Acrylic polymers copolymer with 2- 2-hydroxy

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

Polyurethane-acrylic coatings with interpenetrating polymer networks (IPNs) were synthesized from a two-component polyurethane (PU) and an unsaturated urethane-modified acrylic copolymer. The two-component PU was prepared from hydroxyethylacrylate-butylmethacrylate copolymer with or without reacting with c-caprolactonc and cured with an aliphatic polyisocyanate. The unsaturated acrylic copolymer was made from the same hydroxy-functional acrylic copolymer modified with isocyanatoethyl methacrylate. IPNs were prepared simultaneously from the two-polymer systems at various ratios. The IPNs were characterized by their mechanical properties and glass transition temperatures. 

Block copolymers with hydroxyl segments were prepared by various ways An example utilizes the copper-catalyzed sequential copolymerizations of nBA and 2-[(trimethylsilyl)oxy]ethyl acrylate by the macroinitiator method into B-31 to B-33. The copolymers were then hydrolyzed into amphiphilic forms by deprotection of the silyl groups.313 A direct chain-extension reaction of polystyrene and PMMA with HEMA also afforded similar block copolymers with hydroxyl segments (B-34 and B-35).241-243 In block polymer B-36, a hydroxy-functionalized acrylamide provides a hydrophilic segment.117 Block copolymers of styrene and p-acetoxystyrene (B-37 to B-39), prepared by iron... 

The monomers used for preparation of acrylic polymers vary in nature and can generally be classified as hard (such as methylmethacrylate, styrene and vinyl acetate) or soft (such as ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate). Reactive monomers may also have hydroxyl groups (such as hydroxy ethyl acrylate). Acidic monomers such as methacrylic acid are also reactive and may be included in small amounts in order that the acid groups may enhance pigment dispersion. The practical coating systems are usually copolymers of hard and soft monomers. The polymer hardness is characterized by its glass transition temperature, Tg. The Tg (K) of the copolymer can be estimated from the Tg of the individual Tg (K) of the homopolymers with weight fractions and Wj,... 

Dispersions of copolymers of butadiene with acrylic acid or methacrylic acid in aqueous potassium hydroxide have been mentioned in the patent literature" as a dip for adhering rayon tire cord to rubber. The effect is most evident when carboxyl groups are present in the adhesive, the tie cement, and the cover stocks. The adhesive may be applied as latex, aqueous dispersion, or cement. A patent issued to the Dunlop Company Ltd." describes the use of a styrene-butadiene-itaconic acid copolymer with Gen-Tac Latex (GenCorp) in formulating an RFL (resorcinol formaldehyde latex) type adhesive for bonding a natural rubber compound to Nylon 66 and rayon tire cords. Brodnyan" also claims carboxylic adhesives for rayon, nylon, and Dacron cords. In this case, the tire cords were treated with a mixed polymer latex containing resorcinol-formaldehyde condensate, a butadiene-vinyl pyridine copolymer, an SBR copolymer, and a multifunctional copolymer from methyl acrylate, 2-hydroxy propyl methacrylate, and acrylic acid. A different approach was reported by Badenkov" whereby rayon or nylon tire cords were coated with... 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

A significant number of works are concerned with the development of new membranes for the separation of mixtures of aromatic/alicyclic hydrocarbons [10,11,77-109]. For example, the following works can be mentioned. A mixture of cellulose ester and polyphosphonate ester (50 wt%) was used for benzene/cyclohexane separation [113]. High values of the separation factor and flux were achieved (up to 2 kg/m h). In order to achieve better fluxes and separation factors the attention was shifted to the modification of polymers by grafting technique. Grafted membranes were made of polyvinylidene fluoride with 4-vinyl pyridine or acrylic acid by irradiation [83]. 2-Hydroxy-3-(diethyl-amino) propyl methacrylate-styrene copolymer membranes with cyanuric chloride were prepared, which exhibited a superior separation factor /3p= 190 for a feed aromatic component concentration of 20 wt%. Graft copolymer membranes based on 2-hydroxyethyl methylacrylate-methylacrylate with thickness 10 pm were prepared [85]. The membranes yielded a flux of 0.7 kg/m h (for feed with 50 wt% of benzene) and excellent selectivity. Benzene concentration in permeate was about 100 wt%. A membrane based on polyvinyl alcohol and polyallyl amine was prepared [87]. For a feed containing 10 wt% of benzene the blend membrane yielded a flux of 1-3 kg/m h and a separation factor of 62. 

Asymmetric PEMs with a loosely cross-linked proton conductive layer sandwiched between two primarily hydrophobic layers with limiting methanol swelling have been prepared. A three-component polymer blend (TCB) consisting of poly(4-vinylphenol-co-methacrylate) (PVPMA), poly(butyl methacrylate) (PBM), and acrylic copolymer resin Polaroid B-82 acted as a methanol barrier layer. The proton conductive hydrophilic layer consisted of a random copolymer of 2-hydroxy-2-acrylamido-2-methyl propanesulfonic acid (AMPS) and HEMA, loosely cross-Unked by poly(ethylene glycol) dimethacrylate (PEG-DMA) oligomer. TGA analysis showed that these membranes are thermally stable up to 270 °C. However, their proton conductivity was rather low [172]. Thermoplastic PVDF-SEBS blends compatibUized with MMA block copolymers can be used for solventless fabrication of PEMs [173]. 

The polymer composition raises several interesting points. Hydroxy ethyl methacrylate could be replaced effectively wt./wt. by hydroxy ethyl acrylate. The hydroxyethyl acrylate reacts more readily with melamine resins than carboxylic acids. The acrylic acid is added to give water solubility when neutralised. Note that in the absence of the hydroxy monomer, more acrylic acid would be required to solubilise the polymer. The VeoVa has a softening effect on the copolymer and also contributes water resistance to the film. 

For well-controlled arm number of the star polymers, an efficient approach is the use of multifunctional initiators [157,158]. For instance, the four-armed initiator, NLI-1, which was prepared by the condensation reaction of the hydroxy groups in C(CH20CH2CH2CH20H)4 with a-bromoisobutyric acid, was used in the ATRP of (2,2-dimethyl-l,3-dioxoIane-4-yl)methyl acrylate (DMDMA) with CuBr/bpy as catalyst. After isolation from the polymerization system, four-armed poly(DMDMA)s, such as NLI-2 with Mw/Mn = 1.28—1.41 were obtained, and used in the successive ATRP of MMA, giving star-block copolymers NLB-3. It is known that the cycloacetal ring is unstable in acidic conditions, so the hydrolysis of the block copolymer NLB-3 was accomplished in a 1N HCl aqueous solution to give the amphiphilic star-block copolymer structure NLB-4 as shown in Scheme 3.37 [159]. 

Thermosetting acrylic binder systems utilize copolymers of functional and nonfunctional acrylic (or similar) monomers. The functional monomers are incorporated for reactivity with crosslinkers. The most common functional monomer for reactions is the hydroxyl group. The hydroxyl groups on the acrylic copolymers react with melamine and urea resins (amino resins) and with polyisocyanates. These reactions are shown in Figure 11. The reaction of hydroxy functional polymers with amino resins require acid catalysis and heat. The reaction with polyisocyanates can occur at room temperature as well as at higher temperatures. A number of materials will catalyze the hydroxyl/isocyanate reaction (organotin compounds, acids, amines, metal salts, etc.)(9). 

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