BI GING MN K THUT SN XUT CHT DO GV SON: PHAN TH ANH

PHN 1 CNG NGH SN XUT MT S POLYMER TRNG HP CHNGI: SN XUT POLYETYLEN (PE) I.Nguyn liu Nguyn liu sn xut PE l etylen (C2H4), ch yu thu c t vic cracking du m. Tnh cht ca C2H4: + tonc = -169oC + tos = -103,8oC + Khi lng ring tosi: d(ts) = 0,57 g/cm3 Etylen khng phn cc ( o =0) nn kh trng hp. Lng nhit to ra khi trng hp cao. Monome C2H4 (kh) Stryren (lng) Lng nhit to ra (cal/g) 800 164

MMA (nh tng) 129 Etylen dng sn xut yu cu : C2H4 98% C2H6 1 2% N2 0,5 1% C2H2 0,1 0,3% II.L thuyt trng hp Phn ng trng hp etylen thnh PE c th thc hin theo c ch gc hoc ion. 1.Trng hp gc Peroxit, pesulfat, hp cht azo v cc dn xut alkyl ca cc kim loi khi un nng to ra gc t do. Cc gc t do mi ny d dng phn ng vi etylen: R + CH2=CH2 R-CH2-CH2 Gc ny tip tc pht trin :

R-(CH2-CH2-)CH2-CH2 R-CH2-CH2 + nCH2=CH2 Giai on ny nhit phn ng to ra rt ln do cn phi ly nhit ra khi hn hp phn ng. Nu khng do s tng cao nhit etylen khng phn ng b phn hu v thng km theo ting n. Phn ng pht trin mch ngng l do kt qu kh hot tnh gc polymer R-(CH2-CH2-)nCH2-CH2 + CH2=CH2

R-(CH2-CH2-)nCH=CH2 + CH3-CH2

Trong qu trnh phn ng, do s kt hp ca cc phn t etylen hoc gia monome vi i phn t polymer to ra nhnh. R-(CH2-CH2-)m C H-CH2-CH2-CH3 + nCH2=CH2R-(CH2-CH2-)mCH-CH2 -CH2-CH3 (CH2-CH2)n-1-CH2- C H2

nCH2=CH2 + CH2=CH2 + mCH2=CH2

-(CH2-CH2-)nCH-(CH2 -CH2-)m CH3

2.Trng hp ion ng ch l trng hp etylen theo c ch trng hp ion c xc tc Xigle-Naptha, TiCl3 + Al(R1)3 R1: C2H5

TiCl3 + Al(R1)3 Ti Cl2Cl Al (R1)3 + C H2= C H2 TiCl2Cl Al (R1)3

t0

+

+

t0

CH - C H2

+

+u im: Trng hp etylen c xc tc Xigle-Naptha c nhiu u im nh polymer t nhnh, tnh c l cao. +Nhc im:

Xc tc t, d chy n Sau khi kt thc qu trnh phi tch xc tc ra khi polymer phc tp. III.Cc phng php sn xut PE Nha Polyetylen c nhiu loi: HDPE, LDPE, LLDPE, VLDPE, nhng trong th trng ph bin l 2 loi HDPE v LDPE. HDPE l PE c khi lng ring ln. C th sn xut theo 2 phng php: +p sut trung bnh (30 40 atm) +p sut thp (3 4 atm) LDPE l PE c khi lng ring b. Sn xut theo phng php p sut cao (1500 2500 atm). 1.Phng php p sut cao (P=1500 2500 atm) Phng php trng hp etylen trong pha kh p sut cao v nhit cao (180 200oC) c cht khi u l O2 l phng php c bn sn xut PE c t trng thp, trng lng phn t10.000 45.000. -Cc yu t nh hng n qu trnh trng hp: +Hm lng O2 trong khHiu sut (%) 170 Co

15 10 5

160 C

o

150 C

o

Hiu sut (%) 1350 atm 1150 atm 15 10 5 1000 atm 100 atm

0,01 0,02 0,03 0,04

% Oxi

0,01 0,02 0,03 0,04

% Oxi

Oxi l cht khi u trng hp, tc phn ng ph thuc vo lng O2 trong kh, nhng v nhit v p sut cng nh hng nhiu n n nn s ph thuc ny rt phc tp. Nu nng O2 qu cao, etylen s b phn hu thnh C, H v CH4. VD: 2000 at v 165oC phn hu xy ra ngay 0,075% O2 so vi lng monome. Trong 2 th trn ta thy tt c cc nhit v p sut u c hiu sut cc i v hng v pha O2 t. +Nhit : Tng nhit phn ng n gi tr nht nh s lm tng nhanh qu trnh trng hp v tng hiu sut polymer, trng lng phn t gim.

Tng nhit phn ng ph cng tng theo. +p sut: p sut tng th vn tc phn ng v hiu sut to thnh polymer ln.Vp khi p= 1atm V5000

4000

3000

2000

1000

300

1100

1500

2500

p (atm)

nh hng p sut n vn tc trng hp -Thit b phn ng loi ng c dng dtng=10 30mm -c im ca loi trng hp cao p: +C lin kt i cui mch nhiu (do chuyn mch, t mch) hm lng tinh th +C nhnh CH3, (-C2H5) ln hn cc phng php khc khng cao. K-(CH2-CH2-)x CH2- C H2 + CH2=CH2 K-(CH2-CH2-)x C H- C H2 + CH2=CH2

K-(CH2-CH2-)x CH2-CH2- C H-CH3K (CH2 CH2)x CH CH2 CH2 C H2

-u, khuyt im: +u im: Sn phm sch (v khng dng cht khi u hu c), tnh cch in cao. +Khuyt im: V p sut cao: kch thc thit b b nn nng sut b. Nng lng tiu hao nhiu do qu trnh nn kh. Thit b t, lm t thp c bit, vn lm kn thit b, vn chuyn etylen p sut cao c nhiu kh khn. phng php cao p t sn xut. 2.Phng php sn xut trung bnh (30 40 atm) Trng hp etylen trn xc tc oxit crom c th tin hnh theo phng php gin on v lin tc trong dung mi hoc trong pha kh trng hp cation.

-Cc giai on chnh ca qu trnh: +Chun b xc tc: Trn CrO3 vi cht mang alumino silicat. Yu cu ca xc tc l phi c th tch t do v b mt ca mao qun phi ln Vtd= 1cm3/g F = 400 500m2/g Xc tc s dng dng huyn ph l 0,2-0,6%. +Chn dung mi: Dung mi ch ho tan C2H4 v khng ho tan polymer, ru metylic, xiclohecxan, xng tinh khitCH3OH l dung mi tt nhit no cng khng ho tan polymer nhng ho tan monome. +Tch xc tc ra khi hn hp sn phm: Mun tch xc tc th phi ho tan PE trong dung mi thch hp ri tch xc tc bng my li tm. Sau sy tch dung mi ta c PE em i to ht. -Cc yu t nh hng :[] Lng PE (g/g xc tc)

1,8

110

0,6 10 10PE (g/g xc tc)

20

30

40

p

10[]

20

30

40

p

115-120 C o 125-130 C 135-140 o C 15 100-105 Co

o

1,8

10

135-140 C 0,6

o

5

5

10

15

20

t(pht)

50

10

15

t op

p sut cng ln th [ ] cng ln

M P cng cao

Nhit phn ng cng ln [ ] cng gim

M P cng gim.

