HK1027592A

HK1027592A - Package encapsultants prepared from allylated amide compounds

Info

Publication number: HK1027592A
Application number: HK00106872.0A
Authority: HK
Inventors: R‧A‧舒尔茨; D‧赫尔; 肖朝东
Original assignee: 国家淀粉及化学投资控股公司
Priority date: 1998-07-02
Filing date: 2000-10-27
Publication date: 2001-01-19

Description

Packaging sealants prepared from allylated amide compounds

no marking

Priority from U.S. provisional application 60/091,508 was claimed under 35 USC 119 (e).

The present invention relates to sealant compositions prepared from allylated amide compounds that are useful for protecting semiconductor devices and package metallizations from environmental corrosion and mechanical damage.

Microelectronic devices include millions of circuit elements, primarily transistors assembled in Integrated Circuit (IC) chips, but also resistors, capacitors, and other elements. The integrated circuit element may comprise a single die, an encapsulated single piece, or an encapsulated single or multi-piece assembly. These electronic components are interconnected into circuits and ultimately connected and secured to a carrier or substrate, such as a printed circuit board.

Various materials used in the production of integrated circuits and their associated interconnect materials are susceptible to environmental, moisture, and mechanical damage. Protection is provided by sealing the semiconductor assembly, hereinafter referred to as a package seal. The package sealing may be performed by a transfer molding process in which the chip or integrated circuit assembly is loaded into a mold cavity, compressed and the sealing material is transferred under pressure from a container into the mold cavity. Generally, the sealing material is a thermosetting polymer that can be crosslinked and cured into the final product component. The sealing process may also be carried out by a method known quite roughly as the drop-top method, in which a drop of sealing material is dispensed onto a chip or integrated circuit fixed on a substrate and subsequently cured.

For most commercial and industrial end uses, particularly those using chip-on-board assemblies and multi-chip modules, the sealing process is accomplished using thermosetting polymeric materials. Preferred thermosetting sealing materials must have a viscosity and thixotropic index to allow easy dispensing with a syringe, sufficient adhesion to packaging components, low ionic content to avoid corrosion of package metallization, sufficient mechanical strength, high heat and moisture resistance at application temperatures, and a compatible coefficient of thermal expansion for the materials contacted.

For single chip packaging involving large volumes of merchandise, the damaged die is removed without significant loss. However, discarding a multi-chip package with only one damaged chip can be costly, and the ability to rework damaged components is a manufacturing benefit. At present, one of the fundamental motivations for the development of the semiconductor industry is not only to develop a packaging sealant that can satisfy all the requirements for protecting elements, but also to develop a packaging sealant that can be reworked so that damaged elements can be removed without damaging the substrate.

To achieve the desired mechanical properties and reworkability, relatively high molecular weight thermoplastics are a preferred component of packaging materials. However, these materials have a relatively high viscosity even in the form of solid films, which is a disadvantage for the production process. Thus, there is a need for new packaging sealant compositions that can be dispensed relatively easily to accommodate automated manufacturing processes, and that are secondary processable.

The present invention relates to curable package sealant compositions that include an allylated amide compound, a free radical curing agent, and/or a photoinitiator, and may also optionally include one or more fillers or other additives. The composition may optionally also contain mono-or polyfunctional vinyl compounds.

For the composition, the composition can be designed to be secondary processed by selecting a large amount of monofunctional compound for the composition.

In another embodiment, the present invention is directed to a cured sealant composition produced after curing of the above-described curable sealant composition.

In another embodiment, the present invention is directed to a microelectronic assembly comprising electronic components electrically and mechanically connected to a substrate, which is encapsulated in a cured encapsulant composition, wherein the cured encapsulant is prepared by curing a composition comprising one or more allylated amide compounds, a free radical initiator and/or photoinitiator, and optionally also comprising one or more fillers and/or other additives. The composition may also optionally contain mono-or polyfunctional vinyl compounds.

In another embodiment, the present invention relates to a method for producing an electronic assembly comprising an electronic component mechanically and electrically connected to a substrate and encapsulated within a cured package sealant composition, the method comprising: (a) providing a curable package sealant composition; (b) sealing the electronic assembly with a curable package sealant composition; and (c) curing the composition in situ.

The allylated amides and vinyl compounds used in the package sealant compositions of the present invention are curable compounds in the sense that they are capable of polymerization, with or without crosslinking. The process used in this specification refers to polymerisation with or without cross-linking. As is understood in the art, the cross-linking process is the bridging joining of two polymer chains by an element, a molecular group or a compound, and generally occurs upon heating. As the density of crosslinking increases, the properties of the material can be transformed from thermoplastic to thermoset, thereby increasing the polymeric strength, heat resistance, electrical resistance, and resistance to solvents and other chemicals.

By careful selection of mono-or polyfunctional compounds and their amounts, it is possible to produce polymers with a wide range of crosslink densities ranging from viscous, elastic to tough vitrified polymers. The higher the proportion of polyfunctional compounds which participate in the reaction, the greater the crosslinking density. If thermoplasticity is desired, the packaging sealant of the invention can be prepared from monofunctional compounds to limit the crosslink density. However, small amounts of polyfunctional compounds may be added to impart some crosslinking and strength to the composition, provided that the amount of polyfunctional compound is limited to a level that does not detract from the desired thermoplastic properties. Within these parameters, the strength and elasticity of various package sealing materials can be tailored to the requirements of a particular end use.

The crosslink density can also be controlled to achieve a wide range of glass transition temperatures in the cured package sealant to withstand subsequent processing and handling temperatures.

In those instances where rework of the assembly is necessary, the thermoplastic composition should be selected so that the electronic component can be pried off of the substrate. Any residual package sealant can be easily removed after heating to become soft.

In the packaging sealant composition of the present invention, the allylated amide compound and, if used in combination with the allylated amide compound, the vinyl compound are present in the curable packaging sealant composition in an amount of 2 to 98% by weight, based on the organic components present (excluding any filler).

The package sealant composition also contains at least one free radical initiator, defined as a chemical species that can decompose into molecular fragments with high reactivity and often short lifetimes of one or more unpaired electrons, capable of initiating a chemical reaction by means of a chain-forming mechanism. The free radical initiator is present in an amount of 0.1 to 10%, preferably 0.1 to 3.0% by weight of the allylic amide compound or combination of allylic amide and vinyl compound (excluding fillers) of the free radical cure mechanism to produce rapid cure and long shelf life of the composition prior to cure. Preferred free radical initiators include peroxides such as butyl peroctoate and dicumyl peroxide and azo compounds such as 2, 2 '-azobis (2-methyl-propionitrile) and 2, 2' -azobis (2-methyl-butyronitrile).

Alternatively, the package sealant composition may include a photoinitiator such as sold under the trade name Irgacure by Ciba specialty Chemicals, in place of the free radical initiator, and the curing process may then be initiated by UV irradiation. The photoinitiator is present in an amount of 0.1 to 10%, preferably 0.1 to 3.0% by weight of the allylated amide or allylated amide and vinyl compound present (excluding fillers). In some cases, both photoinitiation processes and free radical initiation processes may be desirable. For example, the curing process may be initiated by UV irradiation, and in a subsequent processing step, the curing is completed by performing a radical curing process using a heating step.

Generally, these compositions cure at temperatures in the range of 50 ℃ to 250 ℃, and the curing process will take place over a period of time of less than 1 minute to 4 hours. As can be appreciated, the time and temperature cure profile can vary for various binder compositions, and different compositions can be designed to provide a cure profile suitable for a particular industrial production process.

Even when the package sealing material is required to have thermoplasticity, easy application is achieved by using a reactive oligomer or prepolymer of relatively low molecular weight and allowing it to cure in situ after application to the electronic components of the component and substrate. The use of the material in the uncured state results in higher processability and the resulting cured thermoplastic sealing material has higher mechanical properties.

