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UV-curing Resins Based on Renewable Raw Materials

Matthias Fies, Holger Endres, Ronald Klagge* Cognis Deutschland, Germany

Over the past 20 years, radiation curing has become a well established coating technology used in

many different applications. Today, an extraordinary variety of acrylic raw materials is at the formulator’s disposal to be chosen for sophisticated and tailor-made formulations.

The majority of those raw materials is of petrochemical origin. However, there is an increasing demand for coating systems that contain a high amount of renewable material. This demand is heard primarily in the wood coating and printing ink industries. The UV curing oils are one example for a coating system that has been developed in order to fulfill this demand.

The industrial oiling of wood is an important application for UV curing oils as they bring along significant advantages over conventionally drying oils: By using UV oils systems it is possible to save large amounts of organic solvents which is an important aspect with regard to environmental concerns. Also, the drying process which is known to be very time-consuming when conventional oxidatively drying oils are used. With UV-curing oils it can be done in not more than a fraction of a second.

If requested by the customer, even the multiple layers in parquet coatings can be assembled using a coating system with a high content of renewable material.

In this presentation the state of the art of renewable raw materials in UV-curing systems is described and further possibilities for applications in the coatings industry are presented.

Radiation curing coating systems are in general formulated from a reactive resin and, optionally, a low viscous reactive diluent. A photoinitiator is added to guarantee an immediate curing upon exposure to UV light. The coating formulation is completed by the addition of additives, pigments and fillers.

Recently, epoxidized fatty oils and their derivatives showed a promising effect when used as reactive

resins.

soybean and linseed oils which are catalytically oxidized by hydrogen peroxide.

Those epoxidized oils are commercially manufactured from unsaturated fatty oils like

[1]

In this reaction virtually all the unsaturated double bonds in the oil are transferred into epoxy rings. Epoxidized soybean and linseed oils are commercially available because they have been used for decades as plasticizers in special applications.

Due to the higher degree of unsaturation of natural linseed oil compared to soybean oil, the former shows a higher degree of epoxidation as well as reactivity.

O O O O C O O O C O O O O C
O
O O
O
C
O
O
O
C
O
O O
O
C

Figure 1: Epoxidized triglyceride (hydrocarbon chains are shown as a straight line)

 

Epoxide

Viscosity

Iodine Value

Saponif. No.

[%]

[mPas at 25 °C]

[mg KOH / g]

[mg KOH / g]

Epoxidized soybean oil

7,0

550

2,5

180

Epoxidized linseed oil

9,7

800

5

175

Table 1: Properties of epoxidized soybean and linseed oils

For UV curing applications the epoxidized oils can be used as such. When irradiated by UV light, a photoinitiator that is able to initiate curing by a cationic mechanism will start the immediate film forming process by a cross-linking ring opening reaction.

Formulations using aliphatic epoxides and polyols have also been decribed in the literature. [2,3]

The epoxy ring can also be opened in a catalytic reaction with acrylic acid. The epoxy acrylates which result from this reaction can be cured in a similar way as the epoxidized oils. The photoinitiator for this curing process has to react according to a free radical mechanism.

Since the viscosity of epoxidized fatty oils increases significantly upon ring opening reaction with acrylic acid it may be necessary to use reactive diluents in the formulation to re-adjust its viscosity.

Epoxidized and fully acrylated linseed oil contains 63 % of renewable raw material, epoxidized and acrylated soybean oil even 71 %.

If only a part of the epoxy rings in an epoxidized fatty oil are reacted and opened with acrylic acid (as shown in figure 2) a resin is obtained that can be cured by both mechanisms, radical and cationic. In such a dual-cure-process the respective advantages of each mechanism combine synergetically.

O

O C O O C O O C
O
C
O
O
C
O
O
C
O C O O OH
O
C
O
O
OH

O

HO OH O O C C O O
HO
OH
O
O
C
C
O
O

Figure 2: Epoxidized soybean oil, partially acrylated

Also polyfunctional glycidyl ethers can be esterified with mixtures of acrylic and fatty acids. One example for this reaction is the bisphenol A diglycidyl ether acrylate modified with a fatty acid.

O O
O
O

OH

O

O O OH O OH O O O
OH O O
OH
O
O

O

Figure 3: Epoxy acrylate modified with lauric acid

The fatty acid used in the manufacture of this product can be saturated as well as unsaturated. Also a dimer fatty acid can be used.

Those fatty acid modified epoxy acrylates provide a harder film than the epoxidized oil acrylates when cured in a radical mechanism.

If a polyunsaturated fatty acid is used it is possible to cure the unsaturated double bonds by an oxidative mechanism in addition to the UV curing of the acrylic double bonds.

A typical fatty acid modified epoxy acrylate contains approximately 30 % of renewable raw material.

The most important resins within the UV curing technology are polyester acrylates.

