WO2009070172A1

WO2009070172A1 - Curable resins containing acetal, ketal, acetal ester, or ketal ester linkages

Info

Publication number: WO2009070172A1
Application number: PCT/US2007/086083
Authority: WO
Inventors: Osama M. Musa; Xinnan Zhang
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2007-11-30
Filing date: 2007-11-30
Publication date: 2009-06-04
Also published as: TW200938534A

Abstract

Thermosetting maieimide, cinnamyl, and styrenic resins contain acetal, ketal, acetai ester, or ketal ester linkages, which linkages are degradable when subjected to heat or acid. The inventive compounds can be used in thermosetting compositions that may need to be reworked, formula (1).

Description

CURABLE RESINS CONTAINING ACETAL, KETAL, ACETAL ESTER, OR KETAL ESTER LINKAGES

BACKGROUND OF THE INVENTION

[0001] This invention relates to curable thermosetting resins containing acetal, ketal, acetal ester, or ketal ester linkages. The acetal, ketal, acetal ester, and ketal ester linkages are degradable when subjected to heat or acid. The invented compounds can be used in reworkable thermosetting compositions.

[0002] Thermosetting resins have been widely used in variety of applications, such as coating, encapsulants, and adhesives. However, many traditional thermosetting resins display poor tractability after curing, which limits their use in those applications for which degradable or reworkable polymers are advantageous. For example, the reworkability of an adhesive used to adhere semiconductor chips to substrates is desired because it is expensive to discard a multi-chip package with only one failed chip. The use of an adhesive that will melt or decompose to allow chip repair or replacement would be an advantage for semiconductor manufacturers. Other industries would benefit similarly from the ability to use reworkabie materials. Thus, there is a need for adhesives, coatings, and encapsulants that can be decomposed and reworked in many applications.

[0003] Maleimide, cinnamyl, styrenic, vinyl ether, oxetane, and benzoxazine groups have rapid curing speed and low moisture uptake after curing. In particular, maleimides are found to have better adhesion and low shrinkage after curing when compared to traditional radical cured systems, such as acrylates. Additionally, maleimide, cinnamyl, styrenic, and vinyl ether functionalities not only can homopolymerize efficiently but also copolymerize with a variety of functional groups, such as acrylate and methacrylate. However, these resin systems can be intractable after curing and not suitable for applications where a depolymerization process is desired, such as debonding adhesives and reworkable adhesives. Therefore, there is a need for reworkabillty in resin systems such as maleimicle, cinnamyl, styrenic, vinyl ether, oxetane, and benzoxazine resins.

BRIEF DESCRIPTION OF THE DRAWING

[0004] Figure 1 is a graph of the results of adhesion tests of cured formulations containing MCA/ Butanediol Divinyi Ether Adduct from Example 1 showing the decrease in adhesion after exposure to high temperatures, and thus the reworkability of the formulations.

SUMMARY OF THE INVENTION

[0005] This invention relates to compounds containing functionality selected from the group consisting of maleimide, cinnamyl, styrenic, vinyl ether, oxetane, benzoxazine, and combinations thereof; and linkages selected from the group consisting of acetal, ketal, acetal ester, ketal ester and combinations thereof. The acetal, ketal, acetal ester, and ketal ester linkages are degradable either through thermal decomposition under exposure to elevated temperature or through chemical decomposition when contacted with acidic medium. Within this specification and claims, the compound may also be referred to as a resin.

[0006] In another embodiment, this invention relates to a hybrid compound containing: a first functionality selected from the group consisting of maleimide, cinnamyl, styrenic, vinyl ether, oxetane, benzoxazine, and combinations thereof; a second functionality selected from the group consisting of acrylate, methacrylate, epoxy, and combinations thereof; and linkages selected from the group consisting of acetal, ketal, acetal ester, ketal ester and combinations thereof.

[0007] In another embodiment, this invention relates to a hybrid compound containing two or more different functionalities selected from the group consisting of acrylate, methacrylate, and epoxy, and linkages selected from the group consisting of acetal, ketal, acetal ester, ketai ester and combination thereof.

[0008] The maleimide, cinnamyl, styrenic, vinyl ether, oxetane, and benzoxazine reactive functionalities have the structures:

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹XR²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S; R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1- 12 carbon atoms, or is Ar as described above.

[0009] The acetal, ketal, acetal ester, and ketal ester linkages have the structures:

in which R⁴, R⁵, R⁶, and R⁷ are independently selected from aliphatic, cycloaliphatic, or aromatic groups, with or without heteroatoms.

[0010] The inventive compounds are synthesized by the reaction of mono- or multi-functional vinyl ether with a carboxylic acid or phenol. The carboxylic acid, phenol, or vinyl ether resins contain maleimide, cinnamyl, styrenic, oxetane, benzoxazine, acrylate, methacrylate, or epoxy functionality. The reaction can be conducted with or without an acidic catalyst, upon heating to 50-150 °C for 0.5-13 hours. [0011] In another embodiment, this invention is a curable and reworkable composition comprising a thermosetting compound containing functionality selected from the group consisting of maleimide, cinnamyl, styrenic, vinyl ether, oxetane, and benzoxazine, and a linkage selected from the group consisting of acetal, ketal, acetal ester, or ketal ester; a curing agent, such as, a peroxide or a super acid; optionally, a crosslinker that is free of acetal, ketal, acetal ester, or ketal ester linkage; optionally, a reactive diluent; optionally, an adhesion promoter; and optionally, an inorganic filler. The crosslinker free of acetal, ketal, acetal ester, or ketal ester linkage and the reactive diluent will contain reactive functionality, for example, selected from the group consisting of maleimide, acrySate, methacryiate, vinyi ether, styrenic, cinnamyl, maleate, fumarate, epoxy, oxetane, benzoxazine, oxazoline, and a combination of those. The reaction product of such a composition is capable of softening under exposure to elevated temperature (for example, a temperature above the curing temperature) or exposure to acid. Softening of the cured product is due to the decomposition of the acetal, ketal, acetal ester or ketal ester linkage in the composition and provides the reworkable aspect of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0012] For the synthetic procedures described hereinafter, reaction temperatures can be any temperature or range of temperatures within the range of temperatures disclosed, and reaction times can be any length of time within the range of times disclosed.

