TW200946560A - Multifunctional nitrones in non-radical systems - Google Patents

Abstract

This invention is a curable composition comprising a multifunctional nitrone and another compound, such as, acrylate, maleimide, cyanate ester, or epoxy. The nitrone undergoes crosslinking with the other compound through cycloaddition or by nitrone dipole mediated ring opening, without the sensitivity to oxygen suffered by free radical curing.

Description

200946560 IX. INSTRUCTIONS: [Technology Leading to the Invention] The present invention relates to an organic chemical system for using a schizophyllin to cure a non-radical intermediate, particularly for curing adhesives, coatings, and sealants. In the 5 ❹ 10 15 Ο - item specific examples - Adhesives, coatings, and seals _ used in electronic applications 先前 [Prior Art] Many curing chemistries used in current adhesives, coatings, and sealants involve free radicals. Triggered. The free radical m is oxygen-sensitive before or during m- ing, ίί::: has the disadvantage of significant shrinkage, resulting in avoiding such problems. [Inventive content] = Ming-a kind of curable composition, including - polyfunctional Compounds are considered to contain pre-forms, filaments, and polymers in the context of nitroxide and others. The compound = diterpene (four), cyanide, and oxygen (four). _ Ring plus ^ or open-loop induced by dipole, the gas experienced cross-linking with other compounds, but not! Free radical curing or crosslinking is subject to oxygen sensitivity. Nitrogen _ chemistry can provide a wide range of cured materials in nitrocellulose and ~ or guest compositions. 匕 1 匕 / visibility 0 curing temperature will depend on the 牿 naked 曰 i industry inside the 'lower curing temperature useful (for example, connected to the substrate _ bare *), the bottom surface), the surface of your package in the electronic package soldering electrical connection ', (at the temperature below the curing temperature B-stage chemistry); higher than 20 200946560 The curing temperature is used, for example, in the use of a curable composition in place of a metal soft solder. The stone ketone is a 1,3-dipole prepared by an easy step of the room temperature condensation reaction between the amine and the amine. As described here:

+

Nitronone is known to participate in the 1,3-dipolar cycloaddition reaction with diP〇lar〇philes (2 7Γ-partner) to produce a cycloadduct. The cycloaddition reaction is insensitive to oxygen and moisture and produces a five-membered ring called isoxazolidine: and/or 1,3 diisoisoxazole pyridinone can also initiate heterocyclic monomers by ring opening ( For example, epoxide

Polymer Co-use: r〇e^ © :>〇 The complex is prepared by reacting a polyfunctional nitrone with a polyfunctional 2 π-coupling. An example of this reaction is shown herein in which bis-sandimide is reacted with a difunctional nitrone. The reaction is at 75. (: Lower dimethylformamide (DMF): 6 15 200946560

❹ 5 10 Exemplary compounds suitable for curing with nitrones include, but are not limited to, compounds containing reactive functionalities with nitroketones such as epoxides, acetoacetic acid vinegar (which contains methacrylate), cis-butyl An enediminoimine (which contains a polyfunctional compound such as bis- and cis-m-butyleneimine), a cyanate ester, and a vinyl group (such as a bismuth bond and a ethene). Such functionality can be added to a wide variety of compounds such as polyesters, poly(butadiene), deuterated olefins, anthrone resins, oxanes, and other such materials. In one embodiment, the compound is selected from the group consisting of epoxides, acrylates, maleimide, and cyanate esters. Demonstration of solid aromatic bis-bis-butyl succinimide with nitrone

The amine (BMI) powder is of a structure wherein X is an aromatic group. Bis-butylene iminoimide resins having such X bridged groups are commercially available and are available, for example, from Sartomer (USA) and HOS-Technic GmbH (Austria). An additional demonstration of the use of a ketone with a ketone in the composition of a difenin containing 7 15 200946560

There is a general structure, 0 person, wherein η is 1 to 3 and X1 is an aliphatic or aromatic group. The X1 entity comprises poly(butadiene), poly(carbonate), poly(urethane), poly(ether), poly(ester), simple hydrocarbon, and contains functionalities such as carbonyl, carboxyl, guanamine, amine A simple hydrocarbon of a formate, urea, or ether. Compounds of this type are commercially available and are available, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc.

Particularly preferred maleimide containing

(c35)-〇- wherein C36 represents a linear or branched chain of 36 carbon atoms (with or without a cyclic moiety)

10 ❹ 8 200946560

Suitable acrylates for use in formulating with the inventive compounds include those having the same 'wherein n is 1 to 6, R1 is -H or -CH3, and χ2 is an aromatic or aliphatic group." Exemplary X2 group contains poly(butyl) Alkene, poly(carbonate), 5-poly(amine phthalate), poly(ether), poly(ester), simple hydrocarbon, and containing functional groups such as carbonyl, carboxyl, decylamine, carbamate, urea, Or a simple hydrocarbon of ether. Commercially available: The material comprises butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (f-)acrylate, and (M)acrylic acid. Lauryl ester, alkyl (meth) acrylate, tridecyl (meth) acrylate, n-octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, B 2-Hydroxy ester of (meth)acrylic acid, isodecyl (meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanediol di(methyl)propionic acid vinegar, 1 , 9-nonanediol di(meth) acrylate, perfluorooctyl (meth) acrylate, I, 10- decane di(meth) acrylate, nonyl phenol polypropoxylate (Methyl) 15 acrylate, and polypentyl ethoxylate tetrahydrofurfuryl acrylate 'from Ky0eisha Chemical Co., LTD; polybutadienyl methacrylate dimethyl acrylate vinegar 9 200946560 (CN302, NTX6513) and polybutadiene dimercapto acrylate (CN301, NTX6039, PRO6270) from Sartomer Company, Inc; polycarbonate amine phthalate dipropylene Oleate (ArtResin UN9200A) is derived from

