CH2-N=C=O

ALKYD TECHNOLOGY
CH2-N=C=O

HISTORY & DEFINITION
H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3

SYNTHESIZED ALKYD
N N
N
H3COH2C CH2OCH3

CH2OR H

CHO-OCN
CH 3

RAW MATERIAL & THEIR EFFECT
CH2OR
N H

COOCH
CH2OR

TYPICAL OF ALKYD
CH2O

DRYING MECHANISM OF ALKYD

SUMMARY OF ALKYD

AMR, 1/10/01
 HISTORY & DEFINITION
CH2-N=C=O

1901 Watson Smith made the first curable resin from PA

CH2-N=C=O
and Glycerol
H3COH2C N CH2OCH3
N
H3COH2C
N
N N
CH2OCH3

1920 Roy Kienle at G.E. Co modified it with vegetable
H3COH2C
N
CH2OCH3 and fish oil
CH2OR H

Roy Kienle applied for a patent but was rejected.
CH 3
CHO-OCN Since 1920, Alkyd technology cannot be patented.
CH2OR
N H

COOCH
CH2OR

By 1964, 594 million pounds per year.
CH2O

By 1965, 575 million pounds per year.
Solvent and Emulsion acrylic were introduced and
took some market share.

To Date, Market of Alkyd is still very strong.

AMR, 1/10/01
 HISTORY & DEFINITION
CH2-N=C=O

The name ALKYD is derived from two words :

CH2-N=C=O

H3COH2C N CH2OCH3
Alcohol and Acid
N N
H3COH2C CH2OCH3
N
N
N

“AL” from the ALCOHOL and KYD from “ACID which
H3COH2C CH2OCH3

was later changed to “KYD” for euphony.

CH2OR H

CHO-OCN
CH 3
It is an oil or fatty acid modified polyester.
CH2OR
N H
CH2OR

Usually with natural oil or fatty acid as a raw material.
COOCH

CH2O
Now, any polyesters modified with mono-functional

synthetic long chain acids are also included as alkyds.

In general, alkyds has long chain mono-functional acids as
a major component.

AMR, 1/10/01
 SYNTHESIZED ALKYD
CH2-N=C=O

CH2-N=C=O

IF OIL IS USED :
H3COH2C N CH2OCH3  First stage is called the split or cracking stage.
N N
H3COH2C
N N
CH2OCH3
It is to convert the oil to be mono glycerides by
N
H3COH2C CH2OCH3
reacting with added tri or tetra functional alcohols.
CH2OR H  Second stage is the polymerization.
CH 3
CHO-OCN

CH2OR
Reaction between the balance of the tri or tetra
N H
CH2OR functional alcohols with added poly functional acids.
COOCH

CH2O

IF FATTY ACIDS ARE USED :

 Just a one stage cook.
 All the calculated ingredients are loaded and cooked to
end point
AMR, 1/10/01
 SYNTHESIZED ALKYD
CH2-N=C=O

I. OIL PROCESS OIL

CH2-N=C=O
POLYOL MONOGLYCERIDE
H3COH2C N CH2OCH3
N N CATALYST
H3COH2C CH2OCH3
N N

H3COH2C
N
CH2OCH3
POLYACID ALKYD RESIN
POLYOL

CH2OR H
CH 3 ANTIOXIDANT
CHO-OCN

CH2OR SOLVENT
N H
CH2OR

COOCH
II. F.A.
CHPROCESS
O
FATTY ACID
2

POLYOL

POLYACID ALKYD RESIN

ANTIOXIDANT

SOLVENT

AMR, 1/10/01
 SYNTHESIZED ALKYD
CH2-N=C=O

ALCOHOLYSIS CH2OOCR CH2OH CH2OOCR

CH2-N=C=O
CATALYST
CH2OCH3
CHOOCR + 2 CHOH 3 CHOH + 2 COOH
H3COH2C N
N N
CH2OCH3
H3COH2C
N N CH2OOCR CH2OH CH2OH
N
H3COH2C CH2OCH3 OIL GLYCEROL MONOGLYCERIDE FATTY ACID