[0013] MALEIMIDE RESINS: The introduction of acetal, ketal, acetal ester, or ketal ester linkages into maleimide resins is achieved by a one-step reaction between a maleimide that contains a carboxylic acid or phenolic functionality and a mono- or multi-functional vinyl ether. The reaction involves heating the starting material mixture to a temperature within the range from about 75° to about 90°C with or without organic solvent for a period of time from about 1 to about 16 hours. If there is residue acid or phenol present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or basic alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product. If a multifunctional maleimide is desired as the reaction product, the choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, a bismaleimide is obtained when the starting maleimide containing carboxylic acid or phenolic functionality is reacted with divinyl ether in a 2:1 molar ratio; when the molar ratio is 1 :1 , the product will contain one maleimide functionality and one vinyl ether functionality.

[0014] Reaction of a maleimide containing a carboxylic acid with a divinyi ether:

[0015] Reaction of a maleimide containing a phenol with a divinyl ether:

[0016] The maieimide containing carboxylic acid or phenol starting material will have the structure as shown in the above reaction scheme, in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups, and A and B are independently selected from hydrogen, aliphatic, cycioaiiphatic, or aromatic groups. X, Z, A and B can be with or without heteroatoms.

[0017] Suitable vinyl ether resins for use as starting material include those having the generic structure in which m is 1 to 6 and Z is an

aromatic or aliphatic group. Exemplary Z entities include poly(butadienes), poly(carbonates), poly(urethanes), ρoly(ethers), ρoly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether. Commercially available vinyl ether resins include cyclohenanedimethanol divinylether, dodecyl- vinylether, cyclohexyi vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinyiether, hexanediol divinylether, octadecylvinylether, and butaπdiol divinylether available from International Speciality Products (ISP); vinyl ether terminated monomers sold under the tradenames VECTOMER 4010, 4020, 4030, 4040, 4051 , 4210, 4220, 4230, 4060, 5015 available from Sigma- Aldrich, inc

[0018] Examples of the inventive maleimide resins include:

[0019] STYRENIC RESINS: The introduction of the acetal, ketal, acetal ester, or ketai ester linkages into styrenic resins is achieved by reacting a styrenic compound in which a hydroxy! group or a carboxylic acid group is directly connected with the phenyl ring with a mono- or multi-functional vinyl ether. The reaction involves heating the starting material mixture to a temperature within the range from about 75° to about 130°C with or without organic solvent for a period of time from about 1 to about 16 hours, preferably with an acidic catalyst, such as para-to!uene sulfonic acid or terephthaiic acid, if there is residue acid or phenolic materia! present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or sodium hydroxide in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping of the solvent from the product.

[0020] If a multifunctional styrenic resin is desired as the reaction product, the choice of starting materϊais and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, as shown below, a bis-styrenic resin is obtained when the molar ratio of styrenic compound to divinyl ether is 2:1 ; when the molar ratio is 1 :1 , the product will contain one styrenic functionality and one vinyl ether functionality.

[0021] Reaction of a styrene in which a hydroxyl group is directly connected with the phenyl ring and a divinyl ether:

[0022] Reaction of a styrene containing a carboxylic acid group and a divinyl ether:

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹ ){R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above; Z is an aromatic, cycloaliphatic, or aliphatic group with or without heteroatoms.

[0023] Suitable vinyl ether resins for reaction with the styrenic resins are selected from compounds described above.

[0024] Examples of inventive styrenic resins include:

[0025] CINNAMYL RESINS: The introduction of the acetal, ketal, acetal ester, or ketaj ester linkages into cinnamyl resins is achieved by reacting a cinnamic acid with a mono- or multi-functional vinyi ether. The reaction involves heating the starting material mixture to a temperature within the range of 50°- 130°C with or without organic solvent for a period of time from about 1 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 , basic alumina, or sodium hydroxide in organic solvent, such as toluene or dtchloromethane, followed by vacuum stripping the solvent from the product.

[0026] If a multifunctional cinnamyl resin is desired as the reaction product, the choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, as shown below, a bis-cinnamyl resin is obtained when the molar ratio of cinnamic acid and divinyl ether is 2:1 respectively; when the molar ratio is 1 :1 , the product wiil contain one cinnamyl functionality and one vinyl ether functionality.

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹XR²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S; R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above; Z is an aromatic, cycloaliphatic, or aliphatic group with or without heteroatoms.

[0027] Suitable vinyl ether resins for reaction with cinnamy! resins are selected from compounds described above.

[0028] Examples of inventive cinnamyl resins include:

[0029] VINYL ETHER RESINS: The introduction of acetal, ketal, acetal ester, or ketal ester linkages into vinyl ether resins is achieved by a one-step reaction from a multifunctional vinyl ether and a multifunctional carboxylic acid. The reaction involves heating the starting material mixture to 130-160 °C with or without organic solvent for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or basic alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product, if a multifunctional vinyl ether resin is desired as the reaction product, the choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, a divinyl ether containing two acetal linkages is obtained when the molar ratio of divinyl ether and dicarboxylic acid is 2:1 respectively; when the molar ratio is 3:2, a larger molecular weight product is obtained:

in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms. Suitable vinyl ether resins are selected from compounds described above.

