3/6/2012

Chng 3: NHA ALKYD & POLYESTER

3.1 Nha Alkyd. Nha Alkyd (Alkyd resins) i din cho mt h Polyme c dng trong cht to mng nh gi thnh r v d s dng. Thut ng alkyd c gi do Kienle and Ferguson bt ngun t al ca alcohol v cid ca acid; cid sau c i thnh kyd, tuy nhin, nha polyeste khng no trong backbone khng c gi tt l alkyds m dng : "unsaturated polyesters." nh ngha ca alkyds m t c chp nhn rng hn l alkyds l nha polyester bin tnh vi acid bo (fatty). Cc nha resins khng bin tnh c gi l polyester bo ha (saturated polyesters). Cc thut ng nh akyd khng du oil-free alkydv polyester bin tnh vi du oilmodified polyester cng c th c tm thy trong cc ti liu.

3/6/2012

3.1.1 NGUYN LIU TNG HP NHA ALKYD: - Polyol - Polyacid - Du hoc acid bo

3/6/2012

Phn loi Alkyds c tng hp t ba thnh phn c bn: polybasic axit, polyols, v (ngoi tr alkyds khng du) fatty acid. Tnh cht v t l ca cc thnh phn quyt nh nhng tnh cht ca resin. S lng kt hp l rt ln, v c im k thut ca mt alkyd resin lin quan n nhiu s thng s. nh hng hm lng du v Loi du Ty thuc vo t l phn trm trng lng ca acid bo trong resin, alkyds c gi tt l du ngn gy (short oil) (<45%), du trung bnh (medium oil) (45 n 55%), hoc du di bo (long oil) (> 55%). Tuy nhin, mt s tr ngi c lin quan n cc thut ng. i khi du di cp n t l phn trm Triglyceride, trong c trng hp t l acid bo phi c tnh li sang Triglyceride. Mt cch gn ng: trng hp 1 = trng hp 2/1,045. Cc loi acid bo c dng cng nh hng ng k n tnh cht ca cc alkyds. Alkyd resins c phn loi kh, bn kh (semidrying), v khng kh (nondrying), ty thuc vo mc bt bo ha (unsaturation) trong cc acid bo (tr s iodine > 140, 125 n 140, v <125, th t tng ng).

3/6/2012

Qu trnh kh oxi ha (Oxidative) nha alkyds, gm vic oxidation t khng kh n cc ni i trong cu trc thnh phn acid bo, ti a khong 50% i vi du bo (di). Sau khi kh, cng mng phim t l nghch vi mc bin tnh acid bo. Alkyds du gy thng cho phim cht lng cao i vi mu sc v duy tr bng tt, nhng cho mm do thp v bm dnh (adhesion) km. Alkyds du bo thng rt tt cho qu trnh phn tn bt mu (pigment dispersion), tnh cht l bin, lu tr n nh. V d v cc tnh cht ca alkyd resins lin quan n hm lng du v cc loi du c hin th trong bng sau:

Oil Type

Oil Length (%) >60

Typical Oil

Properties

Oxidizing

Linseed, safflower, soybean, tall oil fatty acids; wood oil in blends with other oils; dehydrated castor oil Linseed, safflower, soybean, tall oil fatty acids; wood oil in blends with other oils Linseed, safflower, soybean, tall fatty acids; wood oil in blends with other oils; dehydrated castor oil

Soluble in aliphatic solvents; compatible with oils and medium oil length alkyds; good drying characteristics; films are flexible, with reasonable gloss and durability Soluble in aliphatic or aliphatic aromatic solvent mixtures; good drying characteristics, durability, and gloss Soluble in aromatic hydrocarbons; low tolerance for aliphatic solvents; usually cured at elevated temperatures either by heating with manganese driers or with urea or melamine formaldehyde resins Soluble in aliphaticaromatic solvent blends; usually used as a plasticizer for thermoplastic polymers such as nitrocellulose Soluble in aromatic solvents; used as a reactive plasticizer that chemically combines with other resin entities (e.g. melamineformaldehyde resin)

