Phosphoric anhydride-containing epoxy resin

Abstract

To provide: a halogen-free compound for imparting flame retardancy to an epoxy resin; and a curable composition containing an epoxy resin and the compound.SOLUTION: Disclosed herein are compounds of formulas (I) or (II) in the figure. In the formula, R1 and R2 are independently alkyl, alkoxy, cycloalkyl, -O-alkyl-cycloalkyl, -O-cycloalkyl, aryl, or aryloxy; R3 is independently hydrogen, alkyl, cycloalkyl, or aryl; and l is 0, 1, 2, 3, 4, 5, or 6. The compounds of formulas (I) or (II) are curing agents and / or flame retardants.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates generally to epoxy resins, and more particularly to halogen-free, phosphorus-containing epoxy resins. . [Background technology]

[0002] Epoxy resins are used in industrial and residential applications, especially for their chemical resistance, mechanical strength and electrical properties. Epoxy resins are used in both laminates and adhesives. And / or can be used as an insulating material, for example an interlayer insulating film, in electronic devices. To be useful in these applications, epoxy resins must have certain required physical, thermal, and electrical properties. It is necessary to provide insulating and moisture resistant properties. For example, epoxy resins used in electrical applications The fat has a high glass transition temperature (T g It is advantageous to have Summary of the Invention [Problem to be solved by the invention]

[0003] However, epoxy resins can be flammable. Therefore, it is necessary to add flame retardant to epoxy resins. Various approaches have been used to provide flame resistance. Two main approaches have been adopted to reduce the Halogen-containing compounds are used to impart flame resistance to electrical and electronic assemblies. Compounds such as tetrabromobisphenol-A ( TBBA) is a representative flame retardant that is widely used in epoxy resins. Halogen-containing compounds are a common example of halogen-containing compounds. Halogen-containing compounds can be effective, but they have short life spans. During the incineration of electronic components at the end of their life, harmful substances may be generated, so it is important to consider environmental considerations. The second approach is a step beyond the first approach. In response to environmental issues, we use halogen-free compounds to achieve flame retardancy. This is an "environmentally friendly" approach that provides [Means for solving the problem]

[0004] In a first aspect, disclosed herein is a compound of formula I or II: [ka] During the ceremony R 1 and R 2 are independently alkyl, alkoxy, cycloalkyl, -O-alkyl- cycloalkyl, -O-cycloalkyl, aryl, aryloxy, or R 1 and R 2 and taken together form a polycyclic moiety, each aryl or polycyclic moiety being an alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl and optionally substituted with one or more groups independently selected from R 3 is independently alkyl, cycloalkyl, or aryl, each aryl being Independently of alkyl, alkoxy, aryl, aryloxy, alkenyl, and alkynyl and optionally substituted with one or more groups selected from l is 0, 1, 2, 3, 4, 5, or 6; Method for preparing a compound of formula I or II, comprising at least one epoxy resin and a compound of formula I or II A curable composition comprising the compound of formula I, and a curable composition prepared by curing the curable composition. Cured products are also disclosed. The compounds of formulas I and II act as flame retardants, curing agents, or both. do. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] Embodiments of the present disclosure are particularly useful as self-curing compounds and / or to form cured epoxies. The present invention relates to a method for producing a phosphorus-containing epoxy resin which can be used as a component in a curable composition for producing a polymerizable composition comprising the steps of: The phosphorus-containing epoxy resins of the present disclosure may also be used to form cured epoxies formed with other epoxy resins. Heat resistance (e.g., T d and T g In order to increase the hardening property of the curable composition, It can be used with other epoxy resins in

[0006] The phosphorus-containing epoxy resins of the present disclosure may also be formed in part with a phosphorus-containing epoxy resin. It offers the advantage of being halogen-free while acting as a flame retardant for the cured epoxy. Such cured epoxies formed with phosphorus-containing epoxy resins also provide electrical wiring. laminates, interconnect substrates, build-up films, solder masks, castings, and They may also have suitable thermal and electrical properties useful in electronic applications, including adhesives.

[0007] Specifically, the phosphorus-containing epoxy resins of the present disclosure provide improved thermomechanical properties, e.g., improved hardness of the cured epoxy. This can result in an increase in the glass transition temperature of the copolymer.

[0008] The improvements of the present disclosure include the glass transition of cured epoxies formed using phosphorus-containing epoxy resins. Transfer temperature (T g ) to increase the phosphorus-containing epoxy resin. The fat is then mixed in a medium to high range process carried out at a temperature of at least 150°C, preferably at least 170°C. In addition, the present disclosure can be used in applications such as curable compositions formed with the phosphorus-containing epoxy resin. In addition to flame resistance, the composition may also provide other desirable physical properties, such as heat resistance. One method is to remove 5% by weight of the cured epoxy as the sample is heated at a constant rate. The thermal decomposition temperature (T d ) The phosphorus-containing epoxy resin of the present disclosure has a T d Hardening with An epoxy resin can be provided.

[0009] Furthermore, the phosphorus-containing epoxy resin of the present disclosure has a ratio of 10:1 to 1:1, more preferably 6:1 The epoxy to phosphorus molybdenum ratio can range from 1:1 to 2:1, and most preferably from 5:1 to 3:1. The ratio of the stoichiometric ratio can be 1:1.

[0010] As described above, in a first aspect, a compound according to formula I or II, wherein all variables are as defined above, is provided. Disclosed herein are compounds of formula I or II. In one embodiment, the following compounds are represented by formula I: I. In another embodiment, they are encompassed. [ka]

[0011] In one embodiment, each R 3 is independently 1 -C 6 Alkyl, C 3 -C 6 Cycloalkane or phenyl, each phenyl being C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, Phenyl, phenyloxy, C 2 -C 4Alkenyl, and C 2 -C 4 Independent of alkynyl In another embodiment, each R 3 teeth Independently, C 1 -C 4 Alkyl, C 3 -C 6 cycloalkyl, or phenyl, Venyl is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, C 2 -C 4 Alkenyl, and C 2 -C 4 alkynyl, In yet another embodiment, each R 3 are independently methyl, ethyl In yet another embodiment, the aryl group is cyclohexyl, cyclopentyl, cyclohexyl, or phenyl. , each R 3 is independently C 1 -C 4 In a further embodiment, each R 3 is independent In yet a further embodiment, R 3 is methyl.