p sut cng tng, hiu sut to PE cng ln. Nhit thp th hiu sut phn ng thp, nhit cao th hiu sut cao nhng khi tng nhit ln na (125 130oC) th hiu sut gim v khi nhit (135 140oC) th hiu sut rt thp. Khi nhit cng cao th xy ra nhiu phn ng ph nh: ngt mch, oxi ho,.. nn hiu sut gim. -u, nhc im: So vi phng php p sut cao: +u im: -Khng dng cc thit b t tin -Th tch thit b ln nng sut cao gi thnh h. -% tinh th ln (>85%) do t phn nhnh -Khi lng ring d ln hn PEHD So vi phng php p sut thp: +u im: -Xc tc r, an ton khi s dng (t c, khng gy chy n) -D ti sinh dung mi. +Nhc im: -V xc tc l cht rn (CrO3) nn tch xc tc kh khn, mun tch phi ho tan PE ri lc, sau sy tch dung mi phc tp. 3.Phng php p sut thp (3-4 atm) Trng hp etylen trong dung mi c th thc hin c vi cc loi xc tc v cc cht khi u khc nhau, ph thuc vo h thng khi u m cc iu kin trng hp v tnh cht ca polymer thu c s thay i. Dung mi s dng c th ho tan hoc khng ho tan polymer, thng dng: ru metylic, xiclohecxan, n-hecxan, n-heptan, benzen,.. trong ru metylic l dung mi tt trng hp etylen v n ho tan etylen m khng ho tan PE. Xc tc c s dng rng ri trng hp etylen l Xigle-Naptha (TiCl4+Al(C2H5)3) Qu trnh tin hnh: Cho dung mi bezin + xc tc to thnh hn hp huyn ph, cho monome etylen p sut 3-4atm vo thit b phn ng. Nng nhit t t ln 75-80oC, gi to=80oC n khi kt thc phn ng, hiu sut 92 95% . nhit ny PE khng ho tan trong benzin, khi t hiu sut ngi ta tch PE ra khi huyn ph bng li tm. Sau ra sch bng

CH3OH ( tch cc xc tc cn ln li) ri ra li bng nc. Sau PE c sy kh vi hm m W=0,25 0,5%, c to ht, ng bao. Benzin c cha polyetylen t trng thp v hn hp benzin, rc c em i chng tch, lm sch, s dng li. u, nhc im: +u im: -Tin hnh p sut thp nn nng lng tiu hao b nht nng xut sn xut ln gi thnh thp. -Trng lng phn t ca PE ln nn bn c hc, bn nhit cao hn phng php p sut cao. +Nhc im: -Phi hon nguyn dung mi nn dy chuyn sn xut phc tp tn km. ra -PhI tch ht xc tc ra khi PE -Xc tc d chy n khi tip xc vi khng kh IV.Cu to, tnh cht v ng dng ca PE 1.Cu to Phn t polyetylen c cu to mch thng di gm nhng nhm etylen, ngoi ra cn c nhng mch nhnh. PE l polymer khng phn cc, monome lng cc 0 0 . Nu mch nhnh cng nhiu v cng di th kt tinh cng km. PE c kt tinh tng i cao v khc nhau i vi mi loi. Trong PE phn tinh th lm cho mch cng nn bn nhit , bn vi tc dng c hc, cn phn v nh hnh lm cho mch mm. Cu to ca PE ph thuc vo phng php sn xut. HDPE LDPE

S lng nhm -CH3 (nhnh) trong 1000 nguyn t C Tng lng Nhnh Loi cui mch nhnh CH3 PE cao p PE p sut thp 21,5 3,0 4,6 2,0 1,5 2,5 -

Nhnh C2H5 14,4 1 1

PE p sut trung bnh 2,5

Ta thy hai phng php sau nhnh t do c s iu chnh bi xc tc.

Lng nhm khng no tnh trn 1000 nguyn t C; Loi PE Tng lng ni iH-C=CH2 R R1-C=CH2 R2 H R1 C=C R2 H

PE p sut trung 1,1 1,3 bnh PE p sut thp PE p sut cao 0,4 0,5 0,3 0,4

87% 52% 17%

7% 31% 71%

6% 17% 12%

2.Tnh cht ca PE n gin y ta nu ra mt s tnh cht quan trng ca 2 loi PE thng dng l HDPE v LDPE. LDPE HDPE +d=0,92 0,93 (g/cm3) +T trng d= 0,95 0,96 +Khng ht m, mc hp th nc trong +Khng ht m 24h100oC, lc ny ni ngang b gy + Nha rezit l nha ng rn hon ton to thnh polime c mng li dy c, trng thi khng nng chy, khng ho tan trong bt k dung mi no. Mng li khng gian to ra do lin kt nhm metylen v lin kt hydro . c/ Sn xut bt p t nha novolac Thnh phn nguyn liu: - Novolac 42,8 PKL - Ph gia bt g l kim ( g chc, t tp cht, cha nhiu xenlulo, khng cn dng xenlulo trc tip do sn phm bn thn c mu ti cn xenlulo c mu trng) 43,6 PKL - Cht ng rn (urotropin) 6,5 PKL

- Cht lm trn, bng (stearat Zn, Ca...) 0,7 PKL - Cht tr ng rn (CaO, MgO...) 0,9 PKL - Cht mu (ch l mu sm) 4 4,5 PKL * Chun b nguyn liu: Nghin mn nha Novolac Nghin mn v sng bt g ( 960 l/1cm2) * Tin hnh: - Trn 1 t nha nghin mn vi urotropin (m nh) - Trn 1 t nha nghin mn vi cht mu v cc ho cht khc - Trn nha v ph gia (ph gia c cho vo t t). Sau cho hn hp cht ng rn v hn hp cht mu chun b trn vo. u tin trn trong my hai trc nm ngang c cnh khuy hnh ch Z, tip tc trn trn my cn nng 2 trc c t tc nhit < 105oC hoc trn trong my trc vt lin tc. Thi gian trn trn my cn 2 3,5 pht/m, nu trn trong thi gian di s xy ra phn ng ng rn hay b chy ra v dnh vo trc. Sau lm ngui v p, nghin trn my nghin bi ri sng ng bao. * Qu trnh p, gia cng sn phm Nhit p 160 165oC ph thuc vo chiu dy sn phm. p sut p 300 350 KG/cm2. Khi p c kh NH3, N2, H2O, CH2O thot ra nn phi nng chy p ln 1,2 ln trnh hin tng xut hin l xp do kh thot ra trong qu trnh p. Thi gian p 1,5 2 pht/1mm chiu dy sn phm. Trong qu trnh ng rn + Phenol kt hp vi urotropin to nha novolac trc ri sau to rezol -> rezitol -> rezit. + Nha novolac kt hp vi urotropin to rezol -> rezitol -> rezit - CH2 - + CH2O - CH2 O CH2 - CH2 - + 2 N2 (NH3) (CH2)6N4 + Nha ng rn c mng li khng gian tng i dy c nn sn phm hi dn, v vy khi thm ph gia vo th gim c tnh dn ca nha. + Khi qu trnh ng rn kt thc th trong cu to ca nha vn cn mt s nhm CH2OH t do hay ti nhn phenol vn cn v tr hot ng.