Oxidizing

4555

Oxidizing

<45

Nonoxidizing

4060

Coconut oil, castor oil, hydrogenated castor oil

Nonoxidizing

<40

Coconut oil, castor oil, hydrogenated castor oil

3/6/2012

3.1.2 Quy trnh sn xut Alkyds c tng hp t phn ng trng ngng (polycondensation) ca cc axit v ru cho n khi t c mi quan h ch s axit- nht (viscosity) nh trc. P ng thng c thc hin di kh tr (inert gas) hoc hi dung mi gim thiu phn ng oxidation ca cc thnh phn bt bo ha (nh ni i). Trong giai on u ca phn ng, ch s axit gim nhanh chng, v nht tng chm. Cng v sau ch s axit gim chm. Quy trnh sn xut c th theo, phng php nng chy, hoc bng cch s dng mt lng nh dung mi (mt hnh thc azeotrope vi nc) (gi l phng php dung mi). Hn na, trong cc vic chun b sn xut cc polyeste bin tnh vi axit bo, hoc Triglyceride hoc cc acid bo c s dng nh l nguyn liu ban u. Hai qu trnh ny c gi tt l QT monoglyceride hoc qu trnh acid bo.

3/6/2012

So snh Phng php nng chy vi Phng php Dung mi PP nng chy l phng php c nhng vn cn c s dng rng ri, c bit l i vi du alkyds c hm lng du 60% hoc nhiu hn. Phn ng c thc hin ti nhit 220 n 250 C, di mi trng kh tr, c s dng cho vic kh nc, nhng cng l nguyn nhn gy mt polyols v ca phthalic anhydride. Trong phng php dung mi, phn ng esterification c thc hin trong s hin din ca mt s lng nh nc (khng tan)-dung mi, thng l xylene. Qu trnh c thc hin lin tc km theo chng cng ph ca cc dung mi. Cc xylene-hi nc l hn hp ngng t, nc c tch bit vi dung mi v tr v cho thit b phn ng (reactor). Nhit phn ng c qun l bi nhit hon lu (refluxing) , ph thuc vo s lng xylene s dng, 5% l c gi tr bnh thng. Nhn chung, phng php dung mi kim sot tt hn cc sn phm resin, thnh phn, v hu nh khng c thit hi v nguyn liu do qu trnh bay hi.

PP Monoglyceride so vi PP acid bo Khi mt Triglyceride du c gia nhit vi polyols v polybasic axit, cc polyols phn ng vi axit d dng, v to thnh mt hn hp ca Triglyceride v polyeste khng bin tnh. Cch khc phc vn ny l thc hin vic kim sot chuyn ha este (transesterification) ca fatty acid trc khi bc sang phn ng trng ngng (condensation). Vic ny thng c thc hin bng cch

phn ng ca 1 mole Triglyceride vi 2 moles ca glycerol (hoc mt

polyol) nhit 220 n 250 C cho n khi t c l giai on monoglyceride. Catalysts c a thch PbO, Ca (OH) 2 Sau khi hnh thnh monoglycerides, cc axit polybasic v phn cn li ca polyols ang c thm vo, v phn ng condensation c thc hin cho n khi t c nht v ch s axit.

3/6/2012

Phng php acid bo s dng khng phi l Triglyceride m l cc acid bo ca n. Song song vi vic la chn cc thnh phn polyol t do hn, qu trnh ny cho lp li v kim sot trong sn xut tt hn v trng lng phn t v phn b TLPT ca cc resin. Ngoi ra, qu trnh ny cho php phn ng condensation tin hnh tt hn (ch s acid thp), lm thun li hn cho tnh cht kh. S la chn qu trnh sn xut khng ch l vn tm phng php tng hp ph hp nht. C khc bit r rt tnh cht mng phim alkyds gia nhng alkyd c cng thnh phn, nhng khc nhau v phng php tng hp.

3.1.4 Cac thong so ac trng cua nha alkyd + Loai dau: lanh, chu,u nanh( kho, ban kho) + Ham lng dau hoac acid beo % + Loai polyester (polyol ? polyacid ?, . . .) + Co dung moi hay khong? Loai nao? Ham lng ran? + Ty trong (tnh n pha che)

+ CA, COH, . . .
+ Ch so mau + o nht. + Hng dan s dung : % chat lam kho, thi gian kho. + Lnh vc ng dung.

