Polyesters

PHAN TH ANH

KTSX Cht do

Gii thiu
- Thng l sn phm trng ngng ca cc acid carboxylic a chc v ru a chc - Cng l sn phm ca qu trnh trng ngng acid hydroxycarboxylic v trng hp m vng ester (lactones) - Tnh cht ca polyester ph thuc vo nguyn liu ban u

Gii thiu
+ Polyesters mch thng c Mr cao (>10 000) c sn xut t axit a chc v rc a chc hay trng hp lactones thermoplastic polyesters

+ Polyesters c Mr thp ( 10 000) mch thng hoc t nhnh i t acid aliphatic no hay dicarboxylic vng v ru 2 (2&3) chc intermediates for polyurethanes

Gii thiu
+ Polyesters c Mr thp ( 10 000) i t ru di-, tri-, polyfunctional resins + Unsaturated polyesters: polyesters which can copolymerize with unsaturated compounds and are formed from polyfunctional alcohols and polyfunctional unsaturated carboxylic acids v acid polyfunctional (aromatic carboxylic) hay acid bo no hoc khng no alkyd

Nguyn liu
- Acid adipic c s dng ph bin nht - Cc acids dicarboxylic khc nh: oxalic, succinic, and glutaric t quan trng hn. - Cc acid bo carboxylic (azelaic, sebacic) khng hp dn v mt kinh t - Cc acid thm dicarboxylic (phthalic, isophthalic, and terephthalic) thnh thong a vo nh cht iu chnh

Nguyn liu
- Cc diol hay s dng: ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol - Glycerol, trimethylolethane, trimethylolpropane, and hexanetriol are employed to obtain branched polymers. - Trng hp m vng caprolactone

L thuyt to nha

1. precondensate (Mn = 100 - 2000) - 2 giai on HOYO(OCXCOOYO)x H, x1 10 2. polycondensation (Mn > 10 000) HOYO(OCXCOOYO)y H, y100

L thuyt to nha
Secondary Reactions
1) Ether formation to produce diethylene glycol units (Y=C2H4)

L thuyt to nha
Secondary Reactions
2) Tch nc: ethylene glycol acetaldehyde 1,4-butanediol tetrahydrofuran 3) Thy phn carboxyl groups (poorer resistance to hydrolysis) + olefins (discoloration)

L thuyt to nha
Secondary Reactions
4) Ring formation between two adjacent carboxyl groups (particularly pronounced in adipic acid)

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L thuyt to nha
- Phng php c kinh t nht cho sn xut polyester l phn ng ester ha gia acid dicarboxylic v diol - iu kin ester ha cng cho php phn ng trao i ester xy ra vi chnh mch ca n - Khi khng s dng xc tc th ng hc phn ng l bc 3

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L thuyt to nha
- Khi s dng xc tc th ng hc phn ng l bc 2. - Xc tc: acids, bases, kim loi chuyn tip - Trong sn xut thng mi, xc tc c gii hn s dng bi nh hng ca n n phn ng polyurethane pha sau.

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L thuyt to nha

- n mol dicarboxylic acid (HOOCR'COOH) v n+1 mol diol (HOROH). - The degree of polycondensation (n) c tnh:

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L thuyt to nha
- Diol tn tht cng vi nc trong thit b ngng t phn ng ph (ether v aldehyde) - Giai on u ca phn ng kh tr (N2, CO2) c a vo v nc c tch ra nhanh bi ct chng ct t > 130oC - Khi ch s acid t khong 30 th phn ng chuyn sang giai on 2

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L thuyt to nha

- Thng s dng kh mang (CO2) hay cht ti (toluene, xylene) tch nc - Ch s acid trong sn phm yu cu < 1 mg KOH/g tp trong giai on 2 chim phn ln (20 cho 30h)

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Sn Xut

c th sn xut cng nghip theo kiu gin on hay lin tc vi cc phng php khc nhau
-Polyester

- The vacuum-melt and the purgegas-melt methods are preferred, the azeotropic method finds only limited application.

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Sn Xut - Batchwise Vacuum-Melt Method

-

H thng khp kn bao gm: TBPU bnh khuy trn, cnh khuy m neo, ct chng ct, TB ngng t, thng cha v bm chn khng

- Nguyn liu c gia nhit v khuy trn trong TBPU m khng c khng kh, nhit c cp bi in, hi p sut cao, cht ti nhit

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Sn Xut - Batchwise Vacuum-Melt Method

- Giai on u: t = 125 - 220oC, p kh quyn, 90% nc c tch ra - Giai on 2: cc oligoester ngng t vi nhau to polyester t = 175 - 230oC, p gim bc thang 0.005 bar - Nc cn li, diol tha, sn phm ph (aldehyde, ketone) c chng ct tch - Qu trnh c gim st lin tc bi o ch s acid, s nhm -OH v nht
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Sn Xut - Batchwise Vacuum-Melt Method

Example of the preparation of a polyester with an average molecular mass of 2000 from ethylene glycol and adipic acid

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Sn Xut - Batchwise Vacuum-Melt Method

- 86.8 kmol (AA) - 95.6 kmol (EG)
(1.1 kmol EG tha)

t = 130 C (N2) = 10 h
t = 200 oC (chng ct hot ng)

- hydroxyl number (55.5) - acid value (0.7) - (0.515 Pas at 75C) - H2O (0.02 wt %).