For some packaging operations, inert inorganic fillers are used in the packaging encapsulant to adjust the coefficient of thermal expansion closer to that of the interconnect circuitry and to mechanically reinforce the circuit connections. Examples of thermally conductive fillers include silica, graphite, aluminum nitride, silicon carbide, boron nitride, diamond powder, and clay. These fillers are generally present in an amount of 20 to 80% by weight of the total package sealant composition.

Allylated amide compound

Allylated amide compounds suitable for use in the compositions of the invention have structures represented by the following general formulae A and B:or

As used throughout this specification, the symbol C (O) refers to a carbonyl group. For these particular formulae, when the lower case "n" is the integer 1, the compound is a monofunctional compound; and when the lower case "n" is an integer of 2 to 6, the compound is a polyfunctional compound.

Formula A represents compounds wherein:

R⁹is H, withAlkyl or alkyleneoxy of 1 to 18 carbon atoms, allyl, aryl or substituted aryl having the structure:

wherein R is¹⁰、R¹¹And R¹²Each independently of the other is H or an alkyl or alkyleneoxy radical having from 1 to 18 carbon atoms; each X is independently an aromatic group having the structures (I) - (V):

and Q is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species containing up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendant substituents or as part of the main chain in the chain and in which any heteroatom present may or may not be directly attached to X;

or Q is a urethane having the following structure:

wherein R is²Each independently an alkyl, aryl or aralkyl group having 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents; x is O, S, N or P; and n is 0 to 50;

or Q is an ester having the structure:

wherein R is³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents;

or Q is a siloxane having the structure:

-(CR¹ ₂)_e-[SiR⁴-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-

wherein R in each position¹The substituents are each independently H or an alkyl group having 1 to 5 carbon atoms, and R at each position⁴The substituents are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group, and e and g are each independently 1 to 10 and f is 1 to 50;

m is 0 or 1, and n is 1 to 6.

The general formula B represents compounds in which

R⁹Is H, or an alkyl or alkyleneoxy group having from 1 to 18 carbon atoms, or an allyl group, or an aryl or substituted aryl group having the structure:

wherein R is¹⁰、R¹¹And R¹²Each independently of the other is H or an alkyl or alkyleneoxy radical having from 1 to 18 carbon atoms;

z is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy, or arylthio species containing up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents as part of the pendant substituent or backbone and in which any heteroatom present may or may not be directly attached to K;

or Z is a urethane having the following structure:

wherein R is²Each independently an alkyl, aryl or aralkyl group having 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents; x is O, S, N or P; and n is 0 to 50; or Z is an ester having the structure:

or Z is a siloxane having the structure:

-(CR¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-

wherein R in each position¹The substituents are each independently H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group, and e and g are each independently 1 to 10 and f is 1 to 50;

k is an aromatic group selected from aromatic groups having the structures (VI) - (XIII) (although only one bond is drawn to represent the linkage to the aromatic group K, it should be considered to represent any number of such other bonds defined by n):wherein p is 1 to 100;wherein p is 1 to 100;

wherein R is⁵、R⁶And R⁷Are straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species containing up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents as part of the pendant substituent or backbone and in which any heteroatom present may or may not be directly attached to the aromatic ring; or R⁵、R⁶And R⁷Is a siloxane having the structure:

-(CR¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-

wherein R is¹The substituent is H or an alkyl group having 1 to 5 carbon atoms, and R at each position⁴The substituents are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group, e is 1 to 10 and f is 1 to 50;and (XIII)And m is 0 or 1 and n is 1 to 6.

Vinyl Compounds suitable for use in the adhesive compositions of the present invention have a structure represented by one of the following general formulae: [ M-X ]_m]_n-Q or [ M-Z_m]_n-K wherein m is 0 or 1 and n is 1-6. M represents a vinyl group and may be a maleimide moiety having the structure:wherein R is¹Is H or C₁-C₅Alkyl groups of (a); or a vinyl moiety having the structure:

wherein R is¹And R²Is H or an alkyl group having 1 to 5 carbon atoms, or they form a5 to 9 membered ring together with the carbon forming the vinyl group; b is C, S, N, O, C (O), O-C (O), C (O) -O, C (O) NH or C (O) N (R)⁸) Wherein R is⁸Is C₁-C₆Alkyl group of (1). Preferably B is O, C (O), O-C (O), C (O) -O, C (O) NH or C (O) N (R)⁸) (ii) a More preferably B is O, C (O), O-C (O), C (O) -O or C (O) N (R)⁸)。

X is independently an aromatic group having structures (I) - (V):and

preferably X is structure (II), (III), (IV) or (V), more preferably X is structure (II).

Q and Z may each independently be a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species containing up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendant substituents or as part of the backbone and in which any heteroatom present may or may not be directly attached to X;

or Q and Z may each independently be a urethane having the following structure:

or Q and Z may each independently be an ester having the structure:

or Q and Z are each independently a siloxane having the structure:

-(CR¹ ₂)_e-[SiR₄-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-

wherein R in each position¹The substituents are each independently H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are each independently an alkyl radical having 1 to 5 carbon atoms or an aryl radical, and e and g are each independently1-10 and f is 1-50.

Preferably, Q and Z are linear or branched alkyl, alkoxy, alkylene, or alkyleneoxy species containing up to about 100 atoms in the chain, containing saturated or unsaturated cyclic or heterocyclic pendant substituents as described above or said siloxanes, and more preferably, Q and Z are said linear or branched alkyl species or siloxanes.

K is an aromatic group having the structures (VI) to (XIII) (although only one bond is shown to represent the linkage to the aromatic group K, it should be understood that it represents any number of other bonds defined by n):wherein p is 1 to 100;wherein p is 1 to 100;

wherein R is⁵、R⁶And R⁷Are straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species containing up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents or as pendant substituents or as part of the backbone and in which any heteroatom present may or may not be directly attached to the aromatic ring; or R⁵、R⁶And R⁷Is a siloxane having the structure: - (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-

Wherein R is¹The substituent being H or an alkyl radical having 1 to 5 carbon atoms, R in each position⁴The substituents are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group, and e is 1 to 10 and f is 0 to 50;and (XIII)

Preferably K is structure (VIII), (X) or (XI); more preferably K is structure (X) or (XI); most preferably, K is structure (X).

Other composition ingredients

The composition may also contain a coupling agent, depending on the nature of the substrate. Coupling agents, as used herein, are chemical species containing a polymeric functional group for reaction with maleimides and other vinyl compounds and a functional group capable of condensing with metal hydroxides present on the substrate surface. Such coupling agents and preferred amounts for use in compositions for particular substrates are well known in the art. Suitable coupling agents are silanes, silicates, metal acrylates or methacrylates, titanates, and compounds containing a chelating ligand, such as phosphine, mercaptans and acetoacetic acid. If present, the coupling agent is generally used in an amount of up to 10% by weight, preferably 0.1 to 3.0% by weight, based on the maleimide and other monofunctional vinyl compounds.

In addition, the composition may contain compounds that impart additional flexibility and toughness to the resulting cured composition. Such compounds may be any thermosetting and thermoplastic materials having a Tg of less than or equal to 50 ℃ and they are generally polymeric materials characterized by being freely rotatable about chemical bonds such as may be obtained in the presence of carbon-carbon double bonds adjacent to a carbon-carbon single bond, in the presence of ester and ether groups, and in the absence of a ring structure. Suitable such modifiers include polyacrylates, poly (butadiene), poly-THF (polymeric tetrahydrofuran), CTBN (carboxy-terminated nitrile butadiene) rubber and polypropylene glycol. If included, these toughening compounds may be used in amounts of about 15% by weight of the maleimide and other monofunctional vinyl compounds.

Silicones may also be added to the composition to impart elasticity. Suitable siloxanes are isobutyleneoxypropyl terminated polydimethylsiloxanes, and aminopropyl terminated polydimethylsiloxanes, which are commercially available from United Chemical Technologies.

