The Notes for
Polymer and Coatings Science-
Chapter Two- part three

Another synthesis of acrylic acid 
H   H                               H   H
|   |                               |   |
C = C  + H O  + CO  ------------->  C = C
|   |     2                         |   |
H   H                               H   C=O
                                        |
                                        OH
The synthesis of acrylic acid from ethylene, water, and carbon monoxide is carried out at 200 deg C and 60 to 200 atm in tetrahydrofuran, with nickel bromide used as the catalyst.

Acrylic acid can also be synthesized from propylene: 
H   H               H   H            H   H
|   |    oxidation  |   |            |   |
C = C   ----------> C = C     ---->  C = C
|   |               |   |            |   |
H   CH3             H   C=O          H   C=O
                        |                |
                        H                OH
The above is carried out in one step by passing a mixture of 10% propylene, 50% air, and 40% steam over a cobalt molybdenum catalyst at 400-500 deg C.

Synthesis of methacrylic acid from acetone feedstock: 
      O                   OH      H SO
      ||       HCN        |        2  4     ??I can't make further sense
H C - C - CH  ----> CH  - C - CN  ----->  of the notes from here
 3          3         3   |
                          CH
                            3
Synthesis of Esters of Acrylic Acid

Ethyl acrylate is the most commercially available example of an acrylic acid ester: 
     H   H                                  H   H  
     |   |                                  |   |  
HO - C - C - CN  +  CH -CH -OH + H SO  ---> C = C  + NH (+) (-)HSO
     |   |            3   2       2  4      |   |      4          4
     H   H                                  H   C=O
                                                |
                                                O - CH - CH
                                                      2    3
Higher acrylates are prepared by choosing the proper alchol or by the esterification of acrylic acid.

 Methyl methacrylate- cyanohydrin feedstock

Methylmethacrylate is the most important example and it is made from acetone cyanohydrin.

      CH3              H   CH3            H   CH3
      |        conc.   |   |   aq. MeOH   |   |
CH  - C - CN   ----->  C = C   -------->  C = C 
  3   |        H SO    |   |              |   |
      OH        2  4   H   C=O            H   C=O
                           |                  |
                           NH (+)             O-CH
                             3                    3
                           HSO(-)
                              4
The middle product is fed directly into aqueous methanol.

 Synthesis of ethyl acrylate- ethylene feedstock 
H   H                       H   H
|   |                       |   |
C = C + Nc(CO)  + EtOH  --> C = C
|   |         4             |   |
H   H                       H   C=O
                                |
                                O-CH -CH
                                    2   3
Two syntheses of acrylonitrile- ethylene feedstocks

The acetylene route 
H   H                H   H
|   |                |   |
C = C  +  HCN  --->  C = C
|   |                |   |
H   H                H   C
                        |||
                         N
The catalyst is cuprous chloride in HCl, and the reaction is carried out in a liquid phase. The acetylene is passed through a solution of HCN with the catalyst at 80- 90 deg C. The reactor effluent is cooled and passed into water, where the acrylonitrile is extracted, stripped with steam and purified by passage through a series of distillation columns, the last of which operates under reduced pressure.

The ethylene route 
H   H         O       O             OH  CN         H   H
|   |          2     / \     HCN    |   |          |   |
C = C + HCN  ---> H-C = C-H  ---> H-C - C-H  --->  C = C
|   |               |   |           |   |          |   |
H   H               H   H           H   H          H   CN
Dehydration is carried out in the vapor phase over activated alumina at 300 deg C.

Synthesis of acrylonitrile- propylene feedstocks
Ammoxidation of propylene

H   H  NH , O    H   H
|   |    3   2   |   |
C = C  ------->  C = C + 3 H O
|   |            |   |      2
H   CH           H   CN
      3
catalyzed by Bi, U, M at 400 to 500 deg C, 1 to 3 atm

  H   H              H   H
  |   |     3 NO     |   |
2 C = C    ------->  C = C  +  N  +  3H O 
  |   |              |   |      2      2
  H   CH             H   C
        3               |||
                         N
catalysed by silver

 Acrylamide- Acrylamide can be prepared by the hydrolysis of acrylonitrile. 
H   H                 H   H
|   |                 |   |
C = C  +  H O  -----> C = C
|   |      2          |   |
H   C                 H   C=O
   |||                    |              
    N                     NH
                            2


Polymerization of poly(acrylic acid) and poly(methyl methacrylic acid)

Both polymers are water soluble. 
 H   H              H   H
 |   |              |   |
 C = C   ---->  -[- C = C -]-
 |   |              |   |
 H   C=O            H   C=O
     |                  |
     OH                 OH

acrylic acid      poly(acrylic acid)
and 
H   CH3            H   CH3  
|   |              |   |  
C = C   ---->  -[- C = C -]-
|   |              |   |            
H   C=O            H   C=O
    |                  |
    OH                 OH

methacrylic acid  poly(methacrylic acid)
A free radical process using solution polymerization is possible using water as the solvent. Note that for solution polymerization there will be a correlation between the growing polymer molecular weight and viscosity. This differs from the emulsion and suspension polymerizations in water discussed previously.

Initiator- potassium persulfate is added to the silver solution of the acid, with an activator (sodium thiosulfate) and a transfer agent (mercaptosuccinic acid), at a temperature from 50 to 100 deg C.)

If solid polymer is required, a peroxide can be used for the initiator, and benzene may be used as the solvent.

Salts of acrylic and methacrylic acid may also be polymerized in aqueous solution by treatment with FT initiators.

Both acrylic acid and methacrylic acid undergo the carboxylic acid reactions discussed in Organic chemistry.

Alternative routes to acrylic acid ethylene and propylene feedstocks 
H   H                               H   H
|   |                               |   |
C = C  + H O  + CO  ------------->  C = C
|   |     2                         |   |
H   H                               H   C=O
                                        |
                                        OH

H   H               H   H            H   H
|   |    oxidation  |   |            |   |
C = C   ----------> C = C     ---->  C = C
|   |               |   |            |   |
H   CH3             H   C=O          H   C=O
                        |                |
                        H                OH
The above is carried out in one step by passing a mixture of 10% propylene, 50% air, and 40% steam over a cobalt molybdenum catalyst at 400-500 deg C.

Synthesis of ethacrylate The synthesis of ethacrylate from ethylene is shown. 
H   H                       H   H
|   |                       |   |
C = C + Nc(CO)  + EtOH  --> C = C
|   |         4             |   |
H   H                       H   C=O
                                |
                                O-CH -CH
                                    2   3
The above is carried out in one step by passing a mixture of 10% propylene, 50% air, and 40% steam over a cobalt molybdenum catalyst at 400-500 deg C.





Last Update- July 8, 1995- wld