APPLICATION BULLETIN Chemical Intermediates Design Unique Polymers with Sartomers Specialty Monomers

Introduction
Sartomer offers a number of specialty monomers that function as chemical intermediates or building blocks to design unique polymers for a variety of applications. These monomers are high molecular weight, low volatility materials with acrylate and methacrylate ester functionality. The monomer structures are determined by starting raw materials and are aromatic or aliphatic; cyclical, alkane, ester or ether glycols; and monofunctional or multifunctional in nature. They can be reacted with other functional monomers, oligomers, plasticizers, and resins to form tailor-made polymers. This paper displays the reaction mechanisms for Sartomers specialty acrylate and methacrylate monomers and presents some of their features and applications as chemical intermediates.

Figure 1

CH3 or H C C O O R

C H

Safety & Handling

Store all products away from direct sunlight, oxidizing agents and materials that may generate free radicals. Store in a cool area where the ambient temperature does not exceed 90F. Keep container tightly closed until ready to use to avoid loss of reactivity. For optimum results, use within 6 months of receipt of product.

Applications
Sartomers specialty monomers, described on pages 4 through 6 of this bulletin, act as chemical intermediates and are used to produce chemicals that enhance performance properties. These chemical intermediates function in resin modification for a number of applications including:
q q q q q

Safety Precautions
Materials in this bulletin can cause eye and skin irritation and have the potential to cause skin sensitization in susceptible individuals. Handle in accordance with good industrial hygiene practices, which includes minimizing exposure of the product to the eyes, skin, and clothing. Consult the appropriate Material Safety Date Sheet before using any chemical in this bulletin.

Composites Coatings (Emulsion & Solution Polymers) Impact Modifiers for Plastics Ion exchange resins Super-Absorbent Polymers

Conclusions
Although this bulletin is not an exhaustive presentation of the many Sartomer products that can be used as chemical intermediates, it is intended to provide information and initiate some novel reaction ideas. Sartomer has in addition to these monomers a few oligomers that also have acrylate and hydroxyl functionality. Sartomers Product Catalog should be referenced for a complete list of products.

Reaction Mechanisms
Sartomers chemical intermediates are acrylate and methacrylate functional monomers represented by the general structure in Fig 1. They can undergo reactions through a number of mechanisms including free radical polymerization using photoinitiators, peroxides or azo compounds; Michael addition polymerization involving an amine; or reactions with an isocyanate if a hydroxyl group is present. These reaction mechanisms are illustrated in Figures 2 through 5, respectively on page 2 of this bulletin.

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4115 5/98

(Meth) Acrylate Reaction Mechanisms

Free Radical Polymerization Monofunctional (meth)acrylate monomers can be homopolymerized or copolymerized with other chemicals containing C=C double bonds as shown in Figure 2. (Meth)acrylate monomers with functionality > 1 can undergo crosslinking during polymerization.

Figure 2 H Ri* + Initiator n C H CH3 or H C hv, m++, H CH3 or H

C H

C n

C O Monomer

O R

C O Polymer

O R

The Ri* in the reaction sequence above represents a radical generated by 1) high energy electrons (Electron Beam technology) 2 ) photoinitiators (R-C=O-O-R or R-C=O-R) exposed to a UV light source 3) decomposition of peroxides (R-OO-R) or 4) decomposition of an azonitrile compound (R-N=N-R).

Michael Addition Reactions Acrylate monomers can be adducted with a (poly)amine to form an acrylate amine adduct which can then react with an epoxy resin. Reactions with primary amines are preferred for the Michael Addition mechanism. Acrylate monomers with functionality > 1 can undergo crosslinking during addition.

Figure 3
Step 1) Amine-Acrylate Adduct Formation

H nucleophillic addition
R'

R'

N H2

C H

C O

O R

C O

O R

Amine

Monomer

Amine Acrylate Adduct

Step 2) Amine-Acrylate Adduct Reaction with Epoxies

Figure 4
H H H OH O + C C R R C C N C H C H H R H H

R'

C O

O R

C O

O R

Adduct

Epoxy

Highly Crosslinked Polymer

Dual Functionality Reaction Mechanisms

Reactions with Isocyanates (Meth) acrylate monomers containing OH functionality can undergo Free-Radical or Michael Addition Polymerization through the C=C double bond but can also undergo an addition reaction with an isocyanate to form a urethane.

