Fluorinated acrylate resin

Very recently we8 reported on a class of processable heavily fluorinated acrylic resins that exhibit dielectric constants as low as 2.10, very close to the minimum known values. In this chapter we report on the preparation of a series of processable heavily fluorinated acrylic and methacrylic homo- and copolymers that exhibit dielectric constants as low as 2.06, and the factors that affect the reduction of dielectric constant from structure-property relationships is elucidated.9... 

Chen et al. prepared fluorinated acrylate resin [55] by solution polymerization of a mixture of 2-(perfluoro-( 1,1 -iti>isopropyl)-2-propenyl)oxy-ethyl methacrylate (POMA), butyl acrylate (BA), methyl methacrylate (MMA), and methacrylic acid (MA) in the co-solvents of ethyl acetate, butyl alcohol, and toluene using AIBN as initiator. First, POMA was synthesized as the starting reactants from the intermediate perfluoro nonene and 2-HEMA. Consequently, a series of fluorinated acrylate resins was synthesized with the same solid content, whereas the fluorine content in mixed monomers was varied at 0%, 5%, 10%, 15%, 20%, and 25%. Films of the novel fluorinated acrylate resin were made by spreading the resin on a clean Petri dish followed by drying at room temperature. Scheme 6.13 shows the synthesis pathway of the fluorinated acrylate resin. 

Scheme 6.13 Synthesis pathway of the fluorinated acrylate resin. Taken from Ref. [55],...

Name(s) acrylic copolymer, fluorinated acrylic resin, thermoplastic acrylic... 

Processable Fluorinated Acrylic Resins with Low Dielectric Constants... 

In this work we have demonstrated that a new class of heavily fluorinated acrylic and methacrylic resins can be efficiently synthesized and then cured to solid form with radical initiator at elevated temperatures. These cured resins were found to have low dielectric constants, which are close to the minimum known values for Teflon and Teflon AF. In contrast to tetrafluoroethylene, our monomers are processable owing to the fact that they are liquids or low-melting solids, and moreover are soluble in common organic solvents. Lower dielectric constants are obtained as fluorine contents on the polymer backbone or side chain increase, when acrylate is replaced by methacrylate, when ether linkages are present in the fluorocarbon, and when aromatic structure is symmetrically meta-substituted. 

A series of studies has been carried out in our laboratory to design and synthesize new fluorinated epoxy and acrylic resins for the many applications that are possible because of their unique properties.2"5... 

Number of grafted copolymers were prepared by the ozonization and grafting technique. Polyolefins, PE and PP, were grafted with fluorinated acrylates to obtain fluorine content between 11% and 25% that highly modified their properties. Likewise, PE and PVDF have been grafted with various acryhc monomers with the aim to improve their adhesive properties. From these products, it has been possible to attach composite materials, based on epoxy resins, to PE or PVDF. The main copolymers prepared according to this technique are summarized in Table 1. 

Base substrates Conductors Copper-clad laminates Coverlay Adhesive layer Stiffener Polyimide film (PI), polyester film (PET), polyester telephthalate Thin glass-epoxy, fluorinated ethylene propylene (FEP), resin-coated paper Electrodeposited (ED) copper foil, RA copper foil, stainless steel foil, aluminum foil, etc. Epoxy-based, acrylic-based, phenol-based (adhesive-based) PI film, PET film, flexible solder mask Acrylic resin, epoxy resin, phenol resin, pressure-sensitive adhesives (PSAs) PI film, PET film, glass-epoxy, metal boards, etc. 

Using as starting material five fluorinated diols, Maruno et al. [33] reported the synthesis of fluorine-containing epoxy acrylate resins and epoxy methacrylate resins by the two reactions paths shown in Scheme 3. These resins are suitable as... 

Scheme 3 Synthesis of fluorine-containing epoxy acrylated resins.

Maruno, T., Ishibashi, S., and Nakamura, K., Synthesis and properties of fluorine-containing epoxy(meth)acrylate resins,/. Polym. Sci., Part A, Polym. Chem., 32, 3211, 1994. 

