1243174 A71243174 A7
五、發明說明（！） 經濟部智慧財產局員工消費合作社印製 本發明係關於特定的雙_甲矽烷基三級胺之新穎結構及其 製造與用途。 胺基矽纪在無機物（例如，二氧化矽、含矽填孔劑、金屬 氧化物及陶瓷等）與有機物（例如，樹脂）偶合作用中，以有 機物形成互穿的聚合物網路及有機物與矽酮物質之交聯作 用中具有許多用途。大部份的這些矽烷只包括一級或二級 胺耳能度。但是，一級及二級胺官能度可能具有過度反應 ’在最終的應用配方中遭受副反應及隨時間喪失效率。 而且，許多二級胺係利用單、二或三烷氧基官能矽烷合 成的。因此，以矽烷形成不受期望的聚矽氧烷會連累在水 溶液中的應用，例如，安定的立體結構。這些結構附著很差。 本發明的概沭 以化學式（I) [((R^YXRYaSiRtNX之雙-甲矽烷基三級胺 才疋供受制之反應性及良好的附著力，其中Rl及R2是單價 基，R3是二價基，X是含基之單價羰基，γ是氧、氮或硫， a=l至3，而b=l或2，其係根據γ的價而定。 本發明的詳細説明 在以上的化學式I中，每一個R1是單價基，例如，氫、甲 矽烷基、亞胺基、二烷基或以烴官能度較佳，包括芳基、 晞丙基、環烷基、烷基（線型或支化）或芳烷基，其可以包 括雜原子，例如，氧、氮或硫），但不限於此。Ri也可以是 -4 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事*^:填寫本頁) 裝 •k· 經濟部智慧財產局員工消費合作社印製 1243174 Α7 ____Β7__ 五、發明說明（2 ) 甲石夕基έ能度或基έ能度（例如，三曱氧基甲石夕燒基或 乙醯基）。R1的實例是-N=C(CH3)2、-Si(OCH3)3及-CH=CHCH3 。R1是1至1 0個碳原子之烷基最佳，例如，甲基、乙基、 異丙基、環己基或特丁基。 Υ是選自氧、氮或硫之雖原子。b値係根據γ的價而定， 即Y =氧或硫’則b = 1 ’並且γ =氮，則b = 2。Y是氧較佳。 a是3較佳，但是，如果a<3時，則每一個R2是單價基， 其包括烴基、飽和烴、不飽和烴或氰基，但不限於此。R2 是環烷基、烷基（線型或支化）或芳烷基較佳，其可以包括 雜原子，例如，氧、氮或硫。以實例説明的R2包括苯基、 苯乙基、3 -氧丁基或2 -甲氧基丙基。R2是甲基或乙基最佳 R3是二價架橋基，其包括伸烷基、烷基伸芳基、伸芳基 或聚環氧燒輕，但不限於此，但是，以Ci-Ci2伸烷基較佳， 例如，伸丙基或伸丁基，但是，可將其支化，例如，新伸 戊基，環系，例如，二伸甲基環己烷，或不飽和，例如， 二伸甲基環己烯。R3可以包括雜原子取代物，例如，尺3可 以包括或在主鏈上，或在接於主鏈之側鏈上之胺基。如果 R3包括胺耳能度，則每一個其中的胺是三級胺。R3的特殊 實例是伸丙基、正伸丁基、伸苯基、二（伸乙基）乙基胺及 聚氧伸乙基。 X是含單價基之羧基，例如，g同基、g旨基、硫g旨基或酿胺 基。以化學式（11)( R4) bZC(=〇)CH(Q)CH(Q)y<表較佳的X具體 實施例。Z是CH2、0、S或N(其係根據乂是否分別是酮基 本纸張尺度中關家標準（CNSM4規格 -----^ __ (請先閱讀背面之注意事3填寫本頁) -·裝 1243174 A7 B7 五、發明說明（3 ) 、酯基、硫酯基或醯胺基）。Q是Η、烷基、芳基、烷芳基 或（R4)bZC(=0)-。R4是1至20個碳原子之烴部份，其可以包 括雜原子、氫、甲矽烷基或有機聚合物，例如，聚酯、聚 胺基甲酸酯、聚醚、聚硫化物或聚醯胺，其本身可以包括 一或數個 ZCeCOCHQCHQNtfSiR^JYCRib):基。R4是烷基 較佳（線型、環系或支化）、芳基或燒芳基，並以1至4個石炭 原子之烷基更佳。Q是氫較佳。根據在化學式1中，b値係 根據Z的價而定，即Z =氧或硫，則b = 1，並且Z =氮，則 b = 2 ° (請先閱讀背面之注意事Ϊ填寫本頁) 丨裝 ·- X 的特殊實例包括：（CH3)3C0C(=0)CH2CHr， CH3QC(=〇)CH(CH3)CHr, (CH3CH： )0C( = 0)CH2CH(CH3)-. % (CH3)2CHpC( = 0)CH2CH(C6H5)-，CH3〇C(=0)CH2CH[CJ( = 0)OCH3]-， H:C=CH0C(=0)CH2CH2-, C6H5CX：( = 0)CH2CH2-i C6H5CH2OC(=0)CH2CH2-, CH3C(=0)(CH2CH20)5C(=0)CH:CH2 CH3C( = 0)0C6H40C(=0)CH2CHr， CH30C( = 0)CH2CH(CN)-，C6Hu0C( = 0)CH2CHr, H2NC(二0)CH2CH厂， 經濟部智慧財產局員工消費合作社印製 (CH3)2NC( = 0)CH2CHr, (CHACHNHChC^CHfHr，H2C = CHCH2NHC(=0)CH2CH2-， CH3SC( = 0)CH:CH2' CH3(CH2)3SC( = 0)CH2CHr， C6H5SC( = 0)CH:CHrt CH3C( = 0)CH:CHr. C6H5C( = 0)CH2CHr, H2C = CHCH2C( = 