OH CH2 CH2 CH2 OH

OH CH2 CH2OH

OH CH2

OH CH2 OH CH2OH OH

CH2 HO CH2 CH2 OH CH2

CH2 OH CH2OH

+ CaO ngoi tc dng tr ng rn cn tham gia vo qu trnh phn ng nh:

O Ca O

* Tnh cht ca sn phm p: + Khi lng ring d = 1,25 1,4 g/cm3 + Gii hn bn ko k= 400 600 KG/cm2 + Gii hn bn nn n= 1000 1600 KG/cm2 + dn di %= 0,3 0,7% + cng Brinel 25 40 KG/mm + ht nc tng 0,2 0,6% + bn ho hc: bn axit (tr axit c tnh oxi ha mnh), dung dch mui v cc ho cht, khng bn vi kim (do c OH- ca phenol) IV/ Tnh cht, ng dng ca nha phenol-formaldehyt * Tnh cht : Nha rezolic l mt hn hp sn phm phn t thng v nhnh, trng lng phn t t 400 1000. Nha rezolic c tnh n nh cao, cha t phenol t do, bn ha hc v cch in cao .

Nha rezolic nhit thng vn mt tnh chy nht, nng chy v ha tan, ngha l khi bo qun tnh cht ca chng thay i theo chiu hng to thnh polimer mng li v rezolic chuyn dn sang trng thi rezitol. Hm lng phenol t do cao hoc thp cn ph thuc vo t l ca cc cu t, c im v lng xc tc, chiu su ngng t v thi gian sy. Nha rezolic rn thng cha 8 12% phenol t do, nha rezolic lng cha 20 hoc cao hn. Lng phenol t do nhiu n s lm gim tc ng rn v tnh cht c l ca sn phm. Nhng c mt s trng hp cn cha mt t phenol t do trong nha v n lm cho nha d nng chy hn v to mng sau khi ng rn c n hi hn . Hm lng oxy trong nha rezolic (khi iu ch dng xc tc NaOH) c mt s lin kt ete( -CH2-O-CH2-)v khi un nng nha th thy c CH2O ta ra. Trong trng hp dng xc tc NH4OH khng c lin kt ete v un nng nha n 200oC th khng thy CH2O to ra. Nha rezolic c th ha tan hon ton trong nhiu dung mi nh: xilohexanol, phenol, dioxan, butanol... nhng vi iu kin l nhit si ca dung mi trn 100OC lc th cc ni ngang u b ph hy. Tc tng nhit nh hng n ha tan ca rezolic .Nu tng nhit nhanh th lc nha cha kp trng trong dung mi, lng ni ngang tng ln v ngng hn qu trnh ha tan nha. Nu un nng lu th c th lm rezolic tan hon ton. Nha rezolic b ng rn (rezit) : trong giai on rezit mng li tham gia to ra khng nhng ch do lin kt ha hc m cn do lin kt l hc. nhit cao lin kt l hc b ph hy do xut hin mt t tnh n hi, khi lm lnh tnh n hi mt i. Trong nhng iu kin xc nh ( nhit cao v un nng lu) nu dng mt lng phenol tha x l rezit nghin nh th nha ny c th bin thnh nha novolac trong trng hp ny xy ra hin tng t lin kt ha hc gia cc phn t v to ra lin kt vi phenol. *ng dng ca nha rezolic: Nha rezolic lng (khng c nc) p dng rng ri tm vi, si, dng lm bt p, dng lm vt liu p tng, keo dn v sn. +Bt p :

Vt liu p dng bt l hn hp cu t phc tp ch yu t nha novolac v rezolic .Bt p dng lm dng c k thut v sinh hot, dng lm vt liu cch in, chu tc dng ca dng in 20kV to =200oC. +Vt liu p tng: Tectolit l cht do lp, c dng ch to t ca nhng tm vi c tm nha rezolic, vi dng c th l vi thy tinh, vi dt cho, vi tng hp. Tnh cht ca Tectolit: C bn nn, va p cao nhng km bn nc, chu xng du tt nn dng trong cng nghip ch to my. + Keo dn v sn: Nha phenol - formaldehyt c ngha quan trng dng sn xut keo dn v sn. Keo phenol - formaldehyt c bn mi ni cao, chu m v vi khun nhng c nhc im l mng dn gin. Nha phenol - formaldehyt l loi nha tng hp dng sn xut sn. Ngoi nha v ru cn thm 5 10% colophan vo sn. Sn du cao cp iu ch t nha 100%. Sn du Copan l loi sn c iu ch t Copan trn vi du lanh nhit cao t 230 280oC. Sn t nha rezolic tan tt trong cn. Ngoi ra nha rezolic cn dng lm cht dobt.

CHNG VIII: SN XUT NHA URE-FORMALDEHYT I/ Nguyn liu 1/ Ure CO(NH2)2 d = 1,335 g/cm3 tnc= 132,7oC + Cu trc tinh th hnh kim di khng mu hoc hnh lng knh trng. Ure ho tan tt trong nc, trong ru v trong amoniac lng, nhng ho tan t trong este v khng tan trong cloroform. Ure c c tnh kim yu v khi t nng dung dch nc ca ure n 80oC to ra mui amon ca axit cacbamit NH3COOH, khi t cao hn 130oC ure b phn hu thnh CO2 v NH3. + iu ch: NH3 tc dng vi CO2 to thnh cacbamat amon, sau tch nc t cacbamat rn hoc dng chy lng bng cch un nng n nhit 135 150oC v p sut 55 60atm trong autoclave NH2COONH4 CO(NH2)2 + H2O CO2 + 2NH3 2/ Formaldehyt ( CH2O) phn trc II/ L thuyt trng ngng ure vi formaldehyt v cu to ca nha 1/Qu trnh to ra cc sn phm ban u Nhiu kin cho rng mono v dimetylol ure l nhng sn phm u tin ca phn ng ure vi formaldehyt. Ph thuc vo cc iu kin sau: + T l xc nh gia ure v formaldehyt + Mi trng trung tnh hoc kim yu + Nhit phn ng thp Trong mi trng kim yu pH = 7,5 8 v t l ure : formaldehyt = 1 : 1,6 2 th ban u to ra monometylol v dimetylol ure.O C NH2 NH2

+

CH2O

to

NH CO NH2

CH2OH

monometylol ure (tinh th)O C NH2 NH2

+ 2 CH2O

to

NH CO NH

CH2OH CH2OH

Dimetylol ure (tinh th) Monometylol ure c nhit nng chy tnc=111 113oC, cn dimetylol ure khong 121 122oC, chng tan tt trong nc, trong ru metylic, etylic, khng tan trong ete. Trong mi trng axit pH = 1 5 vi t l ure:formaldehyt = 1 : 2 hoc 1 : 1 th to ra sn phm v nh hnh khng trong sut, khng tan.