The composition may also contain organic fillers, such as polymers, to adjust flowability. Other additives known and used in the art may also be used for special purposes, such as adhesion promoters. The selection of the appropriate type and amount of such materials is within the skill of one of ordinary skill in the art.

Example 1

Preparation of bisphenol F-bis (diallylamide)

Bisphenol F (200.3g, 1mol) was dissolved in Tetrahydrofuran (THF) (500mL) in a 2L three-necked flask equipped with a mechanical stirrer and reflux condenser. To this solution was added 1, 2-epoxy-9-decene (308.5g, 2mol) and benzyldimethylamine (0.67g, 5 mmol). The solution was warmed to 80 ℃ for 7 hours and then allowed to cool to room temperature. The solvent was removed in vacuo to yield an oil.

The intermediate isolated above (508.8g, 1mol) was dissolved in THF (1L) and H in a 3L three-necked flask equipped with mechanical stirrer, reflux condenser and internal temperature probe under nitrogen atmosphere₂O (1L). To this solution KMnO was added₄(316g, 2mol) and the resulting mixture was warmed to 80 ℃ for 5 hours. The reaction solution was cooled to room temperature and most of the solvent was removed in vacuo. Dissolving the obtained substance in CH₂Cl₂(1L) filtration and use of H₂O (3X 1L) wash. Separating the organic layer with MgSO 2₄Dried and the solvent removed in vacuo to yield an intermediate diacid.

The above diacid (544.8g, 1mol) is reacted with diallylamine (194.3g, 2mol) and CH in a 3L three-necked flask equipped with a mechanical stirrer, addition funnel and internal temperature probe under nitrogen₂Cl₂(1L) mixing. The solution was cooled to 4 ℃ in an ice bath. Will dissolve in CH₃Cl₂Dicyclohexylcarbodiimide (DCC) (412.7g, 2mol) (300ml) was charged to the addition funnel and the solution was added to the stirred amine solution over a period of 60 minutes. The reaction was stirred on an ice bath for an additional 30 minutes. The mixture was allowed to warm to room temperature and stirred for a further 4 hours. The solution was filtered to remove precipitated Dicyclohexylurea (DCU). The separated organic layer was washed with anhydrous MgSO₄Dried, filtered and the solvent removed in vacuo to yield the bis (diallylamide) product.

Example 2

Preparation of poly (butadiene) bis (diallylamide)

Diallylamine (97.15g, 1mol) was dissolved in acetone (500ml) in a 2L three-necked flask equipped with a mechanical stirrer, addition funnel and internal temperature probe under nitrogen. The solution was cooled on an ice bath. The addition funnel was charged with maleated poly (butadiene) (Ricon 131 MA5, Ricon resins inc., 1766g) dissolved in acetone (500ml) and added to the cooled amine solution over a period of 60 minutes while maintaining an internal temperature of < 10 ℃. The solution was stirred on an ice bath for a further 60 minutes, then allowed to warm to room temperature and stirred for a further 2 hours. The solvent and residual diallylamine were removed in vacuo to give the poly (diallylamide).

Example 3

The dimer bis (diallylamide) or 10, 11-dioctyl

Preparation of 1, 20-eicosylbis (diallylamides)

Dimer acid (sold under the trade name Empol 1024 by Unichema, 20.5g, 35.7mmol) was dissolved in anhydrous water in a 500ml four-necked flask equipped with a reflux condenser, an addition funnel and a magnetic stirrer under a nitrogen atmosphereToluene (250 ml). The solution was warmed to 80 ℃ and oxalyl chloride (12.5mL, 143mmol) was added dropwise over a period of 60 minutes. Will obviously generate CO immediately₂CO and HCl. After the addition was complete the reaction was stirred for an additional 3 hours, allowed to cool to room temperature and the solvent was removed in vacuo to yield an orange yellow oil. IR and¹the H NMR spectroscopic data was consistent with the desired product bis (acid chloride).

Diallylamine (10.0mL) was dissolved in diethyl ether (Et) in a 500mL three-necked flask equipped with a mechanical stirrer, addition funnel, and internal temperature probe under nitrogen₂O) (200 ml). Will dissolve in H₂O (100mL) NaOH (3.2g, 80mmol) was added to the solution. The solution was cooled to 4 ℃ on an ice bath. The above bis (acid chloride) was dissolved in Et₂O (20ml), was placed in an addition funnel and added to the stirred amine solution over a period of 30 minutes while maintaining an internal temperature < 10 ℃. The solution was stirred on an ice bath for an additional 1 hour, then allowed to warm to room temperature and stirred for an additional 4 hours. The organic layer was separated and washed with 5% aqueous HCl (200mL) and H₂O (2X 200mL) wash. The separated organic layer was washed with anhydrous MgSO₄Dried, filtered and the solvent removed in vacuo to yield an orange yellow oil (87%) with IR and¹the H NMR spectroscopic data was consistent with the required bis (diallylamide).

Example 4

Preparation of palmitoyl allylamide

Monoallylamide was prepared from allylamine (57.1g, 1mol), palmitoyl chloride (274.9g, 1mol), and NaOH (40g, 1mol) using the Schotten-Baumenn conditions described above for the synthesis of example 3.

Example 5

allylamide/BMI die attach adhesives

The following reagents were combined and mixed manually to produce a homogeneous chip mounting composition:

nonoyl bis (diallylamide)

(the same general procedure as in example 3 was used

Prepared from nonanedioyl dichloride and diallylamine) 0.521g

Bismaleimide (sold by Henkel as VersalinkP-650) 1.678g

Tert-butyl-2-ethylhexanoate 0.043g

Metal diacrylate (sold by Sartomer as product number 633) 0.023g

Gamma-methacryloxypropyl-trimethoxysilane 0.024g

Silver powder (from Chemet Corporation, RA-0081) 5.148g

An adhesive was used to bond an 80 x 80 mil silicon chip to the following various metal lead frames (Ag/alloy 42 refers to alloy 42, a Fe/Ni alloy of silver; Ag/Cu refers to copper plated silver). After curing for 60 seconds on a hotplate at 200 ℃ (condition 1) and after curing for 60 seconds on a hotplate at 200 ℃ (condition 2) after placing in an oven at 175 ℃ (condition 2), the die shear strength was determined at room temperature (RDSS, room temperature die shear strength) and at 240 ℃ (HDSS, hot die shear strength) using a model HMP 1750 die shear tester with a digital dynamometer DFI 50 (Chatillon). The results are reported here and show commercially acceptable chip shear values. Lead frame curing conditions 1 curing conditions 2

RDSS HDSS RDSS HDSSAg/alloy 421.720.875.650.92 Ag/Cu 2.150.584.650.74 Cu 1.760.483.600.85 Pd 1.941.184.561.25

Example 6

Preparation of benzamido-terminated dimer diamine bismaleimide

Dimer diamine (sold as Versamine 552 by Henkel, 20.0g, 37mmol) was dissolved in diethyl ether (Et) in a 500mL three-necked flask equipped with an addition funnel, magnetic stirrer, internal temperature probe and nitrogen inlet/outlet₂O) (200 ml). Aqueous NaOH (100mL H) was stirred vigorously₂11.7ml of O diluted, 6.25M solution, 73mmol) was added. The solution was placed in a steady flowing nitrogen atmosphere and cooled to 3 ℃ on an ice bath with stirring. Will dissolve in Et₂O (50mL) p-nitrobenzoyl chloride (13.6g, 73mmol) was charged to the addition funnel and the solution was added to the reaction vessel over a period of 60 minutes while maintaining an internal T < 10 ℃. After the addition was complete, the reaction solution was stirred at about 3 ℃ for another 60 minutes, then allowed to warm to room temperature and stirred for an additional 4 hours. The solution was transferred to a separatory funnel and the separated organic layer was washed with distilled water (300mL), 5% aqueous HCl (300mL), aqueous NaCl (250mL), and distilled water (2X 250mL) in that order. Separating organic substance with anhydrous MgSO₄Drying, filtering and removing the solvent in vacuo to yield the dinitro compound as a viscous yellow oil with acceptable properties¹H NMR and IR spectra (30.0g, 96%).

