydroxyl v hp cht amine. Cc hp cht amin hai chc c s dng vi cc prepolyme bt ngun t MDI, cn cc hp cht diol c s dng vi cc prepolyme c tng hp t TDI [6]. Di y l mt s cht ni di mch thng c dng trong tng hp PU.

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Bng 5: Mt s cht ko di mch thng dng trong tng hp PU. Tn Ethylen glycol 1,4-butadiol 1,6-hexandiol Ethylen diamine Cu trc

4) Cht xc tc. Cht xc tc dng trong tng hp PU c tc dng h tr cho phn ng to lin kt urethane gia isocyanate vi polyols hoc cho phn isocyanate v nc. Xc tc cn dng l baz nh amin tam cp(nh DABCO) gip h tr truyn proton hoc acid lewis( nh thic cacboxylat) to phc vi nhm cacbonyl lm tng tnh thn in t ca nhm isocyanate. ng to bt gia

Hnh 4: Diazobicylo [2.2.2]octan (DABCO).

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Hnh 5: Dimethylciclohexylamine

Hnh 6: Dimethyl ethanolmine.

5) Cht hot ng b mt. Thng tn ti di dng copolymer khi polydimethylsiloxanepolyoxyalkylene, silicone du v cc hp cht hu c khc.Trong sn xut PU xp th cht hot ng b mt c vai tr iu chnh kch thc cc l xp, n nh cu trc cc l xp ny v gim thiu cc khuyt tt l trng trn b mt vt liu. Cn i vi cc loi PU khc th cc cht hot ng b mt c s dng nh cc cht ph bt, ngn chn cc khuyt tt b mt cng nh cc vi bt trong lng v trn b mt vt liu. IV. Phn ng tng hp Polyurethane. 1) Phn ng tng hp PU. Polyurethane l sn phm ca qu trnh trng hp bc gia diisocyanate v polyol. Phn ng xy ra gia mt phn t cha nhm isocyanate v mt phn t cha nhm hydroxyl to ra lin kt urethane.

Hnh 7: Phn ng to nhm urethane[7].

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 to c polyurethane th ta phi tin hnh phn ng gia phn t cha hai nhm isocyanate vi phn t cha hai nhm hydroxyl. Cc lin kt urethane c tc dng lin kt cc phn t polyisocyanate vi phn t polyol to polymer dy di.

Hnh 8: Phn ng to polyurethane. Phn ng c bn ca polyurethane l s cng hp gia mt hp cht c H linh ng vi mt hp cht isocyanate vi c ch l vng su trung tm. Trong mt proton t hp cht c cha H linh ng c chuyn qua nit ca hp cht isocyanate[7]. Phn ng ny c xc tc bi i in t t do ca nit trn urethane hoc amin hoc acid lewis v thng c xc tc bi cc hp cht diamine v diol. Di y l c ch to lin kt urethane.

Hnh 9: C ch to lin kt urethane[7]. 2) Cc phn ng ph c th xy ra trong qu trnh tng hp PU. a) Phn ng vi hp cht c cha H linh ng.

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Isocyanate l mt cht c hot tnh mnh vi cc hp cht c cha hydro linh ng, do hp cht no cha hydro linh ng th u c kh nng phn ng vi isocyanate. Nc: Phn ng ca isocyanate vi nc to thnh urea v kh CO2. Phn ng ny lm cho PU b xp v mt tnh linh hot trong sn phm. Khi isocyanate phn ng vi H2O ban u phn ng s to ra acid carbamic. Sau acid ny b phn hy thnh amine v kh CO2. Amine ny c kh nng quay li phn ng vi cc isocyante khc to nn hp cht urea. Di y l minh ha phn ng ca isocyante vi H2O.

Hnh 10: Phn ng ca isocyanate vi H2O[6]. Amine: Phn ng ca amine vi isocyante vi amine to thnh urea. Phn ng gia amine nht cp v isocyanate nhit phng khi khng c cht xc tc thng xy ra rt nhanh. Amine bc ba khng cho phn ng vi isocyanate v khng c H linh ng.

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Hnh 11: Phn ng ca amine vi isocyanate. Acid carboxylic: Acid carboxylic phn ng vi isocyanate to thnh anhydric carbamipue sau anhydric ny b phn hy(do khng bn) to thnh amide.

Hnh 12: phn ng ca acid carboxylic vi isocyanate[1]. b) Phn ng khu mng. Do lin kt N-H ca urethane v urea cn hot tnh[1], [6], [8] chng c th to lin kt vi NCO to thnh allophan v Biure.

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Hnh 13: Phn ng khu mng ca isocyante. c) Phn ng t trng hp isocyanate. Bn thn tc cht isocyanates d xy ra cc phn ng dime ha, trime ha v polyme ha ngay ti nhit thng theo cc phn ng[1],[6], [7], [8].

Hnh 14: Phn ng dime ha ca isocyanate.

Hnh 15: Phn ng trime ha ca isocyanate.

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Hnh 16: Phn ng polymer ha ca isocyanate. V. Cc phng php tng hp Polyurethane. 1) Phng php c dung mi. Dung mi trong phng php ny c dng nhm lm gim nht v thc y qu trnh polymer ha xy ra nhit thp. Qu trnh tng hp gm 2 bc: u tin prepolymer c to thnh t polyol v diisocyante d dn ti s hnh thnh ca nhm isocyante cui mch. Sau chui c tin hnh ni di mch bng cc tc nhn ko di mch(thng dng l diol hoc diamin) nhm lm tng trng lng phn t. Quy trnh thc hin thng c thc hin trong bnh cu thy tinh ba c v c minh ha bi hnh sau:

Hnh 17: Minh ha tng hp PU bng phng php c dung mi[3]. Qu trnh phn ng thng c thc hin trong mi trng kh nit tr trnh hi m v kh oxy(do isocyante d dng phn ng vi hi nc to ra ure v kh CO2).

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Ngoi ra qu trnh khuy trn hiu qu l rt quan trng nhm m bo tnh thng nht ca phn ng v sn phm c a phn tn thp(ng u v mt phn t lng), c bit l giai on khi cho cht ko di mch vo. Qu trnh phn ng bao gm cc tc cht diisocyanate, polyol, cht ko di mch. Quy trnh c th c thc hin nh sau: u tin bnh cu c sy kh v rt chn khng. Sau cho isocyante v polyol vo bnh cu ri tin hnh polymer ha 70oC n 80oC trong khong 2-3 gi. Sau cho dung mi, dung mi ny s lm gim ng k nht ca phn ng ng thi nhit phn ng gim xung 40-60oC. Lc ny cht ko di mch c thm vo t t ng thi nht ca h tng ln ng k do ta phi khuy u v mnh. Phn ng c xem l kt thc khi c nht khng i hoc xc nh ch s isocyanate cn li. u im: Kim sot phn ng tng i d dng tuy nhin phng php ny t c p dng trong cng nghip v c chi ph cao, quy trnh phc tp v gp nhiu kh khn trong vic s dng v thu hi dung mi. 2) Phng php khng dung mi. y l phng php c dng ph bin trong cng nghip hin nay. Qu trnh tng hp c th tin hnh bng qu trnh mt bc hoc hai bc. Quy trnh thc hin thng c minh ha nh hnh sau.