Polyester acrylates are produced in a condensation reaction of a polyol with polycarboxylic acids and acrylic acid. Due to the multitude of possible combinations of these compounds it is possible to provide excellent raw materials for formulations that can be cured to form coatings with tailor-made film properties.

With polyols and polycarboxylic acids that are made from renewable raw materials such a polyester acrylate can contain up to 40 % of renewable material.

Glycerol (as long as it is produced in the fat splitting process), sorbitol and carbohydrate derivatives are examples of those polyols.

Azelaic acid and sebacic acid are good examples for polycarboxylic acids that are made from renewable material. Azelaic acid is commercially produced by ozonolysis of oleic acid and sebacic acid can be obtained by thermolysis of castor oil. Dimer fatty acid is made from soybean fatty acid in a dimerization step. Also this C 36 -fatty acid is used for the manufacture of polyester acrylates.

O O HO OH Azelaic acid C 9 H 16 O 4 O OH HO
O
O
HO
OH
Azelaic acid
C 9 H 16 O 4
O
OH
HO

Sebacic acid

O

C 10 H 18 O 4

HO OH O O Dimer fatty acid C 36 H 64 O 4
HO
OH
O
O
Dimer fatty acid
C 36 H 64 O 4

Figure 4: Polybasic acids made from renewable raw material

The following polyesters in figures 5 and 6 are just two examples for polyester acrylates based on renewable material.

Polyester acrylate based on glycerol and azelaic acid

O O O O O O O O O O O O O O O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
Content of renewable material:
37
%
Viscosity (23 °C):
1 200
mPas

Double Bond Density:

3,2 mmol H 2 /g

Polyester acrylate based on pentaerythritol and dimer fatty acid

O O O O O O O O O O O O O O O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O

Content of renewable material:

36

20 000

%

Viscosity (23 °C):

mPas

Double Bond Density:

2,7 mmol H 2 /g

Figures 5 and 6: Polyester acrylates based on renewable material

Again, because of the high viscosities of the hitherto described epoxy and polyester acrylates the formulator often has to use reactive diluents in his formulations.

Propoxylated glycerol triacrylate (GPTA) is a well known reactive diluent that contains 21 % of renewable material (as long as the glycerol is produced by splitting a natural fat.)

1,10-Decanediol diacrylate has an even higher content of 50 % of renewable material. 1,10- Decanediol is made in the reduction of sebacic esters.

Its low viscosity, excellent cutting power and high reactivity compare to the well known hexanediol diacrylate (HDDA).

With its 77 %, dimerdiol diacrylate contains the highest content of renewable material by far. The dimerdiol which is used for its production is obtained by hydrogenation of dimer fatty esters.

Dimerdiol diacrylate shows not only a very low surface tension, it also supports the matting effect in coating systems due to its partial incompatibility.

 

content

double bond density [mmol H 2 /g]

viscosity

[mPas] (23 °C)

 

renewable

 

material

100 %

80 : 20 1)

60 : 40 2)

GPTA

21

%

5,0

170

66

000

9 000

Dekandiol DA

50

%

6,8

30

10

700

1 060

Dimerdiol DA

77

%

2,7

210

1)

mixture of 80 % epoxy acrylate (approx. 2,000,000 mPas) and 20 % reactive diluent

2)

mixture of 60 % epoxy acrylate (approx. 2,000,000 mPas) and 40 % reactive diluent

Table 2: reactive diluents based on renewable material

In reacting polyfunctional alcohols with a mixture of acrylic and fatty acids, low viscous UV resins can be produced. These UV resins can be used along with polyester and epoxy acrylates to formulate radiation curing coating systems.

O O O O Polyol O O O O
O O
O
O
Polyol
O
O
O
O

Figure 7: Polyester acrylate modified with fatty acids

Both, saturated and unsaturated fatty acids are used in the production of these UV resins that can also be formulated as dual cure systems.

The properties of some selected products are listed in the following table.

 

saturated

unsaturated

polyunsaturated fatty acid

polyester acrylate containing:

fatty acid

fatty acid

viscosity

[mPas]

150

180

210

double

bond

       

density

[mmol H 2 / g]

3,6

3,1

3,1

color

[Gardner]

colorless

6,5

4,4

iodine number

[mg KOH / g]

0

29

43

pendulum

[s]

55

60

57

hardness

renewable

       

material

[%]

33

41

41

Table 3: Properties of polyester acrylates modified with fatty acids

Literature

[1]

Chhim, P.

Inst. Rech. Appl. Polym., Le Mans, Fr., The synthesis of a photocurable oil from

a vegetable oil and examples of applications. Double Liaison - Chim. Peint. (1987), 34(383),

35-8, XVII-XIX.

[2]

Crivello, J. V.; Narayan, R.; Sternstein, S. S., J. Appl. Polymer Science (1997), 64(11), 2073-

2087.

[3]

Mahmood, Mohd. Hilmi et al., J. Sains Nukl. Malays. (1993), 11(1), 1-10.