The dinitro compound (5.0g, 5.9mmol) was dissolved in methanol (MeOH) (25mL) and Tetrahydrofuran (THF) (5mL) in a 250mL three-necked flask equipped with a magnetic stirrer, reflux condenser and nitrogen outlet/inlet. The solution was placed under nitrogen and 5% Pd-C (0.96g) was added with stirring. Ammonium formate (3.4g, 55mmol) was added and the reaction solution was stirred at room temperature for 2 hours. The production of carbon dioxide was immediately observed. The reaction solution was filtered and most of the filtrate solvent was removed by rotary evaporator.The resulting viscous oil was dissolved in Et₂O (150mL), washed with distilled water (150mL), separated and MgSO 2 anhydrous₄And (5) drying. The solvent was removed in vacuo to give the diamine as a viscous brown oil with acceptable properties¹H NMR and IR spectra (3.9g, 84%).

Maleic anhydride (0.5g, 5.1mmol) was dissolved in acetone (10mL) in a 250mL three-necked flask equipped with a magnetic stirrer, addition funnel and nitrogen inlet/outlet. The solution was cooled on an ice bath and placed under a nitrogen atmosphere. A solution of the above diamine (2.0g, 2.60mmol) in acetone (10mL) was placed in an addition funnel and added dropwise to the reaction over 30 minutes. The reaction solution was stirred on an ice bath for a further 30 minutes, then allowed to warm to room temperature and stirred for a further 4 hours. Adding acetic anhydride (Ac) to the resulting slurry₂O) (1.54mL, 160mmol), triethylamine (Et)₃N) (0.23mL, 1.63mmol) and sodium acetate (NaOAc) (0.16g, 1.9 mmol). The resulting slurry was heated to moderate reflux for 5 hours. The reaction was cooled to room temperature and the solvent was removed by rotary evaporator to give a brown oil. Dissolving the material in CH₂Cl₂(250mL) and with distilled water (200mL), saturated NaHCO in that order₃(200mL) and distilled water (200 mL). Separating the organic layer with anhydrous MgSO₄Dried and the solvent removed in vacuo to yield bismaleimide as a brown solid (2.0g, 83%). The attached fat is satisfactory¹H NMR、¹³C NMR and IR spectra and showed trace amounts of acetic acid doping.

Example 7

Preparation of 20-bismaleimide-10, 11-dioctyl eicosane (and isomers)

Maleic anhydride (98.06g, equivalent to 1.02 equivalents of-NH) was placed in a 5L multi-necked flask equipped with a drying tube, thermometer, slow-addition funnel, mechanical stirrer and nitrogen purge₂) Dissolved in 500mL of tetrahydrofuran(THF). Stirring was started and the solution was cooled with a dry ice/water bath. Slow addition of dimer diamine (Versamine 552, Henkel, 245.03g, 0.4477mol) in 250mL THF was started. The addition was carried out within 1 hour. After the addition was complete the ice bath was removed and the solidified diamine was incorporated by rinsing with 375mL of THF through a slow addition funnel. After 1 hour the flask was replaced in the ice bath. 1-hydroxy-benzotriazole (96.79g, equivalent to 0.80 equivalent of-NH) was washed with 50ml THF₂) Added to the flask. When the temperature reached 5 deg.C, slow addition of Dicyclohexylcarbodiimide (DCC) (188.43g, equivalent to 1.02 equivalents of-NH) dissolved in 200mL THF was started₂). The temperature was kept below 10 degrees during the addition. After the addition of DCC was complete, the slow addition funnel was rinsed with 80mL THF. The ice bath was removed. The reaction solution was monitored by IR. When it appeared that the imide had been converted to maleimide (about 4 hours after the DCC addition was complete), the mixture was filtered while the solid was rinsed with THF. The orange-yellow solution was placed in a freezer overnight.

The solution was removed from the refrigerator and allowed to warm to room temperature. To this solution was added hydroquinone (0.0513 g). The partial removal of THF was carried out on a rotary evaporator with the temperature maintained below 28 ℃. The solution was concentrated to about 800 mL. A large number of particles were observed. The solution was placed in a freezer overnight.

The mixture was removed from the refrigerator and allowed to warm. The solid was filtered and rinsed with THF. The filtrate was transferred to a 2L multi-necked flask equipped with a mechanical stirrer, a vacuum tube connected to a trap and a glass tube connected to a drying tube. The remaining THF was removed at room temperature by applying a vacuum and by bubbling air through the mass with stirring. The thick creamy brown-yellow semisolid obtained was placed in a freezer overnight.

The semi-solid is removed from the freezer and warmed. The semi-solid was dissolved in 450mL each of methanol and hexane and washed with 50% methanol/water (4X 250mL) to remove 1-Hydroxybenzotriazole (HOBT). Attempts were made to extract the product with hexane. No delamination was observed after addition of 300mL of hexane. The mixture was additionally washed with water (3X 250 mL). The organic phase was placed in a freezer overnight.

The material was removed from the refrigerator. It is clearly divided into two layers. The upper layer is transparent and appears yellow. The bottom layer was orange-yellow and turbid. The material was allowed to cool and poured into a separatory funnel. The upper layer is the hexane layer and is the desired product. The bottom layer was extracted with hexane (6X 200mL) and was easily separated. The combined extracts were dried over anhydrous magnesium sulfate and filtered while the solid was washed with hexane. The solvent was separated off in a volume of about 750ml on a rotary evaporator at a temperature not exceeding 24 ℃. The remaining solvent was removed using a vacuum/air foaming device at room temperature to give the desired product in 67% yield.

Example 8

Preparation of butadiene-acrylonitrile bismaleimide

Amino-terminated butadiene-acrylonitrile (sold as Hycar resin 1300X 42ATBN by BF Goodrich, where m and n are integers giving a number average molecular weight of 3600) (450g, 500mmol, based on the amine equivalent AEW 450 g) was dissolved in CHCl in a 3L four-necked flask equipped with an addition funnel, mechanical stirrer, internal temperature probe and nitrogen inlet/outlet₃(1000 mL). The stirred solution was placed in a nitrogen atmosphere and cooled on an ice bath. Will dissolve in CHCl₃Maleic anhydride (98.1g, 1mol) (50ml) was charged into the addition funnel and the solution was added to the reaction over a period of 30 minutes while maintaining the internal temperature below 10 ℃. The mixture was stirred on ice for 30 minutes, then allowed to warm to room temperature and stirred for an additional 4 hours. Adding acetic anhydride (At) to the resulting slurry₂O) (653.4g, 6mol), triethylamine (Et)₃N) (64.8g, 0.64mol) and sodium acetate (NaOAc) (62.3g, 0.76 mol). The reaction solution was heated to moderate reflux for 5 hours, allowed to cool to room temperature, and then successively treated with H₂O (1L), saturated NaHCO₃(1L) and H₂O (2X 1L) extraction. The solvent was removed in vacuo to yield maleimide-terminated butadiene acrylonitrile.

Example 9

Preparation of tris (maleimide) derived from tris (epoxypropyl) isocyanurate

Tris (epoxypropyl) isocyanurate (99.0g, 0.33mol) was dissolved in THF (500mL) in a 2L three-necked flask equipped with a mechanical stirrer, internal temperature probe and nitrogen inlet/outlet. To this solution was added hydroxyphenylmaleimide (189.2g, 1mol) and benzyldimethylamine (1.4g, 0.05 wt%). The solution was heated to 80 ℃ for 7 hours. The reaction solution was then cooled to room temperature, filtered and washed with 5% aqueous HCl (500mL) and distilled H₂The filtrate was washed with O (1L). The resulting solid triazinetris (maleimide) was dried under vacuum at room temperature.