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Hnh 18: Tng hp PU bng phng php khng dung mi[3]. Vi phng php mt bc cc monomer polyol, diisocyante, cht ko di mch c phi trn cng mt lc sau tin hnh qu trnh polymer ha thu c sn phm cui cng. i vi phng php hai bc prepolymer ca polyol v diisocyante c to thnh trc. Sau cht ko di mch c thm vo ri tin hnh qu trnh polymer ha. Khi nht ca sn phm t ti nht nh, PU c mang ra khi h phn ng v c tin hnh khu mng nhit cao. Trong c phng php mt bc v hai bc phn ng thng c xc tin thng qua cc cht xc tc v u c thc hin trong mi trng khng dung mi di iu kin khuy trn mnh. Phng php mt bc thng dng tng hp copolymer ngu nhin cn phng php hai bc thng c tng hp trong cng nghip vi s lng ln. VI. Khong st Montmorillonite. 1) S lc v khong st Montmorillonite. Montmorillonite l mt trong nhng vt liu gia cng hu hiu cho vt liu do n c nhng tnh cht c trng quan trng nh: Din tch ring ca b mt t st ln. T trng ln. Kh nng trao i ion(CEC) cao nn d dng bin tnh.

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 T l co cao nn t st d dng c bin tnh. Chnh v nhng tnh cht c trng nh trn m Montmorillonite thng c s dng lm pha gia cng cho vt nanocomposite ni chung v vt liu PU nanocomposite ring. 2) Cu trc ca Montmorillonite.

Hnh 19: cu trc ca Montmorillonite. MMT c cu trc lp 2:1. Cu trc tinh th ca MMT gm hai mng t din SiO4 v xen gia l mt mng bt din MeO6 (vi Me = Al, Mg). Gia cc lp cu trc l cc cation trao i v nc hydrat ho. Trong mng cu trc ca MMT thng xy ra s thay th cc cation. mng bt din Al3+ b thay th bng Mg2+, cn mng t din Si4+b thay th bi Al3+hoc Fe3+. S thay th trn c gi l s thay th ng hnh v lm cho b mt tinh th MMT xut hin in tch m. Cc in tch m ny c trung ha bng cc cation (Na+, K+, Ca2+, Li+) nm gia hai phin st. Cc cation ny d b hydrat ha khi tip xc vi nc v d dng c thay th bng cc cation khc. Chiu dy ca mt lp cu trc l 9,6 Ao i vi trng thi kh. Khi hp th nc th khong cch gia lp cu trc tng ln

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khong 15-20Ao. Khong cch ny cn c th tng ln n 30Ao khi cc cation trao i c thay th bng cc ion v c phn cc, cc phc c kim, cc phn t hu c. VII. ng dng ca PU. Hin nay PU c ng dng rng khp trong mi lnh vc ca i sng hng ngy.Ngoi ra n cng c vai tr quan trng trong nhiu ngnh cng nghip nh sn xut t, xe ng lnh, ng tu bin v ng thi n cng c mt trong cc tin nghi trong gia nh nh t lnh, gh nm, giy, vt liu cch nhit

Hnh 20: Cc ng dng ca PU. B. NANOCOMPOSITE CHNG CHY. I) Qu trnh chy ca polymer. Qu trnh chy ca polyme l s kt hp gia nhit, nhin liu v kh oxy. Di tc dng ca nhit qu trnh nhit phn polyme din ra to thnh cc cht kh d

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chy. Khi nng oxy v cc cht kh d chy t n mt t l nht nh th polyme s chy. Qu trnh chy c miu t nh hnh sau:

Hnh 21: chu trnh chy ca polymer[9]. Mt s phn ng sinh ra nhit trong qu trnh chy: H2 + O2 C + O2 2CO + O2 2H2O 2CO 2CO2 + 58,3 Kcal + 26,4 Kcal +94,5 Kcal

Cc gc t do sinh ra trong qu trnh chy ca polyme l: H* + O2 O* + H2 HO* + CO O* + HO* H* + OH* CO2 + H*

Ba yu t chnh duy tr s chy l s hnh thnh gc t do, xy trong khng kh v lng nhit sinh ra trong qu trnh chy. Do ngn cn qu trnh chy th ta cn gii quyt trit cc vn sau:

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 c ch cc phn ng xy ha sinh ra gc t do hoc tc ng vo cc gc t do ny to ra cc cht t hot ng gp phn ngn cn s chy. Lm gim nhit vng chy v ngn cn s truyn nhit khi chy. Ngn cn s trao i kh xy gia vng chy v mi trng ngoi. II) C ch chng chy ca ph gia[9]. 1) c ch vt l. To thnh lp bo v: Cc ph gia chng chy hnh thnh mt lp than bo v trn b mt polyme. Lp than ny ngn cn xy tip xc vi b mt polyme v ngn khng cho cc cht d chy thot ra ngoi trong sut qu trnh chy. Hiu ng pha long: Cc cht chng chy di tc dng ca nhit chy ca polyme b phn hy thnh nhng cht kh khng bt chy. Cc cht kh ny s gip pha long cc sn phm sinh ra trong qu trnh chy ca polyme pha rn v pha kh. Hiu ng lm lnh: Qu trnh phn hy nhit ca cc cht chng chy c th l qu trnh thu nhit, nh l gim nhit ca polyme xung di lng nhit cn cung cp cho qu trnh chy, dn n m chy b dp tt. 2) C ch ha hc. Phn ng trn pha kh: Cc ph gia chng chy b phn hy nhit s to ra cc cht hoc gc t do c kh nng bt cc gc t do sinh ra trong qu trnh chy, to thnh cc cht t hot ng hn. T lm gim lng cht kh d chy, ngn cn qu trnh ta nhit v qu trnh chy ca polyme b dp tt. Phn ng trn pha rn: Trong qu trnh chy, cc ph gia chng chy phn hy nhit to thnh mt lp than bo v trn b mt polyme, t ngn cn s

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thot ra ca cc cht kh d chy v ngn khng cho b mt polyme tip tc b t nng. III) C ch chng chy ca Nanocomposite.