ESTERIFICATION CH2OOCR O CH 2OH

CH2OR H
CH 3 C
CHO-OCN CHOH + O + COOH + HOCH2 C CH2OH
CH2OR C
N H
CH2OR CH2OH
O CH 2OH
COOCH
MONO PHTHALIC FATTY ACID PENTAERYTHRITOL
CH2O
GLYCERIDE ANHYDRIDE

O O

OC CH2OC
C - O - CH2 - C - CH2O-C O
O CH2OH O CH2OC
C- O - CH2 - C - CH2O-
Portion of ALKYD resin CH2OH
AMR, 1/10/01
O
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

H3COH2C
CH2-N=C=O

N CH2OCH3
MAIN RAW MATERIAL OF ALKYD
N N
H3COH2C CH2OCH3

H3COH2C
N
N
N

CH2OCH3

OIL.
CH2OR H

CHO-OCN
CH 3
FATTY ACIDS.
CH2OR
N H
CH2OR
ACIDS.
COOCH

CH2O

ALCOHOLS.

CATALYSTS.

SOLVENTS.
AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

CH2-N=C=O
OILS
H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N
N
H3COH2C CH2OCH3 DRYING SEMI DRYING NON DRYING
UNSATURATED Saturated
CH2OR H
CH 3
CHO-OCN

CH2OR
N H
CH2OR
VEGETABLE VEGETABLE VEGETABLE ANIMAL
COOCH

CH2O

Saflower oil Soya Oil Coconut oil Fish oil

Linseed oil Tall Oil Castor oil cow fat oil
Sun flower oil Palm Oil Olive oil
DH Castor oil

AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

CH2-N=C=O FATTY ACIDS

H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N
N
H3COH2C CH2OCH3
NATURAL SYNTHETIC
CH2OR H
CH 3
CHO-OCN

CH2OR
N H
CH2OR
Unsaturated Saturated Unsaturated Saturated
COOCH

CH2O

Soya FA Stearin FA Emersol 305 Versatic

Tall Oil FA Coconut FA Cekanoic acid
Oleinic FA Lauric acid

AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

CH2-N=C=O

H3COH2C
N
N
N
CH2OCH3

CH2OCH3
ACIDS
H3COH2C
N N
N
H3COH2C CH2OCH3

CH2OR H
MONO BI TRI
CH 3
CHO-OCN FUNCTIONAL FUNCTIONAL FUNCTIONAL
CH2OR
N H
CH2OR

COOCH

CH2O Benzoic Acid Phthalic Anhydride Trimellitic Anhydride

p-t-Butyl Benzoic Acid Isophthalic Anhydride or
Abietic Acid Adipic Acid 5-sodiosulfo
Crotonic Acid Azelaic Acid isophthalic Acid

AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

CH2-N=C=O
ALCOHOLS
H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N
N
H3COH2C CH2OCH3

CH2OR H
CH 3
BI TRI TETRA
CHO-OCN

CH2OR FUNCTIONAL FUNCTIONAL FUNCTIONAL

N H
CH2OR

COOCH

CH2O

NPG Glycerol PE
Hexane Diol TMP
EG/DEG/PG TME

AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

ACID FUNCTIONAL PROPERTIES

CH2-N=C=O
Benzoic Acid 1 Chain Terminator
H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N
N
Abietic Acid 1 Chain Terminator,
H3COH2C CH2OCH3
Improved drying of long oil alkyd
CH2OR H
CH 3
CHO-OCN

CH2OR
Phthalic Anhydride 2 Workhorse acid; balanced properties
N H
CH2OR

COOCH
Isophthalic Acid 2 Improved hardness; improved chemical
CH2O
resistance

Terephthalic Acid 2 Improved hardness; improved chemical

resistance

Trimellitic Anhydride 3 Water-borne alkyds

AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

POLYOL FUNCTIONAL PROPERTIES

CH2-N=C=O

H3COH2C N CH2OCH3
Ethylene Glycol 2 Flexibility
N N
H3COH2C CH2OCH3
N N

H3COH2C
N
CH2OCH3
Neopentyl Glycol 2 Flexibility;
Improved alkali resistance
CH2OR H
CH 3
CHO-OCN

CH2OR Hexane Diol 2 Good solvent resistance

N H
CH2OR

COOCH

CH2O
Trimethylol Propane 3 Hardness/flexibility balance;
Improved alkali resistance