[0012] In one alternative embodiment, when l is 1, R 3 is methyl, ethyl, cyclo Pentyl, cyclohexyl, phenyl, allyl, or C 2 -C 4 Alkynyl. In embodiments, R 3 is methyl or allyl. In yet another alternative embodiment, R 3 Hame It's chill.

[0013] In another embodiment, R 1 and R 2 is independently C 1 -C 6 Alkyl, C 1 -C 6 Alcoki C 3 -C 6 Cycloalkyl, -OC 1 -C 6 Alkyl-cycloalkyl, -O-cycloalkyl chloroalkyl, aryl, aryloxy, or R 1 and R 2 Together, these form a polycyclic moiety. and each aryl or polycyclic moiety is an alkyl, alkoxy, aryl, aryloxy, one or more independently selected from oxy, arylalkyl, alkenyl, and alkynyl; In a further embodiment, R 1 and R 2 One of them is methi cyclopentyl, cyclohexyl, -OC 1 -C 4 Alkoxy-cyclo Alkyl, -O-cyclopentyl, -O-cyclohexyl, phenyl, phenyloxy Yes or R 1 and R 2 together form a polycyclic moiety, and this phenyl, phenylo The alkoxy or polycyclic moiety is an alkyl, alkoxy, aryl, aryloxy, aryl one or more groups independently selected from alkyl, alkenyl, and alkynyl; In a further embodiment, R 1 and R 2 is C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, phenyl, naphthyl, phenyloxy, benzyl, phenethyl, C 2 -C 6Alkenyl, and C 2 -C 6 one or more independently selected from alkynyl In yet another embodiment, R 1 and R 2 The same thing happens. In the embodiment, R 1 and R 2 is different.

[0014] In a different embodiment, R 1 and R 2 forms an optionally substituted polycyclic moiety, The cyclic moiety can be any of alkyl, alkoxy, aryl, aryloxy, arylalkyl, and acyclic moieties. and optionally substituted with one or more groups independently selected from alkynyl, alkenyl, and alkynyl. In one embodiment, the polycyclic moiety consists of two optionally substituted fused rings. In an alternative embodiment, the polycyclic moiety comprises at least three, optionally substituted, fused rings. The polycyclic moiety is one or more rings selected from the group consisting of P, N, O, and S. For clarity, P, N, O, and / or S may be used to refer to the position of a polycyclic moiety. In a preferred embodiment, the polycyclic moiety is a P, N, At least one of O, S, and C. Preferably, the polycyclic moiety comprises P. Preferably, at least one ring heteroatom in the polycyclic moiety is directly bonded to P. In one preferred embodiment, the heteroatom is O or S. In one preferred embodiment, the heteroatom is The atom is O.

[0015] In one embodiment, the compound of formula I or II is a compound of formula III or IV: [ka] During the ceremony l is 0, 1, 2, or 3; m is 0, 1, 2, 3, or 4; n is 0, 1, 2 , 3 or 4, and when at least one of m and n is not 0, each R 4 and R 5 is independent alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl In one embodiment, each R 4 and R 5 teeth, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, phenyl, naphthyl, phenyloxy, phenyl Ndyl, Phenethyl, C 2 -C 6 Alkenyl, and C 2 -C 6 Independently selected from alkynyl In one embodiment, R 4 and R 5 are the same. Alternatively, they are different There is.

[0016] In one embodiment, m and n are 0. In a further embodiment, l is also 0. .

[0017] In one embodiment, l is 0. In another embodiment, l is 1. In one embodiment, l is 2. In yet another embodiment, l is 3. In these embodiments, l is 1 or 2. In each of these embodiments, (when l is 0, (Except where otherwise), each R 3 is independently 1 -C 6 Alkyl, C 3 -C 6 Cycloal , or phenyl, each phenyl being C 1 -C 6 Alkyl, C1 -C 6 Alkoxy , phenyl, phenyloxy, C 2 -C 4 Alkenyl, and C 2 -C 4 Alkynyl to German In another embodiment, each R 3 is independently C 1 -C 4 In a further embodiment, each R 3 are independently methyl or ethyl. In still further embodiments, R 3 is methyl.

[0018] In an alternative embodiment, m and n are independently 0, 1 or 2, and at least One is 1 or 2. In such a case, each R 4 and R 5 is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, benzyl, phenethyl, C 2 -C 6 Al Kenyl, and C 2 -C 6 In yet a further embodiment, the aryl, aryls and arylalkyls are independently selected from the group consisting of alkynyl, aryls and arylalkyls. , each R 4 and R 5 are independently methyl, ethyl, phenyl, benzyl, phenethyl, In still further embodiments, each R 4 and R 5 are independently phenyl, phenyloxy, benzyl, or phenethyl. In this state, R 4 and R 5 are the same. Alternatively, they may be different.

[0019] In a further embodiment, n is 1 and m is 1. In a further embodiment, R 4 Reach BiR 5 is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, phenyl Ndyl, Phenethyl, C 2 -C 6 Alkenyl, and C 2 -C 6 Independently selected from alkynyl In yet a further aspect, 1 is 0 or 1. In yet a further embodiment, R 4 and R 5 are independently methyl, ethyl, phenyl, benzyl, phenethyl, methoxy , ethoxy, ethenyl, ethynyl. In a further alternative embodiment, R 4 and R 5 teeth In one embodiment, each is independently phenyl, phenyloxy, benzyl, or phenethyl. , R 4 and R 5 are the same. Alternatively, they are different.