Example 10

Preparation of Maleimidoethyl palmitate

Palmitoyl chloride (274.9g, 1mol) was dissolved in Et in a 2L three-necked flask equipped with a mechanical stirrer, internal temperature probe, addition funnel and nitrogen inlet/outlet₂O (500 mL). Adding the solution into distilled H under the condition of vigorous stirring₂O (500mL) NaHCO₃(84.0g, mol) and the solution was cooled on an ice bath under a nitrogen atmosphere. Will dissolve in Et₂O (100mL) hydroxyethylmaleimide (141g, 1mol) was charged to the addition funnel and the solution was added to the reaction over 30 minutes while maintaining an internal T < 10 ℃ during the addition. The reaction solution was stirred on ice for another 30 minutes, then allowed to warm to room temperature and stirred for 4 hours. The reaction solution was transferred to a separatory funnel and in turnThe separated organic layer was washed with distilled water (500mL), 5% aqueous HCl (500mL), and distilled water (500 mL). Separating the organic layer with anhydrous MgSO₄Dried, filtered and the solvent removed in vacuo to yield the aliphatic maleimide.

Example 11

From 5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-tris

Preparation of methylcyclohexane-derived bismaleimide

5-isocyanato-1- (isocyanatomethyl) -1, 3, 3-trimethylcyclohexane (111.15g, 0.5mol) is dissolved in THF (500mL) in a 1L three-necked flask equipped with mechanical stirrer, addition funnel and nitrogen inlet/outlet. The reaction solution was placed in a nitrogen atmosphere and dibutyl tin dilaurate (catalyst Sn11) (6.31g, 10mol) and hydroxyethyl maleimide (141g, 1mol) were added with stirring, and the resulting mixture was heated at 70 ℃ for 4 hours. Hydroxyethylmaleimide (141g, 1mol) in THF (100ml) was charged to the addition funnel. This solution was added to the isocyanate solution over a period of 30 minutes and the resulting mixture was heated at 70 ℃ for an additional 4 hours. The reaction solution was cooled to room temperature and the solvent was removed in vacuo. The remaining oil was dissolved in CH₂Cl₂(1L) with 10% aqueous HCl (1L) and distilled H₂O (2X 1L) wash. The separated organic phase was washed with MgSO₄Dried, filtered and the solvent removed in vacuo to yield the maleimide.

Example 12

Preparation of dimeric divinyl ethers derived from Pripol 2033"dimer divinyl ether" (and cyclic isomers)

In a nitrogen atmosphere, in an assemblyIn a 2L three-necked flask with a mechanical stirrer, bis (1, 10-phenanthroline) Pd (OAc)₂(0.21g, 0.54mmol) was dissolved in a mixture of butyl vinyl ether (8.18g, 81.7 mmoles), heptane (100mL) and "dimer diol" (sold as Pripol 2033 by Unichema, 15.4g, 27.2 mmol). The solution was heated to gentle reflux for 6 hours. The solution was allowed to cool to room temperature and then poured onto activated carbon (20g) and stirred for 1 hour. The resulting slurry was filtered and the excess butyl vinyl ether and heptane were removed in vacuo to yield divinyl ether as a yellow oil. The product has acceptable properties¹H NMR, FT-IR and¹³c NMR spectral features. Typically, the viscosity is 100 cPs.

Example 13

Preparation of dimer diacrylate derived from dimer diol (Pripol 2033)

Dimer diol (sold as Pripol 2033 by Unichema, 284.4g, 500mmol) was dissolved in anhydrous acetone (500mL) in a 1L three-necked flask equipped with a mechanical stirrer, addition funnel and internal temperature probe under nitrogen. To this solution was added triethylamine (101.2g, 1mol) and cooled to 4 ℃ on an ice bath. Acryloyl chloride (90.5g, 1mol) dissolved in anhydrous acetone (100mL) was charged to the addition funnel and added to the stirred reaction solution over a period of 60 minutes while maintaining an internal temperature < 10 ℃. The solution was stirred on ice for an additional 2 hours, then allowed to warm to room temperature and stirred for 4 hours. Most of the solvent was removed by rotary evaporator and the remaining residue was dissolved in CH₂Cl₂(1L). With 5% aqueous HCl (800mL) and H₂The solution was washed with O (2X 800 mL). The separated organic phase was washed with MgSO₄Dried, filtered and the solvent removed in vacuo to give the diacrylate as an oil.

Example 14

Preparation of N-ethylphenylmaleimide

4-Ethylaniline (12.12g) was dissolved in 50ml of anhydrous ether and slowly added to a stirred solution of 9.81g of maleic anhydride in 100ml of anhydrous ether cooled on an ice bath. After the addition was complete, the reaction mixture was stirred for 30 minutes. The pale yellow crystals were filtered off and dried. Acetic anhydride (200ml) was used to dissolve maleamic acid and 20g of sodium acetate. The reaction mixture was heated in an oil bath at 160 ℃. After refluxing for 3 hours, the solution was cooled to room temperature, placed in a 1L beaker in ice water and stirred vigorously for 1 hour. The product was filtered off with suction and recrystallized from hexane. The collected crystals were dried at 50 ℃ and placed in a vacuum oven overnight. FTIR and NMR analysis showed the characteristics of ethylmaleimide.

Example 15

Preparation of bis (alkylene sulfides)

Dimer acid (sold under the trade name Empol 1024 by Unichema) (574.6g, 1mol) and propargyl alcohol (112.1g, 2mmol) were dissolved in toluene (1L) in a 3L three-necked flask equipped with a mechanical stirrer and a Dean-Stark distiller. Adding concentrated H₂SO₄(6mL) and the solution was allowed to reflux for 6 hours until 36mL of H was azeotropically distilled off₂And (4) O. The solution was cooled to room temperature and washed with H₂O (2X 1L) Wash, anhydrous MgSO₄Dried and the solvent removed in vacuo to yield the intermediate product, i.e., a bulk propyl ester, as an oil.

The intermediate ester (650.7g, 1mol) was dissolved in THF (200mL) in a 1L three-necked flask equipped with a reflux condenser, mechanical stirrer and internal temperature probe under nitrogen. Lauryl mercaptan (404.8g, 2mol) and 2, 2' -azobis (2, 4-dimethylvaleronitrile) (sold by DuPont under the trade name Vazo 52) were added and the resulting mixture heated to 70 ℃ in an oil bath with constant stirring for 7 hours. The reaction solution was allowed to cool to room temperature and the solvent was removed in vacuo to give the alkylene sulfide as an oil.

Example A

Preparation of 6-maleimidocaproic acid

6-Maleimidohexanoic acid

The acid-functional maleimide, i.e., 6-maleimidocaproic acid, was synthesized using the well-known method 1. Aminohexanoic acid (100g, 7.6X 10) was placed in a 500mL four-necked flask equipped with a mechanical stirrer, internal temperature probe, and addition funnel^-1mols) was dissolved in glacial acetic acid (50 mL). Maleic anhydride (74.8g, 7.6X 10) dissolved in acetonitrile (75mL)^-1mols) was added to the addition funnel. The solution was added dropwise to aminocaproic acid at room temperature over a period of 1 hour while maintaining the internal reaction temperature below 35 ℃. The reaction solution was stirred for 3 hours after the addition process was completed. The reaction slurry was filtered and the isolated filtrate was dried overnight at 70 ℃ in a vacuum box (P-25 torr) to yield 166g of an off-white solid (95%). Product amic acid exhibits FT-IR and¹the H NMR spectral characteristics fit the data in the literature.

The amic acid described above (166g, 7.2X 10) was placed in a 1L three-necked flask equipped with a mechanical stirrer and a Dean-Stark trap under a nitrogen atmosphere^-1mols) was dissolved in a solution of toluene (200mL), benzene (200mL), and triethylamine (211mL, 1.51 mol). The solution was heated to reflux for 4 hours and the resulting water was collected with a Dean-Stark trap. Distilled water (400mL) was added to the reaction flask to dissolve the product triethylammonium salt, which was isolated primarily from the solution during the reaction. The aqueous layer was separated, acidified to pH-1 with 50% HCl and extracted with ethyl acetate (600 mL). The organic layer was washed with distilled water (400 mL). With MgSO₄The separated organic layer was dried, followed by removal of the solvent in vacuo to yield an off-white solid (76.2g, 50%). The product 6-maleimido determined by SpectroscopyFT-IR and of hexanoic acid with literature material¹H NMR was consistent.