[0030] Examples of inventive vinyl ether resins include:

[0031] OXETANE RESINS: The introduction of acetal, ketal, aceta! ester, or ketal ester linkages into oxetane resins is achieved by the reaction of a compound containing both vinyl ether functionality and oxetane functionality with a multifunctional carboxylic acid or phenol. The synthesis of the vinyl ether/oxetane compound is conducted by reacting a hydroxyl terminated vinyl ether with a halogen terminated oxetane at 60°-100°C under basic conditions in an organic solvent, such as toluene. The formation of acetal, ketal, acetaf ester, or ketal ester linkages occurs through the reaction of the vinyl ether/oxetane compound with carboxylic acid or phenol at a temperature of 75°-160°C, with or without organic solvent, for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product.

[0032] Reaction of a vinyl ether containing oxetane with a multifunctional carboxylic acid:

[0033] Reaction of a vinyl ether containing oxetane with a multifunctional phenol:

in which X, Z₁ and A are as described above; E is selected from Cl, Br, and I.

[0034] Examples of inventive oxetane resins include:

[0035] BENZOXAZINE RESINS. The introduction of acetal, ketal, acetal ester, or ketal ester linkages into benzoxazine resins can be achieved by several synthetic methods, two of which are: 1 ) reaction of a carboxylic acid containing benzoxazine functionality with a multifunctional vinyl ether; and 2) reaction of a vinyl ether containing benzoxazine functionality with a multifunctional carboxylic acid or multifunctional phenol. The formation of the acetal, ketal, acetal ester, or ketal ester linkage involves heating the starting material mixture to 130°-160°C with or without organic solvent for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or basic alumina in organic solvent, such as toluene or d ich I oro methane, followed by vacuum stripping the solvent from the product.

[0036] The synthesis of a carboxylic acid containing benzoxazine functionality can be achieved by several synthetic methods, two of which are: 1 ) reacting a phenol, a formaldehyde, and an amino acid at 30°-130°C with organic solvent, such as dioxane; and 2) reacting a multifunctional phenoi containing carboxylic acid, a formaldehyde, and an amine functionality in a similar way as described above.

in which G and X are as described above; R⁸ and R⁹ are selected independently from aliphatic and aromatic groups with or without heteratoms.

[0037] If a multifunctional benzoxazine is desired product, the choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, a bis-benzoxazine resin is obtained when the molar ratio of carboxylic acid and divinyl ether is 2:1 respectively; when the molar ratio is 1 :1 , the product will contain one benzoxazine functionality and one vinyl ether functionality:

in which X, Z, and G are as described above. Suitable vinyl ether resins are selected from compounds described above.

[0038] The reaction of a multifunctional benzoxazine containing carboxylic acid and a vinyl ether is shown here:

in which X, Z, R and R are as described above.

[0039] Reaction of a vinyl ether containing benzoxazine functionality and a multifunctional carboxylic acid or multifunctional phenol is shown below. The synthesis of a vinyl ether containing benzoxazine functionality is conducted by reacting a phenol, a formaldehyde, and amine containing vinyl ether functionality at 30^D-130°C with organic solvent, such as dioxane. If a multifunctional benzoxazine resin is desired as the reaction product, a multifunctional carboxylic acid or multifunctional phenol is used:

in which X, Z, and G are as described above.

[0040] Examples of inventive benzoxazine resins include:

[0041] HYBRID RESINS: Hybrid resins, for the purposes of this specification and the claims, will have more than one type of reactive functionality selected from the group consisting of maleimide, styrenic, cinnamyl, oxetane, and benzoxazine. The introduction of acetal, ketal, acetal ester, or ketal ester linkages into hybrid resins is achieved by a one-step reaction from a multifunctional vinyl ether and one or more multifunctional carboxylic acids or phenols. The vinyl ether, carboxylic acid or phenol resins will contain functionaiity selected from the group consisting of maleimide, cinnamyl, styrenic, oxetane, and benzoxazine. The reaction involves heating the starting material mixture to 75°-160 °C with or without organic solvent for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or basic alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product. The choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product.

[0042] A hybrid resin containing maleimide and styrenic functionality is obtained when the molar ratio of maleimide, divinyl ether, and styrenic resin is 1 :1 :1 respectively:

in which A, B, X, Z, and G are as described above; A' and B¹ are independently selected from hydrogen, aliphatic, cycloaiiphatic, or aromatic group with or without heteroatoms; suitable vinyl ether resins for the reaction are selected from compounds described above.

[0043] A hybrid resin containing maleimide and cinnamyl functionality is obtained when the molar ratio of maleimide, divinyl ether, and cinnamyl resin is 1 : 1 : 1 respectively:

in which A, B, A', B', X, Z, and G are as described above; suitable vinyl ether resins for the reaction are selected from compounds described above.

[0044] A hybrid resin containing maleimide and oxetane functionality is obtained when reacting a maleimide containing carboxylic acid or phenol and an oxetane containing vinyl ether:

in which A₁ B, A', X₁ Z, and G are as described above.

[0045] A hybrid resin containing maleimide and benzoxazine functionality is obtained when the molar ratio of maleimide, divinyl ether, and benzoxazine resin is 1 :1 :1 respectively:

in which A, B, X, Z, and G are as described above; Y is selected from an aliphatic cycloaliphatic, or aromatic group with or without heteroatoms. Suitable vinyl ether resins for the reaction are selected from compounds described above.

[0046] Another method to obtain a hybrid resin containing maieimide and benzoxazine functionality is by reacting a carboxylate acid containing maleimide and a vinyi ether containing benzoxazine:

in which A, B, X, Z, and G are as described above.

