TW200948834A - Storage-stable polymaleimide prepolymer compositions - Google Patents

Storage-stable polymaleimide prepolymer compositions Download PDF

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TW200948834A
TW200948834A TW098110670A TW98110670A TW200948834A TW 200948834 A TW200948834 A TW 200948834A TW 098110670 A TW098110670 A TW 098110670A TW 98110670 A TW98110670 A TW 98110670A TW 200948834 A TW200948834 A TW 200948834A
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prepolymer composition
polymaleimide
polymaleimide prepolymer
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stable
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TW098110670A
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TWI453223B (en
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Roger Tietze
Yen-Loan Nguyen
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Huntsman Adv Mat Americas Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1565—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

The present invention relates to a storage-stable advanced polymaleimide prepolymer composition including a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol, alkenylphenol ether or mixture thereof in the presence of an amine catalyst; and dioxolane. The storage-stable advanced polymaleimide prepolymer composition may be used in various applications such as prepregs, laminates, printed circuit boards, castings, composites, moulded articles, adhesives and coatings.

Description

200948834 六、發明說明： 【發明所屬之技術領域】 本發明係關於可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物及由其製造之產品，例如預浸片產品。該可安定 貯藏之預形成聚馬來醯亞胺預聚合物組合物包括：⑴在胺 觸媒存在下由聚醯亞胺與烯基酚或烯基酚_之預先反廡形 成之聚馬來醯亞胺預聚合物；及（π)二氧戊環。 本申請案主張優先於2008年3月31曰提出申請之美國專 利申請案第61/040,956號之權利，其以引用方式併入本文 中。 【先前技術】 雙馬來醯亞胺可用作製造加成聚合產物及聚合產物之原 料。舉例而言，美國專利第3,658,764號揭示由不飽和雙馬 來醯亞胺與胺製造之加成聚合產物；美國專利第3,741，942 號闡述自雙馬來醯亞胺與有機二硫醇製造加成聚合產物； 美國專利第4,03 8,251號及第4,065,433號闡述在觸媒存在下 雙馬來醯亞胺與多元酚及多元醇反應來形成加成聚合產 物；且美國專利第4，100，140號闡述由雙馬來醯亞胺與烯基 盼或烯基酚醚製備之加成聚合產物。 鑒於其熱安定性及良好機械性質，由雙馬來醯亞胺製造 之加成聚合產物可在各種預浸片應用中使用。一種以粉末 形式供應之該加成聚合產物係雙馬來醯亞胺基二苯曱烷與 二胺基二苯曱烷之反應產物。隨後可使該粉末加成聚合產 物溶解於諸如N-甲基吡咯啶酮等高沸點溶劑中以供預浸片 139263.doc 200948834 使用。然而，由於此溶液在靜置時會迅速出現沉澱且黏度 增加因而其安定性會受到限制。因此，該溶液必須在即將 使用前調配。 已闡述揭示於美國專利第5，189，128號及第5,637,387號中 • 之加成聚合產物及溶液的改良。美國專利第5，189，128號揭 示由聚馬來醯亞胺與烯基酚或烯基酚醚在特定莫耳量之鹼 性觸媒存在下經確定的反應時間且於確定的反應溫度下反 ❹ 應而製造的加成聚合產物。所得產物展示在較低沸點溶劑 曱基乙基酮中之改良溶解性及改良貯藏安定性，如由不存 在沉澱所證明。貯藏安定性冬又一改良闡述於美國專利第 5,637,387號中，其中在聚馬來醯亞胺已與烯基酚或烯基酚 醚反應後添加啡噻嗪或對苯二酚。然而，加成聚合產物在 室溫條件下貯藏時可隨時間繼續聚合，從而減緩樹脂在層 壓製程中於使用期間之流動。在樹脂流動減緩超出一定程 度時，結合強度會下降，最終導致脫層。因此，為了防止 ❿ 树脂流動減緩，通常需要冷藏，此會提高成本且對於預浸 片使用者而言並非總是可實現。 因此，本發明之一個目的係提供可安定貯藏之改良加成 聚合產物組合物，其基本上可消除對冷藏之需要，而不會 ' 對由其製成的預浸片產品的熱性質及機械性質產生任何不 良影響。 【發明内容】 本發明係關於可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其包含： 139263.doc 200948834 (a) 在胺觸媒存在下由聚醯亞胺與烯基酚、烯基酚醚或其 此合物之預先反應形成的聚馬來醯亞胺預聚合物；及 (b) 下式（5)之二氧戊環：BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to pre-formed polymaleimide prepolymer compositions which can be stably stored and products made therefrom, such as prepreg products. The pre-formable polymaleimide prepolymer composition for stable storage comprises: (1) a polymalan formed by pre-reverse enthalpy of a polyimine and an alkenylphenol or an alkenylphenol in the presence of an amine catalyst An imine prepolymer; and (π) dioxolane. The present application claims priority to U.S. Patent Application Serial No. 61/040,956, filed on March 31, 2008, which is incorporated herein by reference. [Prior Art] Bismaleimide can be used as a raw material for producing an addition polymerization product and a polymerization product. For example, U.S. Patent No. 3,658,764 discloses an addition polymerization product made from unsaturated bismaleimide and an amine; U.S. Patent No. 3,741,942 describes the manufacture of bismaleimide and organic dithiol. Polymerization products; U.S. Patent Nos. 4,03,251 and 4,065,433, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire entire No. 140 describes an addition polymerization product prepared from bismaleimide and alkenyl or alkenylphenol ether. Due to its thermal stability and good mechanical properties, the addition polymerization products made from bismaleimide can be used in a variety of prepreg applications. An addition polymerization product supplied in the form of a powder is a reaction product of a bismaleimine diphenyl decane and a diaminodiphenyl decane. The powder addition polymerization product can then be dissolved in a high boiling solvent such as N-methylpyrrolidone for use in prepreg 139263.doc 200948834. However, since this solution quickly precipitates upon standing and the viscosity increases, its stability is limited. Therefore, the solution must be prepared just prior to use. Improvements in addition polymerization products and solutions disclosed in U.S. Patent Nos. 5,189,128 and 5,637,387 are incorporated herein by reference. U.S. Patent No. 5,189,128 discloses a reaction time determined by the presence of a polymaleimide with an alkenylphenol or an alkenylphenol ether in the presence of a specific molar amount of a basic catalyst and at a determined reaction temperature. The addition polymerization product produced by the reaction. The resulting product exhibited improved solubility and improved storage stability in the lower boiling solvent mercaptoethyl ketone as evidenced by the absence of precipitation. A further improvement of the storage stability winter is described in U.S. Patent No. 5,637,387, in which the phenothiazine or hydroquinone is added after the polymaleimide has been reacted with an alkenylphenol or alkenylphenol ether. However, the addition polymerization product can continue to polymerize over time when stored at room temperature, thereby slowing the flow of the resin during the lamination cycle during use. When the flow of the resin slows down beyond a certain level, the bond strength will decrease, eventually leading to delamination. Therefore, in order to prevent the flow of the resin from slowing down, refrigeration is usually required, which increases the cost and is not always achievable for the prepreg user. Accordingly, it is an object of the present invention to provide a modified addition polymerization product composition which can be stably stored which substantially eliminates the need for refrigeration without the thermal properties and mechanical properties of the prepreg product made therefrom. Nature has any adverse effects. SUMMARY OF THE INVENTION The present invention is directed to a pre-formable polymaleimide prepolymer composition that can be stably stored, comprising: 139263.doc 200948834 (a) from a polyimide and an alkenyl group in the presence of an amine catalyst a polymaleimide prepolymer formed by pre-reaction of a phenol, an alkenyl phenol ether or a compound thereof; and (b) a dioxolane of the following formula (5):