The characteristics of fluoropolymers are summarized in Table 1. Thermal and chemical resistance is in general with most of plastics, elastomers and perfluorinated membranes. Weather resistance with the outdoor durability for more than 20 years is specific for fluorinated paint resins. Surface properties such as water and oil repellency are provided by acrylic polymer-based textile finishes and coatings with long-chain per-fluoroalkyl groups. Electrical properties as well as a low refractive index are important for optoelectronics applications like optical fibers. 

Chem. Descrip. Acrylic resin amine neutralized, fluorinated... 

The feasibility of using prepolymer monomers as the major component of dental resin systems has recently been demonstrated (31). Highly fluorinated acrylate and methacrylate comb type prepolymer monomers were synthesized from a polyfluorinated oligoether-ol as shown in Figs. 9 and 10. These novel monomers are viscous liquids similar to BIS-GMA but of much larger bulk (MW > 10,000) which should minimize pol mierization shrinkage and improve marginal adaptation. 

Many synthetic latices exist (7,8) (see Elastomers, synthetic). They contain butadiene and styrene copolymers (elastomeric), styrene—butadiene copolymers (resinous), butadiene and acrylonitrile copolymers, butadiene with styrene and acrylonitrile, chloroprene copolymers, methacrylate and acrylate ester copolymers, vinyl acetate copolymers, vinyl and vinyUdene chloride copolymers, ethylene copolymers, fluorinated copolymers, acrylamide copolymers, styrene—acrolein copolymers, and pyrrole and pyrrole copolymers. Many of these latices also have carboxylated versions. 

Acrylic acid esterified with cross-linked hydroxymethyl polystyrene or Wang resin reacts smoothly with primary or secondary aliphatic amines at room temperature (Entries 1 and 2, Table 10.6). Only sterically demanding amines or amines of low nucleophilicity (anilines, a-amino acid esters) fail to add to polystyrene-bound acrylate. Support-bound acrylamides are less reactive than acrylic esters, and generally require heating to undergo addition with amines (Entries 4 and 5, Table 10.6). a, 3-Unsaturated esters with substituents in the 3-position (e.g. crotonates, Entry 3, Table 10.6) react significantly more slowly with nucleophiles than do acrylates. The examples in Table 10.6 also show that polystyrene-bound esters are rather stable towards aminolysis, and provide for robust attachment even in the presence of high concentrations of amines. Entry 10 in Table 10.6 is an example of the alkylation of a resin-bound amine with an electron-poor alkene to yield a fluorinated peptide mimetic. 

Sealants - [ELASTOMERSSYNTHETIC - POLYISOPRENE] (Vol 9) - [SEALANTS] (Vol 21) -acrylics [ACRYLICESTERPOLYMERS - SURVEY] (Voll) -barium compds in [BARIUM COMPOUNDS] (Vol 3) -based on liquid polysulfides [POLYMERS CONTAINING SULFUR - POLYSULFIDES] (Vol 19) -defoamersin [DEFOAMERS] (Vol 7) -fiom fluorosilicones [FLUORINE COMPOUNDS,ORGANIC - POLY(FLUOROSILICONES)] (Volll) -hydrocarbon resins in [HYDROCARBON RESINS] (Vol 13) -lecithin in (LECITHIN] (Vol 15) -organolithiumcmpdsinprdnof [LITHIUM AND LITHIUM COMPOUNDS] (Vol 15) -polysulfide curing [PEROXIDES AND PEROXIDE COMPOUNDS - INORGANIC PEROXIDES] (Vol 18) -propylene oxide in mfg of [PROPYLENE OXIDE] (Vol 20) -PVB m [VINYL POLYMERS - VINYL ACETAL POLYMERS] (Vol 24) -rheological measurements [RHEOLOGICAL MEASUREMENTS] (Vol 21) -from styrenic block copolymers [ELASTOMERS SYNTHETIC - THERMOPLASTIC ELASTOMERS] (Vol 9) -use of dispersants [DISPERSANTS] (Vol 8)... 

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