[0047] A hybrid resin containing styrenic and cinnamyl functionality is obtained when the molar ratio of styrenic, divinyl ether, and cinnamyl resin is 1 :1 :1 respectively:

in which A, B, A', B', X, Z, and G are as described above; suitable vinyl ether resins for the reaction are selected from compounds described above ; Q is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alky! group having 1-12 carbon atoms, or is Ar as described above.

[0048] A hybrid resin containing styrenic and oxetane functionality is obtained when reacting a styrenic resin containing carboxylic acid or phenol group and an oxetane resin containing vinyl ether group:

in which A, B, A', X, Z, and G are as described above.

[0049] A hybrid resin containing styrenic and benzoxazine functionality is obtained when the molar ratio of styrenic, divinyl ether, and benzoxazine resin is 1 :1 :1 respectively:

In which A, B, Z, Y, G, and Q are described above; suitable vinyl ether resins for the reaction are selected from compounds described above.

[0050] Another method to obtain a hybrid resin containing styrenic and benzoxazine functionality is to reacting a carboxylate acid or phenol containing styrene and a vinyl ether containing benzoxazine:

in which A, B, Z₁ Q, and G are as described above.

[0051] A hybrid resin containing ciπnamyl and oxetane functionality is obtained when reacting a cinnamyl resin containing carboxylic acid group and an oxetane resin containing vinyi ether group:

in which A, B, A', Z, and G are as described above.

[0052] A hybrid resin containing cinnamyl and benzoxazine functionality is obtained when the molar ratio of cinnamyl, divinyl ether, and benzoxazine resin is 1 :1 :1 respectively:

In which A, B, Z, Y, Z, G, and Q are described above; suitable vinyl ether resins for reaction with cinnamyl resins are selected from compounds described above.

[0053] Another method to obtain a hybrid resin containing cinnamyl and benzoxazine functionality is to reacting a carboxylate acid containing cinnamyl functionality and a vinyl ether containing benzoxazine:

in which A, B, Z, Q, and G are as described above.

[0054] A hybrid resin containing oxetane and benzoxazine functionality is obtained when reacting an oxetane containing vinyl ether group and a benzoxazine containing carboxylic acid group:

which Z, X, G, and A' are described above.

[0055] Examples of inventive hybrid resins include:

[0056] HYBRID RESINS CONTAINING ACRYLATE/METHACRYLATE FUNCTIONALITY. These resins have more than one type of reactive functionality, at least one of which is acrySate or methacrylate. The introduction of acetal, ketal, acetal ester, or ketal ester linkages into hybrid resins containing acrylate or methacrylate functionality can be achieved by several methods, two of which are: 1 ) a one-step reaction from a multifunctional vinyl ether, a multifunctional carboxylic acid or multifunctional phenol containing maleimide, cinnamyl, styrenic, or benzaxozine, and a multifunctional carboxyϋc acid or multifunctional phenol containing acrylate or methacrylate; and 2) a one-step reaction from a vinyl ether containing oxetane or benzaxozine functionality and a multifunctional carboxylic acid or multifunctional phenol containing acrylate or methacrylate functionality. The reaction involves heating the starting material mixture to 75°-160°C with or without organic solvent for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or basic alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product. If a multifunctional hybrid resin is desired as the reaction product, the choice of starting materials and the stoichiometry of the reaction can be controlled to design multi-functionality into the product. For example, a hybrid resin containing maleimide and acrylate or methacyiate functionality is obtained when the molar ratio of maleimide, divinyl ether, and acrylate/methacrylate is 1 :1 :1 :

in which X, Z, A, and B are selected from compounds described above; D is selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups. X, Z, A, B, and D can be with or without heteroatoms. Suitable vinyl ether resins for the reaction are selected from compounds described above.

[0057] A hybrid resin containing styrenic and acrylate or methacyiate functionality is obtained when the molar ratio of styrenic, divinyl ether, and acrylate or metharylate is 1 :1 :1 respectively:

in which A, B, D, G, and Z are as described above.

[0058] Suitable vinyl ether resins for reaction with the styrenic resins are selected from compounds described above.

[0059] A hybrid resin containing cinnamyl and acrylate or methacyiate functionality is obtained when the molar ratio of divinyl ether, cinnamyi, and acylate or methacrylate is 1 :1 :1 :

in which A, B, D, G, and Z are as described above.

[0060] Suitable vinyl ether resins for reaction with cinnamyl resins are selected from compounds described above.

[0061] A hybrid resin containing vinyl ether and acrylate or methacrylate functionality is obtained when the molar ratio of divinyl ether and acrylate is

1 :1 :

in which D and Z are as described above.

[0062] Suitable vinyl ether resins for reaction with acrylate or methacrylate resins are selected from compounds described above.

[0063] A hybrid resin containing benzoxazine and acrylate or methacrylate functionality is obtained when the molar ratio of divinyl ether, benzoxazine and acrylate or methacrylate is 1 :1 :1 respectively:

in which X, Z , D, G, R⁸, and R⁹ are as described above; suitable vinyl ether resins for reaction with acrylate or methacrylate resins are selected from compounds described above.

[0064] Another method to obtain a hybrid resin containing benzoxazine and acrylate or methacrylate is conducted by reacting a vinyl ether containing benzoxazine and a carboxylic acid containing acrylate or methacrylate functionality:

in which Z, D and G are as described above.

[0065] A hybrid resin containing oxetane and acrylate or methacylate functionality is obtained when reacting a vinyl ether containing oxetane functionality and a carboxylic acid containing acrylate or methacrylate functionality:

in which D, Z, and A are as described above.