可藉由在胺觸媒存在下使聚醯亞胺與烯基酚、烯基酚醚 或其混合物於高溫下反應以形成聚馬來醯亞胺預聚合物， 基本上去除所有胺觸媒；且隨後添加二氧戊環來製備可安 疋貝τ藏之預形成聚馬來醯亞胺預聚合物組合物。在另一實 施例中’可藉由固化經本發明之可安定貯藏預形成聚馬來 醯亞胺預聚合物組合物浸潰的織物或纖維來製備預浸片或 層壓板結構。 ~ 【實施方式】 可安定貯藏之預形成聚馬來醯亞胺預聚合物組合物通常 包括（1)在胺觸媒存在下由聚醯亞胺與烯基酚、烯基酚醚或 其混合物之預先反應形成之聚馬來醯亞胺預聚合物丨及 (ii)二氧戊環。吾人已驚奇地發現將二氧戊環添加至聚馬 來醯亞胺預聚合物中可抑制反應進一步進行，由此可消除 或大大地降低進一步聚合，且因此可實質上改良預聚合物 組合物之貯藏安定I本發明之可安定貯藏之預形成聚馬 來醯亞胺預聚合物組合物可在室溫或甚至高於室溫之溫度 下長期貯藏，而不會對處理條件造成不良影響，因此可消 139263.doc 200948834 除對低溫(例如’冷藏條件)貯藏之需[「室溫」意指約 20 C之咖纟必匕外’使用二氧戊環可令人感到吃驚地改良 組合物之其他處理特性H延長使用時限㈣撤)及 減少揮發物含量。 適用聚醯亞胺含有至少兩個下式之基團： XOvThe polymaleimine prepolymer can be formed by reacting the polyiminimide with an alkenylphenol, an alkenylphenol ether or a mixture thereof at a high temperature in the presence of an amine catalyst to substantially remove all of the amine catalyst; And then dioxolane was added to prepare a pre-formed polymaleimide prepolymer composition of the amphibious oxime. In another embodiment, a prepreg or laminate structure can be prepared by curing a fabric or fiber impregnated with the stabilized storage preformed polymaleimide prepolymer composition of the present invention. ~ [Embodiment] The pre-formed polymaleimide prepolymer composition which can be stably stored generally comprises (1) a polyimine and an alkenylphenol, an alkenylphenol ether or a mixture thereof in the presence of an amine catalyst The pre-reacted formed polymaleimide prepolymer oxime and (ii) dioxolane. It has been surprisingly found that the addition of dioxolane to the polymaleimide prepolymer inhibits further reaction, thereby eliminating or greatly reducing further polymerization, and thus substantially improving the prepolymer composition. Storage Stabilization I The pre-formed polymaleimide prepolymer composition of the present invention can be stored for a long period of time at room temperature or even above room temperature without adversely affecting the treatment conditions. Therefore, 139263.doc 200948834 can be surprisingly improved by the use of dioxolane in addition to low temperature (eg 'refrigerated conditions) storage ["room temperature" means about 20 C of curry." Other treatment characteristics H extend the use time limit (4) withdrawal and reduce the volatile content. Suitable polyimines contain at least two groups of the formula: XOv

CC

IIII

HC ❹ co/ 其中R1係氫或曱基。 在另-貝施例中’聚醯亞胺係聚馬來醯亞胺、較佳係下 式之雙馬來醯亞胺： ❹HC ❹ co / wherein R1 is hydrogen or fluorenyl. In the case of the other, the polyiminimide polymaleimide, preferably the dimercaptoimine of the formula: ❹

CII HCCII HC

〇II -C〇II -C

C-II ΟII ,c.C-II ΟII, c.

C·II CH -R1 CTII 〇 其中R1係氫或甲基且X係η=2至20之_CnH2n-、_CH2CH2SCH2CH2-、伸苯基、萘、二曱苯、伸環戊基、U，％三曱基_153_伸 環己基、1,4-伸環己基、1，4_雙·（亞甲基）_伸環己基、或下 式（a)之基團： 139263.doc 200948834C·II CH -R1 CTII 〇 wherein R1 is hydrogen or methyl and X is η=2 to 20 _CnH2n-, _CH2CH2SCH2CH2-, phenyl, naphthalene, diphenyl, cyclopentyl, U, %3曱 _ _ _ _ _ cyclohexyl, 1,4-cyclohexylene, 1, 4 bis (methylene) _ cyclohexylene, or the group of the following formula (a): 139263.doc 200948834

其中R2及R3獨立地為氣、溴、曱基、乙基、或氫且2為直 接鍵、亞曱基、2,2-亞丙基、-CO-、戍 -S〇2_。較佳地，R1係曱基，X係六亞甲基、三甲基六亞甲 基、1，5,5-二曱基-1，3-伸環己基或所示式（a)之基團，其中 Z係亞甲基、2,2-亞丙基或-Ο-，且R2及R3係氫。 聚醯亞胺之實例包括：N，N，-伸乙基-雙馬來醯亞胺、 N，N - 亞甲基-雙馬來酿亞胺、Ν，Ν·-間-伸苯基-雙馬來酿 亞胺、Ν，Ν'-對-伸苯基-雙馬來醢亞胺、ν，Ν'-4,4'-二苯基甲 烷-雙馬來醯亞胺、Ν，Ν’-4,4'-3,3’-二氣-二苯基曱烷-雙馬來 酿亞胺、Ν，Ν·-4,4'-(二苯基醚）-雙馬來醯亞胺、ν，Ν，-4,4，-二苯基砜-雙馬來醯亞胺、Ν，Ν'-4,4'-二環己基甲烷-雙馬來 醯亞胺、Ν,Ν’-α，4,4’-二亞甲基環己烷-雙馬來醯亞胺、 NW-間-二曱苯-雙馬來醯亞胺、Ν,Ν’-對-二曱苯-雙馬來醯 亞胺、Ν,Ν'-4,4·-二苯基環己烷-雙馬來醯亞胺、NW-間-伸 苯基-雙檸康醯亞胺、Ν，Ν’-4,4'-二苯基甲烷-雙檸康醯亞 胺、队：^’-4,4’-2,2-二苯基丙烷-雙馬來醯亞胺、：^，：^’-〇1，1,3-二伸丙基-5,5-二甲基-乙内醯脲-雙馬來醯亞胺、Ν，Ν'-4,4'-二苯基甲烧-雙衣康醯亞胺、Ν，Ν'-對-伸苯基-雙衣康醯亞 胺、Ν，Ν'-4,4’-二苯基曱烧-雙二曱基馬來醢亞胺、Ν,Ν'-4,4’-2,2·-二苯基丙烷-雙二甲基馬來醯亞胺、Ν，Ν’-六亞曱 139263.doc 200948834 基-雙二甲基馬來醯亞胺、Ν，Ν'-4,4·-(二苯謎）-雙二甲基馬 來醯亞胺及Ν，Ν·-4,4'-二苯基砜-雙二甲基馬來醯亞胺。 適用烯基酚及烯基酚醚可包括烯丙基酚、f基烯丙基紛 或其醚。較佳地，該烯基酚及烯基酚醚係下式（i)_(4)之化 合物：Wherein R2 and R3 are independently a gas, a bromine, a decyl group, an ethyl group, or a hydrogen; and 2 is a direct bond, an anthracenylene group, a 2,2-propylene group, -CO-, 戍-S〇2_. Preferably, R1 is a fluorenyl group, an X-based hexamethylene group, a trimethylhexamethylene group, a 1,5,5-diindenyl-1,3-cyclohexylene group or a group of the formula (a) a group wherein Z is a methylene group, 2,2-propylene group or -Ο-, and R2 and R3 are hydrogen. Examples of polyimines include: N,N,-extended ethyl-bismaleimide, N,N-methylene-bismaleimide, anthracene, fluorene--m-phenylene- Bismaleimide, anthraquinone, Ν'-p-phenylene-bis-maleimide, ν, Ν'-4,4'-diphenylmethane-bismaleimide, hydrazine, hydrazine '-4,4'-3,3'-diqi-diphenyldecane-bismaleimide, anthracene, Ν·-4,4'-(diphenyl ether)-double malayan Amine, ν, Ν,-4,4,-diphenyl sulfone-bismaleimide, hydrazine, Ν'-4,4'-dicyclohexylmethane-bismaleimide, hydrazine, Ν' -α,4,4'-Dimethylenecyclohexane-Bismaleimide, NW-m-Diphenylene-Bismaleimide, Anthracene, Ν'-P-Diphenylene-Double Maleidin, anthracene, anthracene '-4,4·-diphenylcyclohexane-bismaleimide, NW-m-phenylene-bis-citraconin, hydrazine, Ν'- 4,4'-diphenylmethane-small citricin, team: ^'-4,4'-2,2-diphenylpropane-bismaleimide, :^,:^'- 〇1,1,3-di-propyl-5,5-dimethyl-ethyl carbazide-bismaleimide, hydrazine, Ν'-4,4'-diphenyl- ketone-double coat醯 胺, Ν, Ν '-p- phenyl-double醯 胺 胺 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 - bisdimethylmaleimide, hydrazine, Ν'-hexa yttrium 139263.doc 200948834 bis-dimethyl dimethylimine, hydrazine, Ν '-4,4·- (diphenyl riddle) - bisdimethylmaleimide and hydrazine, Ν-4,4'-diphenyl sulfone-bisdimethylmaleimide. Suitable alkenyl phenols and alkenyl phenol ethers may include allyl phenol, f-allyl propyl or an ether thereof. Preferably, the alkenyl phenol and the alkenyl phenol ether are compounds of the following formula (i) to (4):