[0020] In another embodiment, n is 1 and m is 0. In a further embodiment, R 4 is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, benzyl, phen Netil, C 2 -C 6 Alkenyl, and C 2 -C 6 alkynyl. In yet a further embodiment, l is 0 or 1. 4 is methyl, ethyl phenyl, benzyl, phenethyl, methoxy, ethoxy, ethenyl, ethynyl Alternatively, R 4 are independently phenyl, phenyloxy, benzyl or phenethyl. In yet another embodiment, R 4 is benzyl.

[0021] In another embodiment, m is 1 and n is 0. In a further embodiment, R 5 is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, benzyl, phen Netil, C 2 -C 6 Alkenyl, and C 2 -C 6 alkynyl. In some embodiments, l is 0 or 1. In still further embodiments, R 5 is methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, ethenyl, and ethynyl. Alternatively, R 5 are independently phenyl, phenyloxy, benzyl or phenethyl; In yet another embodiment, R 5 is benzyl.

[0022] In another aspect, disclosed herein is a method for preparing the above-mentioned compound. , a phosphorus compound of the formula: [ka] an olefin compound of the formula: [ka] This involves reacting at a temperature of about 120°C to about 160°C in the presence of a radical initiator.

[0023] Uses a variety of free radical initiators including azo compounds, organic peroxides, and inorganic peroxides Examples of specific free radical initiators include di-tert-butyl peroxide. , benzoyl peroxide, peroxydisulfate salts, azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclo Hexanecarbonitrile) and 2,2'-azobis(2-methylpropionamidine) The hydrochloride salt is included. Multiple free radical initiators may be used simultaneously or sequentially. In one embodiment, the radical initiator is an organic peroxide, azobisisobutyronitrile or Alternatively, the radical initiator includes di-tert-butyl peroxide.

[0024] The reaction of the phosphorus compound with the olefinic compound can take place in the presence or absence of a solvent. Preferably, water is reacted with the phosphorus-containing compound to prevent foaming, since water may tend to react with the phosphorus-containing compound to cause foaming. is carried out in the absence of water (typically, water is present in an amount of 5% by weight based on the total weight of the curable composition). Water is present in an amount of less than 1 wt%, more preferably less than 3 wt%, and most preferably less than 1 wt%. Using well-known methods, such as heating in a vacuum oven under a stream of dry air or nitrogen, or It can be removed by azeotropic removal of water using an organic liquid such as hexane or toluene. This can be done either with the phosphorus compound itself or with the mixture prior to the reaction.

[0025] For various embodiments, the reaction between the phosphorus compound and the olefin compound is carried out in the presence of a solvent. The solvents are toluene, xylene, mesitylene, 2-butanone, 4-methyl-2 -Pentanone, cyclohexanone, propylene glycol methyl ether acetate (D OWANOL (trademark) PMA), N,N-dimethylformamide (DMF) In various embodiments, the solvent may be, but is not limited to, a phosphorus compound and an olefin. It can be used in an amount of 30% by weight to 60% by weight based on the total weight of the vinyl compound.

[0026] For various embodiments, the molar ratio of the phosphorus compound to the olefin compound is 2:1 to It may be in the range of 1:10, more preferably 1:1.

[0027] For various embodiments, the weight ratio of radical initiator to total reactants is 0.01 wt. % to 5% by weight, more preferably in the range of 0.5% to 2% by weight.

[0028] In one aspect, disclosed herein is a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a) at least one epoxy resin, and b) at least one phosphorus-olefin adduct of formula I, II, III or IV The curable composition comprises:

[0029] To prepare the curable and cured compositions disclosed herein, a variety of epoxy resins can be used. The types of epoxy resins that can be used include aromatic epoxy resins, alicyclic epoxy resins, These include epoxy resins, aliphatic epoxy resins, and combinations thereof.

[0030] In one embodiment, the at least one epoxy resin is selected from the group consisting of divinylarene dioxide. , diglycidyl ether of bisphenol A, diglycidyl ether of bromobisphenol A ether, diglycidyl ether of bisphenol A oligomer or polymer, tetraglycidyl ether Diglycidyl ether of oligomer or polymer of bromobisphenol A, bisphenol Diglycidyl ether of glyceryl F or its derivatives, epoxy novolac resin, epoxy cresol In one embodiment, the divinylarene dimer is a divinyl novolac resin, or a mixture thereof. oxide, divinylarene dioxide, substituted divinylbenzene dioxide, divinyl Naphthalene dioxide, divinyl biphenyl dioxide, divinyl diphenyl ether di oxides, and mixtures thereof.

[0031] Or at least one epoxy resin is a glycidyl ether compound of a polyphenol. The polyphenols are hydroquinone, resorcinol, bisphenol A, and bisphenol B. Nol F, 4,4'-dihydroxybiphenyl, phenol novolac, cresol novolac Lac, Trisphenol (Tris-(4-hydroxyphenyl)methane), 1,1,2 ,2-Tetra(4-hydroxyphenyl)ethane, Tetrabromobisphenol A, 2, 2-Bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane 1,6-dihydroxynaphthalene, and combinations thereof. do.

[0032] Examples of cycloaliphatic epoxy resins include polyols having at least one cycloaliphatic ring. Compounds containing cyclohexyl ether, cyclohexene ring, or cyclopentene ring are oxidized with an oxidizing agent to give epoxy groups. Cyclohexene oxide or cyclopentene oxide obtained by oxidizing Specific examples include hydrogenated bisphenol A diglycidyl ether, 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexyl Xanthane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methyl Cyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl Cyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl) a Dipate, methylene-bis(3,4-epoxycyclohexane), 2,2-bis(3,4 -Epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene- Bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexa Hydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, and These include, but are not limited to, combinations thereof.