N CH2 CO NH2

N CH2 CO N CH2

monometylen ure dimetylen ure 2/ Qu trnh to nha v cu to ca nha ure-formaldehyt T monometylol ure to ra nha mch thng qu trnh xy ra theo tng bcNH CH2OH CO NH2 HO CH2 NH2 NH CH2OH CO

+

CO NH2

+

H2O

NH CH2 NH CO NH2 NH CH2OH CO NH CH2OH CO

Hoc

+

H2O

NH CH2 O CH2 NH

Tng qut: H2N-CO-NH-CH2-[-NH-CO-NH-CH2-]n-NH-CO-NH-CH2OH T dimetylol ure c th to ra nha mch thng v vngNH CH2OH

(n+2) CONH CH2OH

HOCH2 NH CO NH CH2 N CO NH CH N CO NH CH2OH 2 ` CH2OH nCH2OH

+Hoc:CH2OH N CO CH2 NH CO CH2OH N CO CH2 NH COn

H2OCH2OH N CO CH2 NH CO CH2OH

NH CH2 N CH2 N CH2 N CH2

N CH2 N

3/ Qu trnh ng rn ng rn nha UF ch xy ra trong trng hp nha cha cc nhm metylol t do. Lng nhm metylol trong nha cng ln nu lng CH2O ly dng cho phn ng cng nhiu. Nhit v xc tc c nh hng n tc ng rn ca nha. Cht xc tc ng rn nha ure-formaldehyt l cc axit hu c (axit oxalic, axit leic, axit formic....) axit v c (HCl, H3PO4...) mt s mui (clorua amn, clorua km...). III/ Sn xut nha ure-formaldehyt

T l ure/formaldehyt = 1/1,6 2, pH = 7,5 8 (dng dung dch xt nng C%=10% trung ho). Cho axit oxalic hoc axit formic cui qu trnh 0,01 0,02 phn so vi ure Th t cho vo: cho formaldehyt vo thit b phn ng ri dng dung dch NaOH 10% khmg ch pH=7,5 8 sau cho ure vo tin hnh khuy trn. Nhit ban u ca phn ng 40 50oC, trong giai on ny to dn xut mono nn khng nng nhit cao, duy tr nhit ny trong vng 30 45pht. Sau tng nhit ln 80 85oC trong thi gian 20 pht v bo m pH khng thay i. Lm ngui xung 60 65oC, cho thm dung dch axit oxalic nng 10 15% vo nhm mc ch to nha phn t ln hn v xc tc ng rn. Tng thi gian phn ng 4 5 gi/1m. * Sn xut bt p ure-formaldehyt Thnh phn: + Nha (dung dch keo trong nc): 45 PKL + Sunfit-xenlulo: 55 PKL + Cht lm trn: 0,8% so vi nha + Cht xc tc ng rn ( cc mui c tnh axit nh ZnCl2, NH4Cl hoc mui sunfua axit) + Cht mu (mu sng) Qu trnh phi trn tng t nh qu trnh chun b bt p phenol-formaldehyt nhng phi ch nhit v thi gian. Tin hnh sy nhit thp v trong mi trng chn khng. S dng my nghin bi pha ngoi my phi c b phn lm lnh bng nc. * iu kin p: p sut p: 250 280 KG/cm2 Nhit p: 135 145oC Thi gian p: 70 110 giy/1mm chiu dy sn phm Trong qu trnh ng rn c to ra nc Nhn xt: Mng li khng gian tha, cn mt lng nh nhm CH2OH- v NH2 t do. + Nha bt p ure-formaldehyt bn nhit cao nhng km bn vi nc c bit l nc nng Khi lng ring d = 1,35 1,45 g/cm3 ko = 350 500 KG/cm2 nn = 1200 1500 KG/cm2 u = 600 900 KG/cm2 bn nhit (Martens) 100 120oC ht m ( 25oC, thi gian 3 ngy m) 1 1,5% IV/ Tnh cht v ng dng ca ure-formaldehyt.

Nha ure c ng dng rng ri sn xut vt liu p, cht do lp, cht do bt, keo dn, mng ph... - Vt phm t bt p ure formaldehyt dng lm cc dng c in ( chp n, cng tc, cu dao...), chi tit my in thoi, v my thu thanh, hng tiu dng (chu, cc o, vn p...). un nng nhanh th vt phm t nha ure formaldehyt chu nhit 100 118oC, nu un lu th chu c nhit di 75oC. - Cht do lp dng lm bn, trang hong phng, bung li my bay, tu thu, toa tu ho, dng c m nhc... - Cht do bt mipo l loi vt liu nh cch nhit, cch m ch yu i t nha ure formaldehyt. u im c bn ca mipo l nh, dn nhit khng ln vo khng chy nu thm photphat amon vo. Mipo c c im rt qu l ht th m thanh mnh, c bit t tn s trung bnh n cao nn dng n truyn m rt tt khi xy dng nh ht, rp chiu bng... - Keo t ure formaldehyt c s dng nhiu trong cng nghip sn xut vn p, c khi dng lm keo dn snh s, kim loi - Nha ure formaldehyt khng tan trong ru v du, sau khi ng rn th n nh trong dung dch km v chu nc khng m bo. Do tnh a nc ca nha nn mng nha to ra d b m v nt ng thi khng t do cn thit. V vy mun s dng nha ure formaldehyt lm sn th phi bin tnh nha.

CHNG IX: SN XUT NHA MELAMIN-FORMALDEHYT I/ Nguyn liu: 1/ Melamin: (2,4,6 triamino-1,3,5 triasin) dng tinh th melamin l bt tinh th mu trng, c tnh kim yu nhng mnh hn ure, tan trong amoniac lng v dung dch NaOH, KOH, tan km trong nc v dung mi hu c. Melamin c cng thc cu to c biu din nh sau:NH2 N C H2N C N N C NH2

2/ Formaldehyt: xem phn trc II/ L thuyt a t melamin vi formaldehyt Thng thng th t l gia melamin v formaldehyt l: 1/ 2,8 1/3 c dng lm bt p, cn nu 1/3 1/4 dng lm sn. iu kin phn ng: phn ng thc hin trong mi trng trung tnh hoc kim yu pH = 7,5 8 v nhit t 90 98oC. C ch phn ng: tng t nh ure-formaldehyt hay phenol-formaldehyt ban u to ra cc dn xut metylol melamin sau cc dn xut ny lin kt li vi nhau to ra sn phm nha melamin-formaldehyt.C N

t

N C

N C

l RNH CH2OH NH CH2OH HOCH2 NH R NH CH2OH HOCH2 NH R NH CH2OH NH2

NH2 H2N R NH2

+

CH2O

OH-,to

H2N

R

NH2

N

u tip tc un nng mnh hn th to ra:NH CH2OH H2N R NH2 NH CH2OH H2N R NH2 NH CH2 NH R NH CH2 NH R NH NH CH2OH

+

H2N

R

NH CH2OH

+

H2N

R NH2

NH CH2OH

OH-,to

NH CH2OH

Nhng nhm CH2OH t do v NH2 t do c kh nng tham gia phn ng tip tc thc hin qu trnh ng rn to thnh mng li khng gian dy c trong mi trng axit v nhit 130 150oC.NH CH2 NH R NH CH2 NH NH R NH CH2 NH R CH2 NH NH CH2 NH R NH CH2 NH R NH CH2 NH NH CH2 NH R NH CH2OH NH

Do melamin c nhiu nhm inh chc hn nn trong nha c nhiu ni ngang. V vy nha melamin-formaldehyt c chu nc, chu nhit, cng v bng hn so vi nha ure-formaldehyt. III/ Sn xut nha melamin-formaldehyt Cho formaldehyt vo thit b phn ng, iu chnh pH cho n khi pH = 7,5 8. Sau ta cho melamin vo ng thi tin hnh khuy trn, lc ny ta thu c hn hp huyn ph ng nht. Tin hnh gia nhit n nhit 75 80oC do phn ng ta nhit nn hn hp s t nng ln 90 98oC. Gi nhit ny trong khong thi gian 40 60 pht ta thu c nha nh tng trong nc. Khi mun tch nc th h nhit xung v nc s tch thnh lp pha trn hn hp cn li vn l nh tng nhng nht cao hn. * Qu trnh sn xut bt p tng t nh PF v UF Tnh cht ca bt p: + Khi lng ring d = 1,45 1,55 g/cm3 + Gii hn bn ko k 620 750 KG/cm2 + Gii hn bn nn u 650 KG/cm2 + ht m (3 ngy m 25oC) = 0,1 0,15% + bn nhit (Martens) > 120oC IV/ Tnh cht v ng dng ca nha melamin-formaldehyt Cng nh nha ure formaldehyt, nha melamin formaldehyt dng sn xut bt p, cht do tm, keo dn - Vt liu p c sn xut khng nhng t nha melamin formaldehyt n cn t nha melamin ure formaldehyt. iu ch nha c n hi cao ta thm vo cc polymer khc nh: polyamid, phenol formaldehyt, polyvinyl butyral