HOHO

OH ch2ch=ch2 CH2=CHCH3 ⑴ 其中R係直接鍵、亞甲基、亞異 -S Ο 0 " 9 丙基、-0-、-S-、_s〇. 或OH ch2ch=ch2 CH2=CHCH3 (1) wherein R is a direct bond, methylene, iso-S-Ο 0 " 9 propyl, -0-, -S-, _s〇. or

OHOH

(2) 較佳為烯 少—個係 其中R4、R5及R6各自獨立±士盔与+ 询立地為虱或C2-Ci〇烯基 丙基或丙烯基，其限制條件為R4、汉5或“中之 C2-C 1 Q稀基； 139263.doc 200948834(2) Preferably, the olefin is less than one in which R4, R5 and R6 are each independently ± Helmet and + Query is 虱 or C2-Ci 〇 丙基 propyl or propylene, the restrictions are R4, Han 5 or "C2-C 1 Q dilute in the middle; 139263.doc 200948834

R、RAR7各自獨立地為氫或C2-Cl〇烯基、較佳 為晞丙基或稀基’其限制條件為r4、r5、r6_w 一個係C2_C10烯基且R係如式（1)中所定義且R and RAR7 are each independently hydrogen or C2-Cl nonenyl, preferably fluorenyl or dilute, and the restriction conditions are r4, r5, r6_w, one C2_C10 alkenyl group and R is as in formula (1) Defined and

其中R、R、R 、R"、R12及Rl3各自獨立地為氫、Cl。 烷基及C2_Cl〇烯基，較佳為烯丙基或丙烯基，其限制條 件為R8、R9、R〗。、R"、中之至少一個係。·。丨。烯 基且b係〇至10之整數。亦可能使用式（1) (4)化合物之混合 物。 烯基酚及烯基酚醚化合物之實例包括：〇,〇，_二烯丙基_ 雙酚A、4,4’-二羥基-3,3'-二烯丙基二苯、雙（4_羥基_3_烯 丙基笨基）甲烷、2,2-雙（4_羥基-3,5-二烯丙基苯基）丙烷、 〇,〇·-二甲基烯丙基-雙酚A、4,4，_二羥基_3,3，_二甲基烯丙 139263.doc -10· 200948834 基二苯、雙（4-羥基-3-甲基烯丙基苯基）甲烷、2,2-雙（4-羥 基-3,5-二甲基烯丙基苯基）_丙烷、4_甲基烯丙基_2_甲氧基 紛、2,2_雙（4-曱氧基-3-烯丙基苯基）丙烷、2,2-雙（4-甲氧 基-3-甲基烯丙基苯基）丙烷、4,4，_二甲氧基_3,3，_二烯丙基 一本、4,4- 一曱氧基-3,3’-二甲基稀丙基二苯、雙（4_尹氧 基-3-烯丙基苯基）甲烷、雙（4_曱氧基_3_甲基烯丙基苯基） 甲烷、2,2-雙（4-曱氧基_3,5_二烯丙基苯基）丙烷、2,2_雙（4_Wherein R, R, R, R", R12 and Rl3 are each independently hydrogen and Cl. The alkyl group and the C2_Cl nonenyl group are preferably an allyl group or a propylene group, and the limiting conditions are R8, R9, and R. , R", at least one of the departments. ·. Hey. Alkenyl and b is enthalpy to an integer of 10. It is also possible to use a mixture of compounds of formula (1) (4). Examples of alkenylphenol and alkenylphenol ether compounds include: hydrazine, hydrazine, _ diallyl _ bisphenol A, 4, 4'-dihydroxy-3,3'-diallyldiphenyl, bis (4) _hydroxy_3_allylphenyl)methane, 2,2-bis(4-hydroxy-3,5-diallylphenyl)propane, hydrazine, 〇·-dimethylallyl-bisphenol A,4,4,_dihydroxy_3,3,_dimethylallyl 139263.doc -10· 200948834 bisbiphenyl, bis(4-hydroxy-3-methylallylphenyl)methane, 2 , 2-bis(4-hydroxy-3,5-dimethylallylphenyl)-propane, 4-methylallyl-2-methoxylate, 2,2-bis(4-oxime 3-allylphenyl)propane, 2,2-bis(4-methoxy-3-methylallylphenyl)propane, 4,4,-dimethoxy_3,3, _Diallyl one, 4,4-monodecyloxy-3,3'-dimethyl propyl diphenyl, bis(4-indolyl-3-allylphenyl)methane, double (4_decyloxy_3_methylallylphenyl) methane, 2,2-bis(4-decyloxy-3,5-diallylphenyl)propane, 2,2_bis ( 4_

曱氧基-3，5-二曱基烯丙基苯基）丙烷、4_烯丙基藜蘆醚及4_ 甲基烯丙基藜蘆醚。 烯基酚、烯基酚醚或其混合物可在約〇〇5莫耳至2〇莫耳/ 莫耳聚醯亞胺範圍内使用。在另一實施例中，烯基酚、烯 基賴或其混合物可在約〇]莫耳至1G莫耳/莫耳聚醯亞胺 範圍内使用。 適用胺觸媒包括三級、二級及—級胺或含有若干不同類 型胺基的胺及四級銨化合物。該等胺可為單胺或多胺且可 包括：二乙胺、三丙胺、三丁胺、三乙胺、三戊胺、节 胺、四甲基-二胺基二苯基甲燒、N具二異丁基胺基乙 腈、N，N-二丁基胺基乙腈、雜環鹼(例如喹琳、甲疾吡 略咬、咪唾、苯…及其同系物)、以及疏基苯二塞 唑。可提及之適宜四級錄化合物的實 化按及三甲基苯甲氧…丙胺係較佳者下基二甲基_ 胺觸媒可在佔預先反應物總重量之約〇1重量％_ 在另—實_中，胺觸媒可在 先反應物總重量之狀2重量％_5重量％之_ 139263.doc 200948834 用。 聚馬來醯亞胺預聚合物之製備方法包括下述步驟：摻和 聚醯亞胺與烯基酚'烯基酚醚或其混合物並將該摻合物加 熱至約25 C-150C之溫度直至獲得透明熔體。隨後可添加 胺觸媒並於約100°C -140°C溫度下使反應持續適量時間， 此後於真空下去除所有胺觸媒。可藉由於125t下使用〇_ 100泊等級量測樹脂熔體黏度來監測反應進展程度且對於 預形成聚馬來醯亞胺預聚合物而言該反應進展程度可在 20-85泊範圍内。亦可使用膠凝時間作為額外參數並反映 如於約170 C -175 C溫度下測定之總凝膠形成時間且該膠 凝時間可在300秒至2000秒範圍内。 可女疋貯藏之預形成聚馬來醯亞胺預聚合物組合物另外 包括下式（5)之二氧戊環：曱oxy-3,5-dimercaptopropyl phenyl)propane, 4-allenyl veratroleone and 4-methylallyl veridyl ether. The alkenylphenol, alkenylphenol ether or mixtures thereof can be used in the range of from about 5 moles to about 2 moles per mole of polyamidene. In another embodiment, the alkenyl phenol, the alkenyl lysine or a mixture thereof can be used in the range of from about 莫] mol to 1 G mol/molepolyimine. Suitable amine catalysts include tertiary, secondary and amines or amines and quaternary ammonium compounds containing several different types of amine groups. The amines may be monoamines or polyamines and may include: diethylamine, tripropylamine, tributylamine, triethylamine, triamylamine, amide, tetramethyl-diaminodiphenylcarbamate, N With diisobutylaminoacetonitrile, N,N-dibutylaminoacetonitrile, heterocyclic bases (such as quinoline, acetophenone, sodium saliva, benzene, and homologs thereof), and thiophenyl Setazole. The actual quaternary compound which can be mentioned is exemplified by trimethyl benzyl methoxy propylamine propylamine. The lower dimethyl amide catalyst can be about 重量 1% by weight based on the total weight of the prereactant. In another embodiment, the amine catalyst may be used in the form of 2% by weight to 5% by weight based on the total weight of the reactants _ 139263.doc 200948834. The preparation method of the polymaleimide prepolymer comprises the steps of: doping the polyimine with an alkenylphenol 'alkenylphenol ether or a mixture thereof and heating the blend to a temperature of about 25 C-150C Until a clear melt is obtained. The amine catalyst can then be added and the reaction allowed to continue for a suitable amount of time at a temperature of from about 100 ° C to 140 ° C, after which all amine catalyst is removed under vacuum. The degree of progress of the reaction can be monitored by measuring the viscosity of the resin melt using a 〇_100 poise rating at 125 t and the progress of the reaction can be in the range of 20-85 poise for the pre-formed polymaleimide prepolymer. Gel time can also be used as an additional parameter and reflects the total gel formation time as measured at a temperature of about 170 C - 175 C and the gel time can range from 300 seconds to 2000 seconds. The pre-formed polymaleimide prepolymer composition which can be stored by the privet is additionally comprising a dioxolane of the following formula (5):