Negami Chemical Industries Co., LTD; Acrylated Aliphatic Amine 5 Phthalate Oligomers (Ebecryl 230, 264, 265, 270, 284, 4830, 4833, 4834, 4835, 4866, 4881, 4883, 8402 , 8800-20R, 8803, 8804) from Radcure Specialities, Inc; Polyacetate acrylate oligomers (Ebecryl 657, 770, 810, 830, 1657, 1810, 1830) from Radcure Specialities, Inc; Epoxy Acrylic vinegar resin 10 (CN 104, m, 112, 115, 116, 117, 118, 119, 120, 124, 136) was obtained from Sartomer Company, Inc. In one embodiment, the acrylate resin is selected from the group consisting of isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, poly(butadiene) having acrylate functionality, and ruthenium. Group 15 group consisting of poly(butadiene) based on acrylate functionality. Suitable epoxides for the use of hydrazine and nitrone include bisphenol, naphthalene, and aliphatic type epoxides. Commercially available materials comprising bisphenol type epoxy resins (Epiclon 830LVP, 830CRP, 835LV, 850CRP) are available from Dainippon Ink & Chemicals, Inc; naphthalene type epoxide (Epiclon 2〇 HP4032) from Dainippon Ink &amp Chemicals, Inc; aliphatic epoxy resin (Araldite CY179, 184, 192, 175, 179) from Ciba Specialty Chemicals, (Epoxy 1234, 249, 206) from Union 200946560

Carbide Corporation, and (ΕΗΡΕ-3150) are available from Daicel Chemical

Industries, Ltd. Other suitable epoxy resins include cycloaliphatic epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins (eg from Hexion)

Specialty Chemicals RSL 1739), epoxy novolac resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-phenol type epoxy resin, reactive epoxy diluent, and mixtures thereof. Suitable cyanate esters for use in compositions with nitrones contain a general structure

10 15 θ [n=C-〇4—X7 \------------------k one..... where η is 1 or greater and X7 is Hydrocarbyl group. Exemplary X7 bodies comprise bisphenol, phenol or nonanol novolac, dicyclopentadiene, polybutadiene, polycarbonate, polyamine phthalate, polyether, or polyester. Commercially available materials include AroCy L-10, AroCy XU366, AroCy XU371, AroCy XU378, XU71787.02L, and XU 71787.07L, available from Huntsman LLC; Primaset PT30, Primaset PT30 S75, Primaset PT60,

Primaset PT60S, Primaset BADCY, Primaset DA230S,

Primaset MethylCy, and Primaset LECY, available from Lonza Group Limited; 2-allyl phenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanate)-1, 1,1,3,3,3-hexafluoro-1-propanone, diceocyanate, dipropyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-parameter (4-cyanylphenyl) ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanylphenyl)ethane, 2,2,3,4,4,5, 5,6,6,7,7-11 "Acrylonitrile", a vinegar, and 4,4'-bi-nitrate, available from Oakwood Products, Inc. Suitable vinyl ethers for use in compositions with nitrones include those having the general structure 11 20 200946560 π where 11 is 1 to 6 and X 3 is an aromatic or aliphatic group. Exemplary X3 entities include poly(butadiene), poly(carbonate), poly(amine phthalate), poly(ether), poly(ester), simple hydrocarbons, and functional groups such as carbonyl, carboxyl, decylamine, A urethane, urea, or a simple hydrocarbon. Commercially available resins include cyclohexane 5 dinonanol divinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether , 18 ❹ 烧 vinyl ether, and butanediol divinyl ether, obtained from International

Speciality Products (ISP); Vectomer 4010, 4020, 4030, 4040, 4051, 4210, 4220, 4230, 4060, 5015, available from ίο Sigma-Aldrich, Inc. Suitable poly(butadiene) for use in compositions with nitrones comprises poly(butadiene), epoxidized poly(butadiene), maleic fluorene (butadiene), acrylated poly (butadiene), butadiene-styrene copolymer, and butadiene-acrylonitrile copolymer. Commercially available materials include homopolymer butyl bake (Ricon 130, ® 131, 134, 142, 150, 152, 153, 154, 156, 157, P30D) from Sartomer Company, Inc; butadiene and benzene Random copolymer of ethylene (Ricon 100, 181, 184) was obtained from Sartomer Company Inc; maleated poly(butadiene) (Riccm 130MA8, 130MA13, 130MA20, 131MA5, 131MA10, 131MA17, 131MA20, 20 156MA17) ) from Sartomer Company, Inc; acrylated poly(butadiene) (CN302, NTX6513, CN3 (H, NTX6039, PRO6270, Ricacryl 3100, Ricacryl 3500) from Sartomer Inc; epoxidation 12 200946560 Poly(butadiene) (PolyM 600, 605) from the Sartomer Company,

Inc and Epolead PB3600 are from Daicel Chemical Industries.