Example B

Preparation of "dimer diester bismaleimide

"dimer diester bismaleimide" (and cyclic isomers)

Pripol 2033 ("dimer diol", Uniquema, 92.4g, 1.69X 10) in a 1L four-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and an internal temperature probe under nitrogen^-1mols), 6-maleimidocaproic acid (75.0g, 3.55X 10)^-1mols) and H₂SO₄(0.50mL，～8.5×10^-3mols) was slurried in toluene (300 mL). The reaction solution was heated to slight reflux for 2 hours and the resulting water was collected with a Dean-Stark trap. The water in the trap was drained and-50 mL of toluene solvent was distilled from the reaction to remove traces of water and to drive the esterification reaction to equilibrium. The reaction was cooled to room temperature, additional toluene (100mL) was added (in which case diethyl ether is preferably added instead of toluene if it is on a laboratory scale) and saturated NaHCO was used₃The solution was washed with aqueous solution (300mL) and distilled water (300 mL). The organic layer was separated and MgSO 2 anhydrous₄Dried, and the solvent removed in vacuo to yield an orange-yellow oil (107.2g, 68%). The material was further purified by eluting a toluene solution of this resin through a short column of silica gel and alumina. The liquid bismaleimide resin has acceptable FT-IR,¹H NMR and¹³c NMR data. Generally eta.2500 cPs.

Example C

Preparation of "decanediol diester bismaleimide

"Decanediol diester bismaleimide" the general procedure described in example B was used with decandiol (29.5g, 1.69X 10)^-1mols) instead of Pripol 2033. This process yielded a solid, moderately soluble bismaleimide (54.9g, 58%). The product showed satisfactory FT-IR and¹h NMR data.

Example D

Preparation of "Triglycerides Tri (Maleimide)

The protocol described in example B was used while using glycerol (10.4g, 1.13X 10-¹mol) instead of Pripol 2033. The product was a viscous liquid with acceptable FT-IR and¹h NMR data.

Example E

Preparation of "bis (m-nitrobenzyl carbamate) of IPDI

"bis (m-nitrobenzyl carbamate) of IPDI"

Isophorone diisocyanate ("IPDI", 100.0g, 4.5X 10) was placed in a 2L three-necked flask equipped with a mechanical stirrer, reflux condenser and internal temperature probe under nitrogen^-1mols), m-nitrobenzyl alcohol (137.8g, 9.0X 10)^-1mols) and dibutyltin dilaurate (2.8g, 4.5X 10^-3mols) was dissolved in anhydrous toluene (1500 mL). The resulting solution was heated to 90 ℃ for 4 hours. No bands of isocyanate were observed in the IR of the solid portion of the sample. The solution was cooled to room temperature and washed with distilled water (100 mL). The organic layer was separated and the solvent removed in vacuo to yield a yellow liquid with acceptable FT-IR and¹H NMR characteristics.

Example F

Preparation of "bis (m-aminobenzyl carbamate) of IPDI

"bis (m-aminobenzyl carbamate) of IPDI"

The dinitro compound of example E (8.28g, 1.57X 10 g) was placed in a 500ml three-necked round-bottomed flask equipped with a magnetic stirrer under nitrogen^-2mols) was dissolved in ethanol (100 ml). Cyclohexene (28.6ml, 2.82X 10) was added^-1mols) and then 5% Pd/C (4.14g) was added. The resulting slurry was refluxed slightly for 6.5 hours. An aliquot of this solution had a FT-IR at 1529cm^-1And 1352cm^-1No nitro extension vibrational lines are shown. The bulk solution was cooled to room temperature and filtered. Removal of the solvent in vacuo yielded a yellow semisolid (6.6g, 90%) which showed acceptable FT-IR and¹h NMR spectral characteristics.

Example G

Preparation of "bis (m-maleimidobenzylcarbamate) of IPDIBis (m-maleimidobenzyl carbamate) of IPDI

The diamine of example F (6.6g, 1.41X 10) was placed in a 250ml four-necked flask equipped with a magnetic stirrer and an addition funnel under nitrogen^-2mols) was dissolved in acetone (60ml) and cooled to 4 ℃. Maleic anhydride (2.76g, 2.82X 10) dissolved in acetone (20ml) was added over 30 minutes^-2mols). The resulting solution was stirred at 4 ℃ for 1 hour, then allowed to warm to room temperature and stirred overnight. FT-IR analysis showed that the peak intensity was at-1810 cm^-1The absence of the extensional vibrational lines of anhydride was judged to be the absence of residual maleic anhydride.

Acetic anhydride (8.5) was added to the amic acid solution aboveml，9.0×10^-2mols), Triethylamine (1.26ml, 9.0X 10)^-3mols) and sodium acetate (0.88g, 1.1X 10)^-2mols). The resulting solution was refluxed slightly under nitrogen for 4 hours. The reaction was allowed to cool to room temperature and most of the solvent was removed in vacuo. The resulting viscous liquid was dissolved in methylene chloride (200ml) and extracted with distilled water (3X 200 ml). Then using anhydrous MgSO₄The organics were dried, filtered and the solvent removed in vacuo to yield a light brown solid (6, 75g, 76%). This material exhibited acceptable FT-IR and¹h NMR spectral characteristics.

Example H

Preparation of "bis (m-nitrobenzyl carbamate) of DDI1410

"bis (m-nitrobenzylcarbamate) of DDI 1410" (and cyclic isomers)

DDI1410(Henkel, "dimer diisocyanate", 99.77g, 1.65X 10 based on 13.96% NCO, in a 1L four-necked flask equipped with a mechanical stirrer, reflux condenser and internal temperature probe under nitrogen^-1mols), m-nitrobenzyl alcohol (50.8g, 3.32X 10)^-1mols) and dilauryl dibutyl tin (0.5ml, 8.3X 10)^-4mols) was dissolved in toluene (150 ml). The reaction mixture was heated to 85 ℃ for 2.5 hours. FT-IR analysis of an aliquot of the reaction mixture showed that the concentration was 2272cm^-1The lack of spectral lines judged complete consumption of isocyanate functionality. The solvent was removed from the reaction in vacuo to yield a yellow oil (152.4g, 102% (trace toluene)) which solidified at room temperature. The solids exhibited satisfactory FT-IR and¹HNMR spectral characteristics.

Example I

Preparation of "bis (m-aminobenzyl carbamate) of DDI 1410")

"bis (m-nitrobenzylcarbamate) of DDI 1410" (and cyclic isomers)

The diamine product of example H (39.6g, 4.32X 10) was placed in a 1L three-necked flask equipped with mechanical stirrer and reflux condenser under nitrogen^-2mols) and stannous chloride dihydrate (97.55g, 4.32X 10)^-1mols) was slurried in ethyl acetate (300 ml). The reaction mixture was heated to mild reflux and stirred vigorously for 3 hours. The solution was allowed to cool to room temperature and adjusted to pH7-8 with saturated sodium bicarbonate solution. The mixture was passed through a 25 micron filter and the resulting mixture was separated into a cloudy aqueous layer and a moderately clear organic layer. The aqueous layer was separated and washed with ethyl acetate (100 ml). The organic layers were combined, washed with distilled water (300ml), and anhydrous MgSO₄And (5) drying. The slurry was filtered and the solvent removed from the filtrate in vacuo to yield a yellow sticky solid (33.8g, 92%).