二氧戊環可在佔可安定貯藏之預形成聚馬來醯亞胺預聚 合物組合物總重量的約i 〇重量％ 5 〇重量％範圍内使用。在 另一實施例中，二氧戊環可在佔可安定貯藏之預形成聚馬 來酿亞胺預聚合物組合物總重量的約17 5重量％_4〇重量 %、較佳約20重量％-3〇重量％範圍内使用。 可藉由在預先反應結束時將二氧戊環添加至聚馬來醯亞 胺預聚合物中來製備可安定貯藏之預形成聚馬來醯亞胺預 139263.doc 200948834 聚合物組合物。由此形成固體含量高（高達約8〇重量％)且 黏度低（50厘泊或更低）之組合物，其在室溫下或在高於室 溫之溫度下可安定數天而不會出現沉澱或黏度增加。 除上述組份外，亦可視需要在固化前之任一階段將可安 定貯藏之預形成聚馬來醯亞胺預聚合物組合物與一或多種 安定劑、有機溶劑、增量劑 '填充劑、增強劑、顏料、染 料、增塑劑、膠黏劑、橡膠、促進劑、稀釋劑或其任一混 合物混合。The dioxolane can be used in a range of from about 5% by weight to about 5% by weight based on the total weight of the pre-formed polymaleimide prepolymer composition of the shelf stable storage. In another embodiment, the dioxolane may comprise from about 175% by weight to about 4% by weight, preferably about 20% by weight, based on the total weight of the pre-formed polymaleimine prepolymer composition that can be stored in a stable storage. -3〇% by weight range. A pre-formable polymaleimide pre-formed 139263.doc 200948834 polymer composition can be prepared by adding dioxolane to the polymaleimide prepolymer at the end of the pre-reaction. Thereby forming a composition having a high solid content (up to about 8% by weight) and a low viscosity (50 centipoise or less), which can be settled for several days at room temperature or at a temperature above room temperature without Precipitation or viscosity increase. In addition to the above components, the pre-formed polymaleimide prepolymer composition and one or more stabilizers, organic solvents, extenders' fillers may be stored at any stage prior to curing, optionally at any stage prior to curing. , a reinforcing agent, a pigment, a dye, a plasticizer, an adhesive, a rubber, a promoter, a diluent, or a mixture thereof.

可使用之安定劑包括：啡料本身或具有⑴個取代基 之C-取代啡噻嗪或具有一個取代基之N_取代啡噻嗪（例 如，3-甲基-啡噻嗪、3_乙基_徘噻嗪、1〇_甲基-啡噻嗪；3· 苯基_啡嘆嗪、3,7·二苯基+塞嗪；3_氣啡„㈣、2_氣啡嗟 嗪、3-溴啡噻嗪；3_硝基啡噻嗪、3胺基啡噻嗪、二 胺基啡噻嗪；3-磺醯基-啡噻嗪、3,7_二磺醯基-啡噻嗪、 ❹ 3,7-二氰硫基啡噻嗪）；經取代奎寧與兒茶酚、環烷酸銅、 二甲基二硫碳酸辞；磷鉬酸水合物與磷鎢酸水合物。該等 安定劑可以佔預形成聚馬來醯亞胺預聚合物組合物總重量 之約0.1重量％-1〇重量％的量添加至可安定貯藏之預形成聚 馬來酿亞胺預聚合物組合物中。 可添加至可安定貯藏之預形成聚馬來醯亞胺預聚合物组 合物中之有機溶劑包括低沸點溶劑（沸點至高約160°C且較 佳至南約100°C )，例如，酮、二醇醚及二醇醚乙酸酯、 丈二甲氧基丙醇、一甲基甲隨胺及其混合物。可以佔預形 成聚馬來酿亞胺預聚合物組合物總重量至高約3 〇重量％、 139263.doc •13- 200948834 較佳至高約25重量％、且最佳至高約2〇重量％之量將有機 /合劑（當存在時）添加至可安定貯藏之預形成聚馬來醯亞胺 預聚合物組合物中。 可使用之增量劑、增強劑、填充劑、促進劑及顏料包括 (例如）·煤焦油、瀝青、玻璃纖維、硼纖維、碳纖維、纖 、准素、聚乙稀粉、聚丙烯粉、雲母、石棉、石英粉、石 膏、二氧化銻、有機性搬土（bent〇ne)、矽氣凝膠（「氣相 一氧化矽」）、鋅鋇白（lith〇p〇ne)、重晶石、二氧化鈦丁 香酚（eugenoD、過氧化二異丙苯、異丁香酚、碳黑、石 墨、及鐵粉。亦可向該預形成聚馬來醯亞胺預聚合物組合 物中添加其他添加劑，例如，防火劑、流動控制劑（例 如，聚矽氧）、乙酸丁酸纖維素、聚丁酸乙烯酯 '蠟、硬 脂酸酯及諸如此類（其等亦可部分地用作脫膜劑）。 上述可安定貯藏之預形成聚馬來醯亞胺預聚合物組合物 可適用於眾多最終用途中，％如，預浸片、各種厚度之層 壓板、印刷電路板、鑄件、複合材料、模製物件、黏合劑 及塗料中。 可藉由使用可安定貯藏之預形成聚馬來醯亞胺預聚合物 組合物浸潰或塗佈基材來獲得預浸片。該基材包括用於層 壓板之所有基材。其實例包括諸如E玻璃布、NE玻璃布及 D玻璃布等各種玻璃布、天然無機纖維織物、自諸如芳族 聚醯胺纖維或芳族聚酯纖維等液晶纖維獲得之織造織物及 非織造織物、自諸如聚乙料纖維m维或丙稀酸纖 維等合成纖維獲得之織造織物及非織造織物、諸如棉織 139263.doc -14- 200948834 、碳纖維織 天然纖維素 物、亞麻織物或毛氈等天然纖維非織造織物 物諸如牛皮紙、棉紙或紙-玻璃組合型紙等 型織物、及多孔PTFE。 在-個實施例中，使用本發明之預形成聚馬來醯亞胺預 $合物組合物來浸潰或塗佈聚合物基材。該聚合物基材不 文特別限制，只要其係使用聚合物之織造織物、非織造織 物、薄片或多孔體即可。其實例包括液晶聚合物，例如、、，Stabilizers which may be used include: the granule itself or a C-substituted phenothiazine having (1) substituent or an N-substituted phenothiazine having a substituent (for example, 3-methyl-phrothiazide, 3_B徘 徘 徘 嗪, 〇 甲基 甲基 甲基 ; ; ; ; ; ; ; ; ; 甲基 甲基 甲基 甲基 甲基 甲基 啡 啡 啡 啡 啡 啡 啡 啡 啡 啡 啡 甲基 啡 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基3-bromomorphothiazine; 3-nitrophenothiazine, 3-aminophenothiazine, diaminophenothiazine; 3-sulfonyl-phenothiazine, 3,7-disulfonyl-morphine Pyrazine, ruthenium 3,7-dicyaniothiophenothiazine; substituted quinine with catechol, copper naphthenate, dimethyl disulfide carbonate; phosphomolybdic acid hydrate and phosphotungstic acid hydrate. The stabilizer may be added to the pre-formable polymaleimide prepolymer which is stable for storage in an amount of from about 0.1% by weight to about 1% by weight based on the total weight of the preformed polymaleimide prepolymer composition. The organic solvent which can be added to the pre-formed polymaleimide prepolymer composition which can be stably stored comprises a low boiling point solvent (boiling point up to about 160 ° C and preferably up to about 100 ° C in the south). For example, ketones, glycol ethers, and glycol ether acetates, Dimethoxypropanol, monomethylmethanamide, and mixtures thereof, may comprise up to about 3% by weight of the total weight of the preformed polymaleimine prepolymer composition, 139263.doc • 13-200948834 preferably Adding the organic/mixture (when present) to the pre-formable polymaleimide prepolymer composition that can be safely stored in an amount up to about 25% by weight, and optimally up to about 2% by weight. Extenders, reinforcing agents, fillers, accelerators and pigments include, for example, coal tar, asphalt, glass fiber, boron fiber, carbon fiber, fiber, elemental, polyethylene powder, polypropylene powder, mica, asbestos, Quartz powder, gypsum, cerium oxide, organic soil (bent〇ne), helium gel ("gas phase cerium oxide"), zinc lanthanum (lith〇p〇ne), barite, titanium dioxide clove Phenol (eugenoD, dicumyl peroxide, isoeugenol, carbon black, graphite, and iron powder. Other additives such as fire retardants may also be added to the pre-formed polymaleimide prepolymer composition. , flow control agent (eg, polyoxyl), acetic acid butyric acid Vitamins, polybutyric acid vinyl esters' waxes, stearates, and the like (which may also be used in part as a release agent). The above-preparable pre-formed polymaleimide prepolymer composition can be stored Suitable for a wide range of end uses, such as prepregs, laminates of various thicknesses, printed circuit boards, castings, composites, molded parts, adhesives and coatings. Preformed poly-polymers can be used for stable storage. The maleic imine prepolymer composition is impregnated or coated with a substrate to obtain a prepreg. The substrate includes all substrates for the laminate. Examples thereof include E glass cloth, NE glass cloth, and D glass. Various glass cloths such as cloth, natural inorganic fiber fabrics, woven fabrics and nonwoven fabrics obtained from liquid crystal fibers such as aromatic polyamide fibers or aromatic polyester fibers, from m-dimensional or acrylic fibers such as polyethylene fibers Woven fabrics and nonwoven fabrics obtained by synthetic fibers, natural fiber nonwoven fabrics such as cotton woven 139263.doc -14- 200948834, carbon fiber woven natural cellulose, linen fabric or felt, such as kraft paper, cotton Or paper - Combined glass paper fabrics, and porous PTFE. In one embodiment, the preformed polymaleimide pre-form composition of the present invention is used to impregnate or coat a polymeric substrate. The polymer substrate is not particularly limited as long as it is a woven fabric, a nonwoven fabric, a sheet or a porous body of a polymer. Examples thereof include liquid crystal polymers, for example, ,