Hnh 22: C ch chng chy ca nanocomposite[9]. C ch chng chy ca PU nanocomposite ni ring v ca nanocomposite ni chung l to thnh lp bo v trn b mt vt liu. Mu c t nng cng vi s kt hp ca oxy khng kh s sinh ra nhng phn lp silicat, trong lp silicat ny c nhng nhm OH, ng vai tr l tc nhn to thnh lp than bo v. Chng c th lin kt li vi nhau hoc c th phn ng vi polyme to thnh lp v c trn b mt, ngn cn s chy ca vt liu. Nhng nh hng ca qu trnh ny l khng

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nhiu v trong vt liu silicat ch chim rt t (khong 5-7%). Khi vt liu c t nng, cc phn ng v vt l v ha hc din ra. Cc phn ng khu mng theo kiu vt l v ha hc. Khu mng theo kiu vt l to thnh lp v c bo v b mt vt liu. Khu mng theo kiu ha hc s xy ra thng qua cc phn ng ha hc, to thnh cc cht kh, cc cht kh sinh ra ny s i vo lp than lm cho lp than trng phng ln. Qu trnh trng lm lp than dy ln v c tnh cht bo v tt hn lp than bnh thng. Hoc l khi xy ra cc phn ng ha hc s ngn cn s hot ng ca cc gc t do sinh ra trong qu trnh t chy. Do , qu trnh ta nhit b ngn chn. Khi vt liu c khu mng nh vy th n s tr nn bn nhit hn nn kh nng chng chy s tt hn. Bn thn polyme cng c th t xc tc cho qu trnh hnh thnh lp than lm cho thi gian chy ngn li. C ch chng chy ca vt liu nanocomposite khng ngn cn hon ton qu trnh chy m ch lm cho qu trnh chy din ra chm i. IV) Mt s phng php kim tra kh nng chng chy ca vt liu. 1) Phng php o ch s gii hn oxy (LOI). y l phng php o nng xy nh nht c trong hn hp kh xy/nit duy tr s chy ca mu ( o theo tiu chun ATM D2863). Quy trnh c minh ha bi hnh sau:

26

Hnh 23: Phng php LOI[9]. Trong phng php ny mu o c t thng ng trong mt ng thy tinh. Trong ng c dng hn hp kh O2/N2 c thi t di ln. Mu b t chy bng n kim loi. Lc ny ch s oxy c xc nh thng qua biu thc:

Vi: [O2] l nng xy trong lun kh i vo [N2] l nng nito trong lun kh i vo Khi ch s: LOI < 20.95% vt liu d chy LOI = 20.95% bin n nh 20.95% < LOI 100% vt liu c kh nng dp tt ngn la 2) Phng php UL-94. y l phng php dng xc nh tnh d bc chy v s chy nh git ca vt liu. Phng php UL-94 c o theo cc chun: ASTM D635 v ASTM

27

D568. Ty theo s phn loi tnh d chy ca vt liu m c th chia thnh cc chun UL-94V v UL-94HB. UL-94V:

Hnh 24: Phng php UL-94V[9]. Mu c t thng ng, c nh mt u bi gi . t ngn la ngay bn di u cn li ca mu sao cho nghing mt gc 45o trong 10 giy. Ngay sau a ngn la ra ngoi cho n khi ngn la tt. Lp li 2 ln cho tt c 5 mu. Di y l bng nh gi chun UL-94V. Bng 6: Chun nh gi ca phng php UL-94V[9]. Chun nh gi Thi gian chy mu sau mi ln t Tng thi gian chy cho 5 mu sau 2 ln t Thi gian chy v pht sng cho mi mu sau ln t th hai Tm cotton chy do nha chy nh git Mu lm pht sng hay chy n gi gi mu Khng Khng Khng Khng C Khng V-0 10s 50s 30s V-1 30s 250s 60s V-2 30s 250s 60s

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 UL-94HB: Trong phng php ny mu c t nm ngang hoc nghing mt gc 45o so vi ngn la. Mu c t trong 30s hoc n v tr 1 inch. Mu t chun HB nu: - Khng c du hiu ca s chy sau khi ngng t (>30s). - Sau khi ngng t mu chy nhng khng vt qu vch 25(mm) u tin. - Ngn la tt trong khong 25-100 (mm). 3) Phng php nhit lng hnh nn.

Hnh 25: phng php nhit lng hnh nn[9]. Phng php o nhit lng hnh nn l phng php tin tin nht hin nay dng nh gi kh nng chy ca vt liu. y cng l phng php kim nh tnh d bt chy hiu qu nht cho vt liu nanocomposite. Phng php ny c o theo chun ISO 5660-1:1993.

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Nguyn tc kim tra: B mt ca mu c tip xc vi nhit mt cch lin tc t b phn t nng hnh nn (cone heater) trong phm vi 0-100 (KW/m2). Cc cht kh d bay hi sinh ra t mu b t nng c nh la bng tia la in . Cc cht kh d gy chy c thu gom li bng np y (exhaust hood) em i phn tch trong bc k tip. Vic phn tch kh ny c mc ch l tnh ton c t l sinh nhit v nhm nh gi sn lng kh c hi sinh ra t mu. Sn lng khi c nh gi bng cch o s suy gim ca mt chm tia lazer. Mu vt c gn trn mt load cell, ghi li t l tht thot khi lng ca mu trong qu trnh t. Kt qu ca qu trnh kim tra cung cp cho ta nhng s liu sau: Thi gian bc chy (s). Tng lng nhit sinh ra (MJ/m2). T l nhit sinh ra ti a (Kw/m2). T l nhit sinh ra trung bnh sau 180s v sau 300s (KW/m2). Hiu qu nhit ca qu trnh t chy (MJ/kg). Sn lng khi trung bnh (m2/s). Sn lng sinh ra kh CO (g).

C. MT S NGHIN CU V PU NANOCOMPOSITE CHNG CHY. Nghin cu tnh cht chng chy ca PU nanocomposite trn nn st hu c. Lei Song, Yuan Hu, Yong Tang, Rui Zhang, ZuyaoChen, Weicheng Fan. Polymer Degradation and Stability 87 (2005) 111-116. [10] 1) Th nghim. a) Ha cht. nghin cu tnh cht chng chy ca PU trn nn st hu c nanocomposite. Tc gi Lei Song chun b mt s ha cht nh: Sodium montmorillonite(MMT), OMT(MMT c bin tnh bi mui hexadecyl trimethyl ammonium chloride

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(C16), cht chng chy melamine polyphosphate(MPP), polyol c s dng trong nghin cu l Poly(propylene oxide) glycol(polyether) c phn t lng khong 1000, v hp cht 2,4-toluene diisocyanate(TDI).

Hexadecyl trimethyl ammonium chloride(C16).

Melamin polyphotphate(MPP).

2,4-toluene diisocyanate(TDI).

poly(propylen oxide)(PPO).

N,N-dimethylformamide(DMF).

Hnh 26 : Mt s ha cht c tc gi s dng trong nghin cu.