[0033] Examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyols or their aryl groups. alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, glycidyl a A homopolyester synthesized by vinyl polymerization of acrylate or glycidyl methacrylate. Polymers, as well as glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. Some specific copolymers include those synthesized by vinyl polymerization of monomers. Examples include glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl. Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerol Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol Glycidyl ether, hexaglycidyl ether of dipentaerythritol, polyethylene Diglycidyl ether of polypropylene glycol and diglycidyl ether of polypropylene glycol esters, aliphatic polyols such as propylene glycol, trimethylolpropane, and A compound obtained by adding one or more alkylene oxides to glycerin. Polyglycidyl ether of polyether polyol, diglycidyl of aliphatic long chain dibasic acid esters, and combinations thereof.

[0034] The curable compositions disclosed herein may be reactive or non-reactive with the phosphorus-containing epoxy resins of the present disclosure. It may further comprise one or more additional components which may be either reactive. For various embodiments, a curable composition formed from the phosphorus-containing epoxy resin and the composition components. The article comprises combining and mixing the phosphorus-containing epoxy resin of the present disclosure with at least one composition component. and then reacting the resulting composition. Examples of such composition components include: Epoxy resins, polyepoxide resins, cyanate esters, dicyanate esters, poly Cyanate esters, cyanate aromatic esters, maleimide resins, thermoplastic polymers, Polyurethane, polyisocyanate, benzoxazine ring-containing compound, double or triple bond These include, but are not limited to, unsaturated resin systems containing bonds, and combinations thereof. Further examples of additives include benzoxazine, styrene maleic anhydride copolymer. The polymerizable compound may be selected from the group consisting of phenolic novolacs, cyanate esters, and mixtures thereof.

[0035] In an additional embodiment, the curable composition of the present disclosure comprises a phosphorus-containing epoxy resin of the present disclosure and at least one carboxylic acid or carboxylic acid derivative thereof. The thermoplastic resin may be made of at least one reactive and / or non-reactive thermoplastic resin. Examples of such thermoplastic resins include polyphenylene oxide, polyphenylsulfone, polysulfone, and polysulfone. Polyethersulfone, polyvinylidene fluoride, polyetherimide, polyfluoride thalimide, polybenzimidazole, acrylic, phenoxy, and combinations thereof or blends, but are not limited to these.

[0036] The curable composition may comprise about 10% by weight to about 70% by weight of an ethylenediaminetetraacetate based on the total weight of the curable composition. Contains epoxy resin.

[0037] The curable compositions disclosed herein may comprise about 1 wt. % based on the total weight of the curable composition. ~ about 70% by weight of a phosphorus-containing compound. Alternatively, the phosphorus-containing epoxy resin of the present disclosure comprises: In the range of 1% to 20% by weight, or in the range of 1% to 10% by weight, or more preferably The phosphorus content is in the range of 2% to 9% by weight, and most preferably in the range of 3% to 8% by weight. The embodiments of the present disclosure are also useful in semiconductor packaging applications, electrical and They are also useful in other applications requiring flame resistant materials, including automotive and electronic applications, as well as composite applications. In addition, the phosphorus-containing epoxy resin may contain both bromine and halogen atoms. Substantially free of.

[0038] The hardenable composition may further comprise a filler. Examples of fillers include natural silica, fused silica, and the like. , spherical silica, alumina, hydrated alumina, talc, alumina trihydrate, magnesium hydroxide This includes all of the above.

[0039] Electrical laminates may also be prepared from the curable compositions disclosed herein. Printed circuit boards can also be made from the curable compositions and electrical laminates disclosed herein. Optionally, electrical laminates may be prepared from alternating layers of prepregs and conductive materials. The layer includes:

[0040] The hardenable compositions disclosed herein contain at least one hardener ("hardener"). Examples of curing agents include anhydrides, carboxylates ... These include carboxylic acids, amine compounds, phenolic compounds, polyols, and mixtures thereof. In one embodiment, the composition comprises from about 0.01% by weight to about 90% by weight of a curing agent. Examples of the curing agent include dicyandiamide, diaminodiphenylmethane, and diaminodiphenyl Sulfone, polyamide, polyaminoamide, polyphenol, polymer thiol, polycarbonate carboxylic acids, anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride (THPA), methyl tetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), Methylhexahydrophthalic anhydride (MHHPA), Nadic methyl anhydride (NMA), Polyazelaic acid polyanhydride, succinic anhydride, and styrene-maleic anhydride Phenolic hardeners, such as, but not limited to, phenolic acid copolymers. Also used are phenol novolacs, cresol novolacs and bisphenol A novolacs. The curing agent is preferably present in an amount of 2% by weight to 80% by weight based on the total weight of the curable composition. is used in amounts within the range of

[0041] Cure accelerators (or catalysts) include substituted or epoxy-modified imidazoles, such as 2-methyl Contains imidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole Other heterocyclic amines, such as 1,8-diazabicyclo[5.4.0]undeca- 7-ene (also known as DBU) and 1,5-diazabicyclo[4.3.0]nona-5- Ene (also known as DBN) may also be used. Triethylamine, tripropylamine, Tertiary amines, including but not limited to tributylamine and triphenylphosphine Phosphonium salts such as ethyltriflate and phosphine may also be used. triphenylphosphonium acetate, ethyltriphenylphosphonium acetate, and ammonium salts, such as benzyltrimethylammonium acetate and benzyltrimethylammonium Nitium hydroxides can also be used as accelerators. , bromides, chlorides and fluorides) can also be used, but are generally not used in halogen-free applications. The catalyst is preferably present in an amount of about 0.01 weight percent based on the total weight of the curable composition. % to about 2.00% by weight.