[0066] Examples of inventive hybrid resins include:

[0067] HYBRID RESINS CONTAINING EPOXY FUNCTIONALITY. The introduction of acetal, ketal, acetal ester, or ketal ester linkages into hybrid resins containing epoxy functionaϋty is achieved by the reaction of a viny! ether that contains epoxy functionality with a muitifunctional carboxylic acid or multifunctional phenol containing acrylate, methacrylate, maleimide, cinnamyl, styrenic, or benzoxazine functionality. The vinyl ether containing epoxy functionality is synthesized by reacting a hydroxyl terminated vinyl ether with a halogen terminated epoxide at 60°-100°C under basic conditions in an organic solvent, such as toluene. The formation of acetal or acetal ester linkages involves heating the starting material mixture to 75°-160°C with or without organic solvent for a period of time from about 0.5 to about 16 hours. !f there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product. The general synthetic scheme is:

in which A, B, Z, G, D₁ R^a, and R⁹ are as described above; E is selected from Cl₁ Br, and I.

[0068] Examples of inventive hybrid resins containing epoxy functionality include:

[0069] HYBRID RESINS CONTAINING ACRYI-ATE AND METHACRYLATE. These resins contain both acrylate and methacrylate functionality. The introduction of acetal, ketal, acetal ester, or ketal ester linkages into hybrid resins can be achieved by a one-step reaction from a multifunctional vinyl ether, a multifunctional carboxylic acid containing acrylate, and a multifunctional carboxylic acid containing methacrylate. The formation of acetal or acetal ester linkages is accomplished by heating the starting material mixture to 75°-160°C with or without organic solvent for a period of time from about 0.5 to about 16 hours. If there is residue acid present in the product, a suitable work-up procedure involves treating the product mixture with Amberlyst A21 or alumina in organic solvent, such as toluene or dichloromethane, followed by vacuum stripping the solvent from the product. The general synthetic scheme is:

in which Z is described above. [0070] An example of an inventive hybrid resins containing epoxy functionality is:

EXAMPLES

[0071] EXAMPLE 1 : PREPARATION OF MALEIMIDOCAPROIC ACID / 1 ,4- BUTANEDIOL DLVINYL ETHER ADDUCT

[0072] To a pre-heated (90°C oil bath) three-neck round bottom flask was added 4-MEHQ (446 mg, 3.6 mmol) and 1 ,4-butanediol divinyl ether (28.4 g, 200 mmol). Maleimidocaproic acid (MCA) (100 g, 474 mmol) was crushed into small pieces and added into the reaction mixture in ten portions over two hours. The reaction temperature was maintained at 80°- 90°C. Addition of MCA generally causes a decrease of reaction temperature and increase in viscosity. The reaction mixture was stirred for another six hours at 85°C, after which the reaction contents were cooled to ambient temperature. A very small amount of gel was found in the reaction mixture. Toluene (400 mL) was added to dissolve the product mixture; Amberlyst A 21 resin (100 g) was added and the reaction stirred for another hour. The Amberlyst resin was filtered out and the solvent stripped under vacuum to give 63g (57%) of yellow viscous liquid with a viscosity of 5,000mPa.s (25°C). ¹H-NMR (DMSO- Cf₆, in ppm): δ 7.0 (s, 4H), 5.9 (q, 2H)₁ 3.4-3.6 (m, 8H), 2.3 (t, 4H), 1.5 (m, 12H), 1.2 (m, 10H).

[0073] EXAMPLE 2: PREPARATION OF MALEIMIDOCAPROIC ACID / 1 ,4- CYCLOHEXANE-DIMETHANOL DIVINYL ETHER

[0074] To a pre-heated (90°C) three-neck round bottom flask was added A- MEHQ (223mg, 1.8 mmol) and cyclohexanedimethanol divinyl ether (18.4 g, 94 mmol). MCA (50 g, 267 mmol) was crushed into small pieces and added into the reaction mixture in ten portions over two hours. The reaction temperature was maintained at 80°-90°C. Addition of MCA generally causes a decrease of reaction temperature and increase in viscosity. The reaction mixture was stirred for another 17 hours at 85°C, and then cooled to ambient temperature. A very small amount of gel was found in the reaction mixture. Toluene (200 mL) was added to dissolve the product mixture; Amberlyst A 21 (50 g) was added and the reaction mixture stirred for another hour. Due to the high viscosity, removing toluene with rotary evaporator was not successful. Therefore, the product mixture was dissolved in CH₂CI₂ and treated as before with Amberlyst A 21 resin. The solvent was removed by rotary evaporator, and the product mixture heated in a vacuum oven, to give 37g (63%) of highly viscous liquid. ¹H-NMR (CDCI3, in ppm): δ 6.6 (s, 4H), 5.8 (q, 2H), 3.2-3.4 (m, 8H), 2.3 (t, 4H), 1.3-1.6 (m, 26H), 0.9 (m, 2H).

[0075] EXAMPLE 3: PREPARATION OF MALEIMIDOCAPROIC ACID / DIETHYLENE GLYCOL DIVINYL ETHER ADDUCT

[0076] To a pre-heated (90°C) three-neck round bottom flask was added 4- MEHQ (223mg, 1.8 mmoi) and diethyleneglycol divinyl ether (14.9 g, 94 mmol). MCA (50 g, 267 mmol) was crushed into small pieces and added into the reaction mixture in ten portions over two hours. The reaction temperature was maintained at 80°-90°C. Addition of MCA generally causes a decrease of the reaction temperature and increase of viscosity. The reaction mixture was stirred for another 17 hours at 85°C, after which the reaction mixture was cooled to ambient temperature. A very small amount of gel was found in the reaction mixture. Toluene (200 ml.) was added to dissolve the product mixture; Amberlyst A 21 (50 g) was added and the product mixture stirred for one hour. The Amberlyst resin was filtered and the solvent stripped under vacuum to give 30 g (55%) of a yellow viscous liquid with a viscosity of 3,800 mPa.s (25 °C). ¹H-NMR (DMSO-d₆, in ppm): δ 7.0 (s, 4H), 5.9 (q, 2H), 3.4-3.6 (m, 12H), 2.3 (t, 4H), 1.5 (m, 8H), 1.2 (m, 10H).