0)CH2CH2-，CF3C( = 〇）CH2CH2-， [(CH3〇)3Si(CH2)3]2NCH:CH2C( = O)〇[CH2CH2OCi = O)(CH2)4C( = O)O]l0C( = O)CH2CH:- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243174 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 ) 在本發有用的雙（甲矽烷基）胺的特殊實例包括： [(CH3〇)3Si(CH2)3]2 NCH:CH:C( = 0)0C(CH3)：„ [(CH30)3SiCH:CH2CH2N(CH:CH2C( = 0;NH2)CH2-]2. [(CH3):CH 0)3SiCH2CH2 C6H4]: NCH:CH:C( = 0)CH·' [(CH30)3Si0Si(0CH3)2CH2CH2CH2N(CH:CH:C( = 0)NH:)CHr]:. [(CH3CH:0)2Si(CH3)CH2CH:C(CH3):CH:]2NCH2CH2C( = 0)SCH3， [(CH3)2C = N0)3SiCH2CH2C(CH3):CH2]2NCH2CH2C(=0)SCH3， [(CH30)3Si(CH2)3]2NCH2CH2C( = 0)0[CH2CH20C( = 0)(CH:)4C( = 0)0] 10CH2CH2OC( = 0)C H2CH2N[(CH2)3Si(OCH3)3]2.製造方法 自對應的雙-甲矽烷基二級胺與α，β -不飽和羰基化合物（ 包括酮、醋、硫S旨、醯胺及含有至少一個a，β -不飽和鍰基 ，例如，不飽和聚酯、不飽和聚醯胺或乙烯基酯，但不限 於此）之麥克（Michael)加成反應化學製備本發明的胺。含有化合物之α , β -不飽和羰基，即（R4) bZC(=0)CQ=CHQ ，其中R4、Z、Q及b與以上化學式（II)一樣。 適合的酮包括烷基乙烯基酮、烯丙基乙烯基酮及苯基乙 烯基酮。適合的酯包括甲基、乙基、丙基、丁基、苯基及 芊基之丙烯酸酯、甲基丙烯酸酯、巴豆酸酯、肉桂酸酯、 馬來酸酯、山梨酸酯、衣康酸酯及富馬酸酯。含有化合物 (請先閱讀背面之注意事*^填寫本頁) 裝 .- _雜· 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243174 B7 五、發明說明（5 ) 的對應S及N也適用。有機聚合物包括α，β -不飽和羰基官能 基，該官能基包括由二元醇與二酸之濃縮作用製成的不飽 和聚醋，其部份的二酸包括α, β -不飽和談基，例如，冨馬 酸或馬來酸、乙晞基醋及以丙晞酸g旨爲端基之聚醚、聚醒 胺及聚硫化物聚合物。 用於麥克反應之雙-甲矽烷基胺具有化學式 IIItGK^bYXR^.aSiRlNH，在此 R1、R2、R3、a、b 及 Y 與化 學式I 一樣。這些矽挽的特殊實例是雙-(3 -三甲氧基甲矽烷 基丙基）胺、雙- (3 -三乙氧基甲矽烷基丙基）胺、N-(3 -三 甲氧基甲矽烷基丙基）-N-(4 -三甲氧基甲矽烷基丙基）胺及 雙- (3 -三異丙氧基甲矽烷基丙基）胺。這些雙-甲矽烷基胺 可取自Witco公司以SILQUEST® A- 1170爲商標之雙-(3 -三甲 氧基甲矽烷基丙基）胺。而且，也可以使用二胺，其中每一 個胺可與丙烯酸酯反應。例如，可以使用（（R1) bY)aR23_aSi-(<3Η2)η-ΝΗ-(ί：Η2)η-ΝΗ-(<3Η2)η-8ίΙ123_3(Υ(Κ\))3，其中每一個 ” η，’ 各自是1至1 0。而且，在本技藝中可以美國專利申請案第 4,526,996號之指導製備這些胺。 根據在美國專利申請案第4，122,074號之揭示已知麥克加 成反應化學，將其併入本文以供參考。反應以過量的胺進 行較佳，以避免在最終產物中有未反應的丙烯酸酯的存在 。可以濃縮觸媒進行本方法。反應溫度是6 5 °C至140°C及反 應時間典型是6至100小時。以蒸館或過濾、使生成之產物純 化。 用途 -8 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事填寫本頁) 裝 . 經濟部智慧財產局員工消費合作社印製 1243174V. Description of the invention (!) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This invention relates to the novel structure of a specific bis-silyl triamine and its manufacture and use. Aminosilicone is an interpenetrating polymer network formed by organic matter in the coupling of inorganic matter (for example, silicon dioxide, silicon-containing fillers, metal