[0042] The optimum ratio of hardener to phosphorus-containing epoxy is usually expressed as an equivalent ratio. A ratio of 1.00:1 between silyl and reactive hydrogen (-SH, -OH, -NH, or -COOH) or anhydride. The curable compositions of the present disclosure preferably have an equivalent ratio of 1.20:1. An equivalent ratio of 1.00 to 1.00:1.20, more preferably 1.10:1.00 to 1.00: in the range of 1.10, and most preferably in the range of 1.10:1.00 to 1.00:1.05 It is prepared.

[0043] In another aspect, disclosed herein is a method for producing a curable composition comprising the curable composition disclosed herein and A process for preparing a curable epoxy resin composition comprising mixing the epoxy resin composition with at least one curing agent. By curing the curable epoxy resin composition disclosed herein, The cured thermoset products prepared are also disclosed.

[0044] Generally, the cured resin is formed from a phosphorus-containing epoxy resin of formula I, II, III, and / or IV. The curing of the curable composition is carried out in accordance with the present disclosure by first reacting the phosphorus-containing epoxy resin in the curable composition with the This can be done by melting to obtain a homogeneous melt or by dissolving in a suitable solvent. Examples of suitable solvents include ketones, such as acetone and / or methyl ethyl ketone, In some embodiments, the esters may be substituted or unsubstituted, but are not limited to esters and / or aromatic hydrocarbons. The solvent may be used in an amount of up to about 50% by weight, based on the total weight of the curable composition. The solvent can be removed during or at the end of curing by distillation or simple evaporation. .

[0045] The phosphorus-containing epoxy resin of the present disclosure can be mixed with a thermoplastic resin to form a hybrid crosslinked network. The preparation of the curable compositions of the present disclosure can be carried out by dry blending the individual components. and subsequently melt mixed directly in the extruder used to prepare the final article, or in a separate extruder. This can be accomplished by any suitable mixing means known in the art, including premixing in a dispenser. can.

[0046] When softened or melted by the application of heat, the phosphorus-containing epoxy resins and thermoplastic resins of the present disclosure The curable compositions formed from plastic resins can be molded by conventional techniques, such as compression molding, injection molding, gas assisted molding, etc. Injection molding, calendaring, vacuum forming, thermoforming, extrusion and / or blow molding alone The phosphorus-containing epoxy resin and thermoplastic resin of the present disclosure may be used in combination to form or mold the epoxy resin. The curable compositions formed with the plastic resins may also be used in the form of films, fibers, multi-layer laminates or It may be formed into an extruded sheet, spun, or drawn, or may be combined with one or more organic or inorganic materials. Can be compounded.

[0047] Lewis acids may also be used in compositions containing epoxy resins. Lewis acids include, for example, Zinc, tin, titanium, cobalt, manganese, iron, silicon, aluminum, and boron One or a mixture of two or more of the following halides, oxides, hydroxides, and alkoxides: Examples of such Lewis acids and anhydrides of Lewis acids include boric acid, metaboric acid, , optionally substituted boroxines (e.g., trimethoxyboroxine, trimethylboroxine, or triethylboroxine), optionally substituted oxides of boron, alkyl borates, halo Boron fluoride, zinc halides (e.g. zinc chloride) and tend to have relatively weak conjugate bases Other Lewis acids include

[0048] The phosphorus-containing epoxy resin and / or the curable composition formed with the phosphorus-containing epoxy resin include The present disclosure also provides a method for preparing the above-described compositions. Repregs, as well as cured or partially cured phosphorus-containing epoxy resins or phosphorus-containing epoxy resins of the present disclosure. The compositions containing the olefin resins are used to produce molded articles, reinforced compositions, laminates, etc., as described below. , electrical laminates, coatings, molded articles, adhesives, and composite products. The compositions shown may be in the form of dry powders, pellets, homogenous masses, impregnated products and / or compounds. It can be used for a variety of purposes.

[0049] Various additional additives may be added to the curable compositions of the present disclosure. Examples of additives include reinforcing materials, fillers, pigments, dyes, thickeners, wetting agents, lubricants, and flame retardants. Suitable reinforcing materials include, among others, silica, alumina trihydrate, aluminum oxide, Aluminum, aluminum oxide hydroxide, metal oxides, nanotubes, glass fibers, quartz fibers, carbon Fibers, boron fibers, Kevlar fibers and Teflon fibers. The size range of the particulate reinforcing material is from 0.5 nanometers (nm) to 100 microns ( In various embodiments, the fibrous reinforcing material may be in the form of a mat, a cloth, or can be in the form of continuous fibers.

[0050] Embodiments of the curable compositions also help improve the flameout capabilities of the cured composition. In order to achieve this, at least one synergist may be included. Examples of such synergists include alkoxysilane, ... minium, magnesium hydroxide, zinc borate, metal phosphinates, e.g. Exolit OP-930 (available from Clariant), and combinations thereof Further embodiments of the curable composition include, but are not limited to, an adhesion promoter. , such as modified organosilanes (epoxidized, methacrylic, amino), acetylacetonates Other additives may include wetting and dispersing agents, sulfur-containing molecules, and combinations thereof. Coagents such as modified organosilanes, Byk® 900 series and W9010 ( Byk-Chemie GmbH), modified fluorocarbons and their combinations, Foaming agents, such as Byk® A530, Byk® A525, Byk® Trademark) A555, and Byk® A560 (Byk-Chemie GmbH) , surface modifiers such as slip and gloss additives, release agents such as waxes, and polymers. Other functional additives or pre-reaction products to improve properties, e.g., isocyanates, isocyanates, Socyanurates, cyanate esters, allyl-containing molecules or other ethylenically unsaturated compounds , acrylates, and combinations thereof.