以芳族聚醯胺、聚伸苯基苯并噻唑為代表之液致型液晶聚 合物；以芳族聚醋、聚醋醯胺、聚醯胺、芳族聚醯胺樹 脂、聚苯越、聚苯硫謎、聚乙稀、聚丙婦、及含氣樹脂為 代表之熱致型液晶聚合物。根據需要，可端視期望應用或 效能來恰當地選擇該聚合物。根據需要，該等聚合物可單 獨或以組合方式使用。基材厚度不受特別限制。通常，其 為約 3 μηι至 200 μιη。 製k預ik;片之方法不受特別限制，只要其可將可安定貯 藏之預形成聚馬來醯亞胺預聚合物組合物與基材組合在一 起以製造該預浸片即可。在一個實施例中提供一種方法， /、中將上述預形成聚馬來醯亞胺預聚合物組合物浸潰或施 加於基材上且隨後將其在（例如）乾燥器中於8〇(>c至下 加熱1分鐘至90分鐘以使該組合物到達B_階段並由此製造 預改片。預浸片之樹脂含量可在約30重量0/〇_9〇重量％範圍 内。 亦可藉由堆疊一種預浸片或至少兩種預浸片、於該（等） 經堆疊預浸片之上表面及下表面或一個表面上層壓金屬箔 139263.doc -15- 200948834 (例如，鋼箔或鋁箔）並對所得組合件實施加熱及加壓來獲 得具有金屬包層之層壓板。 用於印刷線路板之層壓板及多層板的一般技術可應用於 具有金屬包層之層壓板的模塑條件。舉例而言，通常，多 層式印壓機、多層式真空印壓機、連續模塑機、高壓蒸氣 模塑機或諸如此類係在約〗0(rc _30(rc之溫度及約〇 2 Mpa_ 10 MPa之壓力下使用且加熱時間為約〇 15小時。此外， 亦可能藉由將本發明預浸片與單獨製備的内層線路板組合 在一起且對所得組合件實施層壓模塑來製造多層板。 在具體實施例中，預浸片或層壓板結構包含經可安定貯 藏之預形成聚馬來醯亞胺預聚合物組合物浸潰或塗佈之基 材的固化產物，該可安定貯藏之預形成聚馬來醯亞胺預聚 合物組合物包含⑴在胺觸媒存在下由聚醯亞胺與烯基酚、 烯基酚醚或其混合物之預先反應形成的聚馬來醯亞胺預聚 合物；及（ii)二氧戊環。 實例 實例1.本實例闡釋本發明之可安定貯藏之預形成聚馬 來酿亞胺預聚合物組合物的製備。 調配物 重量份數 N，N'-4，f-二苯基甲烷雙馬來醯亞胺 40-45 4,4’-(曱基亞乙基)雙(2-丙稀基)驗 30-35 三丙胺 〇.1-1.0 1,3-二氧戊環 20-30 璘鶴酸水合物 0.1-1.0 將4,4，-(甲基亞6基）雙（2-丙婦基）齡裝人反應器中並置 139263.doc -16- 200948834 於真空下。將N，N'-4,4’-二苯基曱烷雙馬來醯亞胺添加至該 反應器中並使其與4,4’-(曱基亞乙基）雙（2-丙烯基）酚混合以 形成反應混合物。將反應混合物加熱至132°C並隨後置於 真空下，且隨後在反應混合物變成透明琥珀色溶液時使其 冷卻至100°C。將三丙胺添加至該溶液中並連續攪拌30分 鐘。此後，使溫度升至12(TC並維持於該溫度下且將溶液 於真空下放置1.5小時。移除真空並將1,3-二氧戊環添加至 溶液中且使溫度維持在120°C溫度下直至達成40-45泊之黏 度。隨後使溶液冷卻至50°C，此後添加磷鎢酸水合物。該 預形成聚馬來醯亞胺預聚合物組合物隨後自反應器排出且 於171 °C下展示膠凝時間為963秒。 將該形成聚馬來醯亞胺預聚合物組合物之試樣於4°C、 室溫及50°C下貯藏一段時期且以確定的間隔量測試樣之膠 凝時間（T=171°C )。結果呈現於表1中： 表1 貯藏天數 在4°C下貯藏之 膠凝時間(秒） 在室溫下貯藏之 膠凝時間(秒） 在50°C下貯藏之 膠凝時間(秒> 0 963.0 963.0 963.0 7 980.0 968.0 901.0 14 930.9 945.3 579.0 21 899.3 769.6 355.2 28 801.2 546.8 289.3 35 744.3 465.8 201.6 42 699.6 401.5 膠凝 49 685.1 375.5 膠凝 56 663.0 345.2 膠凝 139263.doc -17- 200948834 此外，吾人觀察到每一試樣經相同時間間隔的沉澱量且 結果呈現於表2中： 表2 貯藏天數 4°C貯藏溫度下 之沉澱量 室溫貯藏溫度下 之沉澱量 50°C貯藏溫度下 之沉澱量 0 無 無 無 7 無 無 無 14 無 無 無 21 無 無 無 28 無 無 無 35 無 無 無 42 無 無 膠凝 49 無 無 膠凝 56 無 無 膠凝 比較實例1中所製備預形成預聚合物組合物的貯藏安定 性與根據實例1但用曱基乙基酮替代二氧戊環製備之預聚 合物組合物的貯藏安定性。將比較預聚合物組合物試樣於 4°C及50°C下貯藏一段時期且以確定的間隔量測該等試樣 之膠凝時間（171°C)。結果呈現於表3中： 139263.doc 18· 200948834 表3(比較） 貯藏天數 4°C貯藏溫度下之 膠凝時間(秒） 50°C貯藏溫度下之 膠凝時間(秒） 0 399.6 399.6 7 328.5 365.0 14 207.1 387.5 21 322.6 249.5 28 180.0 151.6 35 178.7 133.2 41 161.3 30.1 如圖1中所闡釋，本發明之預形成預聚合物組合物當在 室溫下貯藏時經至少56天時間後之膠凝時間（T=171°C )係 大於300秒。此外，與在50°C下貯藏之比較預聚合物組合 物相比，本發明之預形成預聚合物組合物當於50°C下貯藏 一段時間時展示更長膠凝時間。 實例2本實例闡釋本發明之可安定貯藏之預形成聚馬來 醯亞胺預聚合物組合物的製備。 調配物 重量份數 N-N'-4,4’-二苯基曱烷雙馬來醯亞胺 25-30 4,4'-(甲基亞乙基)雙(2-丙稀基)紛 30-35 三丙胺 0.1-1.0 啡隹嗓 0.1-1.0 磷鎢酸水合物 0.1-1.0 1,3-二氧戊環 15-25 乙酸甲氧基丙醇酯 15-25 將4,4’-(甲基亞乙基）雙（2-丙烯基）酚裝入反應燒瓶中並 ❹ __ 139263.doc •19- 200948834 置於真空下。將N,N’-4,4’-二苯基甲烷雙馬來醯亞胺添加至 該反應燒瓶中並與4,4'-(甲基亞乙基）雙（2-丙烯基）酚混合以 形成反應混合物，將該反應混合物加熱至132°C。隨後將 反應燒瓶置於真空下，且在變成透明琥珀色溶液時，使其 冷卻至100°C。將三丙胺添加至該溶液中並連續攪拌30分 鐘。此後，使溫度升至120°C並將溶液於真空下放置1.5小 時。移除真空，添加1,3-二氧戊環，且使混合物維持在 1 20°C溫度下直至達到40-45泊之黏度為止。隨後使混合物 冷卻至50°C，此後添加啡噻嗪及乙酸甲氧基丙醇酯。攪拌 1 5分鐘後，添加磷鎢酸水合物。隨後自反應燒瓶排出預形 成預聚合物組合物。 隨後將該預形成預聚合物組合物之試樣於4°C、室溫及 5 0°C下貯藏一段時期且以確定的間隔量測該等試樣之膠凝 時間（T=171°C )。結果呈現於表4中： 表4 貯藏天數 4°C下貯藏之膠凝 時間(秒） 室溫下貯藏之膠凝 時間(秒） 5CTC下貯藏之膠凝 時間(秒） 0 1827.2 1827.2 1827.2 7 1248.5 1216.5 713.1 14 1240.6 1257.8 710.0 21 1222.5 1259.2 722.8 28 1171.9 1255.9 751.5 35 1162.2 1229.9 733.3 42 1101.0 1212.8 695.5 49 1058.1 1189.1 628.7 56 998.5 1166.9 599.8 139263.doc •20- 200948834 比較實例2中所製備預形成預聚合物組合物的貯藏安定 性與根據實例2但用甲基乙基酮替代二氧戊環製備之預聚 合物組合物的貯藏安定性。將該比較預聚合物組合物之試 樣於4 C及50 C下貯藏一段時期且以確定的間隔量測該等 試樣之膠凝時間（T=171°C)。結果呈現於表5中： 表5 (比較） 貯藏天數 4°C貯藏溫度下之膠凝 50°C貯藏溫度下之朦凝 時間(秒） 時間(秒） 0 402.6 402.6 7 323.6 361.5 14 320.2 ---——-~~-_ __ 340.3 21 290.3 305.2 28 249.6 210.4 35 259.4 156 9 42 256.7 120.8 49 270.1 114 7 56 262.3 ____ ® 如圖2中所闡釋，本發明之預形成聚馬來醯亞胺預聚合 物組σ物虽在至溫及5〇 c下貯藏時經至少56天時期後之膠 . 凝打間（Τ一171 C )係大於300秒。此外，與在5〇°c下貯藏之 .比較預聚合物組合物相比，本發明之預形成聚馬來醯亞胺 預聚合物組合物當在50。〇下貯藏一段時間時展示更長膠凝 時間。 應將上文所揭示標的物視為說明性而非限制性，且隨附 申印專利範圍意欲涵盍屬於本發明真實範疇内之所有此等 修改、改進及其他實施命j。因&，在法律准許之最大程度 139263.doc -21. 200948834 上，本發明之範疇將由下文申請專利範圍及其等效内容之 所容許的最廣泛解釋來確定，且不應由前述詳細說明限定 或限制。 【圖式簡單說明】 圖|及圖2闡釋預形成聚馬來醯亞胺預聚合物組合物於各 種貯藏溫度下隨時間的安定性。 139263.doc 22·Liquid-induced liquid crystal polymer represented by aromatic polyamine, polyphenylene benzothiazole; aromatic polyacetate, polyacetamide, polyamine, aromatic polyamide resin, polyphenylene, A heat-induced liquid crystal polymer represented by polyphenylene sulfide, polyethylene, polypropylene, and a gas-containing resin. The polymer can be properly selected depending on the desired application or performance, as desired. These polymers may be used singly or in combination as needed. The thickness of the substrate is not particularly limited. Usually, it is about 3 μη to 200 μηη. The method of preparing the sheet is not particularly limited as long as it can combine the pre-formed polymaleimide prepolymer composition which can be stably