3/6/2012

ng dng Alkyd resins l loi nha cho tnh bm dnh, tnh cht kh tt. Mng phim c c t n c tnh mm do v bn thi tit (durability) tt. Bng cc cch bin tnh khc nhau , mt s tnh cht c th c ci thin. im yu ca alkyds l nhy cm vi qu trnh thy phn bi kim. Sau y l m t s lc vi loi alkyd resins:

Alkyds Du bo tan trong dung mi hydrocarbon mch thng (aliphatic solvents). Thng c p dng bng cch qut, chng c s dng trong sn trang tr bn ngoi v sn tng, cng nh trong hng hi v bo v kim loi. Chng cng c s dng rng ri trong sn bng khng mu.

Alkyds du trung bnh tan trong hn hp dung mi aliphatic v aromatic. Loi kh trong khng kh c s dng cho cc ng dng cng nghip xe, chng hn nh lp lt (primers) v lp bn trong (undercoatings), sn cho kim loi. Cc loi khng b oxi ha (nonoxidizing) thng c s dng nh l cht ha do trong sn nitrocellulose.

Alkyds du gy tan trong dung mi thm khng tan trong aliphatic. Loi kh trong khng kh c s dng trong lp lt (ng rn nhit) (baking primers) v sn men, bng mt mnh n hoc cng vi cc resins khc, chng hn nh ur hoc melanine resins. Cc loi khng kh (nondrying) ch yu c s dng trong sn nitrocellulose hoc kt hp vi ur hoc melanine resins trong cc sn phm ng rn bng nhit v bng axit.

3/6/2012

3.1.5 Mot so alkyd bien tnh tieu bieu:

+ Vinyl hoa nha Alkyd.

+ Uralkyd

3/6/2012

+ Epoxy Ester

3.2 Nha Polyester bao hoa khong dau.

10

3/6/2012

Polyester resins, ging nh nha alkyds, l sn phm ca phn ng esterification ca di-hoc polyhydric Alcohol vi di-hoc poly- axit hoc anhydrides. Tuy nhin trong thc t, c nhiu phc tp hn, c nhiu loi alcohol v acid khc nhau c s dng tng nha polyester. Khng ging nh alkyd, khng c s bin tnh bng acid bo, v cu trc ca nha n gin hn. i khi di-axit aliphatic mch di nh azelaic acid v sebacic axit c th c s dng trong mt s cc cng thc polyester, cc axit carboxylic (khng ging nh hu ht cc acid bo) khng c cha ni i lin hp hoc khng lin hp. Do Polyesters khng hnh thnh mng phim bng c ch oxi ha (oxidative), y cng l im khc bit ca n i vi tt c alkyds lm kh bng khng kh.

Trn thc t, Polyester resins l cht to mng chuyn i ha hc. c tnh ng rn (ni mng) ty thuc vo tnh cht ca cc nhm chc hot ng cn li ca n. Nha polyesters c th chia lm 2 loi: polyesters (bo ha) saturated, l Polymers mch thng, mach nhnh, mch vng c mang nhm carboxyl, hoc hydroxyl nhng khng c bt bo ha (ni i); v unsaturated polytesters c cu trc tng t, nhng c bit l trong mng cn nhng ni i bt bo ha c th to mng (crossling) nh gc t do. Saturated polyesters hnh thnh mng nh phn ng condensation polymerization vi cc loi nha khch nh nha amino formaldehyde, epoxies, hoc polyisocyanates c cha cc nhm hot ng. Cc nhm hot ng trn saturated polyesters c th l mt trong hai nhm hydroxyl hoc nhm carboxylic axit (tu thuc vo thit k qu trnh tng hp v t l cc thnh phn c bn (acid, alcohol)). Tu thuc vo polyme hnh thnh,cc nhm cn li trn polymer v cc nhm hot ng ca cht khu mng (cross linker), chuyn haca cc saturated polyester c th xy ra nhit thng hoc nhit cao.

11

3/6/2012

To mng nhit thng, h to mng hai thnh phn. nhit cao, cc resins c th c trn ln li vi nhau. V d hnh thnh urethanes vi polyisocyanates (qua nhm hydroxyls) l mt phn ng nhit phng. Chuyn i cc amino resins (bng hydroxyl polyester), cc epoxy resins (bng carboxylated resin) l chuyn i nhit cao. Cha kha tng hp resin l t l cc monomer. Thng dng nht, mt lng tha polyol c s dng, cho nha c tha nhm hydroxyl (thng cui mch).Trng hp cn c carboxylated polymer, dng lng tha axit.