[0077] EXAMPLE 4: PREPARATION OF 3-MALEIMIDOPROPIONIC ACID / DLETHYLENE GLYCOL DLVINYL ETHER ADDUCT

[0078] To a pre-heated (90°C) three-neck round bottom flask was added 4- MEHQ (223mg, 1.8 mmol) and diethyleneglycol divinyl ether (22.1 g, 140 mmoi). MPA (50 g, 296 mmol) was added into the reaction mixture in ten portions over 1.5 hours. The reaction temperature was maintained at 80- 90°C. After the reaction mixture was stirred for another 6.5 hours at 85°C, the reaction mixture was cooled to ambient temperature. A very smal! amount of gel was found in the reaction mixture. Toluene (200 mL) was added to dissolve the product mixture after which Amberlyst A 21 resin (50 g) was added and the product mixture stirred for one hour. After filtration, the solvent was stripped under vacuum to give 50 g (72%) of a yellow viscous liquid with viscosity of 13,000 mPa.s (25 °C). ¹H-NMR (DMSO-Cf₆, in ppm): δ 7.0 (S, 4H), 5.9 (q, 2H), 3.54-3.7 (m, 12H), 2.6 (t, 4H), 1.2 (m, 6H).

[0079] EXAMPLE 5: PREPARATION OF S-MALEIMIDOPROPIONIC ACID / CYCLOHEXYL VINYL ETHER ADDUCT

[0080] To a pre-heated (90°C) three-neck round bottom flask was added A- MEHQ (223mg, 1.8 mmo!) and cyclohexyi vinyl ether (23.8 g, 188 mmol). MCA (5Og, 267mmol) was crushed into smaller pieces and added into the reaction mixture in ten portions over two hours. The reaction temperature was maintained at 80°-90°C. Addition of MCA generally causes a decrease of the reaction temperature. After the reaction mixture was stirred for another 17 hours at 85°C, the solution was cooled down to ambient temperature and very small amount ge! was found in the reaction mixture. Toluene (200 mL) was added to dissolve the product mixture, after which Amberlyst A 21 resin (50 g) was added to the product mixture and stirred for one hour. The Amberlyst resin was filtered and the solvent stripped under vacuum to give 49g (77%) of a yellow viscous liquid with a viscosity of 300 mPa.s (25°C). ¹H- NMR (DMSO-Cf₆, in ppm): δ 7.0 (s, 2H), 5.9 (q, 1 H), 3.4-3.6 (m, 3H), 2.3 (t, 2H), 1.5-1.7 (m, 8H), 1.2 (m, 11 H).

[0081] EXAMPLE 6: PREPARATION OF ISOEUGENOL / 1 ,4-BUTANEDIOL DMNYL ETHER ADDUCT

[0082] To a 250 nriL round bottom flask, equipped with a thermometer and stir bar, were added butanediol divinyl ether (20 ml_, 126 mmol) and isoeugenol (42.6 g, 260 mmol). This solution was stirred for 15 minutes; then, phthalic acid (1.06 g, 6.4 mmol) was added. The reaction flask was placed into a 125°C oil bath. After stirring at 125°C for eight hours and at ambient temperature for another ten hours, the reaction mixture was diluted with toluene (200 mL). Amberlyst A21 resin (10Og) was added and the reaction mixture stirred for one hour. A small amount of isoeugenol still remained as indicated by NMR. NaOH (solid) was added to the mixture and stirred for one hour until no excess amount of isoeugenol was detected. The reaction mixture turned from yellow to dark red after addition of NaOH. The solvent was removed under vacuum to give 35g (60%) dark red viscous liquid with viscosity of 17,000 mPa.s (25°C). ). ¹H-NMR (DMSO-d₆, in ppm): δ 7.0 (S, 2H)₁ 6.9 (d, 2H), 6.8 (d, 2H), 6.4 (d, 2H), 6.2 (m, 2H), 5.3 (q, 2H), 3.3-3.7 (m, 10H), 1.8 (d, 6H), 1.3-1.5 (m, 10H).

[0083] EXAMPLE 7: PREPARATION OF BIS-(4-VINYL OXY BUTYL) ISOPHTHLATE AND ADIPIC ACID ADDUCT

[0084] Bis-(4-vinyl oxy butyl) isophthlate (2.0 g, 5.5 mmol) (VECTOMER 4010), adipic acid (0.4 g, 2.8 mmol), and acetone (1 g) were mixed in an aluminum boat. The mixture was heated to 80°C for ten minutes to remove the solvent, and then heated to 130°C. Once a homogeneous sample was obtained, the aluminum boat was placed in a pre-heated oven at 150°C for 30 minutes to give the product with approximately 100% yield. ¹H-NMR (DMSO-d₆, in ppm): δ 8.5 (s, 2H)₁ 8.2 (d, 4H), 7.7 (t, 2H), 6.5 (dd, 2H), 5.8 (q, 2H)₁ 4.4 (m, 8H), 4.2 (d, 2H), 3.9 (d, 2H), 3.5 (m, 2H), 3.3 (m, 2H), 2.3 (t, 4H), 1.5-1.7 (m, 20H), 1.3 (m, 6H).