- 156 kmol H2O - acid value 55 H2O, EG, SPP c chng ct mgKOH/g - Lm lnh t = 110 C - Polyester (7.7 kmol)
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-p gim 0.01 bar (t = cons) - = 15 h

Sn Xut - Purge-Gas Melt Method

- Qu trnh ny khc vi vacuum-melt method, trong giai on 2 cc cht c th chng ct c tch ra nh kh tr (N2, CO2) sc qua hn hp p thp. - Phng php ny lm tng kh nng tch diol

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Sn Xut - Azeotropic Method

- Quy trnh ny tin hnh p sut kh quyn vi s c mt ca dung mi tr (toluene, xylene) - Quy trnh vacuum-melt c th kt hp vi quy trnh ny d dng tch nc v hi lu dung mi - iu kin phn ng m hn t = 125 - 190 oC, dung mi trong sn phm cui c tch bi chn khng

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Quality Specifications and Testing

- Cc thng s quan trng ca polyester s dng cho sx polyurethane: + hydroxyl number (DIN 53 240) + acid value (DIN 53 402) + water content (DIN 53 979) + color number (iodine number, DIN 6162; Hazen/APHA, DIN 53 404) + viscosity (DIN 53 015)
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Quality Specifications and Testing - Acid value l gi tr quan trng, cng nh cng tt v nh hng mnh n polyurethane + tng tc vi isocyanate ngt mch + tng tc vi isocyanate to amide v CO2 (gy bt kh) + l xc tc thy phn polyurethane + < 1 mg KOH/g + Cc vt metals, acids or bases, fats, silicone oils, and other surface-active agents cn trnh

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Tnh cht vt l
- Pure polyadipates of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol are waxy crystalline substances with softening points around 40 50 C regard to elasticity, tensile strength, and notch resistance - Khi s dng kt hp vi cc diol khc lm xut hin mt s u im - 1,2-Propanediol, 1,3-butanediol, diethylene glycol, and neopentyl glycol afford liquid polyadipates
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Tnh cht vt l

- high viscosity (ca. 600mPas at 75C) Mw = 2000 - = 1.1 - 1.5 g/cm3 - flash points (DIN 51 758) lie above 200 C - ignition points (DIN 51 794) above 400 C - Polyesters tan trong acetone, ethyl acetate, and toluene

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Tnh cht ha hc
- Nhm hydroxyl cui mch chu trch nhim chnh cho tnh cht ca polyester - Polyester d b thy phn v to ra nhm chc acid v n nh l autocatalytic cho phn ng tip theo - Gim kh nng thy phn bng cch tng tnh k nc cho polyester vi vic s dng diols hay dicarboxylic acid mch di

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Storage and Transportation

- Cn trnh tip xc vi hi m v t > 120 oC - The products are either stored in sealed, air-tight drums at ambient temperature or in heated, insulated containers under nitrogen at 70 110 C. As liquids they are transported in barrels or in heatable, insulated bulk containers; as solids they are transported in drums.

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Nha polyester khng no - UPE

- UP l nha nhit rn c nht trung bnh n thp, thng dng ha tan trong monomer ng trng hp (styrene). - UP ng rn khi c cht khi mo nhit thng (10 - 40oC) - Nha Vinyl ester c tng hp t LER v acrylic acid

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UPE Nguyn liu

Unsaturated Dicarboxylic Acids Maleic anhydride

Fumaric acid

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UPE Nguyn liu

Vic s dng acid fumaric thay cho anhydride maleic l ci thin kh nng n nh nhit v tnh cht c hc ca sn phm

- Nhc im ca acid fumaric so vi anhydride maleic gi thnh cao v hm lng nc cao

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UPE Nguyn liu

Saturated Dicarboxylic Acids Phthalic hp l. - Isophthalic acid: nha n nh nhit tt, bn c hc, bn ha cht hn Phthalic acid - Terephthalic acid: bn va p cao, n nh nhit, bn thi tit.
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acid:

dng

dng

anhydride trong tt c cc nha, gi

UPE Nguyn liu

- Tetrahydrophthalic anhydride: bn va p nhng gii hn bn thi tit, s dng ch yu trong sn, thn xe t - Adipic acid: mch mm, ha do cho nha - Hexachloroendomethylenetetrahydrophthalic acid (HET): kh nng chy thp, bn ha cht

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UPE Nguyn liu

Diols
- Ethylene glycol: r, gim r kh nng tng hp vi styrene ca UP, thng s dng kt hp vi cc diol khc diethylene glycol, dipropylene glycol, or butylene glycol. - 1,2-Propanediol: tng hp tt vi styrene, vn cha kh hon ton sau khi ng rn trong khng kh, tnh cht c l tt
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UPE Nguyn liu

- Diethylene glycol v dipropylene glycol: nha mm v tng s hp th nc, s dng kt hp vi 1,2propanediol iu chnh tnh cht c v ch s khc x. - Neopentyl glycol: tng kh nng n nh nhit, bn ha cht, thi tit. Kt hp vi isophthalic acid cho sn ph m c cht lng cao

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UPE Nguyn liu

Monomers for Cross-Linking UP Resins. - Vinyl, allyl, and acrylic compounds are suitable monomers for the cross-linking of UP resins - Styrene 25 45 wt %.

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