Ltd ; and acrylonitrile and butadiene copolymers (Hycar CTBN series, ATBN series, VTBN series and ETBN series) were obtained from Hanse Chemical. The suitable deuterated olefins used in the composition with nitrone are obtained by selective hydrosilation reaction of anthrone and diethyl-based materials.

Got

, wherein it is 2 or more, Π 2 is 1 or more, and χΐι>ιΐ2. This specialty material is commercially available and is available, for example, from National Starch and Chemical Company. 10

Suitable fluorenone with nitrone for the composition contains a general structure

X5 - a reactive oxirane resin wherein η is 0 or any integer and X4 and X5 are hydrogen, methyl, amine, epoxy, decyl, hydroxy, acrylate, methacrylate, decyl, phenol, or ethylene A functional group, R2 and RHH, -CH3, vinyl, stupid, or any hydrocarbon structure having more than two carbon atoms. Commercially available materials include KF8〇12, KF8〇〇2, KF8003^KF-1001 > X-22-3710 > KF6001 ^ X-22-164C > KF2001' X-22-170DX, X-22- 173DX, X~22-174DX, X-22-176DX, 13 15 200946560 KF-857, KF862, KF80CU, X-22-3367, and X-22-3939A from Shin-Etsu Silicone International Trading (Shanghai) Co ., Ltd. Suitable styrenic compounds for use in compositions with nitrones include one

5

10

15 general structure, ................. Z n resin, where η is 1 or greater, R4 is -η or -CH3, And X6 is an aliphatic group. Exemplary X3 entities include poly(butadiene), poly(decarboxylate), poly(urethane), poly(it), poly(ester), simple hydrocarbons, and functional groups such as carbonyl, carboxyl, guanamine a simple hydrocarbon of a carbamate, urea, or ether. Such resins are commercially available and are available, for example, from National Starch and Chemical Company or Sigma-Aldrich Co. For some applications, one or more fillers or spacers or both may be added to the curable composition and are typically added for improved rheological properties, stress reduction, and bondline control. . Examples of suitable non-conductive fillers include emulsified, oxidized, oxidized, feldspar, mica, ash, carbonate, titania, sand, glass, barium sulfate, sulphur, carbon black, organic Fillers, and organic polymers (including but not limited to, ethylene-based polymers such as tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene oxide, and ethylene). Examples of suitable conductive fillers include carbon black, graphite, gold, silver, copper, Gu, He, Lu, Ming, carbon carbide, gasification side, diamond, and aluminum oxide. The granules can be of any suitable size ranging from nanometer size to several glutinous rice, 14 20 200946560 ^,, #疋No use as a filler or spacer (the separator is typically a larger size with a greater uniformity of size) ). Selecting such dimensions for any end use is within the skill of those skilled in the art. The dip can be determined by the practitioner to any amount suitable for the end use selected. Eight [Embodiment] ° Synthesis Example

10 The melting point, curing temperature, net heat of polymerization, and the heat of polymerization of the curable composition containing the compound and other compounds are determined by a differential scanning calorimeter (DSC). Thermogravimetric analysis (tga) was performed by a TGA (TA 2950) thermogravimetric analyzer.

Example 1 Synthesis of nitrone A

溶 A solution of potassium hydroxide (23.71 g' 〇.3593 mol) in 108 mL of ethanol was slowly added to a solution of N-mercaptohydroxylamine hydrogenated hydrogen (3 〇.〇〇g, 〇. 3557 mol) in 18 mL of water. The resulting precipitate was filtered by vacuum filtration and discarded. A 500 mL four-necked round bottom flask was equipped with a condenser and a mechanical stirrer, and was charged with a suspension of 1,4-benzenedialdehyde (9,29 g, 437.1437 mol) in 54 mL of ethanol. A solution of mercaptohydroxylamine (filtrate) was added dropwise to this suspension. The mixture was mixed overnight. Then the precipitate was vacuum filtered and washed with water. The solid product was dried overnight under vacuum at room temperature. The yield is approximately 41%. Ih_nmr was recorded in DMSO (solvent) and proved to be the desired product. The melting point is 252 ° C. When the sample is heated from 4 〇〇c to 3 ) (), the polymerization heat is 15 20 200946560 435J/g. The TGA I page shows the weight loss in 。2 〇.4伙,于为乃,和于纲. C is 77,8%. Example 2 Synthesis / G succinone oxime

13 2 == Preparation of the same procedure as nitrone A, except that i, _3-mono-acid' was substituted for 1,4-ben.