Figure 5
H CH3 or H H CH3 or H

R'

Isocyanaate

H Monomer

O Urethane

Cyclic Monomers
SR-203 Tetrahydrofurfuryl Methacrylate (MW 170)

Hydroxyl Functional Monomers

CD-570 - EO (2) Hydroxy Ethyl Methacrylate (MW 190)

O O CH3
High Tg (75C) Excellent solvency properties

CH3 O O
Low skin irritation More flexibility than HEMA

O
2

OH

CD-571 - EO (5) Hydroxy Ethyl Methacrylate (MW 274) SR-340 - Phenoxyethyl Methacrylate (MW 206)

CH 3

CH 3 O O
Moderate Tg (54C) Improved heat resistance

O
5

OH

O
More flexibility than CD-570 Water solubility

CD-572 - EO (10) Hydroxy Ethyl Methacrylate (MW 414)

SR-423 - Isobornyl Methacrylate (MW 223)

CH3 O O
Low skin irritation High water solubility Flexibility

CH3 O H3C O CH3

High Tg (110C) High hardness

OH
10

SR-604 - Propylene Glycol Monomethacrylate (MW 405)

CH3 O
CD-612 - Ethoxylated Nonylphenol Methacrylate (MW 464)

OH O H3C
4

O
O O CH3 O
4

Low skin irritation High water solubility Flexibility

Low odor Low Tg (-12C) Excellent pigment wetting properties

Specialty Monomers
CD-513 - Propoxylated Allyl Methacrylate (MW 244)

Alkane Monomers
SR-313 - Lauryl Methacrylate (MW 254)

O O CH3

CH3 O CH3

O
O

O CH3
Low Tg (-65C) Hydrophobic backbone

Allylic and methacrylate functionality Low odor Low skin irritation

CD-550 - Methoxy Polyethylene Glycol (350) Methacrylate (MW 494)

SR-324 - Stearyl Methacrylate (MW 338)

O O

O O CH3
Low Tg Excellent wetting properties Water solubility

O
8

CH3

CH 3
Moderate Tg (38C) Low melt point (21C) Hydrophobic backbone

SR-493 - Tridecyl Methacrylate (MW 268) CD-552 - Methoxy Polyethylene Glycol (550) Methacrylate (MW 693)

O O CH3
Lower Tg than CD-550 High water solubility

O
16

CH3

CH
Low skin irritation Hydrophobic backbone Flexibility

Crosslinking Monomers
SR-709 - Metallic Monomethacrylate ( MW 167) Alkane Backbone

O O CH3
Metallic modified Slight water solubility

CH3 O O O

Zn

OH

CH3

SR-206 - Ethylene Glycol Dimethacrylate (MW 198) SR-214 - Butanediol Dimethacrylate (MW 226) SR-297 Butylene Glycol Dimethacrylate (MW 226) SR 239 - Hexanediol Dimethacrylate (MW 254)

Ether Backbone

Multifunctional Monomer
CH3 O O O O
SR-350 - Trimethylolpropane Trimethacrylate (MW 338)

CH3

O O CH3 H3 C

CH3 CH2 O O O

SR-231 - Diethylene Glycol Dimethacrylate (MW 242) SR-205 - Triethylene Glycol Dimethacrylate (MW 286) SR-209 - Tetraethylene Glycol Dimethacrylate (MW 330) SR-210 - Polyethylene Glycol (200) Dimethacrylate (MW 330) SR-603 - Polyethylene Glycol (400) Dimethacrylate (MW 598) SR-252 - Polyethylene Glycol (600) Dimethacrylate (MW 754)

CH3

Cyclic Backbone Ethoxylated Bisphenol A Dimethacrylate

CH3 O O O

Fast Cure Response Excellent Chemical, Heat Resistance

O O CH3 O

CH3 C H3C

Note: Acrylated versions of the monomers presented here are also available.

SR-348 - 2 Mole Ethoxylated (MW 452) CD-540 - 4 Mole Ethoxylated (MW 572) CD-541 - 6 Mole Ethoxylated (MW 660) SR-480 - 10 Mole Ethoxylated (MW 808) SR-9036 - 30 Mole Ethoxylated (MW 2156)

CD-401 - Cyclohexane Dimethanol Dimethacrylate (MW 280)

CH3 O O
Melt Point 55 60o C Excellent Weatherability

CH3 O O

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond SARTOMER Companys control. The listed properties are illustrative only, and not product specifications. SARTOMER Company disclaims any liability in connection with the use of the information, and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.