- Nha tm melamin c bit l nha tm t vi thy tinh v vi thu tinh c gi tr rt ln v mt k thut v n rt bn. Nha tm melamin t vi xenlulo v giy dng sn xut vt liu trang hong ( bc tng nh, lm mt bn gh), vt liu xy dng. - Keo t nha melamin formaldehyt c dng nhiu trong ngnh g. So vi mi dn t nha ure formaldehyt th mi dn t nha melamin formaldehyt c kh nng chu nc si trong thi gian di v gi thnh cng t hn keo ure formaldehyt. - Nha melamin formaldehyt khng bin tnh th khng trn vi cc cu t khc trong sn c. n c th tan vo trong cc dung mi hu c v trn tt vi cc loi nha khc th phi bin tnh nha. Khc vi nha ure formaldehyt bin tnh nha ny c bn nc v bn kh quyn cao, trn tt vi nha polyester, mng sn chu tc dng ca cc cht n mn, chu nhit v bn mu, tnh cht in mi tt. Sn l sn phm trn dung dch nha ete ho vi dung dch nha polyester trong du thu du v sau khi sy 120oC th mng sn c bn cao v bng

CHNG X: SN XUT NHA EPOXY I/Nguyn liu: 1/ Difenylonlpropan (hay 4,4- dioxy aiphenyl propan hay tn thng mi l bisphenolA, dian )CH3 HO C CH3 OH

iu ch: -Bisphenol-A iu ch bng cch cho phenol tc dng vi axeton trong mi tng axit mnh nhit 40-50oC. Axit thng dng l H2SO4, HCl. Thi gian phn ng khong 15-20h.2OH

+

CH3 C O

CH3

Xt, to

CH3 HO C CH3 OH

+

H2O

-Bisphenol-A c Tnc =155oC, cu trc tinh th mu trng c th lm bng da, khng tan trong nc. 2> Epiclohidrin.H2C CH CH2 Cl O iu ch: -i t glyxeryl u tin cho hai kh HCl tc dng vi glixerin nhit 110-115oC trong mi trng axit c c un nng.CH2 OH CH OH CH2 OH

+

HCl

CH3COOH CH 2

to

CH Cl

CH2 OH

Cl

Diclohydrin glyxeryl Sau cho xt c c un nng voCH2 Cl CH Cl CH2 OH

toH2C CH Cl O CH2

+

NaOH

+

NaCl

+

H2O

-i t propylene: Clo ho propylen p sut 18 kg/cm2 v nhit 800oC to ra clorua allil, sau cho clohydrin tc dng ln ni i v cui cng dng kim kh HCl ca iclohydrin to ra piclohydrin. CH2 = CH CH3 + Cl2800oC, 18at

CH2 = CH CH2 Cl + HCl

CH2 = CH CH2 Cl + HOCl

CH2 CH ClCH2 Cl CH OH CH2 Cl

CH2 ClCH2 + NaCl

OH

+

NaOH

H2C CH Cl O

+

H2O

Epiclohydrin l mt cht lng khng mu, khng tan trong nc nhng tan trong cc dung mi hu c (C6H6, xeton,). Nhit si ts=118oC, d20oC ( g/cm3 ) = 1,1751,180. II/ L thuyt to nha epoxy: 1> Phn ng a t nha epoxy Nu tha piclohidrin th c th thu c te diglixit dioxi difenyl propan. phn ng xy ra trong mi trng NaOH:CH3 H2C CH Cl H2C O O CH CH2 O CH2

+

HO

C CH3 CH3 C CH3

OH

NaOH

O CH2

CH O

CH2

+ 2 NaCl +2 H2O

C ch: +piclohidrin theo nhm epoxy tc dng vi hydro ca dioxydifenyl propan:CH 3 H2C Cl CH O CH 3 H2 C CH CH 2 O C CH 3C H3 H2C CH C H2 O C C H3 CH 3 H2C O CH C H2 O C CH 3 O CH 2 CH O CH 2 O CH 2 C H OH C H 2 Cl Cl O H

CH 2

+

HO

C CH 3

OH

O

CH 2 CH CH 2 Cl OH

Cl OH

+To ra nhm epoxy mi do t HCl:NaO H

+ 2 N aCl + 2 H 2 O

+Cc sn phm ban u tip tc ngng t vi ioxdifenil propan:

CH3 H2C O NaOH CH CH2 O C CH3 CH3 H2C O CH CH2 O C CH3 O CH2 CH OH CH2 O O CH2 CH O CH2

CH3

+ HO

C CH3 CH3 C CH3

OH

OH

Cng thc tng qut:CH3 H2C O CH CH2 O C CH3 O CH2 CH CH2 O OHn

CH3 C CH3 O CH2 CH O CH2

Ta thy nha epoxy trng thi khng ng rn l nhng mch polyete di, trong nhm hydroxyl t do nm cch nhau mt khong cch tng i xa. Hai u mch l nhm epoxy. Nhm epoxy v hydroxyl c kh nng phn ng vi nhiu cht v ph thuc vo nh chc ca cc chc m c th thu c hoc nha nhit do bin tnh hoc nha ng rn khng nng chy v khng tan. Qu trnh xy ra chu nh hng ca t l cu t: T l mol E/D T l mol Mp ng lng Nhit mm, o NaOH/E C epoxy 2 1,1 451 314 43 1,4 1,3 791 592 84 1,25 1,3 1133 862 100 1,2 1,3 1420 1176 112 T l E/D cng thp th KLPT cng cao, ng lng epoxy cng tng, nhit mm tng. Cho xt t t, 2-3 ln bi v -Cl c th b thu phn trong mi trng kim to thnh OH lm bin i nguyn liu ban u. III/ C ch mg rn nha epoxy 1/ ng rn bng amin -Thng thng ngi ta dng di hoc tri hoc polyamin, khng dng monoamin v s khng to mng li khng gian. -Cc cht ng rn thng dng nht l: etylen diamin (ng rn ngui hoc di 60oC ), dietylen diamin, dietylen triamin (ng rn nhit cao ), trietylen triamin c tc dng gn ging vi polyamin. -Phn ng ng rn:

CH3 H2C CH O CH2 O C CH3 R1 " NH2 CH3 H2C CH O CH2 O C CH3 O CH2 CH CH2 O OHn

CH3 O CH2 CH CH2 O OHn

C CH3

O CH2 CH CH2 O

+ H2N

CH3 C CH3 O CH2 CH CH2NH R1" NH2 OH

NH2 t do cn li tip tc tn cng vo u epoxy ca mch diepoxy khc lm ko di mch -Cc phn ng ph xy ra: nhit cao nhm OH phn ng vi u NH2 ca cht ng rn amin.CH OH CH NH R1 " NH2

+NH2 R1 " NH2CH OH

+

H2 O

Hoc nhit cao nhm OH phn ng vi u epoxy ca mch:CH O CH3 CH O CH2 O C CH3 O CH2 CH OH CH2 O CH3 C CH3 O

