Phenolic resin (PF)

PHAN TH ANH

KTSX Cht do

Gii thiu
- L sn phm trng ngng gia phenol v cc aldehydes - 1872 Von BAYER - 1902 BLUMER tng hp novolacs thay cho vecni - 1909 BAEKELAND s dng ch yu cho vecni, cch in... - 1930s von Euler, Hultzsch, Megson, Ziegler, and others s dng cho cc lnh vc khc: keo dn, mc in, sn,...

Phn loi

- Tu thuc vo xc tc v t l cu t m chia nha PF ra lm 2 loi: nha novolac v nha rezolic. + Novolacs: nha nhit do, c trng bi cu ni methine (alkylphenol novolacs) + Resols: nha nhit rn, c trng bi nhm hydroxymethyl v cu ni dimethylene ether (alkylphenol resols)

Nguyn liu - cc phenol

Phenol - Tinh th hnh kim, khng mu v c mi hc c trng. + d (45oC) = 1,0545 g/cm3 + tnc = 40,9oC + ts = 182,2oC - Ht m, nhit thng tan 27% trong nc to dung dch ng nht. - Rt c, gy bng da, kch thch nim mc (0,005 mg/l)
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Nguyn liu - cc phenol

Crezol ( CH3C6H4OH )
OH CH3 CH3 o-crezol(35%) m-crezol(37-49%) CH3 p-crezo(25%)

OH

OH

Nguyn liu - cc phenol

Xilenol (CH3)2C6H3OH
OH CH3 CH3 CH3 1,2,3 Xilenol OH CH3 CH3 CH3 CH3 1,2,6 Xilenol 1,3,4 Xilenol H3 C CH3 1,2,4 Xilenol OH OH CH3 H3 C 1,2,5 Xilenol OH OH CH3

1,3,5 Xilenol
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Nguyn liu - cc phenol

Rezorsin: C6H4(OH)2
OH

OH

- Rezorsin c 3 v tr hot ng rt mnh hn phenol

Nguyn liu - cc aldehyde

Formaldehyt (andehyt formic) CH2O
H C H O

- Cht kh khng mu, c mi hc, gy kch thch nim mc. + d = 0,8153 g/cm3 + tnc = -92oC + ts = -21oC - Dng ch yu dng Formalin (33 60 v%, 33 37 m%)
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Nguyn liu - cc aldehyde

Formaldehyt (andehyt formic) CH2O - C kh nng t trng hp nhit thp polyformaldehyt (parafoc), khi un nng formaldehyt.
n HCHO * CH2O * CH2O n

n HCHO n

- Bo qun: 7 12% metylic

Nguyn liu - cc aldehyde

- Khi tan trong nc n dng hydrat ho (metylenglycol) HCOH + H2O HO CH2 OH - Dng hydrat ho ny d bt c nng no cng to ra polyoxymetylglycol
2 HO CH2 OH HO CH2 O CH2 OH + H2O

HOCH2OCH2OH + n HOCH2OH HO-(-CH2O-)n+1CH2OH + H2O

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Nguyn liu - cc aldehyde

3-Furaldehyde C5H4O2 Urtrpin (CH2)6N4

Hexamethylenetetramine,

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L thuyt trng ngng

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L thuyt trng ngng

Cc yu t nh hng n qu trnh trng ngng Cu to ho hc ca nguyn liu
- Cu to khc nhau th nh chc khc nhau dn n kh nng phn ng khc nhau. - Resols: cc phenol c 3 v tr hot ng ?

- Novolacs: cc phenol c 2 v tr hot ng ?

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L thuyt trng ngng

Cc yu t nh hng n qu trnh trng ngng T l mol C6H5OH/CH2O
- P:F (mol) = 1:1 ch yu to ra cc octo v para monometylol phenol. - P:F (mol) = 1:2 hoc cao hn ch yu to ra cc di v tri metylol phenol.

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L thuyt trng ngng

Cc yu t nh hng n qu trnh trng ngng pH ca mi trng
- pH < 7 xc tc ion H+ (HCl, H2SO4), t l

C6H5OH/CH2O = 6/5 hoc 7/6 to nha nhit do. - pH > 7 xc tc l OH- (NaOH, NH4OH, Ba(OH)2), t l C6H5OH/CH2O = 5/6 hoc 6/7 to nha nhit rn.