[0051] For various embodiments, the resin sheet is made of the phosphorus-containing epoxy resin and / or hardener of the present disclosure. In one embodiment, multiple sheets are bonded together. The laminated board can be formed by the above-mentioned method, and the sheet includes at least one resin sheet. The phosphorus-containing epoxy resin and / or the curable composition formed with the phosphorus-containing epoxy resin may also be It can also be used to form a resin-clad metal foil. For example, a metal foil, such as a copper foil, can be Phosphorus-containing epoxy resins and / or curable compositions formed with the phosphorus-containing epoxy resins of the present disclosure It can be coated with

[0052] For various embodiments, the phosphorus-containing epoxy resin and / or curable composition of the present disclosure comprises: It can be applied to a substrate as a coating or adhesive layer. The epoxy resin and / or composition may be molded or laminated in the form of powder or pellets. Alternatively, the substrate, such as a fiber reinforcement, may be impregnated with the phosphorus-containing material of the present disclosure. The epoxy resin and / or the curable composition can be cured by applying heat. Cut.

[0053] The heat required to provide suitable curing conditions may depend on the proportions of the compositional components that make up the curable composition and the nature of the compositional components used. In general, the curable composition of the present disclosure may be cured by heating it at a temperature in the range of about 25°C to about 250°C, preferably 100°C to 220°C, depending on the presence or amount of a curing agent or the type of compositional components in the curable composition. The time required for heating may be from 60 seconds to 24 hours, and the exact time will vary depending on whether the curable composition is used as a thin coating or a relatively thick molded article or laminate or as the matrix resin of a fiber reinforced composite, particularly in electrical and electronic applications, such as when applied to non-conductive materials and subsequently curing the curable composition. The present invention includes the following aspects. Section 1. A compound of formula I or II, [ka] During the ceremony R 1 and R 2 is independently alkyl, alkoxy, cycloalkyl, -O-alkyl-cycloalkyl, -O-cycloalkyl, aryl, aryloxy, or R 1 and R 2 and together form a polycyclic moiety, each aryl or polycyclic moiety is optionally substituted with one or more groups independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; R 3 is independently hydrogen, alkyl, cycloalkyl, or aryl, each aryl being optionally substituted with one or more groups independently selected from alkyl, alkoxy, aryl, aryloxy, alkenyl, and alkynyl; l is 0, 1, 2, 3, 4, 5, or 6; However, the following compounds are not included: [ka] Section 2. Each R 3 is independently hydrogen or methyl. Section 3. R 1 and R 2 is methyl, methoxy, cyclopentyl, cyclohexyl, -O-cyclopentyl, -O-cyclohexyl, phenyl, phenyloxy, or R 1 and R 2 taken together form a polycyclic moiety, said phenyl, phenyloxy, or polycyclic moiety being optionally substituted with one or more groups independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl. Section 4. R 1 and R 2 The compound according to any one of items 1 to 3, wherein Section 5. R 1 and R 2 The compound according to any one of items 1 to 3, wherein Section 6. R 1 and R 2 The compound according to any one of claims 1 to 3, wherein optionally substituted polycyclic moiety is formed. Section 7. A compound according to any one of items 1 to 3 or 6 of the following formula: [ka] During the ceremony, Each R 4 and R 5 is independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; l is 0, 1, 2, or 3; n is 0, 1, 2, 3, or 4, and m is 0, 1, 2, 3, or 4. Section 8. Item 8. The compound according to item 7, wherein m and n are 0. Section 9. 8. The compound according to item 7, wherein m and n are independently 1 or 2. Section 10. Each R 4 and R 5 But independently, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, benzyl, C 2 -C 6 Alkenyl, and C 2 -C 6 is alkynyl, Item 10. The compound according to item 7 or 9, wherein l is 0 or 1. Section 11. Each R 4 and R 5 are independently methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, ethenyl, or ethynyl. Section 12. Each R 4 and R 5 is independently phenyl, phenyloxy or benzyl. Section 13. R 4 and R 5 The compound according to any one of items 7 or 9 to 12, wherein Section 14. R 4 and R 5 The compound according to any one of items 7 or 9 to 12, wherein Section 15. 15. The compound according to any one of clauses 7, 9 to 12, or 14, wherein n is 1 and m is 1. Section 16. Item 16. The compound according to item 15, wherein n is 0. Section 17. R 5 17. The compound according to claim 7, 9 to 12, 14, 15 or 16, wherein is benzyl. Section 18. Item 18. The compound according to any one of items 1 or 3 to 17, wherein l is 0. Section 19. Item 18. The compound according to any one of items 1 or 3 to 17, wherein l is 1. Section 20. Item 18. The compound according to any one of items 1 or 3 to 17, wherein l is 2. Section 21. Item 18. The compound according to any one of items 1 or 3 to 17, wherein l is 3. Section 22. Each R 3 But independently, C 1 -C 4 Alkyl, C 3 -C 6 cycloalkyl, or phenyl, each phenyl being C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, phenyl, phenyloxy, C 2 -C 4 Alkenyl, and C 2 -C 4 22. The compound according to any one of clauses 19 to 21, optionally substituted with one or more groups independently selected from alkynyl. Section 23. Each R 3 23. The compound according to claim 22, wherein is independently methyl, ethyl, cyclopentyl, cyclohexyl, or phenyl. Section 24. A phosphorus-containing compound of the formula: [ka] an olefin compound of the formula: [ka] 24. A method for preparing the compound according to any one of items 1 to 23, comprising reacting in the presence of a radical initiator at a temperature of about 120° C. to about 160° C. Section 25. 25. The method of claim 24, wherein the radical initiator comprises an organic peroxide, azobisisobutyronitrile, or both. Section 26. 26. The method of claim 25, wherein the radical initiator comprises di-tert-butyl peroxide. Section 27. 27. The method of any one of claims 24 to 26, wherein the reaction occurs in the presence of a solvent. Section 28. 27. The method of any one of claims 24 to 26, wherein the reaction occurs in the absence of a solvent. Section 29. a) at least one epoxy resin, and b) at least one compound according to any one of claims 1 to 23 1. A curable composition comprising: Section 30. Item 30. The curable composition according to item 29, wherein the at least one epoxy resin comprises an aromatic epoxy resin, a cycloaliphatic epoxy resin, an aliphatic epoxy resin, and combinations thereof. Section 31. Item 31. The curable composition according to item 30, wherein the at least one epoxy resin is divinylarene dioxide, a diglycidyl ether of bisphenol A, a diglycidyl ether of bromobisphenol A, a diglycidyl ether of an oligomer or polymer of bisphenol A, a diglycidyl ether of an oligomer or polymer of tetrabromobisphenol A, a diglycidyl ether of bisphenol F or a derivative thereof, an epoxy novolac resin, an epoxy cresol novolac resin, or a mixture thereof. Section 32. Item 31. The curable composition according to item 30, wherein the at least one epoxy resin is a glycidyl ether compound of a polyphenol, and the polyphenol is selected from the group consisting of hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, phenol novolac, cresol novolac, trisphenol (tris-(4-hydroxyphenyl)methane), 1,1,2,2-tetra(4-hydroxyphenyl)ethane, tetrabromobisphenol A, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 1,6-dihydroxynaphthalene, and combinations thereof. Section 33. At least one epoxy resin is an alicyclic epoxy resin selected from the group consisting of polyglycidyl ethers of polyols having at least one alicyclic ring, or compounds containing cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent; or The at least one epoxy resin may be selected from the group consisting of hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl- ... Item 31. The curable composition according to item 30, comprising: -methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, methylene-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene-bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, and combinations thereof. Section 34. Item 31. The curable composition according to item 30, wherein the at least one epoxy resin is an aliphatic epoxy resin selected from the group consisting of a polyglycidyl ether of an aliphatic polyol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, a homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, and a copolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and another vinyl monomer. Section 35. Item 32. The curable composition according to item 31, wherein the divinylarene dioxide is selected from the group consisting of substituted divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof. Section 36. Item 36. The curable composition of any one of items 29 to 35, wherein the composition further comprises a benzoxazine, a styrene maleic anhydride copolymer, a phenolic novolac, a cyanate ester, or a mixture thereof. Section 37. Item 37. The curable composition according to any one of items 29 to 36, wherein the epoxy resin is present in an amount ranging from 1 wt% to 70 wt% based on the total weight of the curable composition. Section 38. Item 38. The curable composition according to any one of items 29 to 37, wherein the phosphorus-containing compound according to any one of items 1 to 23 is present in an amount ranging from 10% by weight to 70% by weight based on the total weight of the composition. Section 39. Item 39. The hardenable composition according to any one of items 29 to 38, wherein the composition further comprises a filler selected from the group consisting of natural silica, fused silica, spherical silica, alumina, hydrated alumina, talc, alumina trihydrate, magnesium hydroxide, and combinations thereof. Section 40. Item 40. A prepreg prepared from the curable composition according to any one of items 29 to 39. Section 41. Item 41. The prepreg according to item 40, further comprising a reinforcing component. Section 42. Item 42. The prepreg according to item 41, wherein the reinforcing component comprises a fiber, a fabric, or a combination thereof. Section 43. 40. An electrical laminate prepared from the curable composition of any one of claims 29 to 39. Section 44. Item 44. A printed circuit board prepared from the electrical laminate of item 43. Section 45. 44. The electrical laminate of claim 43, wherein the electrical laminate comprises alternating layers of prepreg and conductive material. Section 46. Item 40. A curable epoxy resin composition comprising the composition according to any one of items 29 to 39 and at least one curing agent. Section 47. Item 47. The curable composition according to item 46, wherein the composition comprises 0.01% by weight to 90% by weight of a curing agent. Section 48. Item 48. The curable composition according to any one of items 46 to 47, wherein the curing agent is selected from the group consisting of anhydrides, carboxylic acids, amine compounds, phenolic compounds, polyols, and mixtures thereof. Section 49. 40. A process for preparing a curable epoxy resin composition comprising mixing (i) the composition of any one of paragraphs 29 to 39, and (ii) at least one curing agent. Section 50. Item 29 to 39 or 46 to 48. A cured thermoset product prepared by curing the curable epoxy resin composition according to any one of items 29 to 39 or 46 to 48. EXAMPLES