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b) Qu trnh chun b polyether/OMT/cht chng chy. OMT, MPP, polyether c t trong l chn khng 80oC v c sy kh trong vng 12h nhm loi nc. Sau OMT, MPP c trn chung vi polyether bng cch khuy trn u trong vng 4h nhm lm cho OMT, MPP phn tn tt vo trong polyether. Lc ny tc gi thu c polyether nanocomposite. c) Tng hp PU nanocomposite chng chy trn nn st hu c. Quy trnh tng hp c miu t theo s sau.

Hnh 27: Qui trnh tng hp PU nanocomposite. Quy trnh tng hp c tin hnh qua hai bc. Bc mt: TDI c a vo hn hp polyether nanocomposite v tin hnh phn ng 80oC trong vng 90 pht vi t l mol NCO/OH l 2:1 to thnh prepolymer. Bc 2: Diol, glycerine, DMF c a vo prepolymer, phn ng polymer ha c tin hnh 80oC trong 30 pht thu c PU nanocomposite. so snh kh nng chng chy ca PU c v khng c cht chng chy tc gi tin hnh chun b bn mu. Tt c cc mu ny u c tin hnh theo mt quy trnh nht nh nhm lm cho PU c tnh cht nhit nh nhau. Di y l bng chun b mu.

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Bng 7: Bng mu c tc gi chun b. Mu PU PU-OMT PU-MPP PU-OMT-MPP PU trng PU+OMT(5%wt) PU+MPP(6%wt) PU+OMT(5%wt)+MPP(6%wt) Thnh phn

2) Kt qu. kim tra kh nng an xen ca vt liu tc gi s dng phng php nhiu x tia X(XRD)

Hnh 28: Gin XRD ca MMT, OMT, PU/OMT v PU/OMT/MPP Nanocomposite. T gin XRD(hnh 28) ca MMT, OMT, PU/OMT v PU/OMT/MPP Nanocomposite tc gi xc nh c khong cch gia hai lp t st cha bin tnh l d001/MMT=1,3 v d001/OMT=2,1 . S dng C16 bin tnh t st lc

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ny khong cch gia hai lp t st c nong rng ra vi d001/PU-OMT=4,8

. T

y tc gi kt lun rng thu c cu trc an xen rt tt bao gm nhiu chui PU xp chng ln v an xen trong OMT. Bn cnh tc gi cng nhn thy rng khi b sung MPP vo th MPP nh hng rt thp ti kh nng an xen ca vt liu. a) Kim tra tnh cht c l. kim tra tnh cht c l ca vt liu tc gi tin hnh o bn ko ca vt liu kt qu c cho trong bng sau. Bng 8: Tnh cht c l ca PU v cc mu. Mu PU trng PU-OMT PU-MPP PU-OMT-MPP bn ko(MPa) 1.53 0.02 2.91 0.03 2.11 0.03 3.58 0.04

T bng 8 cho ta thy bn ko ca PU/OMT, PU/MPP, PU/OMT/MPP u cao hn hn so vi PU trng. kt bn ko cho ta thy rng hn 90% s tng bn ko t c l do thm vo 5%wt OMT. iu ny c tc gi gii thch l do cc OMT ng vai tr nh nhng b si t lm tng bn ko ca vt liu. Khi OMT, MPP cng c a vo PU trng ta thy bn ko ca vt liu tng r rt iu ny c tc gi l gii nh sau: OMT ng vai tr nh nhng b si t lm tng bn ko ca vt liu, MPP khi a vo lm xut hin lin kt hidrogen gia nhm amine ca MPP v nhm isocyante ca PU t cng lm tng bn ko ca vt liu. T y tc gi kt lun rng khi cho OMT, MPP vo

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PU nn th c hai u gp phn lm tng bn ko ca PU t ci thin c tnh cht c l ca vt liu. b) Kh nng chu nhit. kim tra kh nng chu nhit ca vt liu tc gi tin hnh kim tra bng phng php phn tch nhit trng lng(TGA).

Hnh 29: Gin TGA ca PU, PU/OMT, PU/MPP v PU/OMT/MPP nanocomposite. T gin TGA hnh 29 cho ta thy PU trng c qu trnh gim cp nhit xy ra trong khong t 200 -380oC v qu trnh gim cp xy ra hon ton khong 630oC. Khi c s hin din ca MPP nhit gim cp ca hn hp PU/MPP xy ra ti nhit thp hn so vi PU trng. Nguyn nhn l do s phn hy sm ca cht chng chy MPP thc y s hnh thnh cc dn sut ca acid phophoric. Acid ny thc y qu trnh gim cp ca hn hp PU/MPP xy ra nhanh hn ng thi cng xc tc cho qu trnh to thnh lp than trn b mt vt liu.

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Tng t, khi c mt ca OMT. Do OMT phn hy sm cng lm cho nhit gim cp ca hn hp PU/OMT xy ra sm hn so vi PU trng. Tuy nhin sau khi phn hy OMT hnh thnh ln mt lp than kh dy trn b mt vt liu t lm gim s tht thot nhit cng nh tht thot khi lng so vi PU trng. Khi OMT v MPP cng c phi trn vo PU, nhit gim cp ca hn hp tuy xy ra nhit thp hn so vi PU trng nhng t l tht thot nhit cng nh tht thot khi lng li thp hn rt nhiu v qu trnh gim cp hon ton xy ra nhit cao hn hn so vi PU trng. c) Kh nng chng chy. kim tra kh nng chy ca mu, tc gi tin hnh kim tra bng phng php nhit lng hnh nn v phng php o ch s gii hn oxygen(LOI). T l tht thot nhit(HRR) l mt thng s quan trng nht nh gi kh nng chy ca mu.

Hnh 30: gin HRR ca PU, PU/OMT, PU/MPP PU/OMT/MPP Nanocomposite. T hnh 30 cho thy:

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 PU trng c t l tht thot nhit rt ln c trng bi gi tr pHRR rt cao(923kw/m2). Gi tr pHRR rt cao cho thy kh nng d bt chy ca PU trng. Khi thm 5%wt OMT th t l tht thot nhit gim ng k v gim 57% so vi PU trng. iu ny c gii thch l do s phn hy sm ca OMT. OMT phn hy to thnh mt lp tro bao ph ln b mt vt liu, t ngn cn s tht thot nhit ra bn ngoi mi trng, ng thi ngn cn s khuch tn ca oxi ln b mt vt liu, t lm gim s chy ca vt liu. Khi thm 6%wt MPP, gin HRR xut hin hai nh r rt. iu ny c tc gi gii thch l do s phn hy sm ca cht chng chy MPP lm thay i c ch oxi ha ca qu trnh gim cp PU. Gi tr pHRR gim r rt(76%) khi c s hin din ca OMT v MPP trong mu do OMT thc y qu trnh hnh thnh lp than bo v trn b mt vt liu ng thi to iu kin thun li cho cht chng chy phn tn tt vo PU nn t lm tng tnh chng chy ca vt liu. Thng qua phng php nhit lng hnh nn kt qu c cho trong bng sau. Bng 9: Kt qu phng php nhit lng hnh nn. M u HRR(kw/m2) MLR(g/sm2) Specific extinction area (m2/kg) CO release amount (kg/kg) CO2 release amount (kg/kg) Vi HRR: T l tht thot nhit. MLR: T l tht thot khi lng. PU 923 0.4 1399 2.33 3.67 PU/OMT 472 0.24 473 0.37 1.91 PU/MPP 563 0.27 488 2.33 3.67 PU/OMT/MP 243 0.14 415 0.33 1.71

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T bng 9 cho ta kt qu: Khi thm OMT hay MPP vo PU th HRR v MLR gim ng k. iu ny c gii thch thng qua gin HRR. Khi OMT v MPP cng c thm vo PU nn th lng kh CO v CO2 thot ra l rt thp. T l kh CO v CO2 thot ra ph thuc vo hm lng OMT c trong mu trong khi c s hin din ca MPP khng lm nh hng ti hm lng kh CO v CO2 thot ra. T y cho thy vic b sung OMT vo PU lm gim s lng sn phm kh d chy, d phn hy t gip n nh nhit cho qu trnh chy. Khi OMT v MPP cng c a vo PU nn th c ch chng chy ca vt liu c tc gi gii thch nh sau: Trong qu trnh chy ca PU/OMT/MPP nanocomposite. MPP b phn hy to thnh NH3, H2O v cc dn sut ca acid photphoric. NH3 c tc dng thc y qu trnh to lin kt ngang vi NCO ca PU. Cc dn sut ca acid photphoric thc y qu trnh phn ng vi cc sn phm d phn hy ca PU v OMT t to thnh mt lp than trn b mt vt liu. S hin din ca OMT lm tng mc cn tr s khuch tn nhit ra bn ngoi, ng thi ngn cn s tip xc gia oxi v b mt vt liu. T lm gim ng k kh nng bt chy ca vt liu. Kt lun: Khi thm OMT v MPP vo PU nn khng nhng ci thin c tnh cht c l m cn lm tng kh nng chng chy ca PU. Thng qua phng php nhit lng hnh nn cho ta thy c s kt hp tt gia cht chng chy MPP v st hu c OMT. OMT v MPP cng tng cng s hnh thnh ca lp tro nhit cao. Kh nng chng chy ca PU cha OMT v MPP l tt hn so vi PU ch cha OMT hoc MPP.

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Chng chy cho TPU v ng dng lm v bc dy cp. D. Tabuani, F. Bellucci, A. Terenzi, G. Camino. Polymer Degradation and Stability 97 (2012) 2594-2601. [11]. 1) Th nghim a) Ha cht. Trong bi ny tc gi s dng TPU c chun b sn t polyether. C30B, cht chng chy melamine cyanurate(CM).

Hnh 31: Melamine cyanurate(CM). b) Chun b hn hp TPU/C30B/CM. TPU c trn nng chy vi C30B v CM bng my n hai vt vi tc vt l 250rpm ti nhit t 180-190oC. 2) Kt qu. kim tra v so snh kh nng bt chy ca vt liu tc gi tin hnh tng hp 5 mu vi hm lng t st v cht chng chy khc nhau. Bng 10: Thnh phn chun b ca cc mu. Mu C30B TPU TPU-0CM-5C30B TPU-23CM-0C30B TPU-18CM-5C30B TPU-23CM-5C30B TPU(%w/w) 100 92.9 77 74.9 69.9 CM(%w/w) 23 18 23 C30B(%w/w) 100 7.1 7.1 7.1

39

a) Hnh thi. Tc gi kt lun, hnh thi polymer hu nh khng nh hng ti kh nng chng chy ca vt liu. M kh nng chng chy li ph thuc vo kh nng phn tn ca ph gia vo polymer nn. kim tra kh nng phn tn ca ph gia vo polymer nn tc gi tin hnh kim tra bng phng php nhiu x tia X.

Hnh 32: Gin XRD ca C30B v cc mu. T th hnh 32 ta thy khong cch gia cc khong t st c bin tnh l kh nh(d = 1.8 ). t st bin tnh(C30B) c a vo TPU th khong cch ). Khong cch gia cc khoang st gia cc khoang st tng rt nhiu(d = 4.7 TPU vi nhm Hydroxyl trong C30B[12]. Vi cc mu c cha c cht chng chy CM v C30B th khong cch gia cch gia 2 lp t st nh hn(d = 4.0 b) Tnh cht nhit. ). iu ny c l gii l do s cn tr ca CM trong qu trnh ph gia phn tn vo TPU nn.

tng c tc gi gii thch l do s tng tc hidrogen gia nhm cacbony trong

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 kim tra tnh cht nhit ca vt liu tc gi tin hnh kim tra bng phng php phn tch nhit trng lng TGA.

Hnh 33: gin TGA ca TPU v cc mu. S phn hy nhit c xc nh l nhit ti s tht thot khi lng l 2%. T th hnh 36 ta thy qu trnh phn hy nhit ca TPU xy ra trong khong t 295-550oC. Qu tnh phn hy TPU din ra trong 2 bc. Bc 1: S phn hy u tin xy ra khong 300-375oC l do qu trnh phn hy ca phn on cng dn ti s hnh thnh ca diisocyanate v diol ng thi gii phng CO2. Bc 2: Xy ra trong khong t 375-550oC. Qu trnh phn hy xy ra phn on mm. Cc sn phm to ra trong bc ny l mt hn hp cc phn t xut pht t cc phn mnh polyol. T th TGA(hnh 33) ta cng thy C30B v CM nh hng kh nhiu ti tnh cht nhit ca TPU. C30B lm cho nhit tip xc gia b mt vt liu vi nhit gim khong 30oC. Cn CM do d phn hy v bay hi cng lm gim c 15oC.

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So snh gin TGA(hnh 33) ca TPU-18CM-5C30B v TPU-23CM-5C30B cho ta thy hu nh khng c s khc bit khi tng hm lng CM trong hn hp. T cho thy, s nh hng ca C30B l ln hn so vi CM. c) c tnh chy. kim tra kh bt nng chy cng nh s tht thot nhit ca vt liu. Tc gi tin hnh kim tra bng phng php nhit lng hnh nn v phng php o ch s gii hn oxygen(LOI). Di y l kt qu ca phng php nhit lng hnh nn v LOI. Bng 11: kt qu ca phng php nhit lng hnh nn v LOI. Mu THR (Mj/m2) TPU TPU-0CM-5C30B TPU-23CM-0C30B TPU-18CM-5C30B TPU-23CM-5C30B T bng 11 ta thy: T l tht thot nhit s gim ng khi trong mu c s hin din ca C30B hoc CM hay c hai. TPU nanocomposite c cha 5%wt t st cho thy t l gim tht thot nhit so vi TPU trng l 76%(t 2250kw/m2 gim xung cn 532kw/m2). Tuy nhin thi gian bt chy li sm hn so vi TPU trng. Khi CM c thm vo TPU, kh nng bt chy ca mu gim ng thi t l tht thot nhit, t l tht thot khi lng gim xung tuy nhin s gim ny l nh hn so vi TPU c cha C30B. 180 167 155 152 148 pkHRR (kw/m2) 2250 532 712 340 355 32 23 41 42 38 TTI(s) PI (pkHRR/TTI) 71 23 17 8 9 23.0 0.2 21.6 0.2 22.5 0.2 24.5 0.2 24.8 0.2 LOI(%)

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 Trong c 2 mu TPU-0CM-5C30B v TPU-23CM-0C30B vi kt qu o LOI th kh nng chy khng c ci thin. Trong mt s trng hp s c mt ca C30B cn gy ra s gim ch s LOI khong 1.4%. Khi c s kt hp gia CM v C30B th t l tht thot nhit ca TPU c ci thin r rt(gim 85%). iu ny c gii thch l do khi CM v C30B c a vo TPU, khi vt liu chy C30B phn hy to thnh mt lp tro trn b mt vt liu. Lp tro ny c tc dng ngn cn s khuch tn nhit ca vt liu ra bn ngoi mi trng ng thi ngn cn qu trnh khuch tn ca Oxi khng kh ln b mt vt liu. CM khi b phn hy to ra kh khng chy. Cc kh ny c vai tr lm gim hoc pha long cc sn phm chy ca kh d chy. Chng gp phn lm gim i s hot ng ca cc gc t do sinh ra trong qu trnh chy. Bn cnh s phn hy CM l mt qu trnh thu nhit t lm gim nhit ca vt liu xung di nhit cn thit cho qu trnh chy. Chnh cc yu t ny gp phn lm gim s chy ca vt liu. Kt lun: Khi thm C30B v CM vo mu khng nhng lm tng kh nng chng chy ca vt liu m cn lm tng thm tnh cht c l ca vt liu. T y nng cao kh nng ng dng ca vt liu. Khi mu cha ng thi c C30B v CM th kh nng chng chy t c l cao hn hn so vi mu ch cha C30B hoc CM. S kt hp gia cht chng chy v t st c bin tnh trong qu trnh n nh nhit ca PU xp nanocomposite. M. Modesti, A. Lorenzetti, S. Besco, D. Hrelja, S. Semenzato, R. Bertani. R.A. Polymer Degradation and Stability 93 (2008) 21662171. [13] 1) Th nghim. a) Ha cht.

43

t st c bin tnh bi Diphophonium(DP). t st cha bin tnh MMT v OMLS(OMLS hay C30B). Diisocyanate c s dng l MDI v hp cht polyol c s dng l polyester polyol. Bn cnh tc gi cn s dng mt s xc tc nh DMHCA, PMDETA. Cc cht hot ng b mt copolymer polysiloxane polyether. Cc cht to bt s dng hn hp ca 1,1,1,3,3-pentafluoro butane v 1,1,1,2,3,3,3-heptafluoro propan v cht chng chy c s dng trong nghin cu ny l hp cht chng chy ca photpho l aluminium phosphinante vit tt l IPA. Di y l cng thc ca mt s cht m tc gi s dng trong bi nghin cu.

Diphenylmethyl diisocyanate(MDI).

N,N-dimetyl cyclohexylamine(DMHCA).

1,1,1,3,3-pentafluorobutane.

Pentametyldietylentriamine (PMDETA).

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Aluminium phosphinate(IPA). Hnh34 :Mt s hp cht c s dng trong bi. b) Qu trnh tng hp PU xp cng nanocomposite. PU xp cng c chun b bng 2 bc: Bc 1: Cho t st c bin tnh bi diphotphonium vo polyol sau khuy u thu c hn hp polyol. Sau cho vo hn hp polyol cc cht nh cht xc tc, cht hot ng b mt, cht chng chy v cht to bt sau tin hnh khuy trn hn hp trong mt pht vi tc khuy trn cao. Bc 2: Cho MDI vo hn hp polyol sau tin hnh khuy trn nhanh trong vng 15s nhm to hn hp ng nht. Sau ra mt ci khun nh v c t ngoi khng kh thc y qu trnh polymer ha. 2) Kt qu. kim tra v so snh kh nng chng chy ca cht chng chy IPA tc gi tin hnh tng hp nm mu. Bng 12: Bng chun b mu. Mu Ref IPA IPA-MMT IPA-OMLS IPA-DP PU trng PU c tng hp vi cht chng chy IPA. PU c tng hp vi cht chng chy IPA v MMT. PU c tng hp vi IPA v OMLS(OMLS hay C30B) PU c tng hp vi IPA v DP( DP l t st c bin tnh bi diphotphonium). Ghi ch

45

a) Hnh thi. kim tra hnh thi ca PU tc gi tin hnh kim tra bng phng php nhiu x tia X.

Hnh 35 : Gin XRD ca REF v cc mu. T hnh ta nhn thy rng: Khi thm MMT hay DP vo PU xp th khong cch gia cc lp t st c nong rng ra nhng khng nhiu iu ny c th c gii thch l do khng c s tng tc gia MMT hay DP vi PU nn. T y tc gi kt lun rng khi MMT v DP c thm vo trong PU xp th vt liu ch t c cu trc an xen tng i thp. Khi thm OMLS vo PU th khong cch gia cc lp t st c bn c nong rng ra. iu ny c tc gi gii thch l do xut hin tng tc hydrogen gia nhm carbonyl ca PU v nhm hydroxyl ca OMLS. b) n nh nhit.

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 kim tra kh nng n nh nhit ca mu tc gi tin hnh kim tra bng phng php nhit trng lng(TGA).

Hnh 36: gin TGA ca PURef xp v cc mu[7]. T gin TGA hnh 36 ta thy: Gim cp nhit do qu trnh oxy ha xy ra qua hai giai on: o Giai on u: Lin kt ca chui polyol b phn hy to thnh cc cht d bay hi nh andehid, ceton, CO2 v H2O o Giai on 2: s phn hy ca cc nhm isocyanate v vng thm. PURef xp c t l tht thot khi lng kh ln v mt hon ton khi lng khong 660oC. a IPA vo PU xp, t l tht thot khi lng gim xung nhng khng nhiu. Khi IPA-OMLS, IPA-MMT, IPA-DP c thm vo PU nn th nhit phn hy tng ln v t l tht thot

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khi lng gim. iu ny c tc gi gii thch l do s phn hy sm ca t st to thnh lp ro cn trn b mt vt liu, t ngn cn s tht thot nhit v t l gim khi lng ca vt liu. ng thi ngn cn qu trnh khuch tn ca oxi khng kh vo vt liu t lm gim kh nng chy cng nh bt chy ca vt liu. c) Kh nng chng chy. kim tra kh nng chng chy ca vt liu tc gi tin hnh kim tra bng phng php LOI v phng php nhit lng hnh nn. Di y l bn kt qu ca phng php LOI. Bng 13: Kt qu ca phng php LOI. Mu Ref IPA IPA-MMT IPA-OMLS IPA-DP T bng 13 cho thy: PURef l vt liu d chy(LOI<20.95). Khi thm cht chng chy IPA vo PU(IPA) th kh nng chng chy ca mu tng ln. Lc ny mu c kh nng dp tt ngn la(LOI=25.6). Khi thm MMT vo PU c cha cht chng chy IPA th MMT nh hng khng nhiu ti qu trnh chy ca vt liu bng chng cho ta thy l hu nh khng c s thay i ch s LOI. Khi OMLS c thm vo PU c cha IPA th kh nng chng chy ca vt liu tng. Nguyn nhn l do kh nng phn tn ca OMLS tt hn LOI(%) 20.6 0.5 25.6 0.5 25.7 0.5 26.5 0.5 26.7 0.5

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MMT, chnh s phn tn tt lm cho OMLS to c lp than tt hn MMT t ngn cn kh nng chy tt hn so vi MMT. Khi DP c thm vo th ch s LOI tng nh so vi OMLS, nguyn nhn l do kh nng chng chy hiu qu ca DP so vi OMLS. Bn cnh phng php o ch s gii hn oxi tc gi cng s dng phng php nhit lng hnh nn kim tra kh nng bt chy cng nh chng chy ca mu. Bng 14: Kt qu ca phng php nhit lng hnh nn. Mu pHRR [kW/m2] Ref IPA IPA-OMLS IPA-MMT IPA-DP 217 148 158 169 139 THE [MJ/m2] 26.786 23.324 23.325 22.989 21.910 14.442 14.801 13.750 12.921 13.824 TSR THE/TML [kJ/m2g] 2076 1952 1994 2034 1857 TSR/TML [g-1] 1120 1239 1175 1143 1189 Char yield % 22.8 28.0 33.5 31.5 28.7

Ghi ch: o THE: Tng lng nhit sinh ra. o TSR: Tng lng khi sinh ra. o THE/TML: Tng lng nhit sinh ra/t l tht thot khi lng. o TSR/TML: Tng lng khi sinh ra/t l tht thot khi lng. o Char yield: Hm lng lp tro sinh ra. T bng 14 cho ta thy: Tng lng nhit sinh ca cc mu u gim so vi PURef nhng gim r rt nht l mu c cha IPA-DP(gim 13%). Nguyn nhn l do s c mt ca photpho c trong t st. Bn cnh t s THE/TML gim mnh(10.5%) khi trong PU xp c s kt hp gia cht chng chy IPA

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v DP. iu ny ch ra c mt s c ch nh hay mt s pha long xy ra trn pha kh. Khi IPA c kt hp vi DP, t l TSR/TML gim mnh. Nguyn nhn c tc gi gii thch l do s phn hy sm ca t st, to nn mt lp ro cn hu hiu t ngn cn c lng khi sinh ra. Do c photphonium t l TSR/TML trong PU xp c cha IPA-DP cao hn hn so vi PU xp c cha IPA-MMT hay IPA-OMLS c thm vo PU. Lc ny c ch chng chy c th c gii thch nh sau: Trong qu tnh chy IPA phn hy thc y qu trnh hnh thnh v pht trin cc dn xut photpho c cha acid t lm xc tc phn ng kh nc, dn n s hnh thnh v tch t ca lp tro trong pha rn. Thm vo di tc dng ca nhit , hp cht chng chy phn hy to thnh cc gc t do c tc dng bt cc gc t do sinh ra trong qu trnh chy t lm gim kh nng chy ca vt liu. Tuy nhin s hot ng ca photpho trong pha kh th thp hn trong pha rn. Kt lun: S dng cht chng chy cha photpho vi mt hm lng nh cho thy tnh chng chy hiu qu ca n. Hp cht chng chy trn c s photpho c kh nng chng chy hiu qu trn c pha rn v pha kh. t st ch ng vai tr thc y qu trnh hnh thnh lp than bo v trn b mt vt liu do hiu qu chng chy s khng cao. nh hng ca cu trc ha hc trong qu trnh chy v tnh cht nhit ca TPU nanocomposite. M. Berta, C. Lindsay, G. Pans, G. Camino. Polymer Degradation and Stability 91 (2006) 1179-1191. [14] 1) Th nghim. a) Ha cht.

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 tng hp TPU tc gi s dng mt s ha cht nh MDI, polyol ethylen oxide cui mch l poly(propylen oxide), C30B, cht ko di mch 1,4-butadiol, xc tc DABCO....

Methylen diphenyl diisocyanate(MDI).

Poly(propylen oxide)(PPO).

Diazobicylo [2.2.2]octan (DABCO).

1,4-butanediol.

Hnh 37: Mt s ha cht s dng trong nghin cu. b) Qu trnh tng hp TPU nanocomposite trn nn t st. Qu trnh tng hp TPU nanomcomposite c miu t thng qua s sau:

Hnh 38: Qu trnh tng hp PU nanocomposite. Qu trnh tng hp c m t thng qua hai bc:

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 Bc mt: a C30B vo polyol sau tin hnh khuy trn u trong vng mt gi nhm thu c hn hp polyol nanocomposite. Bc hai: Cho MDI, cht ko di mch, xc tc vo hn hp polyol nanocomposite ri tin hnh qu trnh polymer ha nhm thu c sn phm cui cng l PU nanocomposite. Trong bi ny tc gi tin hnh tng hp mu TPU vi cc polyol c trng lng phn t khc nhau nhm so snh kh nng chng chy ca mu. Di y l bng tng hp cc mu. Bng 15: Cc mu v thnh phn dng tng hp mu.

2) Kt qu. a) Hnh thi. kim tra hnh thi tc gi tin hnh kim tra bng phng php nhiu x tia X v knh hin vi in t truyn quang TEM.

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Hnh 39 : nh TEM ca PU nanocomposite(mu NC-I v NC-II). T hnh cho ta thy cc ht t st phn b rt u trong cu trc ca vt liu. Khong cch gia cc lp t st l kh ln v s phn b ca t st vo polyol rt u to ra vt liu nanocomposite c cu trc an xen cao. b) Tnh cht nhit. C ch phn hy do nhit ca PU c miu t thng qua hnh sau:

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Hnh 40: C ch phn hy do nhit ca PU. T hnh 40 ta thy c ch phn hy do nhit c th chia lm 3 bc: Bc mt v hai: PU s b phn hy to thnh hp cht ca ancol v isocyanate. Trong hai bc ny qu trnh bay hi do s phn hy ca PU c ngn chn bi qu trnh dime ha ca isocyanate hnh thnh nn cabordiimide. Sau carbondiimide ny s phn ng vi ancol to nn mt hp cht thay th tng i n nh. Bc 3: Xy ra s phn hy mt s cc hp cht c hnh thnh t bc mt v hai. Bn cnh qu trnh trime ha cng c th xy ra to

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ra mt vng su tng i bn hn. Cui cng l s gim cp nhit cao v hnh thnh ln mt lng nh lp tro trn b mt vt liu. c) Tnh cht chng chy. kim tra kh nng chng chy ca mu tc gi tin hnh kim tra bng phng php nhit lng hnh nn. Di y l kt qu ca phng php nhit lng hnh nn. Bng 15: kt qu ca phng php nhit lng hnh nn. TTI(s) PU I II III IV PU 29 35 26 22 NC-PU 29 33 17 25 HRRpeak(kw/m2) PU 2561 2254 2647 2664 NC-PU 918 641 848 797 PI(HRR/TTI) PU 88 64 102 102 NC-PU 32 19 50 50 HRRave(kw/m2) PU 741 637 768 775 NC-PU 344 363 444 435 SEAave(m2/kg) PU 176 235 165 235 NC-PU 305 412 172 412

Ghi ch: TTI: Thi gian bt chy ca mu. HRRpeak: T l tht thot nhit cao nht. HRRave: T l tht thot nhit trung bnh. PI: T l tht thot nhit/thi gian bt chy ca mu. SEA: Vng dp tt hon ton. T bng 15 cho ta thy: T bng 15 cho ta thy t l tht thot nhit HRR ca NC-PU u gim so vi PU mu. iu ny c tc gi gii thch l do s phn hy sm ca t st hnh thnh lp tro trn b mt vt liu. Lp tro ny c tc dng ngn cn qu trnh chy v ngn cn s khuch tn ca oxi ln b mt vt liu t ngn cn qu trnh chy v lm gim cc cht kh d chy phn tn ra bn ngoi.

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 Thi gian bt chy TTI ca NC-PU l tng t hoc gim nh so vi PU mu. iu ny c th c gii thch l do s phn hy sm ca cc cht hu c trn b mt ca t st lm tng kh nng bt chy ca vt liu. SEA vng dp tt hon ton ca NC-PU l ln hn so vi PU mu. iu ny cng c tc gi gii thch l do s hnh thnh ca lp tro trn b mt vt liu ngn c v dp tt qu trnh chy ca vt liu. Kt lun: T l tht thot nhit ca PU-NC gim ng k do s hnh thnh ca lp t st trn b mt vt liu. Tuy nhin thi gian bt chy li gim so vi PU mu nguyn nhn l do s phn hy sm ca cc cht hu c c trong t st. T y c th kt lun rng: Hm lng lp tro trn b mt ca vt liu cng ln t l tht thot nhit cng gim t cho thy kh chng chy ca vt liu cng cao. Lp tro dy kh nng chng chy tt v ngc li. D. KT LUN. Vic kt hp cht chng chy vi t st c bin tnh to thnh mt lp than ng nht trn b mt vt liu trong sut qu trnh chy. Lp than ny c tc dng ngn cn s tip xc ca xi trn b mt polyme v to thnh mt lp cch nhit ngn cn cc sn phm d chy thot ra ngoi. Lm qu trnh chy ca polyme dn dn b dp tt. t st c bin tnh hu c khi trn vo polyme nn ch gp phn to thnh mt lp than mng trn b mt polyme ngn cn lng nhit thot ra ngoi nhiu. V vy khi thm t st vo polyme nn th s nh hng tch cc n nhng thng s trong php o nhit lng hnh nn (nh pHRR, MLR, THR, HRR,...). Tuy nhin hiu qu chng chy ca t st khng cao . Do t st khng ng vai tr ch yu trong qu trnh chng chy polyme nn. Cht chng chy khi trn vi polyme nn m khng phn tn ng u th s lm cho hiu qu chng chy ca polymer gim. Nhng nu kt hp t st c

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bin tnh vi hp cht chng chy cha photpho hay nito th hiu qu chng chy ca polymer tng ln r rt. S kt hp tt gia t st v cc hp cht chng chy khng nhng lm tng tnh cht c l ca vt liu m cn nh hng tch cc n qu trnh chng chy ca vt liu. E. TI LIU THAM KHO. [1] Zoran S Petrovic, Polyurethanes (Chapter 8), Pittsburg State University, Kansas. Polymer Research Center, Pittsburg, Kansas. [2] Polyurethane Coatings. Vol. 51, No. 11, November 1959. [3] Changdo Jung. Synthesis of thermoplastic polyurethanes and

polyurethane nanocomposites under chaotic mixing conditions. A Dissertation Presented to the The Graduate Faculty of The University of Akron. August, 2005. [4] Feina Cao, Shape memory polyurethane nanocomposites. The Graduate Faculty of the University of Akron, May 2008. [5] Shawna M. Liff, Preferential Nanoreinforcement of Thermoplastic Polyurethane Elastomers with Dispersed Nano-Clay. Department of

Mechanical Engineering, June 2, 2005. [6] Clemitson, Ian (2008), Castable polyurethane elastomers, CRC Press Taylor & Francis Group, United States of America. [7] G. Behrendt, B. W. Naber. The chemical recycling of polyurethanes. Journal of the University of Chemical Technology and Metallurgy, 44, 1, 2009, 323. [8] [10] Hong Ngc Cng. Polymer i cng. i Hc Khoa Hc T Nhin, 3/2010.

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[9] P. Kiliaris, C.D. Papaspyrides. Science 35 (2010) 902958.

Polymer/layered silicate (clay)

nanocomposites: An overview of flame retardancy. Progress in Polymer

[10] Lei Song, Yuan Hu, Yong Tang, Rui Zhang, ZuyaoChen, Weicheng Fan. L. Song et al. Study on the properties of flame retardant polyurethane/organoclay nanocomposite. Polymer Degradation and Stability 87 (2005) 111-116. [11] D. Tabuani, F. Bellucci, A. Terenzi, G. Camino. Flame retarded Thermoplastic Polyurethane (TPU) for cable jacketing application. Polymer Degradation and Stability 97 (2012) 2594-2601. [12] F. Chavarria, D.R. Paul. Morphology and properties of thermoplastic polyurethane nanocomposites: Effect of organoclay structure. Polymer 47 (2006) 7760-7773. [13] M. Modesti, A. Lorenzetti, S. Besco, D. Hrelja, S. Semenzato, R. Bertani. R.A. Michelin. Synergism between flame retardant and modified layered silicate on thermal stability and fire behaviour of polyurethane nanocomposite foams. Polymer Degradation and Stability 93 (2008) 21662171. [14] M. Berta, C. Lindsay, G. Pans, G. Camino. Effect of chemical structure on combustion and thermal behaviour of polyurethane elastomer layered silicate nanocomposites. Polymer Degradation and Stability 91 (2006) 1179-1191.

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