stored with the substrate to manufacture the prepreg. In one embodiment, a method is provided in which the preformed polymaleimide prepolymer composition is impregnated or applied to a substrate and subsequently placed in, for example, a dryer at 8 Torr ( >c is heated down for 1 minute to 90 minutes to bring the composition to the B-stage and thereby produce a pre-modified sheet. The resin content of the prepreg sheet may be in the range of about 30% by weight/〇9% by weight. The metal foil 139263.doc -15- 200948834 may also be laminated on the upper surface and the lower surface or a surface of the stacked prepreg by stacking a prepreg or at least two prepregs (for example, Steel foil or aluminum foil) and heating and pressurizing the resulting assembly to obtain a laminate having a metal cladding. The general technique for laminates and multilayer boards for printed wiring boards can be applied to laminates having metal cladding. Molding conditions. For example, generally, a multi-layer press, a multi-layer vacuum press, a continuous molding machine, a high-pressure vapor molding machine, or the like is at about 00 (rc _30 (temperature of rc and about 〇 2 Mpa_ 10 MPa pressure and heating time is about 15 small Further, it is also possible to manufacture a multilayer board by combining the prepreg of the present invention with a separately prepared inner layer wiring board and subjecting the resulting assembly to lamination molding. In a specific embodiment, the prepreg or laminate The structure comprises a cured product of a substrate impregnated or coated with a pre-formable polymaleimide prepolymer composition that can be stably stored, the preservable pre-formed polymaleimide prepolymer composition Containing (1) a polymaleimide prepolymer formed by pre-reacting a polyimine with an alkenylphenol, an alkenylphenol ether or a mixture thereof in the presence of an amine catalyst; and (ii) dioxolane. EXAMPLE 1. This example illustrates the preparation of a prestable polymaleimine prepolymer composition of the present invention which can be stably stored. Formulation parts by weight N, N'-4, f-diphenylmethane double horse醯iamine 40-45 4,4'-(decylethylene) bis(2-propenyl) 30-35 tripropylamine 〇.1-1.0 1,3-dioxolan 20-30 璘Acid hydrate 0.1-1.0 Juxtaposed in 4,4,-(methylbenzylidene) bis(2-propanyl) aged human reactor 139263.doc -16- 200948834 N.N'-4,4'-diphenylnonane bismaleimide was added to the reactor and made with 4,4'-(mercaptoethylene) bis (2 The -propenyl)phenol is mixed to form a reaction mixture. The reaction mixture is heated to 132 ° C and then placed under vacuum, and then allowed to cool to 100 ° C as the reaction mixture becomes a clear amber solution. Add tripropylamine to The solution was stirred continuously for 30 minutes. Thereafter, the temperature was raised to 12 (TC and maintained at this temperature and the solution was placed under vacuum for 1.5 hours. The vacuum was removed and 1,3-dioxolane was added to the solution. The temperature was maintained at 120 ° C until a viscosity of 40-45 poise was achieved. The solution was then cooled to 50 ° C, after which phosphotungstic acid hydrate was added. The preformed polymaleimide prepolymer composition was then discharged from the reactor and exhibited a gel time of 963 seconds at 171 °C. The sample forming the polymaleimide prepolymer composition was stored at 4 ° C, room temperature and 50 ° C for a period of time and the gelation time of the test sample was determined at a certain interval (T=171°). C). The results are presented in Table 1: Table 1 Gelation time of storage at 4 ° C (seconds) Gelation time stored at room temperature (seconds) Gelation time stored at 50 ° C (seconds) 0 963.0 963.0 963.0 7 980.0 968.0 901.0 14 930.9 945.3 579.0 21 899.3 769.6 355.2 28 801.2 546.8 289.3 35 744.3 465.8 201.6 42 699.6 401.5 Gelation 49 685.1 375.5 Gelation 56 663.0 345.2 Gelation 139263.doc -17- 200948834 In addition, we observe The amount of precipitation to each sample at the same time interval and the results are presented in Table 2: Table 2 Storage days 4 ° C Storage temperature at the storage temperature Precipitation at room temperature Storage temperature 50 ° C storage temperature at the storage temperature 0 No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No The storage stability of the composition was compared to the storage stability of a prepolymer composition prepared according to Example 1 but substituting mercaptoethyl ketone for dioxolane. The prepolymer composition samples were compared at 4 ° C and 50 °. C under The gelation time (171 ° C) of the samples was measured