Methyl methacrylate copolymers, radiation

A number of methods such as ultrasonics (137), radiation (138), and chemical techniques (139—141), including the use of polymer radicals, polymer ions, and organometaUic initiators, have been used to prepare acrylonitrile block copolymers (142). Block comonomers include styrene, methyl acrylate, methyl methacrylate, vinyl chloride, vinyl acetate, 4-vinylpyridine, acryUc acid, and -butyl isocyanate. 

An effective method of NVF chemical modification is graft copolymerization [34,35]. This reaction is initiated by free radicals of the cellulose molecule. The cellulose is treated with an aqueous solution with selected ions and is exposed to a high-energy radiation. Then, the cellulose molecule cracks and radicals are formed. Afterwards, the radical sites of the cellulose are treated with a suitable solution (compatible with the polymer matrix), for example vinyl monomer [35] acrylonitrile [34], methyl methacrylate [47], polystyrene [41]. The resulting copolymer possesses properties characteristic of both fibrous cellulose and grafted polymer. 

The most stable resin for many of our purposes has proven to be a copolymer of ethyl methacrylate and methyl acrylate. This comes as little surprise the Rohm and Haas Company has for years sold a durable resin based on these two monomers, Acryloid B-72 (6,28). We have also prepared polymers of similar physical properties based on methyl methacrylate and ethyl acrylate and have found that their behavior is practically the same - the methyl and ethyl groups apparently do not become seriously involved in crosslinking. As reported elsewhere( 23), rather than crosslink, Acryloid B-72 tends to chain break under visible and near-ultraviolet radiation, although at a very slow rate. Polyvinylacetate is another polymer used in the care of museum objects that tends more to chain break than crosslink under these conditions(23), but it is not our purpose to discuss its properties at this time. 

Photo transformations in films of copolymers of a-(2-hydroxy-4-metha-cryloyloxyphenyl)—(2,6-dimethylphenyl)nitrone (HMDN) with methyl methacrylate (MMA) showed that, on radiation at 366 nm, an increase of the steric effect in the A-aryl group leads to a decrease of the refractive index (468, 469). 

Consideration of the relationship between the effects of radiation on homopolymers and copolymers raises the question of the variation from homopolymer behaviour with sequence length. Every copolymer has a distribution of sequence lengths for each comonomer. At what minimum sequence length does methyl methacrylate not show the high scission of PMMA The future will probably see the development of processes for making polymers with controlled mini-block sequences to maximize a number of properties such as scission yield, adhesion, flexural strength, Tg.. 

Figure 41. A plot of sensitivity to Mo (5.4k) x-ray radiation and 20 kV electron beam radiation for several resists. EPB is epoxidized polybutadiene, P(GMA-EA) is a copolymer of glycidyl methacrylate and ethyl acrylate (COP), PGMA is poly (glycidyl methacrylate), PBS is poly (butene-1 -sulfone), FBM-1 is poly (2,2,3,3-tetrafluoropropyl methacrylate), P(MMA-MA) is a copolymer of methyl methacrylate and methacrylic acid, PMMA is poly (methyl methacrylate). (Reproduced with permission from Ref. 56J...

The styrene copolymers were prepared by bulk polymerization at 100°, using benzoyl peroxide as initiator. Methyl methacrylate styrene mole ratios in the feed were 10 90, 25 75, 50 50, 75 25, and 90 10. Conversions varied from 4.5 to 8.1%. Methyl methacrylate a-methyl-styrene copolymers were prepared using benzoyl peroxide at lower a-methylstyrene ratios and U.V. or Co60 gamma radiation to initiate copolymerization at the highest a-methylstyrene ratios, in which reaction is very slow. The mole ratios in the monomer feed were 12 88, 28 72, 54 46, 78 22, and 91.5 8.5. 

UV absorption spectra, fluorescence emission spectra and photostabilization effect of 2-(2-hydroxy-4-acryloyloxyphenyl)-2/7-benzotriazole and of its polymer bound forms were studied in poly-CK-l,4-polybutadiene [337]. The following activity series was found copolymer with methyl methacrylate > homopolymer > monomer. It seems that chromophoric units incorporated into a macromolecule behave cooperatively (causing self-absorbance of the emitted radiation). 

Haller, R. Feder, M. Hatzakis, and E. Spiller, Copolymers of methyl methacrylate and methacryhc acid and their metal salts as radiation sensitive resists, 7. Electrochem. Soc., 126,154 (1979) M. Hatzakis, PMMA copolymers as high sensitivity electron resists, J. Vac. Sci. Technol. 16,1984 (1979). 

O Driscoll reports that several polymer-monomer combinations were used in the controlled preparation of homo- and block polymers by ultrasonic radiation(108). Similarly, Fujiwara reports the preparation of poly(styrene-b-methyl methacrylate) by ultrasonic degradation of polystyrene(109). The utility of ultrasonic irradiation is limited since yields are usually low, and the block copolymer is often contaminated with relatively large amounts of the homopolymers. 

---