Glycerol 3 Hardness/flexibility balance

Pentaerythritol 4 Hardness; reactive,

Increased cross linking
AMR, 1/10/01
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

Fatty Acid Compositions of some of the more Common Vegetable Oils

CH2-N=C=O
Fatty Acid Cocon Palm Palm Peanu Rice Castor DCO
CH2OCH3
ut Oil Kernel Oil t Bran Oil
H3COH2C N
N N Oil Oil Oil
H3COH2C CH2OCH3
N N Caprylic-8 CH3(CH2)6COOH 6 3
N
H3COH2C CH2OCH3 Capric-10 CH3(CH2)8COOH 6 4

Lauric-12 CH3(CH2)10COOH 44 51
CH2OR H
CH 3 18 17 1 1
CHO-OCN
Myrtstic-14 CH3(CH2)12COOH

CH2OR Palmitic-16 CH3(CH2)14COOH 11 8 48 15 17 2

N H
CH2OR 6 2 4 5 2 1
Stearic-18 CH3(CH2)16COOH
COOCH
Oleic CH3(CH2)7CH=CH(CH2)7COOH 7 13 38 53 42 7 9
CH2O
Ricinoleic CH3(CH2)3CH-CH
OH 2-CH=CH(CH2)7COOH
87 8

Linoleic CH3(CH2)4CH=CH-CH2-CH=(CH2)7COOH 2 2 9 24 37 3 83

Linolenic CH3CH2-CH=CH-CH2-CH=CH-CH2-CH=CH(CH2)7COOH 2 2

Eleostearic CH3(CH2)3CH=CH-CH=CH-CH=CH(CH2)7COOH
Licanic O
CH3(CH2)3CH=CH-CH=CH-CH=CH(CH2)4C(CH2)2COOH

Iodine Value 7.5-10.5 14-23 44-54 88-100 99-115 81-91 145-155

AMR, 1/10/01 Saponification Value 250-264 245-255 195-205 198-206 180-190 176-187 200-204
 RAW MATERIAL & THEIR EFFECT
CH2-N=C=O

Fatty Acid Compositions of some of the more Common Vegetable Oils

CH2-N=C=O Sunflo Soya Tall Grape Safflow Tung Linsee Oiticica
Fatty Acid
wer Oil Bean Oil* Seed er Oil Oil d Oil Oil
H3COH2C N CH2OCH3
N N Oil Oil
H3COH2C CH2OCH3
N N Caprylic-8 CH3(CH2)6COOH Contain
N 4%
H3COH2C CH2OCH3 Capric-10 CH3(CH2)8COOH hydrox
y acids
Lauric-12 CH3(CH2)10COOH
CH2OR H
CH 3 Myrtstic-14 CH3(CH2)12COOH
CHO-OCN
Palmitic-16 CH3(CH2)14COOH 11 11 5 9 8 4 6 7
CH2OR
N H 6 4 2 4 3 1 4 5
CH2OR
Stearic-18 CH3(CH2)16COOH

COOCH Oleic CH3(CH2)7CH=CH(CH2)7COOH 29 25 48 20 13 8 22 6

CH2O Ricinoleic CH3(CH2)3CH-CH

OH 2-CH=CH(CH2)7COOH

Linoleic CH3(CH2)4CH=CH-CH2-CH=(CH2)7COOH 52 51 45 67 75 4 16

Linolenic CH3CH2-CH=CH-CH2-CH=CH-CH2-CH=CH(CH2)7COOH 2 9 1 3 52

Eleostearic CH3(CH2)3CH=CH-CH=CH-CH=CH(CH2)7COOH 80

Licanic CH3(CH2)3CH=CH-CH=CH-CH=CH(CH2)4C(CH
O 2)2COOH
78

Iodine Value 125-136 120-141 130-138 130-140 140-150 160-175 155-205 140-160

Saponification Value 188-194 185-195 192-194 185-195 188-194 189-195 188-196 186-193
AMR, 1/10/01
 TYPICAL OF ALKYD
CH2-N=C=O

CH2-N=C=O CHARACTERIZING AN ALKYD

H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N

H3COH2C
N
CH2OCH3

BASED ON OIL LENGTH .
CH2OR H
CH 3

BASED ON THE TYPE OF OIL/FA.
CHO-OCN

CH2OR
N H
CH2OR
Whether air drying or non drying oil / FA.
COOCH

CH2O

BASED ON CHAIN STOPPED OR NOT.