Example J

Preparation of "bis (m-maleimidobenzylcarbamate) of DDI1410

"bis (m-maleimidobenzylcarbamate)" of DDI1410 (and cyclic isomers)

Maleic anhydride (15.4g, 1.57X 10) was placed in a 2L four-necked flask equipped with a mechanical stirrer, internal temperature probe and addition funnel under nitrogen^-2mols) was dissolved in acetone (300 ml). The solution was cooled to about 4 ℃ on an ice bath. The diamine prepared in example I (63.4g, 7.48X 10) was added in 30 min²mols) in acetone (70ml) was added to the maleic anhydride solution from an addition funnel, maintaining the internal temperature below 10 ℃. The resulting solution was stirred for 1 hour, then allowed to warm to room temperature and stirred for 2 hours.

To the amic acid solution was added acetic anhydride (24.7ml, 2.62X 10)^-1mols), Triethylamine (6.25ml, 4.48X 10)^-8mols) and manganese acetate tetrahydrate (0.37g, 1.50X 10^-3mols). The solution was heated to gentle reflux for 6.5 hours and then allowed to cool to room temperature. Most of the solvent was removed in vacuo and the resulting black liquid was dissolved in diethyl ether (500 ml). The solution was washed with distilled water (500 ml). The separated organic layer was then washed successively with saturated aqueous sodium bicarbonate (500ml) and distilled water (500 ml). Isolating the organics with anhydrous MgSO₄Drying and removal of the solvent in vacuo yielded a viscous orange-yellow oil. FT-IR exhibited by such a substance,¹H NMR and¹³the C NMR spectral characteristics were consistent with the expected bismaleimide product.

Another embodiment of the present invention includes a package sealant comprising an allylamide compound having the structure:orWherein Q and Z may be an ester of the structureOr is

Wherein p is a number from 1 to 100,

each R³May independently be an alkyl or alkoxy chain having up to 100 atoms in the chain and which may contain aryl substituents, or

A siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group containing 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

The inventionAnother embodiment of (a) includes the maleimides described herein, having the formula [ M-X_m]_n-Q and [ M-Z_m]_n-K, wherein Q and Z can be an ester of the structureOr is

Wherein p is a number from 1 to 100,

A siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50. Another embodiment of the present invention includes the vinyl compounds described herein having the structureAndwherein B is C, S, N, O, C (O), C (O) NH or C (O) N (R)⁸) Wherein R is⁸Is C₁To C₆An alkyl group. Another embodiment of the present invention includes an ethylene compound as described herein having the structureAndwherein Q and Z may be an ester of the structureOr is structured as

Wherein p is a number from 1 to 100,

each R³May independently be an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents:

or a siloxane of the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

Another embodiment of the present invention includes a package sealant as described herein comprising an anionic or cationic cure initiator. The type and amount of these initiators are known in the art.

Other embodiments of the invention include those described in the following sections.

1. A package sealant comprising an allylated amide compound; a curing initiator selected from the group consisting of free radical initiators, photoinitiators, and combinations thereof; optionally one or more fillers and one or more adhesion promoters;

the allylated amide compound has the formula

Wherein m is 0 or 1, n is 1 to 6, and

(a)R³is H, an alkyl group having 1 to 18 carbon atoms, an alkyleneoxy group having 1 to 18 carbon atoms, an allyl group, an aryl group, or a substituted aryl group having the structureWherein R is¹⁰、R¹¹And R¹²Independently H or alkyl having 1 to 18 carbon atomsOr an alkyleneoxy group; (b) x is an aromatic group selected from the group consisting of aryl groups of the following structures:and

(c) q is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species having up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups on the chain or as part of the chain and any heteroatom present therein may or may not be directly attached to X.

2. A packaging sealant containing an allylated amide compound according to section 1, wherein Q is a linear or branched alkyl group having up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendant from the chain or as part of the chain, and wherein any heteroatom present may or may not be directly attached to X.

3. The packaging sealant containing an allylated amide compound according to section 1, wherein Q is a urethane having the structure

Wherein R is²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and may contain aryl substituents; x is O, S, N or P; and v is 0 to 50.

4. The packaging sealant containing an allylated amide compound according to section 1, wherein Q is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl group having 1 to 5 carbon atoms, or an aryl group, e and g are independently 1 to 10, and f is 1 to 50.

5. The packaging sealant containing an allylated amide compound according to section 1, wherein Q is an ester having the structure:

wherein R is³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents.

6. The packaging sealant according to section 1 containing an allylated amide compound, wherein Q is an ester having the structure:

wherein p is a number from 1 to 100,

each R³May be solely an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents;

7. The packaging sealant according to section 1 containing an allylated amide compound, wherein Q is an ester having the structure:

wherein p is a number from 1 to 100,

each R³May independently be an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents;

8. A package sealant comprising an allylated amide compound; a curing initiator selected from the group consisting of free radical initiators, photoinitiators, and combinations thereof; and optionally one or more fillers and one or more adhesion promoters;

the allylated amide compound has the formula

Wherein m is 0 or 1, n is 1 to 6, and

(a)R⁹is H, an alkyl or alkyleneoxy radical having from 1 to 18 carbon atoms, an allyl radical, an aryl radical, or a substituted aryl radical having the structure

Wherein R is¹⁰、R¹¹And R¹²Independently H or an alkyl or alkyleneoxy group having 1 to 18 carbon atoms; (b) k is an aryl group selected from the aryl groups of the following structures:wherein p is 1 to 100;wherein p is 1 to 100;

wherein R is⁵、R⁶And R⁷Is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species having up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups on the chain or as part of the backbone in the chain and in which any heteroatom present may or may not be attached directly to the aromatic ring; or

R⁵、R⁶And R⁷Is a siloxane having the structure of- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-, wherein R¹The substituent being H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e is 1 to 10, f is 1 to 50;and (XIII)

And

(c) z is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species having up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups on the chain or as part of the chain and any heteroatom present therein may or may not be directly attached to K.

9. The packaging sealant containing an allylated amide compound according to section 8, wherein Z is a linear or branched alkyl group having up to about 100 atoms in the chain, which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendant from the chain or as part of the chain, and wherein any heteroatom present may or may not be directly attached to K.

10. The packaging sealant containing an allylated amide compound according to section 8, wherein Z is a urethane having the structure

Wherein each R²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and which may contain aryl substituents; x is O, S, N or P; and v is 0 to 50.

11. The packaging sealant containing an allylated amide compound according to section 8, wherein Z is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_k-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

12. The packaging sealant containing an allylated amide compound of section 8, wherein Z is an ester having the structure:

13. The packaging sealant containing an allylated amide compound of section 8, wherein Z is an ester having the structure:wherein p is a number from 1 to 100,

14. The packaging sealant containing an allylated amide compound of section 8, wherein Z is an ester having the structure:wherein p is a number from 1 to 100,

15. The packaging sealant according to any of sections 8 to 14, which contains an allylated amide compound, wherein K isWherein p is 1 to 100;

16. the packaging sealant according to any of sections 8 to 14, which contains an allylated amide compound, wherein K isWherein R is⁵、R⁶And R⁷Is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy,Alkylene amines, alkylene sulfides, aryl, aryloxy, or aryl sulfides, having up to about 100 atoms in the chain, may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent to the chain, or as part of the chain, and wherein any heteroatom present may or may not be directly attached to the aromatic ring.

17. The packaging sealant comprising an allylated amide compound according to any of paragraphs 8 to 14, wherein K is

18. The package sealant according to any one of sections 1 to 17, wherein the curing initiator is selected from anionic and cationic initiators.