3.2.1 Nguyen lieu: Polyols va Polyacid thong dung

Equivalent Weight 31 59

Alcohol Ethylene glycol (EG) 1.6-Hexanediol (HD)

Functionality 2 2

Neopentyl glycol (NPG)

Diethylene glycol (DEC) Triethylene glycol (TEG) Bisphenol A (BA) Trimethylol ethane (TME) Trimethylol propane (TMP) Pentaerythritol (Penta)

2
2 2 2 3 3 4

52
53 75 114 40 44,7 34

12

3/6/2012

Acid Benzoic acid Succinic acid Adipic acid Phthalic anhydride (PA) Isophthalic acid (IPA) Terephthalic acid (TA) Trimellitic acid Trimellitic anhydride (TMA)
*Used as a chain terminator

Functionality 1* 2 2 2 2 2 3 3

Equivalent Weight 122 59 73 72 83 83 70 64

13

3/6/2012

Classification of Saturated Polyesters Saturated polyesters for use as binders in paints and coatings may be classified according to their molecular weight and their functionality. High molecular weight polyesters are predominantly linear, thermoplastic polymers with molecular weights from 10,000 to 30,000. Generally, they are copolyesters containing terephthalic and/or isophthalic acid and aliphatic diacids and a blend of diols. In contrast to terephthalic acid homopolyesters, they exhibit better solubility in solvents. In coatings, they impart a high degree of flexibility paired with excellent surface hardness and stability. High molecular weight linear polyesters may be used as physically drying binder components in paints, although the majority of uses are in baking enamels for highly flexible coatings, such as coil and can coatings in combination with amino resins or other suitable hydroxyl-reactive cross-linkers. Certain special grades of high molecular weight polyesters are ground and used as thermoplastic powder coatings.

14

3/6/2012

Low molecular weight polyesters range from 500 to 7000 and are, in general, not suitable as physically drying binders. Because of their low degree of polymerization, they carry a great many functional terminal groups. Low molecular weight polyesters may be linear or branched; by variation of the manufacturing process, it is possible to incorporate mostly either hydroxyl or carboxyl end groups, or both kinds. By themselves, low molecular weight polyesters are not satisfactory film formers. They require a reaction partner capable of reacting with the end groups of the polyester and causing the formation of a cross-linked, duroplastic film. Amino resins and polyisocyanates are suitable as such cross-linking agents for hydroxyl polyesters, whereas epoxy resins and polyoxazolins may be used for carboxyl polyesters. By proper selection of the reactants, the formulator can design products ranging from twocomponent or one-pack solvent-borne enamels with amino resins or blocked polyisocyanates to powder coatings or, via the salt formation of carboxyl polyesters, water-soluble stoving paints.

By reacting the native terminal groups of polyesters (i.e., hydroxyls or carboxyls) with at least bifunctional monomers or oligomers, saturated polyesters may be further modified in many ways. Solubility Naturally, chemical composition will be the dominant factor in determining the solubility of a polyester; however, this dominance may be exhibited either directly or indirectly (by affecting the morphology). The solubility of polyesters decreases rapidly with increasing crystallinity. Highly crystalline copolyesters are insoluble in many common solvents. They can be dissolved only in blends of phenol and o-dichlorobenzene at higher temperatures. Polyesters of medium crystallinity are soluble in methylene chloride; weakly crystalline polyesters will also dissolve in aromatic hydrocarbons, such as toluene. Amorphous polyesters will dissolve in a variety of polar solvents, such as esters, etheresters, ketones, and aromatic and chlorinated hydrocarbons. Within the amorphous polyesters, chemical composition will have a direct effect on solubility. Thus, shifting the glycol ratio in a polyester from ethylene glycol toward neopentyl glycol will enhance the solubility of the resulting polyester.

15

3/6/2012

Chemical Properties Polyesters all contain the hydrolytically unstable ester linkage, the chemical resistance of saturated polyesters is much superior to their alkyd cousins. Alkyds are severely compromised in this respect by the presence of the triglyceride. So improved are the resistance properties of the saturated polyesters (and, more particularly, the unsaturated polyesters discussed below) compared to alkyds that they have found wide uses in highly chemical-resistant systems for severe exposures. Generally speaking, polyesters have excellent stability toward light, oxygen, water, and many chemicals. The weakest spot in the polymer chain is the ester group, with its potential sensitivity to hydrolysis. Accordingly, degradation may occur, provided there is an environment that combines moisture with acids or alkali or other catalytically active materials, plus the possibility for the moisture to permeate into the polyester. Chemical resistance can be upgraded by the selection of the cross linking resin and the design and functionality of the resin itself. For example, if the polyol of the polyester is selected so that it has no hydrogens on the carbon atom that is "beta to" (or once removed from) the hydroxyl, then the resultant ester is more hydrolytically stable.