[0085] EXAMPLE 8: PREPARATION OF (BIS-(4-VINYL OXY BUTYL) ADIPATE) AND ADIPIC ACID ADDUCT

[0086] Bis-(4-vinyl oxy butyl) adipate (2.0 g, 5.8 mmol) (VECTOMER 4060), adipic acid (0.43 g, 2.9 mmol), and acetone (1 g) were mixed in an aluminum boat. The mixture was heated to 80°C for 10 minutes to remove the solvent followed by heating to 130°C. Once a homogeneous sample was obtained, the aluminum boat was placed in a pre-heated oven at 150^αC for 30 minutes to give the product with approximately 100% yield. . ¹H-NMR (DMSO-d₆, in ppm): δ 6.5 (dd, 2H), 5.8 (q, 3H), 4.2 (d, 2H), 3.9 (m, 14H), 3.3-3.7 (m, 12H), 2.3 (m, 20H), 1.5-1.7 (m, 44H), 1.3 (m, 9H).

[0087] EXAMPLE 9: CURING AND DEGRADATION BEHAVIOR OF

MALEIMIDOCAPROIC ACID / 1 , 4-BUTANEDIOL DIVINYL ETHER ADDUCT FROM EXAMPLE 1

[0088] A mixture of 98% MCA/ butanediol divinyl ether adduct and 2% 1 ,1-di- (tert-amylperoxy)cyclohexane (USP-90MD) was cured in a Differential Scanning Calorimeter (hereinafter "cured by DSC") at a heating rate of 10°C/min under N₂ and exhibited a curing peak at 121 °C and the start of degradation at about 220°C. [0089] A second mixture of the MCA/ butanedio! divinyl ether adduct was cured with 2% 1 ,1-di-(tert-amylperoxy)cyclohexane at 150°C in an oven for 30 minutes. A thermal gravimetric analysis of the cured sample was performed at a heating rate of 10°C/minutes and showed a weight loss of 10% at 241 °C.

[0090] EXAMPLE 10: DEGRADATION BEHAVIOR OF NEAT MCA/ BUTANEDIOL

DiVlNYL ETHER ADDUCT FROM EXAMPLE 1

[0091] Hot-stage IR analysis was performed on the MCA/ butanediol divinyl ether adduct from Example 1 at temperatures ranging from 25° to 325°C and indicated that the MCA/ butanediol divinyl ether adduct started to degrade at 225 °C.

[0092] EXAMPLE 11 : CURING AND DEGRADATION BEHAVIOR OF MCA /

DlETHYLENE GLYCOL DIVINYL ETHER ADDUCT FROM EXAMPLE 3

[0093] A mixture of 98% MCA/ diethylene glycol divinyl ether adduct and 2% 1 ,1-di-{tert-amylperoxy)cyclohexanewas cured by DSC at a heating rate of 10°C/minute under N₂ and exhibited a curing peak at 124°C and the start of degradation at 220°C:

[0094] A second mixture of MCA/ diethylene glycol divinyl ether adduct was cured with 2% 1 ,1-di-(tert-amylperoxy)cyclohexaneat 150°C for 30 minutes. Thermal gravimetric analysis of the cured sample was performed at a heating rate of 10°C/minute and showed 10% weight loss at 250°C.

[0095] EXAMPLE 12: CURING AND DEGRADATION BEHAVIOR OF MPA / BUTANEDIOL DIVINYL ETHER ADDUCT FROM EXAMPLE 4

[0096] A mixture of 98% MPA/ butanediol divinyl ether adduct and 2% 1 ,1-di- (tert-amylperoxy)cyclohexane was cured by DSC at a heating rate of 10°C/minute under N₂ and exhibited a curing peak at 125^σC and the start of degradation at 200°C. [0097] A second mixture of MPA/ butanediol divinyl ether adduct with 2% 1 ,1- di-(tert-amylperoxy)cyclohexane was cured at 150°C for 30 minutes. Thermal gravimetric analysis of the cured sample was performed at a heating rate of 10°C/minute and showed 10% weight loss at 200°C.

[0098] EXAMPLE 13: CURING AND DEGRADATION BEHAVIOR OF MCA / CYCLOHEXYL VINYL ETHER ADDUCT FROM EXAMPLE 5

[0099] A mixture of 98% MCA/ cyclohexy! vinyl ether adduct and 2% 1 ,1-di- (tert-amylperoxy)cyclohexane was cured by DSC at a heating rate of 10°C/minute under N₂ and exhibited a curing peak at 130°C and the start of degradation at 220°C.

[00100] A second mixture of MCA/ cyclohexyl vinyl ether adduct was cured with 2% 1 ,1-di-{tert-amylperoxy)cyclohexane at 150°C for 30 minutes. Thermal gravimetric analysis of the cured sample was performed at a heating rate of 10°C/minute and indicated a 10% weight loss temperature at 240°C.

[00101] EXAMPLE 14: ADHESION TEST OF CURED MCA / BUTANED!OL DIVINYL ETHER ADDUCT FROM EXAMPLE 1

[0100] A composition of MCA/ cyclohexyl vinyl ether adduct and 2% 1 ,1-di- (tert-amylperoxy)cyclohexane was disposed between a ball grid array package (CABGA36) and an epoxy fiberglass board (FR4) and cured at 150°C for 30 minutes. Die shear strength of the cured MCA/ butanediol divinyl ether adduct was tested at 25°C and 150°C after exposing the cured adhesive to 250°C for two minutes. The data presented below indicate that the shear strength of the cured sample dropped significantly after exposure to elevated temperature.

[0101] EXAMPLE 15: ADHESION TEST OF CURED FORMULATION CONTAINING MCA/ BUTANEDIOL DLVINYL ETHER ADDUCT FROM EXAMPLE 1

[0102] Formulations were prepared to contain 2% 1 ,1-di-{tert-amylperoxy)- cyclohexane and 10%, 30%, and 50% MCA/ butanediol divinyl ether adduct, and a bismaleimide without the acetal linkage. Die shear tests on the cured formulations with three different levels of MCA/ butanediol divinyl ether adduct were conducted first at 25°C, and then at 150°C after exposure to 250°C for two minutes. In al! three cases, the adhesion dropped significantly after exposure to the elevated temperature (Figure 1 ).