Example 3 Synthesis of nitrone c Η h3cv β ^Λτ. Knowledge 0 ©Ν fii The following reaction flow chart first prepares the start corpse H3 2 +

OH ohc~0^°y^^y〇^_cho ο ο 5_L The bottom of the flask is equipped with a cold (9), bubbler, and mechanical transfer device, and t is filled with 4_hydroxybenzene plate (1U2g, 〇. 〇911m〇丨), triethylamine (17.05g > 689.i689mol) 'DMAP (〇.9476g > 0.0078mol) > 10 200946560 and 100mL CH2C12. The contents were cooled to below 10 ° C in an ice bath. Dioxachloride (10.25 g, 0.0455 mol) was charged to the addition funnel and added dropwise to the reaction flask. The mixture was stirred at 1 CTC, the condenser and ice bath were removed and the solution was warmed to room temperature and stirred overnight. The mixture was then filtered. The filtrate was washed with water and brine and twice with sodium bicarbonate. In order to purify the product from the baseline at TLC, a broken gel (10.0 g) was added to the solution for 1 hour. Once the baseline was removed and checked by TLC, the solvent was removed and b-NMR was carried out in CDC 13 and the presence of diacid was confirmed.

°θ

A solution of potassium hydroxide (2.84 g, 0.0506 mol) in iimL of ethanol was slowly =, and a solution of SU methyl methylamine ruthenium chloride (4 2 g, 〇. 5 〇 6 mol) in 2 mL of water was added. The resulting solid precipitate was stirred for 15 minutes, then removed and discarded. The 100 mL one-neck round bottom flask is equipped with a condenser and a stirrer and is filled with a difunctional aldehyde.

15 (, 0.0253 mol) (as shown in the above reaction scheme) in a 0 mL suspension. The remaining from the N-methylhydroxylamine hydrogenation 't liquid substance was added to the suspension. The new product produces a precipitate β which is stirred with a new mixture of precipitates, then vacuum filtered and washed with water. The solid product was allowed to stand in vacuum and room two: dry overnight. The yield was approximately 45.0%. A-nmr was completed in DMSO and proved to be the desired product. The melting point is 152 ° C. 200946560

Example 4 Synthesis of nitrone D

The nitrone D was prepared according to the following reaction scheme starting from 4-hydroxybenzaldehyde:

N-methylhydroxylamine hydrogen chloride

KOH / EtOH

® A solution of slanting water (20.14 g, 0,359 mol) in 108 mL of ethanol was slowly added to a solution of N-mercaptohydroxylamine hydrogenation (30.00 g, 0.359 raol) in 18 mL of water. The resulting solid precipitate was stirred for 15 minutes, removed by vacuum filtration and discarded. A 500 mL four-necked round bottom flask was equipped with a condenser and a mechanical stirrer, and was charged with a suspension of 4-benzoquinone (36, 55 g, 0.299 mol) in 71 mL of ethanol. The remaining material from the N-methyl amine vaporized argon solution was added to the suspension. The new product produces a precipitate. The new mixture with the precipitate was stirred overnight, then vacuum filtered and washed with water. The solid product was dried under vacuum at room temperature _ overnight. The yield was approximately 67.0%. b-NMR was completed in DMS0 and proved

For the desired product. The melting point is 232 ° C. The synthesis of Example 5 is _ E

Preparation of nitrone E according to the following reaction scheme starting from 3-hydroxybenzaldehyde: 200946560

Bismuth-methylhydroxylamine hydrogen sulfide

KOH / EtOH CH3

溶液 A solution of potassium hydroxide (20.14 g, 359.359 mol) in 10 mL of L ethanol was slowly added to a solution of N-mercaptohydroxylamine hydrogen chloride (3 〇 00 g, 359 359 〇l) in i8 mL of water. The resulting solid precipitate was stirred] [5 min, removed by vacuum filtration and discarded. A 500 mL four-necked round bottom flask was equipped with a condenser and a mechanical stirrer, and was loaded with a suspension of 3-3⁄4 benzoquinone (36.55 g, 0.299 mol) in 71 mL of ethanol. The remaining material from the N-mercaptohydroxylamine hydrogen chloride solution was added to the suspension. The new product produces a precipitate. The new mixture with the precipitate was stirred overnight, then vacuum filtered and washed with water. The solid product was dried under vacuum at room temperature overnight to yield a good yield of nitrone. iH-NMR was completed in DMS0 and described as product. The melting point is 205. (:. Also Example 6 Synthetic nitrone jp Φ

The starting 4-c-block oxygen was first prepared according to the following reaction scheme.

K2C〇3 15 200946560 (33.31g'0.2m〇i) was added to 4-hydroxybenzaldehyde (24.5 g, 0.2 mol) in DMF > The mixture was stirred for 15 minutes. Bromopropyne (15,12 raL) was added and the resulting solution was stirred at room temperature overnight. The mixture was diluted with ethyl acetate and taken to remove K2C03. The cake is washed with acetic acid. The filtrate was taken in a sep. funnel, washed with water (4×2 〇〇mL) and brine and dried over anhydrous Benzaldehyde (29.5 g, 92%) was provided as a clean h NMR spectrum by solvent evaporation under vacuum. According to the following reaction scheme, then benzaldehyde is used to prepare the nitrone:

Triethylamine (26.14 mL, 0.187 mol) was added to a suspension of N-methylhydroxylamine hydrogenation (丨5 66g, 〇]87m〇1) in cj^ch (75mL). 15 minutes. The precipitate was filtered off and washed with CH2C12 (25 mL). The filtrate was added dropwise to a stirred solution of aldehyde (2 〇g, 〇. 125mol) in CH2C12 (丨5 〇mL). Warm stirring overnight. Evaporate CH2C12; add ice-cold water (5〇mL) to the residue, filter out the precipitated solids and wash it in cold water (20mL) and cold acetone (40mL) and dry in a vacuum oven. iH NMR spectroscopy (DMSO) ketone product (14.2 g, 77%). Melting point 132. 〇. Example 7 Synthesis of nitrone g 20 200946560 • h3c'