BASED ON MODIFICATIONS.
Rosin, Acrylic, Urethane, Silicone, etc.

AMR, 1/10/01
 TYPICAL OF ALKYD
CH2-N=C=O

CH2-N=C=O BASED ON OIL LENGTH

H3COH2C N CH2OCH3
N N
H3COH2C CH2OCH3
N N

H3COH2C
N
CH2OCH3
VERY LONG OIL > 65 % PRINTING INK,
OIL BASED STAIN.
CH2OR H
CH 3
CHO-OCN

CH2OR LONG OIL 55 % - 65 % ARCHITECTURAL,

N H
CH2OR
MAINTENANCE.
COOCH

CH2O

MEDIUM OIL 45 % - 55 % MAINTENANCE,

PRIMER.

SHORT OIL < 45 % INDUSTRIAL COATING;

NC,AC,PU,STOVING.

AMR, 1/10/01
 TYPICAL OF ALKYD
CH2-N=C=O

CH2-N=C=O
MODIFIED ALKYD
H3COH2C N CH2OCH3
N N
H3COH2C
N N
CH2OCH3 STYRENE FAST DRY, GLOSS
N
H3COH2C CH2OCH3
VINYL TOLUENE FAST DRY, GOOD ALKALI RESISTANCE
CH2OR H

CHO-OCN
CH 3 ACRYLIC BETTER WEATHERING
CH2OR
N H
CH2OR
EPOXY ADHESION, CHEMICAL RESISTANCE
COOCH

CH2O
PHENOLIC HARDNESS, CHEMICAL RESISTANCE
ISOCYANATE TOUGHNESS & FAST DRY
SILICONE BETTER HEAT WEATHERING
NATURAL RESIN FAST DRY, BETTER ADHESION
POLYAMIDE THIXOTROPIC
AMR, 1/10/01
 DRYING MECHANISM OF ALKYD
CH2-N=C=O

AIR DRY / ORGANOMETAL

CH2-N=C=O

CH2OCH3 CH=CH-CH=CH
H3COH2C
N
N
N Alkyd Resin Alkyd Resin
H3COH2C CH2OCH3
N N Drier O2
N
H3COH2C CH2OCH3
O O

Alkyd Resin CH-CH=CH-CH Alkyd Resin

CH2OR H

CHO-OCN
CH 3 OO .
Alkyd Resin Alkyd Resin
CH2OR
N H
CH2OR
CH-CH=CH-CH .
COOCH

CH2O
OO . + Alkyd CH=CH-CH=CH Alkyd

Alkyd Resin CH-CH=CH-CH Alkyd Resin

Alkyd Resin CH-CH=CH-CH Alkyd Resin

Alkyd Resin CH-CH=CH-CH Alkyd Resin

AMR, 1/10/01
 DRYING MECHANISM OF ALKYD
CH2-N=C=O

NITROCELLULOSE
CH2-N=C=O

H3COH2C N CH2OCH3
N N
H3COH2C
N N
CH2OCH3 H2CONO2 H ONO2 H2CONO2 H ONO2
N
H3COH2C CH2OCH3 O O
H H H OH
H O OH H H O OH H

CH2OR H
OH H H O OH H H
CH 3 OH H H H H H
CHO-OCN O O
CH2OR
N H H ONO2 H2CONO2 H ONO2 H2CONO2
CH2OR

COOCH n
CH2O
NC is a thermoplastic resin made by nitrating raw cellulose, common
NC has a Tg about 50 oC, which is hard, fast dry, Brittle, yellowing &
poor adhesion.