[0054] material DOPO (9,10-dihydro-9-oxopropyl ether) available from Sanko Co., Ltd. (10-oxa-10-phosphaphenanthrene-10-oxide) Bz-HCA (8-benzyl-9,10) available from Sanko Co., Ltd. -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) Methylnadic Acid Free Available from Sinopharm Chemical Co. Water (MNA) Methyltetrahydrofuran available from Sinopharm Chemical Co. Water phthalate (MTHPA) Di-tert-butyl available from Sinopharm Chemical Co. Peroxide 2-Ethyl-4-methylphenyl available from Sinopharm Chemical Co. Lumidazole (catalyst) DEN (commercially available) available from Blue Cube Operation LLC. Mark) 438 (Novolac epoxy resin) EPICLON HP-7200H (Novolac Epoxy Resin) available from DIC. ) Benzoxazine available from Sinopharm Chemical Co. SMA2000 (styrene maleic anhydride copolymer) available from Cray Valley. polymer) XZ-92741 available from Blue Cube Operation LLC. KPH-F2003 (F) available from Kolon Industries, Inc. phenol novolac)

[0055] Test Method

[0056] Preparation of Laminates The varnish was impregnated into 2116 glass cloth. The glass cloth containing the resin was baked in a treater. Six prepregs were stacked together and the surfaces were coated with a 35 μm standard The stack was then laminated in a hot press at 200°C for 90 minutes. I nat it.