• Benzyl bromide

The starting 4-benzyloxybenzoic acid was prepared according to the following reaction scheme: Ο k2co3/dmf Potassium carbonate (13.57 g) was added to a solution of 4-hydroxybenzaldehyde (10 g, 81.9 mmol) in DMF (75 mL) ' 98.2 mmol). The mixture was stirred at room temperature for 15 minutes. Benzyl desert (9.73 mL, 81.9 mmol) was added and the mixture was stirred overnight at room temperature. Ethyl acetate (5 mL) was added and the precipitate was filtered and washed ethyl acetate (50mL). The filtrate was washed with water (4 x 200 mL) and brine (1 mL). The organic layer was dried over anhydrous MgSCU and evaporated. The product was dried in vacuo and submitted to 1H NMR. NMR indicated the pure compound (15.2 g, 87%). The nitrone was prepared according to the following reaction scheme using 4-benzyloxybenzaldehyde:

Triethylamine (13.02 mL, 93.3 mmol) was added to a suspension of N-decylamine (m.p. The mixture was mixed for 20 minutes. The precipitate was filtered and washed with dichloromethane (20 mL). <RTI ID=0.0>>>>> Dichloromethane was evaporated, and cold water was added to the residue (100 mL) and stirred for 15 min. The precipitate was filtered, washed with EtOAc EtOAc EtOAc (EtOAc) The nitrone G has a melting point of 117 ° C and is miscible with other resins 5 . Example 8 Synthesis of nitrosone oxime

The starting dimesylate was prepared according to the following reaction scheme:

WeS02CI/Et3N CH2Ci2 99% q〇 Add diethylamine (6.8 mL) in dimer diol (Uniqema) (9.07 g, 16.2 mmol) in CH2C12 (100 mL) at 0 ° C, then drop by 10 min. MeSC^Cl ( 2.77 mL, 35, 7 mmol) was added. After stirring at the same temperature for 2 hours, when T.L.C. indicated that the starting material disappeared (developed through the uv chamber), water (100 mL) was added, and the mixture was diluted with Et EtOAc (300 mL). The organic layer was washed with water (3×10 mL) and brine and dried over anhydrous The solvent was evaporated and the product was dried <RTI ID=0.0> 22 15 200946560 Preparation of dialdehyde from dimesylate according to the following reaction scheme:

A suspension of K2C03 (21.63 g, 156 mmol) and 4-hydroxybenzaldehyde (I5.66 g, ❿ 128 mmol) in DMF (500 mL) was stirred at room temperature for 5 min. A solution of the dimesylate in DMF (50 mL) was added dropwise, and the mixture was stirred at 8 CTC for 6 hr. After T.L.C (Thin Layer Chromatography) indicated the disappearance of the starting material, the reaction mixture was cooled to room temperature and diluted with a 1:1 mixture of ethyl acetate and hexane (500 mL). The precipitate was filtered and washed with heptane: ethyl acetate (1:1, 200 mL). The filtrate was taken in a sep. funnel, washed several times with water (4×400 mL) and then washed with brine (3·mL). The organic layer was dried over anhydrous MgSO.sub.4 (30 min), and solvent was evaporated from &lt;RTI ID=0.0&gt;&gt;&&&&&&&&&&&&&&&&&& Reaction Scheme: Synthesis of nitrone from dialdehyde:

Q Et3N, CH2CI2 93%

N'ch3 23 200946560

Add triethylamine (6.26 mL '44.9 mmo〇) to a suspension of N-mercaptohydroxylamine hydrogenation (3.75 g, 44,9 mmol) in CH2Cl2 (20 inL). Mix the mixture for 15 min. Filter the precipitate and pass CH The mixture was washed with EtOAc (250 mL). Wash with barium and dry on anhydrous yigS〇4. Solvent evaporation to provide a viscous liquid. It was dried using Kugelrohr at 60 °C for 3 hours to form squalane as a very viscous liquid (4.24 g, 93%). The viscosity is 7000 mPa · s at 50 ° C. This reaction is highly reproducible. 10 Characteristics Implementation Your sloping theory is formulated with various molar ratios to formulate the above-mentioned nitrate I in a curable composition comprising one or more of the following resins. The composition contained no solvent. The net resin and composition were cured by a differential scanning calorimeter (DSC), and the curing temperature (cured T1 and solid) and heat (AH) were recorded in the tables for each example. (15 above, the melting point is also determined by Dsc.) Using thermogravimetric analysis (TGA) to determine weight loss And completed by TGA (TA 2950) instrument. 参 cis-butenylene diimide (TMI)

Cyanate ester (CE) 24 200946560

NCO

OCN double F epoxide (epoxide) h&lt;H〇-

Acrylic

Bis-m-butylene diimide (BMI)

Wherein C36 represents a linear or branched chain of 3 6 carbon atoms (with or without a cyclic moiety)