Claims

WHAT IS CLAIMED

1. A compound containing a functionality selected from the group consisting of maleimide, cinnamyl, styrenic, vinyl ether, oxetane, benzoxazine, and combinations thereof, and a linkage selected from the group consisting of acetai, ketal, acetal ester, ketal ester, and combinations thereof.

2. The compound according to claim 1 having a structure selected from the group consisting of:

in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteratoms, and A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms.

3. The compound according to claim 1 having a structure selected from the group consisting of:

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an aikyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alky! group having 1-12 carbon atoms, or Ar as described above; R³ is an alky! group having 1-12 carbon atoms, or is Ar as described above; Z is an aromatic, cycloaliphatic, or aliphatic group with or without heteroatoms.

4. The compound according to claim 1 having a structure selected from the group consisting of:

in which A and B are independently se!ected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above; Z is an aromatic, cycloaliphatic or aliphatic group with or without heteroatoms.

5. The compound according to claim 1 having a structure selected from the group consisting of:

in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms. and

in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms.

6. The compound according to claim 1 having a structure selected from the group consisting of:

in which X and Z are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms; A is selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms.

7. The compound according to claim 1 having a structure selected from the group consisting of:

in which X and Z are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms; G is selected from -N(R¹J(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N₁ O, or S. R¹ and R² are independently selected from hydrogen, an alky! group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above; R⁸ and R⁹ are selected independently from aliphatic, cycloaliphatic, and aromatic groups with or without heteratoms.

8. The compound according to claim 1 having a structure selected from the group consisting of

in which X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms, and A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms.

9. The compound according to claim 1 having a structure selected from the group consisting of

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above; Z is an aromatic, cycioaiiphatic, or aliphatic group with or without heteroatoms.

10. The compound according to ciaim 1 having a structure selected from the group consisting of

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; X and Z are independently selected from aliphatic or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroarormatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

11. The compound according to claim 1 having a structure selected from the group consisting of

and

in which A, B, A', and B' are independently selected from hydrogen, aliphatic, cycioaliphatic, or aromatic groups with or without heteroatom; X and Z are independently selected from aliphatic, cycioaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

12. The compound according to claim 1 having a structure selected from the group consisting of

and

in which A₁ B, A', and B' are independently selected from hydrogen, aliphatic, cycloaiiphatic, or aromatic groups with or without heteroatom; X and Z are independently selected from aliphatic, cycloaiiphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatϊc ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

13. The compound according to claim 1 having a structure selected from the group consisting of

wh A, B, and A' are independently selected from hydrogen, aliphatic, cycloafiphatic, or aromatic groups with or without heteroatom; X and Z are independently selected from aliphatic, cycloaiiphatic, or aromatic groups with or without heteroatom.

14. The compound according to claim 1 having a structure selected from the group consisting of

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; X, Y, and Z are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹J(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

15. The compound according to claim 1 having a structure selected from the group consisting of

in which A₁ B, A', and B' are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; Z is selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G and Q are independently selected from -N(R¹ )(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

16. The compound according to claim 1 having a structure selected from the group consisting of

in which A, B, and A' are independently selected from hydrogen, aliphatic or aromatic groups with or without heteroatom; Z is selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

17. The compound according to claim 1 having a structure selected from the group consisting of

iii and

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; Z and Y are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G and Q are independently selected from - N(R¹)(R²), -SR³, -OR³, Ar₁ or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

18. The compound according to claim 1 having a structure selected from the group consisting of

and

in which A, B, and A' are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; Z is selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an aikyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

19. The compound according to claim 1 having a structure selected from the group consisting of

in which A and B are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; Z and Y are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; G and Q are independently selected from - N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

20, The compound according to claim 1 having a structure selected from the group consisting of

in which Z and X are independently selected from aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; A is selected form hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatoms; G is selected from -N(R¹XR²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms; Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S. R¹ and R² are independently selected from hydrogen, an alkyl group having 1-12 carbon atoms, or Ar as described above; R³ is an alkyl group having 1-12 carbon atoms, or is Ar as described above.

21. A hybrid compound having: a functionality selected from the group consisting of maleimide, styrenic, cinnamyl, vinyl ether, oxetane, and benzoxazine; a functionality selected from the group consisting of acrylate, methacrylate, epoxy; and a linkage selected from the group of acetal, ketal, acetal ester, ketal ester, and combinations thereof.

22. The compound according to claim 21 having a structure selected from the group consisting of:

23. The compound according to claim 21 having a structure selected from the group consisting of:

and

in which

X and Z are independently selected from the group consisting of aliphatic, cycloaliphatic, or aromatic groups with or without heteratoms;

A, B, R⁸, R⁹, and D are independently selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups;

G is selected from -N(R¹)(R²), -SR³, -OR³, Ar, or an alkyl group having 1-12 carbon atoms;

Ar is an aromatic or heteroaromatic ring or fused ring having 3-10 carbon atoms within the ring structure, in which the heteroatom may be N, O, or S;

R¹, R² and R³ are independently selected from hydrogen, an aikyl group having 1-12 carbon atoms, or Ar as described above; in which X, Z, A, B, and D can be with or without heteroatoms.

24. A hybrid compound containing two or more functionalities selected from the group consisting of acrylate, methacrylate, epoxy, and combinations thereof, and one or more linkages selected from the group consisting of acetal, ketal, acetal ester, and ketal ester.

25. The compound according to claim 24 having a structure selected from the group consisting of:

and

in which D is selected from hydrogen, aliphatic, cycloaliphatic, or aromatic groups with or without heteroatom; Z is an aromatic, cycloaliphatic or aliphatic group with or without heteroatoms.