Similarly, the light stability, exterior durability, and heat resistance of a formulation may be optimized by the selection of components. Aromatic polyols such as bisphenol A may improve heat resistance, but the aliphatic materials are preferred for light stability and durability. There is much opportunity for property design and custom tailoring through molecular engineering in the synthesis of polyesters. Perhaps even more opportunity exists when molecular engineering is used by the coatings chemist in the final use of the polyester in the coating formulation.

The effect of the design of the cross linker and its combination with the polyester will also have a great effect on the final properties of the coating. Triglycidyl isocyanurate-cured systems will, for example, give far better exterior durability in powder coatings than will the use of the more conventional bisphenol A-based epoxies (Fig. 13-4). Again, using the same polyester, excellent exterior two-pack urethanes will be produced using hexamethylene di-isocyanate-based cross linkers (Fig. 13-5). Toluene diisocyanate cross linkers will, conversely, produce very poor exterior systems, but these systems will have better heat and chemical resistance.

16

3/6/2012

Properties and Applications Polyester coatings, especially cross-linked ones, exhibit excellent flexibility or even elasticity, and they show very good impact, scratch, and stain resistance. Their good adhesion properties, especially to metals, combined with good corrosion protection and weather resistance, have made them indispensable in a number of fields. Application and markets for saturated polyesters are varied and extensive. In the automotive industry, they are used as anti-chip surfacers over cathodic electro-deposited primers and as colored base coat vehicles for base coat/clear coat metallics. Here, the inherent toughness and flexibility of the polyester is valued. These systems are cured with the melamine cross linkers and often modified with cellulose acetate butyrate to maintain flow properties. Polyester melamines are also used on trim components and auto accessories. Other applications include appliance coatings, flexible can coatings (inside and out) for food and beverage containers, and coatings for metal furniture and light fixtures. Polyester coatings, especially siliconized polyester coil coatings for exterior metal siding, benefit from the exceptional durability and excellent flexibility of these resins, which help resist the effects of post cure forming operations.

Two-pack, ambient-cured urethanes based on polyesters cured with hexamethylene diisocyanate and, to a lesser extent, isophorone diisocyanate-based cross linkers are now used extensively as high performance maintenance finish coats for structural steel.They are often employed over intermediate coats based on epoxies and aromatic urethanes and zinc-rich primers based on organic and inorganic vehicles.

17

3/6/2012

Carboxylated polyester reactions with epoxy systems

18

3/6/2012

19

3/6/2012

3.3 Polyester khong no bat bao hoa

Acid Maleic anhydride Fumaric acid

Remarks Employed as an acid and a source of unsaturation in unsaturated polyesters Employed as an acid and a source of unsaturation in unsaturated polyesters

20

3/6/2012

21

3/6/2012

Application and Properties of Unsaturated Polyesters

Unsaturated polyesters have very large markets in non-coating applications, such as laminates, encapsulants. press mold applications, and hand lay-ups, particularly when used in combination with fiberglass reinforcement. Pleasure boats, bathroom fixtures, swimming pools, translucent panels and tanks, piping, drip pans, and other equipment (for the chemical, plating, and photographic industries especially) are fabricated from unsaturated polyesters. As coating and lining materials, unsaturated polyesters are typified by systems having high gloss, fast cure, short pot life, and very high build capabilities. The coatings are generally hard and very impact resistant. They are not flexible systems, and a high volume shrinkage on polymerization may result in poor adhesion unless good surface preparation and suitable primers are employed. Chemical resistances are very good in spite of the ester group. As is noted with the saturated polyesters, optimum chemical resistance may be designed into these systems by the selection of the ingredientsiso- or terephthalic acids, bisphenol A, and NPG-based polyols.

In coatings, the largest polyester applications are as radiation curing systems in furniture and wood finishing. Large volumes are also consumed as gel coats (polyester coatings sprayed onto molds) for boats and bathroom fixtures and in two-pack automotive refinish applications (including fillers and putties).

22