实施 Example 9 DSC of a composition containing nitrone A and a cyanate ester The nitrone A and the cyanate ester (CE) were blended in various molar ratios. The DSC scan indicates a two-stage cure process, and as the amount of nitrone decreases, the cure temperature increases. The results are reported in Table 1. Table 1: DSC data components of nitrone A and cyanate ester Mohr ratio cure T1 △ HI cure T2 ΔΗ2 nitrone A: CE 1 : 0.5 154〇C 59J/g 188〇C 776J/g nitrone A : CE 1:1 156〇C 63J/g 192〇C 1054J/g 25 200946560 nitrone A : CE 0.5 : 1 147〇C 160J/g 208〇C 1051J/g nitrone A : CE 0.2 : 1 144〇C 70J/ g 214〇C 655J/g Example 10 contains a composition of nitrone A, cyanate, and epoxide

DSC nitrone A is blended with the cyanate (CE) and double F epoxides shown above in various molar ratios. The composition was cured by Dsc. The results are reported in Table 2. Reference 2: DSc data component of nitrate y △, cyanate ester, and epoxide Mohr ratio curing T1 △ HI curing T2 ΔΗ2 nitrone A: CE: epoxy 1:1:1 152〇C 16J/g 202 〇C 482J/g nitrone A : CE :epoxy 0.5 : 1 : 1 196 〇C 792J/g 氺:fe氺* 氺氺氺3({氺nitrone A : CE : epoxy hedo 1 : 0.5 : 1 207〇C 377J/g 250〇C llj/g nitrone A : CE : ring gas 1 : 0.5 : 0.5 198〇C 156J/g 236〇C 26J/g DSC peak in the second login is very extensive combined with τι T2. At the third and fourth registrations, most of the curing occurs during the first exotherm, so ΔΗ2 is low for such curing.

Example 11 TGA containing nitrone oxime and epoxide composition TGA nitrite A combined with epoxide was tested by TGA at 20 (TC weight loss compared to cyanate, epoxide, and cyanate) a control sample with a 1:1 molar ratio of epoxide. TGA data for the substance

Component --------- Mo Erbi Weight Loss Temperature CE -------- Net (Control) 4.75% 200°C Epoxide Net (Control) 1.66% 200°C 26 200946560

Epoxide epoxide net (control) 3,2% 200°C nitrone A: epoxide 0.5 1 34.1% 200°C nitrone A: epoxide 0.2 : 1 33.8% 2〇〇°C

Example 12 DSC containing a composition of nitrone C, cyanate, epoxide, maleimide, and acrylate

The nitrate C is blended with cyanate esters, cyanate esters and epoxides, maleimide, and acrylates and cured by DSC. The results are reported in Table 4 and indicate that comparison with, for example, nitrone A, the introduction of an aliphatic backbone into the nitrone will reduce the heat of polymerization. Table 4 · Nitronone c, cyanate ester, epoxide, cis-butane diimide, and C

10 Components Mohr Ratio Curing T1 Δ HI Curing D 2 ΔΗ 2 Nitron Ketone C : CE 1:1 123〇C 80J/g 197〇C 560J/g Compound 1:1:1 126〇C 46J/g 205. . 604J/g nitrone C: TMI 1:1 107°C 47J/g 253〇C 204J/g: acrylate 1:1 133〇C 71J/g 269〇C 454J/g Example 13 contains nitrone oxime and cyanide Acid esters, epoxides, acrylates, and

DSC &amp; D of the composition of maleimide has a nitrone function and a phenolic functionality. Nitronone 〇 $ Aromatic acid, cyanate ester and epoxide, maleimide, and acrylic acid blended and cured by DSC. The results are reported in Table 5 and indicate that the two-stage curing process, which does not show the second m-peak, is based on the first-exothermic complete reaction. Table 5, nitrate-d, cyanate, epoxide, acrylate, and cis-butadiene-component Moer-specific cure △ HI Τ Curing Τ 2 ΔΗ2 27 15 200946560 Nitron D: Epoxide 0.5 : 1 : 1 140°C 32J/g 205〇C llOJ/g nitrone D: epoxide 1:1:1 138〇C 84J/g 169〇C 157J/g nitrone D CE 1:1 132〇C 362J/g 202〇C 543J/g nitrone D ----- CE 0.5 : 1 135〇C 382J/g 199〇C 88J/g nitrone D CE 0.4 : 1 141°C 721J/g 水氺本*氺氺氺氺氺 氺氺 D D ·&quot; —~~ ^CE 0.25 : 1 138〇C 142J/g 188〇C lOOJ/g Nitrate D acrylate 172〇C 16J/g 225〇C 638J/g nitrone D ~ ~ — nitrone D-—~~ nitrone D —_ —--- ----— 丄· 1 Acidate 0.5 : 1 165〇C 9J/g 257〇C 355J/g _TMI —__ 0.5 : 1 107 °C 47J/g 253〇C 204J/g 1:1 140°C 42J/g 225〇C 418J/g The presence of phenolic functionality on D and E can present additional functionality and knife straightness and/or aromaticity The opportunity to add these nitrones. The phenolic group can be reacted with a compound or a resin having a functionality of a hydroxy group. This &lt;1 = may contain additional functionality that does not react with the phenolic hydroxyl group, thereby adding this additional 1 month b to the nitrone. Further, the compound may be composed of a variety of lengths and branched aliphatic chains or a combination of aliphatic groups and aromatic groups to add molecular weight and/or grouping to the nitrate. The invention encompasses such nitrones. Example 14 DSC nitrone E containing a composition of nitrone E, cyanate ester, epoxide, acrylate, and maleic acid imide with cyanate ester, cyanate ester and epoxide, cis-butane The enediamine, and the acrylate are blended and cured by DSC. The results are reported in Table 6 and indicate that the nitrone E-curing compound is slower than the nitrone D. Table 6: DSC data for nitrone e, cyanide, epoxide, acrylate, and maleimide 28 200946560 Component Mobi cured T1 ΔΗ1 Cured T2 ΔΗ2 Nitron E: CE: Epoxy Compound 0.5 : 1 : 1 170 ° C 44 J / g 221 〇 C 243 J / g Tricholium E : CE : Epoxide 1:1:1 142 〇 C 19 J / g 171 ° C 185 J / g nitrone E : CE 1.5 : 1 132〇C 436J/g 227〇C 926J/g nitrone E : CE 1:1 133〇C 454J/g 229〇C 572J/g nitrone E : CE 0.5 : 1 135〇C 51J/g 178〇 C 123J/g nitrone E : CE 0.25 : 1 137〇C 6.8J/g 192〇C 295J/g nitrone E: propionate 1:1 160°C 24J/g 252〇C 548J/g nitrone E: Acrylate 0.5 : 1 158〇C 28J/g 275〇C 331J/g Nitron E: TMI 1:1 126〇C 32J/g 241〇C 441J/g Shishenone E: TMI 0.5 : 1 264〇 C 127J/g