[0057] Glass transition temperature (T g ) T g TA Q2000 (TA Ins The measurements were performed using a differential scanning calorimetry (DSC) made by truments. The temperature range was 40°C to 210°C, and a heating rate of 20°C / min was used. Two heating cycles were performed. The run was run and the curve for the second cycle was the T curve for the "half-height" method. g Used to determine It was.

[0058] Thermal decomposition temperature (T d ) T d is defined as the temperature at which there is a 5% weight loss in nitrogen. IPC-TM650-2. Measured using a TA Q50 (TA Instruments) according to 4.24.6. The heating rate was 10° C. / min.

[0059] Time to delamination at 288°C (T288) T288 is TA Q400 (TA Inst. The time to delamination was measured after the temperature reached 288°C. It was determined as the time elapsed until a sudden dimensional change occurred.

[0060] Dielectric constant (D k ) / dissipation factor(D f ) The dielectric constant and dissipation factor of the laminate samples were measured according to ASTM D-150. In accordance with the standard, an Agilent 16453A test fixture was used at 25°C and 1GHz. ent Determined by an E4991A RF impedance / material analyzer.

[0061] Copper peel strength (CPS) Copper peel strength was measured using a variable angle peel fixture that maintained the desired 90° peel angle throughout the test. The slip / peel resistance was measured using an IMASS SP-2000 slip / peel tester equipped with a copper A 2" x 4" piece of copper clad laminate was cut for etching. Two strips of 5-inch graphite tape were placed along the sample and on both sides of the laminate. The laminate pieces were then placed lengthwise on the surface, spaced at least 0.5 inches apart. The sample was then placed in a Pro benchtop etcher. The sample was removed from the etcher and properly Once dry, the graphite tape was removed to expose the copper strips. A blade was used to pull up each copper strip. The laminate was then placed in the IMASS tester. The copper strip was clamped and the copper peel test was performed at a pulling speed of 2.8 inches / min for 9 h. It was performed at an angle of 0°.

[0062] Press Cooking Test (PCT) The copper unclad laminate was cut into four pieces measuring 2 inches by 3 inches. Accurately weigh and autoclave (Thermo Electron Corp. 800 The sample was treated with water vapor at 121°C for 1 hour. The surface water was wiped off. The samples were then accurately weighed again and the average water absorption was calculated.

[0063] UL94 Flame Retardant Test Each of the five specimens (13 cm × 12 mm) was placed in a standard UL94 test chamber (At The device was ignited twice for 10 seconds in a UL94 chamber (VW-1). After removing the ignition source, the device was The time until the fire was extinguished was recorded as the burning time. The burn time must be less than 10 seconds for each ignition, and less than 50 seconds total burn time for 10 ignitions. The following examples are offered to illustrate, but not limit, the scope of the disclosure.

[0064] Example 1 DOPO (172.50 g) was melted at 140° C. MNA (143.55 g) and Di-tert-butyl peroxide (3.74 g) was gradually added over 45 minutes. The mixture was heated at 140-160°C for 8 hours. The final product was It was a light brown solid at room temperature.

[0065] Example 2 DOPO (323.15 g) was melted at 140°C. MTHPA (250.68 g) and The mixture was gradually added with di-tert-butyl peroxide (11.08 g) over a period of 70 minutes. The mixture was heated at 140-160 °C for 7 h. The product was a light brown solid at room temperature.

[0066] Example 3 Bz-HCA (30.52 g) and MTHPA (16.70 g) were mixed at 160° C. Di-tert-butyl peroxide (0.78 g) was added dropwise to the reaction mixture. Heated for 7 hours at 160° C. The final product was a light brown solid at room temperature.

[0067] Examples 4 to 6 Examples 4 to 6 show the results when the compounds of Examples 1 and 2 were mixed with an epoxy resin and cured. The results obtained are described below. The formulation showed a high Tg (>180°C), which indicates that the new phosphoric anhydride hardens the epoxy. It was shown that thiocarbamate is an effective hardener for curing the oxidized silica.

[0068] [Table 1]

[0069] Examples 7 to 9 The following table shows the compounding process and the laminate evaluation. All of the examples 7 to 9 of the present invention are , achieving a V-0 UL94 rating, and the phosphoric anhydride is similar to the comparative example XZ-92741 It was shown that the composition of Example 7 can act as an effective flame retardant at 0.0 at 1 GHz. 074D f This is because the phosphoric anhydride is cured with epoxy. It has an advantage over the widely used XZ-92741 in f indicates that The water absorption was high because too much anhydride was used in the formulation. When the formulation was further modified with SMA, the resulting laminates of Examples 8 and 9 had Compared to the comparative example, the overall performance is well-balanced, e.g., high T g , excellent heat resistance, excellent Excellent copper peel strength, moderate water absorption, relatively low D f showed.

[0070] [Table 2]

Claims

1. A phosphorus-containing compound of the formula: [C4B] an olefin compound of the formula: [Case 5A] A process for the preparation of a compound of formula (IV) comprising reacting in the presence of a radical initiator at a temperature of 120° C. to 160° C. The method of preparation, wherein the radical initiator comprises an organic peroxide, azobisisobutyronitrile, or both. [C3A] During the ceremony, Each R ３ are independently hydrogen or methyl; Each R ４ and R ５ is independently １ -C ４ Alkyl, C １ -C ４ Alkoxy, phenyl, phenyloxy, benzyl, C ２ -C ６ Alkenyl, and C ２ -C ６ alkynyl, l is 0, 1, 2, or 3; n is 0, 1, 2, 3, or 4, and m is 0, 1, 2, 3, or 4.

2. The method of claim 1 , wherein the radical initiator comprises di-tert-butyl peroxide.

3. 3. The process of claim 1 or 2, wherein the reaction occurs in the absence of a solvent.

Images