Typical Short Oil Alkyd is used to upgrade

Performance and Durability
AMR, 1/10/01
 DRYING MECHANISM OF ALKYD
CH2-N=C=O

POLYURETHANE
CH2-N=C=O

H3COH2C N CH2OCH3 FA OH
N N CH3
H3COH2C CH2OCH3 FA
N N
NCO
H3COH2C
N
CH2OCH3
OH
OH Alkyd Polyol + Toluene di-isocyanate

CH2OR H
OH NCO
CH 3 FA
CHO-OCN
FA
CH2OR
N H
CH2OR H
COOCH FA
FA O-C-N N-C-O OH
CH2O
O HO FA OH OH
OH CH3 OH
OH OH FA FA
H
OH O-C-N N-C-O
FA FA FA
O HO
FA
OH CH3

AMR, 1/10/01
 DRYING MECHANISM OF ALKYD
CH2-N=C=O

AMINO CROSSLINKING
CH2-N=C=O

H3COH2C N CH2OCH3
N N Amino resin N – CH2OC4H9 OH
H3COH2C
N N
CH2OCH3
CH2OC4H9
+ Short oil alkyd
N
H3COH2C CH2OCH3 H+
OH
Short oil alkyd COOH
CH2OR H
CH 3
Amino resin N – CH2OC=O
CHO-OCN

CH2OR
+ C4H9OH
N H CH2OC4H9
CH2OR

COOCH

CH2O Amino resin NH – CH2OH + COOH

H+ Short oil alkyd

COOH

Short oil alkyd OH

O
Amino resin NH – CH2
+ H2O

AMR, 1/10/01
 SUMMARY OF ALKYD
CH2-N=C=O
TYPICAL OILS
RESIN MODIFICATION, %
AND FATTY ACID
80 70 60 50 40 30 20
CH2-N=C=O 200
AROMATIC SOLVENT ALIPHATIC SOLVENT LINSEED
H3COH2C N CH2OCH3
TUNG
IODINE VALUE OF OIL OR FATTY ACID

N N
H3COH2C CH2OCH3
N N
N SAFFLOWER
H3COH2C CH2OCH3 Faster Air Dry
150 DEHYDRATED
CASTOR
SOYA
CH2OR H
CH 3 TALL OIL
CHO-OCN  Spraying
• Brushing
CH2OR
application
application COTTONSEED
N H  Lacquer
RESIN - LIKE OIL - LIKE •Flow ability
CH2OR 100 type dry RICE
PROPERTIES PROPERTIES •Grinding
COOCH
High Viscosity PEANUT
ease
High Initial
CH2O •Can Stability
gloss CASTOR
OLIVE

50
Slower Air Dry

SHORT OIL MEDIUM OIL LONG OIL COCONUT

ETHYLHEXOIC
0 ACID
20 30 40 50 60 70 80
AMR, 1/10/01
OIL LENGTH, %
 SUMMARY OF ALKYD
CH2-N=C=O
TYPICAL OILS
RESIN MODIFICATION, % AND FATTY ACID
80 70 60 50 40 30 20
CH2-N=C=O 200
Fast air dry LINSEED
H3COH2C N CH2OCH3 Metal finishes & TUNG
N N
H3COH2C CH2OCH3 Primer Coating Architectural finishes
N N
for Interior Coating
IODINE VALUE OF OIL OR FATTY ACID

N SAFFLOWER
H3COH2C CH2OCH3
4-Hours air dry
150 Maintenance of DEHYDRATED
CASTOR
Appliance coating SOYA
CH2OR H
CH 3 • Baked Industrial Finishes TALL OIL
CHO-OCN
•Nitrocellulose Alkyd Lacquer
CH2OR •Acid curing Finishes COTTONSEED
N H
CH2OR 100 RICE
COOCH PEANUT
CH2O CASTOR
OLIVE

50 • Baked Alkyd-Amino
• Low yellowing
NC-Alkyd Lacquer
Acid curing Finishes

SHORT OIL MEDIUM OIL LONG OIL COCONUT

ETHYLHEXOIC
0 ACID
20 30 40 50 60 70 80
AMR, 1/10/01
OIL LENGTH, %
 SUMMARY OF ALKYD
CH2-N=C=O
R
COOH COOH COOH COOH
R
CH2-N=C=O

OH OH R R
H3COH2C N CH2OCH3 R
N N
H3COH2C CH2OCH3
N N
N
H3COH2C CH2OCH3
OH R R R
R

CH2OR H R
CH 3
CHO-OCN OH OH OH R
R
CH2OR
N H
CH2OR

COOCH
OH OH R R
CH2O R

OH R R R
R

OH OH R R
HO HO HO HO
OIL FREE SHORT OIL MEDIUM OIL LONG OIL
AMR, 1/10/01 OH EX = 50 % OH EX = 29 % OH EX = 6 % OH EX = 0 %