Example 15 A DSC nitrone containing a nitrone and epoxide-containing composition can also be ring-opened, so that a ring such as an epoxide or oxocyclobutane will be ring-opened by a nitrone dipole. Several nitrones are used in combination with the epoxide and cured by DSC. The results are reported in Table 9. 5 Table 9: DSC data for nitrone and epoxides Component Mohr ratio Curing T1 △ HI Nitron A epoxide 1 : 0,5 239. . 1173 J/g nitrone A epoxide 1:1 242. . 1042J/g nitrone A epoxide 0.5 : 1 247〇C 795J/g nitrone A epoxide 0.2 : 1 250〇C 600J/g nitrone C epoxide 0.5 : 1 227〇C 578J/g nitrone C epoxide 1:1 223〇C 625J/g nitrone D epoxide 0.5 : 1 182〇C 350J/g 29 200946560 nitrone D: epoxide 1:1 183〇C 496J/g Example 16 Contains The properties of the composition of nitrone F, acrylate, epoxide, maleimide, and cyanate were measured by DSC. The nitrone F exhibited a melting point of 132 ° C in a neat form and a heat of polymerization of 1531 J / g. It can be mixed with other resins. TLC analysis indicated that the nitrone F 5 was clearly non-polar. DSC data is reported in Table 10. Table 10: DSC data component of nitrone F. Moerbi solid 4匕T1 △ HI Solid 4匕T2 ΔΗ2 Nitron F: Acrylate 1:1 218〇C 692J/g No nitrone F: Epoxide 1 1 166. . 1029J/g without nitrone F: TMI 1 1 210°C 533J/g without nitrates F: CE 1 1 164〇C 956J/g 258〇C 363J/g Investigation of nitrone F differs from epoxide The TGA characteristics of the molar ratio are shown in Table 11. Table 11: TGA number of nitrone F, epoxide, acrylate, and cyanate 10 Weight loss nitrone F according to component molar ratio of 200 ° C 14% nitrone F epoxide 0.1 : 1 2% Nitronone F epoxide 0.2 : 1 4% nitrone F epoxide 1:1 2.50% nitrone F acrylate 1:1 4.80% nitrone F CE 1:1 2.30% Evaluation of nitrone F and epoxide The mechanical properties of the cyanate ester combination (cobalt acetonide as 30 200946560 catalyst, 1% by weight); the results are reported in Table 12. The amount of nitrone F was increased from 0.2 moles to Q4 molar axis δη in the composition, whereas the curing temperature was lowered by U). (:. The loading of nitrone F also improves the Tg (ionization transfer temperature) of the cured material by 2 〇 i. Mechanical Properties Control: Epoxide: Cyanate Moir Ratio 2 : 1 〇. 2 Mo Nit Ketone jp + control substance 0.4 molar nitrone F + control curing peak 180 ° C » 241 ° C 180. ' 245 ° 170 ° C, 241 ° C Δ Η (J / g) 168, 131 ! 3 〇 &gt; 211 158 , 347 Tg ( DMA ) ^8°C -—*------ 98〇C l〇5°C E'@25C 6.80 E+09 7.71 E+09 5 86 E+09 Tg ( TM A ) _91°C 106°C lll〇C CTE &lt; Tg 1 _ I J Example 17 Foundation, 67.5 _丨_ 1 - ΓΛ Also... 64.5 71.4 ..... Which work double, 叼 既 、, 汉 汉Lost _

The DSC and TGA of vinegar are called the curing properties and TGA characteristics of different resins. Shi Xiao _ ^ is better than the nitrates 酉 A to 卩 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ UbL·i〇A of imine, acrylate, and cyanate solidified T1 ΔΗ1 Curing T2 ΔΗ2 The weight loss at 200〇C is diminished. The increase in nitrocellulose molecular weight can reduce ΔΗ. All nitrone oxime groups