for a period of time and at defined intervals. The results are presented in Table 3: 139263.doc 18· 200948834 Table 3 (Comparative) Storage days 4 ° C storage temperature Gelation time (seconds) Gelation time at 50 ° C storage temperature (seconds) 0 399.6 399.6 7 328.5 365.0 14 207.1 387.5 21 322.6 249.5 28 180.0 151.6 35 178.7 133.2 41 161.3 30.1 As illustrated in Figure 1, the present invention The preformed prepolymer composition has a gel time (T = 171 ° C) for at least 56 days after storage at room temperature for more than 300 seconds. In addition, prepolymerization compared to storage at 50 ° C The pre-formed prepolymer composition of the present invention exhibits a longer gel time when stored at 50 ° C for a period of time compared to the composition. Example 2 This example illustrates the pre-formed polyma of the stable storage of the present invention. Preparation of quinone imine prepolymer composition. Formulation parts by weight N-N'-4,4'-diphenylnonane bismaleimide 25-30 4,4'-(methyl-AB Base) bis(2-propanyl) 30-35 tripropylamine 0.1-1.0 morphine 0.1-1.0 phosphotungstic acid hydrate 0.1-1.0 1,3-dioxolan 15-25 methoxypropanol acetate 15-25 4,4'-(methylethylene)bis(2-propenyl)phenol was charged to the reaction flask and ❹__ 139263.doc •19- 200948834 placed under vacuum. N,N'-4,4'-diphenylmethane bismaleimide was added to the reaction flask and mixed with 4,4'-(methylethylene)bis(2-propenyl)phenol To form a reaction mixture, the reaction mixture was heated to 132 °C. The reaction flask was then placed under vacuum and allowed to cool to 100 ° C when it became a clear amber solution. Tripropylamine was added to the solution and stirring was continued for 30 minutes. Thereafter, the temperature was raised to 120 ° C and the solution was allowed to stand under vacuum for 1.5 hours. The vacuum was removed, 1,3-dioxolane was added, and the mixture was maintained at a temperature of 1200 ° C until a viscosity of 40-45 poise was reached. The mixture was then cooled to 50 ° C, after which time phenothiazine and methoxypropanol acetate were added. After stirring for 15 minutes, phosphotungstic acid hydrate was added. The preformed composition is then pre-formed from the reaction flask. The sample of the preformed prepolymer composition is then stored at 4 ° C, room temperature and 50 ° C for a period of time and the gelation time of the samples is measured at defined intervals (T = 171 ° C). ). The results are presented in Table 4: Table 4 Storage days gelation time at 4 ° C (seconds) Gelation time at room temperature (seconds) Gelation time at 5 CTC (seconds) 0 1827.2 1827.2 1827.2 7 1248.5 1216.5 713.1 14 1240.6 1257.8 710.0 21 1222.5 1259.2 722.8 28 1171.9 1255.9 751.5 35 1162.2 1229.9 733.3 42 1101.0 1212.8 695.5 49 1058.1 1189.1 628.7 56 998.5 1166.9 599.8 139263.doc • 20- 200948834 Preformed prepolymer composition prepared in Comparative Example 2 The storage stability of the prepolymer composition prepared according to Example 2 but with methyl ethyl ketone instead of dioxolane was determined. The comparative prepolymer composition samples were stored at 4 C and 50 C for a period of time and the gelation time (T = 171 ° C) of the samples was measured at defined intervals. The results are presented in Table 5: Table 5 (Comparative) Storage days 4 ° C storage temperature gelation 50 ° C storage temperature condensation time (seconds) Time (seconds) 0 402.6 402.6 7 323.6 361.5 14 320.2 -- -——-~~-_ __ 340.3 21 290.3 305.2 28 249.6 210.4 35 259.4 156 9 42 256.7 120.8 49 270.1 114 7 56 262.3 ____ ® As illustrated in Figure 2, the pre-formed polymaleimide of the present invention is pre-formed. The polymer group σ substance is stored at a temperature of 5 ° C for at least 56 days after the gel. The condensate (Τ 171 C ) system is greater than 300 seconds. In addition, the preformed polymaleimide prepolymer composition of the present invention is at 50 compared to the prepolymer composition stored at 5 °C. A longer gel time is displayed when stored under the armpit for a period of time. The above-identified subject matter should be considered as illustrative and not limiting, and the scope of the appended claims is intended to cover all such modifications, improvements and other embodiments. The scope of the present invention is determined by the broadest interpretation of the scope of the claims below and the equivalents thereof, and should not be Limit or limit. BRIEF DESCRIPTION OF THE DRAWINGS Figure | and Figure 2 illustrate the stability of a preformed polymaleimide prepolymer composition over time at various storage temperatures. 139263.doc 22·

