Reactions of Methylol Containing Polymers

 

Acrylic resins containing pendant amine groups can be obtained by the use of acrylamide or methacrylamide. One method of producing pendant methylol groups on the polymer chain is by the reaction of an amide containing polymer with formaldehyde, to produce methylol groups.

 

VyWVWWpA/V

c=o c=o

I I

NH, NH,

 

vywwvvywv

C=0 C=0

 

+ 2HCHO

 

NH NH

I I

CH2OH CH2OH

 

Acrylamide containing polymer

 

Methylolated polymer

 

Acrylic polymer backbone

 

Figure 1-46

The methylol groups are normally stabilised by reaction with an alcohol (usually propanol or butanol) to form an alkoxy methylol group.

 

vywvwvywv

c=o c=o 1 1

VWVVVVVWVVVVVV

+ 2C<HeOH —► C=0 С— О

NH

I

NH

1

1 1 NH NH

і і

1

CH2OH

1

CH2OH

1 1 ch2o— C4H9 CH20— C4He

Acrylic polymer backbone AV’/V

 

Both the methylol and alkoxy methylol groups will readily react with epoxy, carboxy, hydroxy and amino groups. In addition the unstabilised methylol groups readily undergo self condensation.

> 0 0 > > 0 0 >

> и 11 > > 11 11 >

S-C — NH — СН2ОН + H — О — CHj— NH— C-£—► S — C — NH — СН,—О — СН,— NH— C -4 + НгО

Подпись: ^ heatПодпись: + HCHCimage46Acrylic polymer backbone ЛДЛ/V

Figure 1-48

The methylol groups will condense with alkoxy methylol groups

Подпись: I-о о

II II

C — NH — CH2OH + C„HB— О — СН2— NH— С-

image47 Подпись: + С„НвОН

^ heat

Polymer backbone ттптш Acrylic polymer backbone
figure 1-49

The alkoxy methylol groups will also self condense under the appropriate conditions of heat and acid catalysis.

Both the methylol containing polymer and the methylol ether containing polymer will undergo similar reactions with epoxy, carboxyl and hydroxyl groups. These reactions are the basis for a major proportion of the thermosetting acrylic surface coating systems.

(xiv) Reactions of Methylol Containing Polymers with Epoxy Groups

Подпись: — NH — CH,OH + Reactions of Methylol Containing Polymers Подпись: i OH " Acrylic polymer backbone ДЛА/V

a) Epoxy groups

C —NH—CH2—OH + HO—R-| ► J—C —NH —CH2—O—R-| + H20

О " ‘ О *

Polymer backbone…………………….. ………………. Acrylic polymer backbone /s/s/s/s/

Подпись:

Reactions of Methylol Containing Polymers
image48
Подпись: CH2— NH
image49
Подпись: + H2O
image50
Подпись: +

Acrylic polymer backbone

Figure 1-53

Reactions of Methylol Containing Polymers

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