+H2C

+u im : cht ng rn ny c th ng rn cc chi tit ln hoc dn gch p tng. +Nhc im : amin c v kh iu chnh thi gian chun b . 1> ng rn bng axit hai chc: (cht ng rn nng ), ng rn bng anhidric. -Thng dng l cc anhidric ca axit dicacboxilic, anhidric malic, anhidric phetalic -Phn ng ng rn vi axit hai chc:CH3 H2C O CH CH2 O C CH3 140-180oC R2 CH2 COOH CH3 H2C O CH O C CH3 O CH2 CH CH2 O OH n CH3 C CH3 O CH2 CH CH2 OOC OH R2 " COOH O CH2 CH CH2 O OH n CH3 C CH3 O CH2 CH O CH2

+ HOOC

V xy ra phn ng ng rn khc. To ra sn phm ph l nc khc vi loi cht ng rn amin, nc to ra bay hi li l xp nn cht ng rn axit t dng -Phn ng ng rn vi anhidric

V d: anhidric phtalic Phn ng tin hnh nhit cao t 180-220oC v qua cc giai on sau: Trc tin:CH OHCO

+

CO O

CH O CO

COOH

Sau :CH O CO CH O CO

+COOH

H2C CH OCOO CH2 CH

OH

2/ ng rn bng nhng cht ng rn khc -Ngoi hai cht ng rn trn ta cn dng cc hp cht c hai hay nhiu nhm nh chc d ng rn nha epoxy nh: nha phenol-formaldehyl, polyamine (-NH-CO-) , ure(melamin)-formaldehyl. -ng rn bng hai cht ng rn trn th nha sau ng rn c nhiu vng thm trong mch, c cng lm tng bn c hc, bn nhit , trong nha c lin kt ete, este lm cho mch mm, trong nha c nhm OH t do to nn bm dnh tt, trong nha c s lin kt ngang khng nhiu ( khng qu tha nh UF) lm mch khng qu cng. Do nha epoxy va bn nhit , bn c hc, bm dnh tt vi hu ht cc vt liu khc. IV/ Sn xut nha epoxy 1/ Sn xut nha epoxy phn t thp:(M=370-600 vC) Sn xut to ra c hai loi : ED-5: ti a 500 vC; ED-6: ti a 600 vC hoc tng t T l mol: Dian 1 Epi 2 NaOH 2 (dung dch 15% ) u tin nhit thng cho epiclohidrin vo TB phn ng, ri cho dian vo khuy u vi s vng 300 vng/pht, to huyn ph ng nht. Sau cho 65% lng NaOH vo, un nng 60-65oC, gi trong mt gi. Chop tip 22% lng NaOH vo nng nhit ln 65-70oC gi trong 2 gi . Cui cng cho ht 13% lng NaOH cn li , nng nhit ln 70-75oC gi trong 45 pht.

n y qu trnh iu ch nha epoxy xem nh kt thc. Tin hnh ra nha mc ch l tch ht mui NaCl v NaOH d (nu c), ra t 3-5 ln bng nc nng 50-60oC. Nu ch ra bng nc nng th nha khng tan trong nc do NaCl v NaOH pha trong nha khng tan ra ht. C th kt hp ra bng nc nng v toluen. Ra bng khuy trn cho nha tan trong toluen to ra nht thp. Mui v NaOH d ni ln trn c ht ra. C th tch NaCl v NaOH d bng cch sau: -Chng tch nc (trc khi chng phi cho toluen vo v khuy u nha tan trong toluen ). Sy nhit cao 75-85oC v p sut chn khng ( 600-650mmHg ). Hn hp ng ph toluen v H2O bc ln c lm lnh s phn lp, nc c tch ra v toluen quay tr li thit b. Khi nc c tch gn ht th mui trong nha bt u kt tinh. Ta tin hnh lc nha di li lc kch thc l nh. -Sau tin hnh chng ct toluene p sut chn khng v nhit ( nhit si ca toluen 112oC ) p sut Tnh cht:

Tnh cht 30% anhydric maleic 1000 8,65 100

un [KG/cm2] va p [KG.cm/cm2] bn nhit (Martens) ht m (7 ngy m, to phng)

ED-6 ED-5 65% 7% 10% 40% polyetylen hexametylen polyetylen anhydric polyamin diamin polyamin maleic 1000 750 --7,1 100 7,0 100 0,04 0,05% -100 -100

2> ng dng: -Sn, vecni, keo dn -Lm vt liu compozit ( vi si vi thu tinh , si cacbon ) -Trn vi nhiu polymer khc lm vt liu p (vi PVC, phenolformaldehyt)

CHNG XI: SN XUT NHA POLYESTE I/ Phn loi nha: Cch 1: + PEs no: l PEs iu ch t axit v ru a chc no + PEs khng no: l PEs iu ch t hoc axit hoc ru a chc khng no Cch 2: + PEs nhit do: thu c t axit v ru 2 chc + PE nhit rn: thu c t hoc axit hoc ru 3 chc tr ln (thng l ru 3 chc) II/ Nguyn liu 1/ Cc ru: d20(g/ml) Tn Nhit si Nhit ng c o o ( C) ( C) Etylen glycol (EG) 197,5 -13 1,1155 Dietylen glycol (DEG) 245,8 -8 1,1184 1,2-propylen glycol (PG) 187,4 -1,0381 Glyxeryl 290 17,9 1,2638 Pentaeritric -260 -Ru alylic (C2H3-CH2OH) 96,7 -129 0,845 2/ Cc axit: Dng axit 2 chc hoc anhydric ca axit 2 chc - Axit phtalic (izophtalic, metaphtalic, terephtalic)COOH COOH COOH

COOH

COOH COOH

Nhng ch c anhydricphtalic t axit izophtalic - Axit maleicHOOC C C H H COOH

anhydric maleicO CO C H CO C H

ng phn trans gi l axit fumaric - HOOC-(CH2)-COOH n = 2: axit succinic n = 3: axit glytalic n = 4: axit adipic n = 7: axit azelaic

n = 8: axit xebacic III/ L thuyt to nha polyeste im c bit ca qu trnh polyeste ho l phn ng cn bng v thun nghch. Nhng do hng s cn bng khng ln nn phn ng ph thuc nhiu vo iu kin chuyn dch cn bng v pha to ra polymerHO R1 " OH

+

HOOC R COOH

xt, to

HO R1" OOC R COn

O R1" OCO R

2n H2O

+

COOH

Mun chuyn dch cn bng v pha phi th tch nc v dng xc tc c tnh ht nc. Cc phn ng ph: + Ru phn:HO HO R1 " OOC R R1 " O COn

O R1 " OCO R COOH

+ HOy

R1 " OH COOH

R1 "x OH

+

HOOC *

R CO

O

R1 " OCOR

Phn ng ru phn do tc dng ca ru n este, t mch ti este to mt cu ni ete v mt axit a chc. + Axit phn:HO R1 " OOC R COn

O R1" OCO R COOH R CO

+y

HOOC R1 " COOH R1 " OCOR COOH

HO

R1 " OOCx

R COOH HOOC + *

O

Do phn ng thun nghch v c phn ng ph nn trng lng phn t trung bnh khng cao thng nh hn 30.000 Qu trnh to polyeste xy ra thao tng bcXt, 98 110oC

HO R1 " OH

+

HOOC

R COOH

HO

R1 " OOC R COOH

+ H2O

monoesteHO R1" OOC R COOH + HO R1 " OH HO R1" OOC R COOH + HOOC R COOH HO R1" OOC R COO " R1 OH

+ H2O

HOOC R COO R1" OCO R COOH

Vn tc phn ng v tnh cht ca polyeste ph thuc vo cu to ho hc ca cc nguyn liu: + Nu ru 2 chc v axit 2 chc th to polyeste nhit do + Nu ru 3 chc tr ln v axit 2 chc th to polyeste nhit rn

+ Ru bc 2 v bc 3 kh phn ng hn ru bc 1 (tc l vn tc phn ng b hn ru bc 1) + cng ca polyeste (ca mng sn) - Theo th t gim dn ca axit Axit maleic > phtaleic > adipic > xebacis > limonic - Theo th t gim dn ca ru Pentaeritric > glyxerin > EG > DEG + Cc polyeste mch thng c kt tinh cao do c th ko siHO CH2 CH2 OH

+ HOOC

COOH

HO

CH2 CH2 OOC

COn

OH

PET c cng ln, khng dng ko si m lm v chai nc do nhit thng th trong sut, cn khi un nng th c mu c. Nu dng axit metaphtalic th to ra PEs c kt tinh thp + Nu thay axit fumaric bng axit xebacis mch thng th kt tinh tng. Nu thay EG bng DEG th kt tinh gim do DEG c lin kt O+ Vn tc phn ng v trng lng phn t trung bnh ph thuc vo cu to v ng lng chc ca nguyn liu ban u. IV/ Sn xut nha polyeste Trc y ngi ta dng phng php 1 giai on tc l un nng hn hp nhit cao. u im l tng thi gian phn ng gim cn nhc im l tn tht nguyn liu nhiu ( nht l cc anhydric v axit thng hoa). V vy phng php ny t s dng. Phng php 2 giai on: + Giai on u: un nng hn hp nhit thp 98 120oC phn ln l to ra cc monoeste, gi thi gian thch hp + Giai on sau: nng nhit ln n 260 280oC v gi nhit ny n khi CA cn 1 25 th ngng phn ng. Cui cng lm lnh n nhit 150 180oC, nu dng polyeste lng th em ng thng cn nu dng polyeste rn th rt ra bng ti kim loi, lm ngui, em p, nghin, sng. CA: s mg KOH phn ng trung ho cc axit t do trong polyeste. gim CA th phi un nng v phi dng hi ca hn hp diphenyl mi to c nhit cao. giai on u c nhit thp th dng hi p sut nh. Hn hp hi bay ln ch yu l ru, ngoi ra c anhydric hoc axit do ru ko theo v nc. thit b phn ly: ru, anhydric v nc phn thnh hai lp; nc trn, ru v anhydric di. Ru v anhydric ngng t cho quay tr li thit b phn ng cn nc tch ra ngoi. * Polyeste khng no (PEsKN) ch yu i t axit khng no, ru phn ln l ru no 2 chc.

a/ Phn loi - PEsKN loi maleatO CO C H O CH COO

-

PEsKN loi acrylat PEsKN loi thng (EG + AP + AM)C C

OH OCO CH CH2

- PEsKN loi do: thay mt phn AP bng axit 2 chc mch thng hoc thay mt phn EG bng glycol mch di (DEG,DPG) - PEsKN bn mi trng: thm cht n nh quang ( nh benzophenol hoc thay mt phn styren bng MMA) - PEsKN bn ho hc: dng nguyn liu c vng thm (thay mt phn EG bng bisphenol-A) - PEsKN bn nhit: thay mt phn AP bng dn xut halogen ca axit 2 chc (axit tetraclophtalic hoc axit tetrabromphtalic)Cl Cl Cl Cl COOH COOH

- PEsKN loi thng: EG-AP-EG-AM-EG-AP... b/ ng dng chnh ca PEsKN Lm vt liu composite + Nha nn (cht lin kt) + Ph gia ( cc loi si, vi...) + Cht ng rn ( styren, MMA) dng 20 30 PKL so vi PEsKN + Cht khi u (i vi PEsKN-styren): MEKPH3C C2H5 O C OH HOOC O C CH3 C2H5 H3C C2H5 O O C COOH HOOC C CH3 C2H5

Lm vt liu composite c th dng tay, my, chn khng. Khi lm vt liu composite th cht nn ( hay cht lin kt ) l nha trn vi ph gia. Cht nn gip to hn hp vi ph gia thnh mi trng lin tc. Khi tc dng lc (nu ch c nha th dn, nu ch c ph gia th ri rc v th lc phn b khng u) ln mi trng lin tc th lc phn b u nn kh nng chu lc tt.

Si thu tinh dng lm vt liu composite c x l cht lin kt b mt. Nu si khng x l th si v nha khng bm dnh tt v si l hp cht v c v nha l hp cht hu c bm dnh vi nhau km. Cht lin din: RMX R: gc hydrocacbon khng no lin kt vi ni i ca nha hoc vi cht ng rn (styren) X: halogen hoc ete b thu phn to lin kt OH (lin kt vi si) M: Si, Cr S lin kt gia nha nn v ph gia xy ra + Giai on 1: thu phnCH2 CH Cl Si Cl Cl H2C C O C CH3 O CrCl2 CH2 CH

+

3 H2O

HO Si OH OH H2C C

+

3 HCl

CH3 O Cr(OH)2

+

O 4 H2O (HO)2Cr

C

+

4 HCl

CrCl2 OH

OH

+ Giai on 2: to lin kt CH2 CH CH2 CH HO Si OH HO Si OHO H O H O H O H

CH2 CH CH2 CH O Si O O Si O O

M M M M //////////////////////////////////////////////////// b mt si /////////////////////////////////////// //////////////////////////////////////////////////// ////////////////////////////////////// Ni i s tham gia trng hp vi hydrocacbon khng no ca nha hoc styrene. Si c x l bn hn si thng rt nhiu 20 30 ln.

H2C C CH3 O HOCr OH O H O HH O O H C O CrOH

H2C C CH3 O HOCr OH O H O HH O O H C O CrOH to

H2C C CH3 O -OCr OH O O C O Cr O

H2C C CH3 O Cr OH O O C O CrO--

M M M M M M M M ////////////////////////////////////////////////////////// ///////////////////////////////////////////////// V/ Tnh cht, ng dng Tnh cht ca nha polyeste khng no ph thuc vo thnh phn nguyn liu ban u v iu kin tng hp. trng thi khng ng rn nha c th c nht thp, trung bnh hoc cao. trng thi ng rn cc polyeste ny l vt liu rn, trong sut hoc khng trong sut. Vt liu trong sut cho nh sng i qua n 92% khi tip xc vi nh sng c bc sng ngn th nha s b vng. Polyeste ng rn bn axit, dung dch mui axit v trung tnh, cc dung mi c cc, nhng khng bn kim, kton, anilin, CS2 Nhc im ca polyeste khng no l co ngt ln, chu nhit khng cao, bn va p khng t Polyeste khng no c dng ph bin sn xut cht kt dnh ( ph gia cho xi mng), mng ph, vt liu composite, vt liu p v cht do thy tinh

CHNG XII:

SN XUT NHA POLYAMID, POLYURETAN, POLYCACBONAT, SILICON

I/Nha polyamid 1/ Nguyn liu a/ Caprolactam Caprolactam tinh khit si 262,5oC hoc 120oC (10mmHg) nng chy i nhit 68,5 69oC, d ha tan trong nc v trong a s dung mi. b/ Axit 11-aminoundecanic Axit 11-aminoundecanic nng chy 188 190oC. Phn ng iu ch n t axit rixinolic nh sau:CH3 (CH2)5 CH CH2 CH CH (CH2)7 COOH 2CH2 CH (CH2)8 COOH Br (CH2)10 COOH CH3 (CH2)5 CHO + CH2 CH (CH2)8 COOH