Claims (1)

200948834 七、申請專利範圍： 1. 一種可安定貯藏之箱游士胃 預$成聚馬來酿亞胺預聚合物組合 物，其包含： ⑷在胺觸媒存在下由聚醯亞胺與烯基酚、烯基酚醚或 其&物之預先反應形成之聚馬來醯亞胺預聚合 物；及 ‘ （b)下式（5)之二氧戊環：200948834 VII. Scope of application for patents: 1. A safe and stable storage box for the pre-polymerization of the pre-male, which comprises: (4) from the polyamine and the alkene in the presence of an amine catalyst a polymaleimide prepolymer formed by pre-reaction of a phenol, an alkenyl phenol ether or a &< (b) a dioxolane of the following formula (5): 2.如請求項丄之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其中該聚醯亞胺係下式之雙馬來醯亞胺：2. A pre-formed polymaleimide prepolymer composition as claimed in the claims, wherein the polyimine is of the formula bismaleimide: 〇II〇II R1R1 其中 R1 係氫或曱基且)U^'n=2之CnH2n_、_CH2CH2SCH2CH2_ 、伸苯基、奈、二甲苯、伸環戊基、i，5,5_三曱基_丨，3•伸 環己基、1，4-伸環己基、“κ亞甲基）_伸環己基、或 下式（a)之基團： 139263.doc 200948834 R2 R3CnH2n_, _CH2CH2SCH2CH2_, phenyl, naphthyl, xylene, cyclopentyl, i,5,5-tridecyl-丨, 3·extension ring, wherein R1 is hydrogen or fluorenyl and U^'n=2 Hexyl, 1,4-cyclohexylene, "κ methylene"-cyclohexylene, or a group of the following formula (a): 139263.doc 200948834 R2 R3 - (a) 其中r2及R3獨立地為氯、溴、曱基、乙基、或氫且z 為直接鍵、亞甲基、2,2-亞丙基、-CO-、-Ο-、-S-、-SO-或-S〇2-。 3. 如請求項2之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其中Ri係甲基，X係六亞曱基、三曱基六亞 甲基、1，5,5-三曱基-L3-伸環己基或式（a)之基團，其中z 係亞甲基、2,2-亞丙基或―小且尺2及R3係氫。 4. 如請求項2之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物’其中該雙馬來醯亞胺係N，N，_4,4I_二苯基甲烷 雙馬來醯亞胺。 5. 如請求項1之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其中該烯基酚或烯基酚醚係以下式之 化合物：- (a) wherein r2 and R3 are independently chloro, bromo, decyl, ethyl or hydrogen and z is a direct bond, methylene, 2,2-propylene, -CO-, -Ο-, - S-, -SO- or -S〇2-. 3. A pre-formed polymaleimide prepolymer composition as claimed in claim 2, wherein Ri is methyl, X is hexamethylene, tridecylhexamethylene, 1,5, 5-trimethyl-L3-cyclohexylene or a group of formula (a) wherein z is methylene, 2,2-propylene or "small and 2 and R3 are hydrogen. 4. The pre-formed polymaleimide prepolymer composition as claimed in claim 2, wherein the bismaleimide N, N, _4, 4I-diphenylmethane double mala Imine. 5. A pre-formed polymaleimide prepolymer composition as claimed in claim 1, wherein the alkenylphenol or alkenylphenol ether is a compound of the formula: ch2=chch2 其中R係直接鍵、亞甲基、亞異丙基、-〇-、-s-、-SO-或-S02-; 139263.doc 200948834 OHCh2=chch2 wherein R is a direct bond, methylene, isopropylidene, -〇-, -s-, -SO- or -S02-; 139263.doc 200948834 OH (2) 其中R、R5及R6各自獨立地為氫或C2_Ci〇烯基，其限 制條件為R4、R5或R6中之至少—者係C2_Ci〇烯基；(2) wherein R, R5 and R6 are each independently hydrogen or C2_Ci nonenyl, and the restriction condition is at least one of R4, R5 or R6, which is a C2_Ci nonenyl group; (3) 立地為氫或C2-Ci()烯基， 中之至少一者係C2_ClO烯 其中R4、R5、R6及R7各自獨 其限制條件為R4、R5、R6戍R7 基且R係如式（1)中所定義；且(3) The site is hydrogen or a C2-Ci() alkenyl group, at least one of which is a C2_ClO alkene wherein each of R4, R5, R6 and R7 is independently restricted to R4, R5, R6戍R7 and R is as defined As defined in (1); and 其中 R8、R9、Rl0、 11 OHWhere R8, R9, Rl0, 11 OH R12及R13各自獨立地為氫、 R 1 4烷基&C2-C1()烯基，其限制條件為尺8、r9、Rl〇、 R11、R12 及 R13 中夕 s 〆 〉、一者係C2-CiQ烯基且b係〇至i〇之 登数。 139263.doc 200948834 6. 如請求項1之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其進一步包含選自鱗鶴酸水合物及填钥酸水 合物之安定劑。 7. 如請求項6之可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物，其進—步包含二酵醚。 8. —種用於製備可安定貯藏之預形成聚馬來醯亞胺預聚合 物組合物的方法，其包含以下步驟： (a) 在胺觸媒存在下使聚醯亞胺與烯基紛、稀基紛醚或 其渴•合物於高溫下反應，以形成聚馬來醯亞胺預聚 合物； (b) 實質上地去除所有該胺觸媒；且 (c) 將二氧戊環添加至該聚馬來醯亞胺預聚合物中，以 形成該可安定貯藏之預形成聚馬來醯亞胺預聚合物 組合物。 9. 如請求項8之方法’其進一步包含在步驟（b)之後將安定 劑添加至該聚馬來醯亞胺預聚合物中之步驟。 10. —種可安定貯藏之預形成聚馬來醯亞胺預聚合物組合 物，其係藉由如請求項8之方法製備。 11-種預浸片’其包含經可安定貯藏之預形成聚馬來醯亞 胺預t s物組合物浸潰或塗佈之織物或纖維的固化產 忒可安定貯藏之預形成聚馬來醯亞胺預聚合物組合 物包含： (a)在胺觸媒存在下由聚酿亞胺與稀基#、稀基盼喊或 見〇物之預先反應形成之聚馬來酿亞胺預聚合 139263.doc 200948834 物·，反 (b)下式（5)之一氧戊環：R12 and R13 are each independently hydrogen, R 4 4 alkyl & C 2 -C 1 () alkenyl, and the limitation conditions are 尺 8 , r 9 , R 〇 , R 11 , R 12 and R 13 、 s 〆 〉 C2-CiQ alkenyl and b is the number of 〇 to i〇. 139263.doc 200948834 6. The pre-formed polymaleimide prepolymer composition of claim 1 which is stable to store, further comprising a stabilizer selected from the group consisting of targituric acid hydrate and hydrazone acid hydrate. 7. A pre-formed polymaleimide prepolymer composition as claimed in claim 6 which further comprises a di-ether ether. 8. A process for the preparation of a shelf stable pre-formed polymaleimide prepolymer composition comprising the steps of: (a) bringing the polyimine and the alkenyl group in the presence of an amine catalyst , the dilute ether or its thirst compound is reacted at a high temperature to form a polymaleimide prepolymer; (b) substantially removes all of the amine catalyst; and (c) dioxolane Addition to the polymaleimide prepolymer to form the shelf stable pre-formed polymaleimide prepolymer composition. 9. The method of claim 8 which further comprises the step of adding a stabilizer to the polymaleimide prepolymer after step (b). 10. A pre-formed polymaleimide prepolymer composition which is stable to storage and which is prepared by the method of claim 8. 11-prepreg sheet comprising a pre-formed polymalam that can be stably stored by solidification of a fabric or fiber impregnated or coated with a pre-formed polymaleimide pre-ts composition that can be stably stored. The imine prepolymer composition comprises: (a) a polymaleimine prepolymerization formed by the pre-reaction of polystyrene with a dilute base, a dilute base or a sputum in the presence of an amine catalyst 139263 .doc 200948834 物·, 反 (b) One of the following formula (5) oxylan: 12. -種層餘結構，其包含經可安定貯藏之預形成聚馬來 醯亞胺預聚合物組合物浸潰或塗佈之織物或纖維的固化 產物，該可安定貯藏之預形成聚馬來醯亞胺預聚合物組 合物包含： ⑷在胺觸媒存在下由㈣亞胺與烯絲、烯基紛喊或 其/昆σ物之預先反應形成之聚馬來醯亞胺預聚合 物；及 (b)下式（5)之二氧戊環：12. A residual layer structure comprising a cured product of a fabric or fiber impregnated or coated by a pre-formable polymaleimide prepolymer composition that is stable to storage, the pre-formed poly-horse that can be stably stored The imine imine prepolymer composition comprises: (4) a polymaleimide prepolymer formed by the pre-reaction of a (iv) imine with an olefin, an alkenyl group or a quinone in the presence of an amine catalyst. And (b) dioxolane of the following formula (5): 139263.doc139263.doc
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