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L thuyt trng ngng

Cc yu t nh hng n qu trnh trng ngng pH ca mi trng
- NaOH: to ra nha c mu nu sm, tan trong nc thnh h nh tng. - Ba(OH)2 cho nha c mu sng hn - NH4OH: nha to ra khng tan trong nc m tan trong cn.
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L thuyt trng ngng

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L thuyt trng ngng Novolac

OH OH

CH2O

CH2 OH

monometylol phenol
OH CH2 OH CH2OH

dimetylol phenol (rt t)

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L thuyt trng ngng Novolac

OH CH2 OH OH CH2 OH CH2 OH OH OH H
+

OH CH2

OH

OH

OH H
+

OH CH2 CH2 OH CH2 O CH2

OH

+ +

HOCH2 OH

OH H
+

HOCH2

cu ni metylen ete
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L thuyt trng ngng Resol

- C 3 trng thi ca nha resol trong qu trnh tng hp: + resol (A-stage) + resitols (B-stage) + resites (C-stage)

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L thuyt trng ngng Resol

OH OH OH CH2 OH CH2 OH CH2 OH HOCH2 OH CH2 OH CH2 OH

CH2O

OH-

monometylol phenol

dimetylol phenol

trimetylol phenol

- Trong mi trng OH- th cc nhm metylol c vn tc phn ng b.

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L thuyt trng ngng Resol

OH CH2 OH OH OH CH2 OH CH2OH OH CH2 OH CH2 O CH2 CH2OH OH CH2
n

HOCH2

CH2 OH CH2OH OH CH2 OH CH2OH

OH-

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L thuyt trng ngng

Structure de la Baklite (1909)

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L thuyt trng ngng

- C th chuyn Novolac sang Resol (150oC)

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Sn xut - Novolac

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Sn xut - Resol
Figure 1. Phenolic resin plant a) Outlet tap; b) Heating; c) Stirrer; d) Evacuation system; e) Thermometer; f ) Reflux condenser; g) Main condenser; h) Threeway tap; i) Reflux and separation vessel; j) Reflux return with siphon; k) Receiver

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Sn xut - Resol
Example [11]. Condensation: 846g (9 mol) phenol and 1600 g formaldehyde solution (30 %, 16mol) are mixed at 20 C and the pH adjusted to 9.5 10 by addition of concentrated aqueous sodium hydroxide solution with stirring (ca. 110mL 38% sodium hydroxide). The mixture is heated to 60 C and kept for 4 h at this temperature. The decrease in formaldehyde concentration is monitored by titration with hydroxylamine hydrochloride. At the end of the reaction only ca. 1% formaldehyde is present. The mixture is cooled, and carefully neutralized almost completely with ca. 5% hydrochloric acid with stirring. The reaction solution must not become acidic and should have a pH of ca. 7.2 7.5. Water and excess phenol are subsequently distilled off in vacuum, such that the inner temperature may reach 60 C at maximum (at 1.5 kPa). 1360 g of viscous resin is obtained as residue.
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URE-FORMALDEHYT

- Cc yu t nh hng: + 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.

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URE-FORMALDEHYT-Qu trnh to nha

NH2 NH2

NH CH2O CO NH2

CH2OH

Monometylol ure
O C NH2 NH2

NH CH2O CO NH

CH2OH CH2OH

Dimetylol ure

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URE-FORMALDEHYT-Qu trnh to nha

- 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.

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URE-FORMALDEHYT-Qu trnh to nha

- T monometylol ure to ra nha mch thng qu trnh xy ra theo tng bc

NH CH2OH CO NH2 HO CH2 NH2 NH CH2OH CO

CO NH2

H2O

NH CH2 NH CO NH2 NH CH2OH CO NH CH2OH CO

H2O

NH CH2 O CH2 NH

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URE-FORMALDEHYT-Qu trnh to nha

- T dimethylol ure c th to ra nha mch thng v mch vng:

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

+
CH2OH N CO CH2 NH CO CH2OH N CO CH2 NH CO

H2O

CH2OH N CO
n
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CH2 NH CO CH2OH

NH CH2 N CH2 N CH2 N CH2

N CH2 N

URE-FORMALDEHYT-Sn xut

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URE-FORMALDEHYT-Sn xut

Figure 3.Plant for the batchwise production of etherified amino resins a) Rawmaterial feed; b) Stirred kettle; c) Condenser; d)Vacuum pump; e) Separating vessel (water separator); f) Product vessel; g) Pump
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