+

HBr

Br

(CH2)10 COOH H2N

+

CH3 CH (CH2)8COOH Br

+

NH3

(CH2)10 COOH

+

HBr

c/ Axit adipic C th iu ch axit ny t cc sn phm ha hc khc nhau: phenol, furfurol, xiclohexan, axetylen, andehytTng hp axit adipic t phenol tin hnh qua cc giai on:OH OH

+OH

3 H2

+

HNO3

HOOC

(CH2)4 COOH

+

NO2

+

H2O

Nhit nng chy ca axit adipic l 151oC d/ Hexametylen diamin c tng hp t axit adipic, nhit si 14mmHg l 90 92oCHOOC NC (CH2)4 COOH

+4 H2

NH3

-4 H2O (300 375oC)

NC

(CH2)4 CN

(CH2)4 CN

+

H2N

(CH2)6 NH2

2/ L thuyt to thnh nha polyamid Ph thuc vo nguyn liu ban u m nhm amid trong polyamid c th nh hng theo cc chiu khc nhau + Polyamid c to ra t axit a chc (2) v amin 2 chc:

CH2 NH2 CH2 NH2

+

COOH COOH

-2 H2O

H2C H2C

H N N H

C O C O

+ Polyamid c to ra t aminno axit (hoc lactam ca amino axit 5 10% H2O)

n H2N n (CH2)4 CH2

(CH2)5 COOH CO NH

H

NH (CH2)5 COn

OH

+n

(n-1) H2O OH

+

H2O

H

NH (CH2)5 CO

i vi lactam ch dng nc trong thi gian u v trong qu trnh trng ngng to ra nc th nc tham gia phn ng thy phn lactam Mun nhn c polyamid th c th dng cc axit 2 gc nhng vi iu kin s nhm metylen trong phn t khng c di 4, c ngha dng axit adipic v cc ng ng cao hn n. Phn ng to polyamid l phn ng thun nghch theo tng bc v to ra sn phm ph l nc. V vy tng hiu sut to ra polymer th phi tch bt nc. Nu tha mt trong cc tc nhn phn ng th c kh nng to ra mch polymer m u mch c cha nhm ca tc nhn tha v do lm ngng phn ng pht trin mch.n HOOC (CH2)4 COOH

+ (n+1) H2NH

(CH2)6 NH2 NH (CH2)6 NH2n

NH (CH2)6 NHCO (CH2)4 CO

+ 2n H2O

3/ Tnh cht, ng dng Tnh cht ca polyamid ph thuc vo trng lng phn t trung bnh ca polymer, cu to ca cc monome ban u v s lin kt hydro Loi nha Nhit nng chy (oC) Polyamid-6 210 215 Polyamid-7 220 225 Polyamid-9 Polyamid-11 Polyamid-6-6 Polyamid-6-10 204 210 186 187 255 264 215 223

Khi tng s nguyn t C t 6 7 th c kt tinh ln hon mch c s nguyn t C t 9 11 nn c nhit nng chy cao hn. Polyamid 6-6 gm 6 nguyn t C v 6 nhm amin c nhit nng chy tng do s lin kt H tng. Polyamid-6O NH CH2 CH2 NH CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 O C NH CH2 CH2 CH2 CH2 CH2 C OO

C NH

CH2 CH2

CH2 CH2

CH2 C O

C O C O

NH

Polyamid 6-6CH2 CH2CH2 C O NH CH2 CH2 CH2 CH2 CH2 CH2 NH O CH2 CH2 CH2 CH2 CH2 CH2 NH C CH2 CH2 CH3 C CH2 CH2 CH3

CH2 CH2

CH2 C O

NH

Polyamid 6-6 c lin kt hydro ln hn polyamid-6 nn nhit nng chy cao hn. Polyamid c nhit nng chy cao nn c tnh cht c l cao, bn nhit ln, vt liu c ma st b v th c dng lm vt liu bi trn. Polyamid Tnh cht 6 11 6-6 3 Khi lng ring d (g/cm ) 1,14 1,04 1,14 k[KG/cm2] 500 800 500 700 800 1100 2 -u[KG/cm ] 700 1000 1000 1100 n[KG/cm2] Modun n hi E ( KG/cm2) -5000 600 1100 1000 2000 1000 1200 16000

II/ Polyuretan L polymer c to ra t polyizocyanat vi polyol -[-OCNH R NH COO R1 O -]nnOC = N R N = CO + n HO R1 OH + Cc cyanat thng dng: Hexametylen diizocyanat: OCN (-CH2-)6-NCO 2,4-Toluen diizocyanat:

CH3 NCO NCO

+ Cc phn ng ph: R NCO + H2O R1 NH2 + R NCO 2R NCO + H2O R NCO + R1OH R NCO + R2COOH ng dng: - Nha xp polyuretan - Vt liu composite III/ Polycacbonat iu ch t Dian v fosgenCH3 HO C CH3 OH

RNH2 + CO2 R1 NH CONH R RNH CONH R + CO2 RNHCO CO R1 RNHCO R2 + CO2

+

NaOH, to COCl2 H

O O R O C

n

OH

+ 2n NaCl

bn nhit ln do mch c vng v nhm + Khi lng ring d = 1,2 g/cm3 + Gii hn bn ko k= 650 750 KG/cm2 + Gii hn bn nn n= 790 900 KG/cm2 + Gii hn bn un u= 800 1200 KG/cm2 + bn nhit (Martens): 115 125oC Polycacbonat cng, trong sut, d trn mu, khng c, c th thay th cho melamin-formaldehyt chu nhit cao, bn ln IV/ Silicon Nng lng lin kt gia Si, C vi cc nguyn t khc Lin kt Si Si Si C Si H Si F Si Cl Nng lng lin kt E(Kcal/mol) 42,5 58 75 143 85 Khong cch gia 2 nguyn t (Ao) 1,9 1,93 1,64 1,54 2,0

O O C

Si O C-C CH CF C Cl CO

89 58,6 87,3 104 70 75

-1,54 1,54 1,35 1,42 1,69 1,77 1,43

Si bn ha hc, bn nhit do c nng lng lin kt vi cc nguyn t khc ln hn C lin kt vi cc nguyn t . * Phng php iu chRSi 2 RSi O C2H5 O C2H53

+2

H2O

RSi

O C2H5

2

OH

+

C2H5OH

OH

R(C2H5O)2Si O Si(OC2H5)2R

+H2O + C2H5OH

R(C2H5O)2Si R(C2H5O)2Si

O Si(OC2H5)2R

+

H2O

R(C2H5O)2Si

O Si(OC2H5)R OH

O Si(OC2H5)R OH + HO Si(OC2H5)2R R(C2H5O)2Si O Si(OC2H5)R O Si(OC2H5)2R

+ H2O

Tip tc phn ng cho n khi to ra polymerR (C2H5O)2Si O Si(OC2H5)R On

Si(OC2H5)2R

* Tnh cht ca Silicon + Khi lng ring d = 1,9 g/cm3 + Gii hn bn un u > 500 KG/cm2 + bn nhit (Martens): > 200oC + ht m (trong 24 ngy m nhit thng): 0,25g/dm2