19. A package sealant according to any of sections 1 to 18, further comprising a compound having the following structure:orWherein m is 0 or 1, n is 1 to 6, and

(a)R¹and R²Is H, or is an alkyl group having 1 to 5 carbon atoms, or together with the carbon atoms forming the vinyl group, forms a5 to 9 membered ring;

(b) b is C, S, N, O, C (O), C (O) NH or C (O) N (R)⁸) Wherein R is⁸Is an alkyl group having 1 to 5 carbon atoms;

(c) x is an aryl group selected from the group consisting of aryl groups of the following structures:and

and

(d) q is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent or as part of the chain and in which any heteroatom present may or may not be directly attached to X; or

(d) Q is a urethane having the structureWherein R is²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and may contain aryl substituents; x is O, S, N or P; and v is 0 to 50; or

(e) Q is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently alkyl or aryl groups having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(f) Q is an ester having the structure:

20. The packaging sealant of section 19, wherein Q is an ester having the structure:or isWherein p is 1 to 100, and

each R³May independently be an alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents; or

Each R³Can independently be a siliconAn alkylene oxide having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

21. A package sealant according to any of sections 1 to 18, further comprising a compound having the structure:orWherein m is 0 or 1, n is 1 to 6, and

(c) k is an aryl group selected from the group consisting of aryl groups of the following structures:wherein p is 1 to 100;wherein p is 1 to 100;wherein R is⁵、R⁶And R⁷Is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups on the chain or as part of the backbone in the chain and in which any heteroatom present may or may not be attached directly to the aromatic ring; or

R⁵、R⁶And R⁷Is a siloxane having the structure of- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-, wherein R¹The substituent being H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e is 1 to 10, f is 1 to 50;and (XII)And

(d) z is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent or as part of the chain and in which any heteroatom present may or may not be directly attached to K; or

(e) Z is a urethane having the structureWherein each R²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and may contain aryl substituents; x is O, S, N or P; and v is 0 to 50; or

(f) Z is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, the R4 substituent at each position is independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(g) Z is an ester having the structure:

22. A curable adhesive composition according to paragraph 21, wherein Z is an ester having the structure:or the following steps:

wherein p is 1 to 100, and

each R³May independently be an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents; or

Each R3 can independently be a siloxane of the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or alkyl having 1 to 5 carbon atoms, R at each position⁴The substituents are independently alkyl or aryl groups having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

23. A method of making an electronic assembly comprising an electronic component mechanically and electrically connected to a substrate and encapsulated in a cured encapsulant composition, the method comprising:

(a) there is provided a curable package sealant composition as set forth in any one of paragraphs 1 to 22,

(b) sealing the electronic assembly with a curable sealant composition; and is

(c) The composition is cured in situ.

24. An electronic assembly made according to the method described in section 23.

Claims

the allylated amide compound has the formula

Wherein m is 0 or 1, n is 1 to 6, and

(a)R⁹is H, having from 1 to 18 carbon atomsAlkyl, alkyleneoxy having 1 to 18 carbon atoms, allyl, aryl, or substituted aryl of the structureWherein R is¹⁰、R¹¹And R¹²Independently H or an alkyl or alkyleneoxy group having 1 to 18 carbon atoms;

(b) x is an aromatic group selected from aryl groups having the following structure:and

(c) q is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species having up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups or as part of the chain and wherein any heteroatom present may or may not be directly attached to X; or

(d) Urethane having the structure Q

Wherein R is²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and may contain aryl substituents; x is O, S, N or P; and v is 0 to 50; or

(e) Q is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl group having 1 to 5 carbon atoms, or an aryl group, e and g are independently 1 to 10, and f is 1 to 50.

(f) Q is an ester having the structure:

wherein R is³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents; or (g) Q is an ester having the structure:wherein p is a number from 1 to 100,

or a siloxane of the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(h) Q is an ester having the structure:wherein p is a number from 1 to 100,

2. A package sealant comprising an allylated amide compound; a curing initiator selected from the group consisting of free radical initiators, photoinitiators, and combinations thereof; and optionally one or more fillers and one or more adhesion promoters;

the allylated amide compound has the formulaWherein m is 0 or 1, n is 1 to 6, and

(a)R⁹is H, an alkyl or alkyleneoxy radical having from 1 to 18 carbon atoms, an allyl radical, an aryl radical, or a substituted aryl radical of the structureWherein R is¹⁰、R¹¹And R¹²Independently H or an alkyl or alkyleneoxy group having 1 to 18 carbon atoms;

(b) k is an aryl group selected from the group consisting of aryl groups of the following structures:wherein p is 1 to 100;wherein p is 1 to 100;

R⁵、R⁶And R⁷Is a siloxane having the structure of- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-, wherein R¹The substituent being H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e is 1 to 10, and f is 1 to 50.

And

(c) z is a straight or branched chain alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species having up to about 100 atoms in the chain which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent groups on the chain or as part of the chain and wherein any heteroatom present may or may not be directly attached to K; or

(d) Z is a urethane having the structureWherein R is²Independently an alkyl, aryl or aralkyl group having from 1 to 18 carbon atoms; r³Is an alkyl or alkoxy chain containing up to 100 atoms and which may contain aryl substituents; x is O, S, N or P; and v is 0 to 50; or

(e) Z is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having l to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(f) Z is an ester of the structure:wherein R is³An alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents;

(g) z is an ester having the structure:wherein p is a number from 1 to 100,

or is a siliconAn alkylene oxide having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(h) Z is an ester having the structure:wherein p is a number from 1 to 100,

3. A packaging sealant according to claim 1 or 2, wherein the curing initiator is selected from anionic and cationic initiators.

4. A package sealant according to any one of claims 1 to 3, further comprising a compound having the structure:or

Wherein m is 0 or 1, n is 1 to 6, and

(a)R¹and R²Is H, or is an alkyl radical having from 1 to 5 carbon atoms, or is reacted with to form BThe carbon atoms of the alkenyl group together form a5 to 9 membered ring;

and

(d) q is a straight or branched alkyl, alkoxy, alkylamine, alkylthio, alkylene, alkyleneoxy, alkyleneamine, alkylenethio, aryl, aryloxy or arylthio species which may contain saturated or unsaturated cyclic or heterocyclic substituents as pendent from, or as part of, the chain and wherein any heteroatom present may or may not be directly attached to X; or

(e) Q is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(f) Q is an ester of the structure:wherein R is³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain and may contain aryl substituents.

(g) Q is an ester having the structure;wherein p is a number from 1 to 100,

(h) Q is an ester having the structure:wherein p is 1 to 100, and

Each R³Can independently be a siloxane of the structure- (CR)¹ ₂)e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, wherein the R1 substituent at each position is independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

5. A package sealant according to any one of claims 1 to 4, further comprising a compound of the structure:orWherein m is 0 or 1, n is 1 to 6, and

R⁵、R⁶And R⁷Is a siloxane having the structure of- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CH₃)_g-, wherein R¹The substituent being H or an alkyl group having 1 to 5 carbon atoms, R in each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50;and (XII)And

(f) Z is a siloxane having the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, f is 1 to 50; or

(g) Z is an ester having the structure:wherein R is³Is an alkyl or alkoxy chain containing up to 100 atoms in the chain, which chain may contain aryl substituents; or

(h) Z is an ester having the structure:wherein p is a number from 1 to 100,

or a siloxane of the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, where R in each position¹The substituents are independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atomsE and g are independently 1 to 10, f is 1 to 50; or

(i) Z is an ester having the structure:wherein p is 1 to 100, and

each R³May independently be an alkyl or alkoxy group containing up to 100 atoms in the chain and may contain aryl substituents; or

Each R³Can independently be a siloxane of the structure- (CR)¹ ₂)_e-[SiR⁴ ₂-O]_f-SiR⁴ ₂-(CR¹ ₂)_g-, wherein the R1 substituent at each position is independently H or an alkyl group having 1 to 5 carbon atoms, R at each position⁴The substituents are independently an alkyl or aryl group having 1 to 5 carbon atoms, e and g are independently 1 to 10, and f is 1 to 50.

6. A method of making an electronic assembly comprising an electronic component mechanically and electrically connected to a substrate and sealed in a cured encapsulant composition comprising:

(a) there is provided a curable package sealant composition according to any one of 1 to 5,

(b) sealing the electronic assembly with a curable sealant composition; and is

(c) The composition is cured in situ.