31 200946560

Ο 绡 G G ----^ 石 亩 & & 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1:1 1:1 1:1 1:1 1:1 石 石 石 石 石 石 石 石 石Γ Same as G: Epoxy like 1:1

The mechanical properties of nitrone G were also investigated and the results are reported in the table below. Acetyl i and cobalt were used as curing initiators in an amount of 1 |: %. t 14 : mechanical properties of nitrone G, epoxide and nitrite mechanical properties control epoxide: cyanate molar ratio 2 : 1 CoAcAc (III) 0.4 mol 嗣 g + control ^ (DSC, completely Cured) 122.2. . 110.9 ° C curing peak (ΤΠ &amp; Τ 2) 180 ° C, 241 ° C 174 ° C » 217 ° C Tg ( TMA ) 88 〇 C 96 〇 C &quot; cTE &lt; Tg 63.6 78.9 7 (GPa, 25.) 6.8 6.0 ~~ Tg (DMA ) 88〇C 99〇C Example 18 TGA and DSC of a composition containing nitronium, acrylic acid vinegar, militaris oxime, and biscis dimethyl sulfoxide (Mirt scanning calorimeter) and TGA (thermogravimetric analysis) were used to evaluate the properties of nitrone oxime in various resin formulations. The TGA results indicate that nitrone η exhibits good thermal stability and exhibits minimal weight loss with cyanate ester blending at 200 ° C 32 5 200946560 0.37%. The results are revealed in Table μ. Table 15: TGA and DSC number of nitrone oxime, acrylate, cyanate, and bis-methyleneimine. Molybdenum cure Τ1 Δ HI Curing T2 ΔΗ2 at 200〇C ----- —^ ------ — Weightless nitrone oxime Net 265〇C 125J/g None 1.62% Nitrogen H: ΒΜΙ ι:ι 96〇C 60J/g 267〇C 188J/g 0.46% Nitrononone : 丙酸酸 g ι:ι 127〇C 88J/g 260〇C 248J/g 1,17% nitrone H : CE 1:1 153〇C 356J/g M 4\%\ σ 〇 37% nitrate Ketone H: Epoxide Xiangtian, W: 1:1 ----- | 2.00%

5

Dream product &gt;5 is used as an adhesive and encapsulant, especially for semiconductor seals.) Adhesive to the substrate. 丄 : : : : : : 充 充 充 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 料 料 料 料 料 底部 底部 底部 底部 底部 底部 底部 底部 底部 底部 底部 底部 底部Encapsulant. Therefore, the semiconductor; and the composition of the solder as described herein adheres to the substrate r spot; the semiconductor connected to the substrate, 1 in the semi-conductor &quot;sitr township red money is said to be a shame filling. The upper semi-conductive micro-matrix and gold-connected array of the array are placed on the bottom of the array and the bottom-filled county is formed. Figure 2 depicts flip chip semiconductor with soft solder and substrate. _ 33 15

Claims (1)

200946560 X. Patent application scope: 2. 5 - Curable composition 'includes π 厶铷, 甘, I ώ丄 ώ丄 驷 驷 驷 驷 驷 驷 — — — — — — — — — — — — — — —. a group consisting of free % oxide, cyanate diimine, and combinations thereof. Employees butenes According to the application of the above paragraph, the at least one other SHb compound is selected from the group consisting of epoxides and cyanogens. 3. The curable composition according to claim 3, wherein the at least one other curable compound is selected from the group consisting of acrylate and maleimide 10. 4. The curable composition according to claim 1, wherein at least one of the other curable compounds is selected from the group consisting of 34 15 7200946560 P Ο Ο ο ο jsj - 甘χ|ϊ 7H36 represents a linear or branched chain of 36 carbon atoms with or without a cyclic moiety), a curable composition of any of the four, and a combination thereof 5. According to the scope of the patent application, the medium nitrone is selected from 10 3 Η3〇^οθ 35 200946560 10 (nitrone E), And 36 200946560 a group consisting of (nitrone oxime). Q 6. A semiconductor package comprising a semiconductor adhered to a substrate with a composition comprising a nitrone and at least one other fixable compound. 7. The semiconductor package according to claim 6, wherein one of the other curable compounds is selected from the group consisting of an epoxide, a cyanic acid, a propionic acid, a maleimide, and the like. The group consisting of nitrone is selected from Hi^〇rcH3 10 (nitrone A), ❿H3C|〇ef · ηΛ 0〇xe - CHS V_y/X (nitrone B), 37 200946560 (Shi Xiaotong with E), 10 And 38 200946560 a group consisting of (nitrone oxime). 8. A semiconductor package electrically connected to a substrate by a solder joint, wherein a gap formed by the solder joint between the semiconductor and the substrate is filled with a composition comprising nitrone and at least one other curable compound. 9. The semiconductor package of claim 8 wherein one of the other curable compounds is selected from the group consisting of an epoxide, a cyanate, an acrylate, a maleimide, and the like. Group, nitrone is selected from 10 G 39 200946560 (nitrone D), (nitrone E), 10 H3C, And 40 200946560 The group formed Ο ❹ 41 200946560 VII. Designated representative map: (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: None ❹10 VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: