GVHD: TS Hunh i Ph

M u Nguyn liu, phn ng tng hp

Cng ngh sn xut

Tnh cht ng dng

Gii thiu:
nh ngha Tn gi Cu trc

Lch s hnh thnh v pht trin

NH NGHA: Polyisocyanurate (PIR) l mt loi nha nhit rn c mt kt mng cao c tng t phn ng polycyclotrimerization ca diisocyanate.
Tn gi: Polyisocyanurate (PIR) Polyiso ISO
Lin kt isocyanurate

Cu trc ca polyisocyanurate vi cc lin kt isocyanurate bn, khng c hydro linh ng v mt kt mng cao

PIR khng bin tnh: Mt kt mng cao Gin, b, d v vn Khng ng dng c Bt PIR bin tnh: + Gim tnh v vn + Tnh khng chy cao + Tnh cch nhit tuyt vi

Bt polyisocyanurate c bin tnh bi urethane c thng mi ha vo nm 1996. Sn phm bt Polyisocyanurate gip tng kh nng khng chy ngn v tng n nh ca nha nhit cao. Haggis ca I.C.I. Anh pht trin mt dng bt c thng mi ha vi tn thng mi l Hexafoam vo nm 1968.

Bt tng t c thng mi ha Hoa K bi Cng ty Upjohn vo nm 1969 vi tn thng mi Kode 25 v bi cng ty Celotex Corp vi tn thng mi l Thermax K t , bt PIR bin tnh t urethane c s dng ngy cng rng ri trn ton th gii trong ngnh cng nghip xy dng.

Trong nhng nm gn y, sn phm bt isocyanurate bin tnh ngy cng c nh gi cao v kh nng khng chy nh c cc mi lin kt n nh nhit nh amide, imide, v mi lin kt carbodiimide.

Nhng bt ny th hin n nh nhit cao hn v kh nng khng chy tt hn so bt polyisocyanurate bin tnh t urethane.

Nguyn liu
Isocyanate
H xc t|c

Phn ng tng hp Bin tnh

Isocyanate monomer (Trimerization)

Cht bin tnh (polyol,)

Xc tc

Cht ph gia :cht to bt, cht hm bt chy, cht to mu, chng oxi ha

Bt Polyisocyanurate (polyiso, PIR)

1.1. Polyisocyanates 1.2. Polyols 1.3. Cht to bt 1.4. Cht hot ng b mt 1.5. Antioxidants 1.6. To mu 1.7. Xc tc 1.8. Cht ni ngang v m rng mch 1.9. Epoxides 1.10. Cht hm bt chy

II. Tng hp

Isocyanate bo c tng hp u tin bi Wurtz nm 1849 Isocyanate thm c tng hp bi Hoffmann

Polyisocyanate thm c s dng tng hp foams i t isocyanate

Isocyanate bo khng s dng do phn ng chm vi nhm OH.

II. Tng hp

S dng ch yu dng oligomer:

Methylene diphenyl diisocyanate (MDI)

Toluene diisocyanate (TDI),

PIR

II. Tng hp
Tnh cht vt l ca MDI

Polyol l cht bin tnh quan trng ca PIR:

Isocyanate Xc tc Cht to bt, Polyol

PIR bin tnh Urethane

Bao gm: polyol polyester v polyol polyether

Polyester bo
Axit 2 chc (axit adipic, axit phtalic ) Glycol (EG, PG, DEG...) Polyester bo

Polyester bo c th c iu ch bng phn ng m vng lactone, v d vi epsilon-caprolactone

Polyester thm
c iu ch t s chuyn v ester ca PET ti ch Trn vi polyester bo to ra bt PUR v PIR

Du caster
Mt glycerol ester ca axit ricinoleic Cha nhm OH th cp

To bt na cng

c phn loi lm 4 nhm:

polyoxyalkylene polyol
graft polyol (polymer polyol)

PHD polyol polytetramethylene ether glycol (PTMEG).

Polyoxyalkylene Polyol: iu ch bng cch trng hp anion ca alkylene oxides nh ethylene hay propylene oxides

f l s nhm chc ca cht khi mo, R l cht khi mo, n l s mol ca cc phn t alkylene oxide v R l H hay CH3

Graft Polyol (Polymer Polyol)

Bao gm acrylonitrilegrafted, acrylonitrile- v styrene-grafted polyether polyol
Nng thp t 20 n 21% Cao hn t 30-50% Acrylonitrilestyrenegrafted polyether polyol

Polyol cha polyurea phn tn

c sn xut bng phn ng TDI vi polyether polyol cha hydrazine di s khuy mnh
u im ca PHD polyol bao gm tnh cht to bt ln
Bin tnh foam mm do, foam co tnh n hi cao

Polytetramethylene Ether Glycol (PTMEG)

Polymer ha m vng cyclic ether v d nh tetrahydrofuran (THF) sn xut PTMEGs hoc poly (oxytetramethylene) glycol.

Cht to bt
mt th{nh phn khng th thiu

Hp cht Ha hc ha hc phn ng vi nhm isocyanate to CO2 Cht lng ts thp, khng phn ng vi nhm Vt l isocyanate

C ch to bt bng nc t nhm isocyanate Mt s nhc im 1. Lm nhit phn ng cao hn

2. nht cao 3. Trong h thng bt cng t l trn cao

linh ng ca h thng to bt trong khun km

cho hiu qu trn km

4. Chi ph h thng cao . Gn y phn no ci thin c cc nhc im.

- L cc cht lng tr c nhit si thp chng b bay hi do nhit sinh ra t cc phn ng. - Cc cht to bt vt l bao gm:
Carbon dioxide ho lng

C5hydrocar bon

Hp cht c cha fluorine

Azeotrop es khng c halogen

 Xc tc cho isocyanate-based polymeric foams bao gm PIR c tng hp bi phn ng trimerization ca isocyanate monomer vi s c mt ca cht bin tnh nh polyols

Cyclotrime rization xc tc

Blowing xc tc

Xc tc to gel

oxazolidon e xc tc

carbodiimi de xc tc

Phn ng cyclotrimerization ca polymer isocyanate

Phn ng to nhm chc polyurethane

Gm mt cyclotrimerization xc tc v mt urethane xc tc

Trong mt s trng hp ch s dng xc tc cyclotrimerization cng c th c.

Isocyanate cyclotrimerization xc tc c trnh by bng di

PIR vi cc lin kt isocyanurate c bn nhit cao hn nhiu so vi bt PUR. Tuy nhin, tng tnh chng chy i vi mt s ng dng, ta cng c th thm vo cht hm bt chy (fire-retardant) Gim s sinh ra ca cc kh d bt chy v th kh nng chy ca PIR gim xung. Cc loi cht hm bt chy c th s dng bao gm loi reactive (c lin kt ha hc vi polymer) v additive (ph gia thm vo khng to lin kt ha hc vi bt.

 Nhm isocyanate c 6 kiu phn ng:

Cng Kt ta Nhit phn ca hp cht cng Dimerization
Phn ng ng vng ca 3 hp cht isocyanate Polymer ha theo c ch gc t do

PIR c tng hp t phn ng cyclotri merizatio n

a,b- diphenyl alliphanate Phenyl isocyanate ethyl alcohol ethyl carbonate mt lng nh nhit C 1200 phng phenyl isocyanate dimer. 125C triphenyl isocyanurate N-methylmorphorine hiu sut rt cao

Kogon ngh c ch cyclotrimerization bi amine bc 3 nh sau xc tc

II. Tng hp
Amine v olen oxide to ra ion lng cc
T hp lin hp amineimine

Trong : R la H, alkyl, P=O, hoc nhm ure

Aldehydes to ra ion lng cc

 Sayigh ngh c ch khc ca phn ng cyclotrimerization trn c s xc tc c bit

 Xc tc acid

Xc tc Amine

II. Tng hp
Xc tc Base

PIR khng bin tnh c cu trc kt mng ngang cao gin, b, d v vn

LIN KT BIN TNH

BIN TNH

CHT TO XP T L NCO/OH

MT NI NGANG

CHT BIN TNH

Polyol

bo/polyester ca polyol thm/ nha phenolic resol lin kt urethane Acid dicarboxylic lin kt amide

Polyepoxide lin kt 2-

oxazolidone Dianhydride thm lin kt imide Xc t|c to lin kt carbodiimide

Lin kt urethane:

T l NCO/OH

Lin kt isocyanurate

Tnh d v vn
Lin kt urethane Tnh d ch|y

Polyol thm
PET ti ch Mannich polyol

u im

Nhc im

+t khi sinh ra +H{m lng tro cao - chc thp n nh theo hng thp - nht cao gia cng kh khn

Nha resol
Nha furan

OH phenol OH methylol

Lin kt urethane

furfuryl alcohol

Formaldehyde

Bt PIR

+ H{m lng tro cao (98%) + mm do cao + bn nn cao

Bin tnh 2-Oxazolidone

Bin tnh amide Bin tnh imide Bin tnh carbodiimide Bin tnh diamine thm bc 2

 bn nhit ca cc lin kt:

Hydro linh ng

isocyanurate

2-oxazolidone

urethane

Lin kt 2-oxazolidone: lin kt urethane vng nhng khng c hydro linh ng bn nhit.

Tng t nh lin kt 2-oxazolidone, lin kt amide cng c bn nhit cao hn lin kt urethane, do , bt PIR cng c bin tnh bng dicarboxylic acid to lin kt amide.

PIR bin tnh vi adipic acid

C ch phn ng to lin kt imide

To bt

3,3,4,4, Benzophenonetetracarboxylic Dianhydride (BTDA)

diphenylmethane diisocyanate (MDI)

120oC Khng dung mi

Bt PIR

+ Khng cn dung mi + Khng cn cht to bt

Isocyanate

a t Xc tc
PMPO

Lin kt carbodiimide

+ Quy trnh 1 bc + Khng cn cht to bt + Nhit phng

Quy trnh

Sn phm

+ Hm lng tro cao (99.1%) + Thi gian chy xuyn di + Khi lng mt do v vn thp (5 10%)

Diamine thm bc 2 Diamine thm bc 2 vi cu trc nh trn to ra bt PIR bin tnh ure cha nhm th N- (N-substituted ureamodified polyisocyanurate foam) bi phn ng gia nhm amino vi nhm isocyanate:

Quy trnh cn tm Quy trnh khc,

Quy trnh slabstock

Phng t do

B nguyn liu, xc t|c

Lp ph trn u trn

Bm

Bung thi kh nng

Dao ct

Lp ph di

Con ln p

Phn ng, to bt, Cp nhit ng rn

Cu trc composite

Phin tm

Phng gii hn

50 - 65oC

Phng t do Tnh chy H xc tc Khng yu cu v tnh chy ca hn hp Tha m~n yu cu v thi gian phn ng

VS

Phng gii hn Yu cu v tnh chy ca hn hp Yu cu v thi gian phn ng, v m bo tnh chy Kh iu khin hn iu khin bi b phn c|n (laminator) Gn nh chnh xc

Mt c iu khin tt hn khi lng Chiu dy tm Da v{o s phng n ca bt Khng iu khin chnh x|c

Mt mt vt liu

Khng ng u trn to{n tm Nhiu do phi gt bin

ng u
t hn

Rt lin tc hn hp to bt lng ln bng ti ng bng u trn di chuyn c.

Ngi ta cn t thm mt lp ph pha trn v p vo khi bt bng thit b thch hp.

Ch n dc H

A H

VB W

Bt c trng th|i n nh

Cng ngh phun

L{ cng ngh c nht ca bt PIR v{ PUR + To c|c lp c|ch ly khng mi ni + C th ph c nhiu b mt phng, khng phng

Tht tho|t nguyn liu, g}y nhim mi trng nh hng ca kh quyn v{ nhit ln vt liu.

CN c

CN rt ti ch

Tnh kh|ng ch|y v{ nhit Khi pht sinh

Ph|t thi HCN

Th nghim The Bureau of Mines flame penetration test

Th nghim Large-scale fire tests

Tc nhn kh khi:

Nguyn tc l b sung thm cht kh khi vi t l 1/10 phn polyol c trong polycyanurate Cc tc nhn l aldehydes thm nh benzaldehyde, furfural, p-hydroxybenzaldehyde, v cinnamaldehyde Trong , Benzaldehyde cho kh nng kh khi tt nht.

Hin nay vt liu polyisocyanuarate c s dng rng r~i:

Trong x}y dng Trong cng nghip ( du m , ha cht v.v) Trong lnh vc i hi k thut cao ( ch to t{u con thoi,)

NG DNG

PIR c s dng l{m c|c tm c|ch nhit hoc c phun v{o c|c loi vt liu trong x}y dng nhm tng tnh chu nhit:

Dng phun (xp) Dng tm

L kim loi v nha cng ph b mt, tm bt PIR c th gip n nh gi tr R-. Th nghim cho thy rng gi tr R n nh ca bt cng vi l kim loi vn khng thay i sau 10 nm. L kim loi, nu c ci t mt cch chnh xc cng c th hot ng nh mt ro cn bc x .

Hin nay cc cng ty xy dng trn th gii ang s dng ngy cng nhiu hn cc dng tm cho cc cng trnh ln ca h

Lm ng

Tnh cht ca ng lm t PIR:

Vt liu cch nhit hiu qu Nh Kh nng khng thm kh tt Chu lc nn tt Khong nhit s dng rng Khng gy kh khn v nguy him trong qu trnh lp t C kh nng cch in tt

c NASA s dng trong ch to b phn mang nhin liu cho tu con thoi i vo v tr

Nhng ngi thc hin:

Nguyn L Mnh Ch Nguyn Qu|ch Triu Dng ng Giang Ho{i Nguyn Vn Ho{ng Nguyn Thanh Huyn Phan Cng Khanh ng Khoa Th|i Ngc Thng L nh Tng Lu Quc To{n V0904069 V0900475 V0900885 V0900932 V0901052 V0901163 V0901223 V0902555 V0903190 V0902820