oxides, ceramics, etc.) with organic matter (for example, resin) and organic matter and There are many uses for the cross-linking action of silicone substances. Most of these silanes include only primary or secondary amine ear energy. However, primary and secondary amine functionality may have overreactions ′ suffer from side reactions and loss of efficiency over time in the final application formulation. Moreover, many secondary amines are synthesized using mono-, di-, or trialkoxy-functional silanes. Therefore, the formation of undesired polysiloxanes with silanes can hinder applications in aqueous solutions, such as stable stereostructures. These structures have poor adhesion. The general outline of the present invention is based on the chemical formula (I) [((R ^ YXRYaSiRtNX bis-silyl tertiary amine) for controlled reactivity and good adhesion, where R1 and R2 are monovalent radicals, and R3 is divalent Group, X is a monovalent carbonyl group containing group, γ is oxygen, nitrogen or sulfur, a = 1 to 3, and b = 1 or 2, depending on the valence of γ. The detailed description of the present invention is in the above formula I In the above, each R1 is a monovalent group, for example, hydrogen, silyl, imino, dialkyl or hydrocarbon functionalities are preferred, including aryl, methyl, cycloalkyl, alkyl (linear or branched) Or aralkyl, which can include heteroatoms, such as oxygen, nitrogen, or sulfur), but is not limited to this. Ri can also be -4-This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) (Please read the note on the back first? Matters * ^: Fill out this page) Equipment • k · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1243174 Α7 ____ Β7__ 5. Description of the Invention (2) Degree or radical energy (for example, trimethoxymethylsulfanyl or ethynyl). Examples of R1 are -N = C (CH3) 2, -Si (OCH3) 3, and -CH = CHCH3 R1 is preferably an alkyl group of 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, cyclohexyl or tert-butyl. Υ is an atom selected from oxygen, nitrogen or sulfur. B 値It depends on the value of γ, that is, Y = oxygen or sulfur 'then b = 1' and γ = nitrogen, then b = 2. Y is oxygen is better. A is 3 is better, but if a < 3, then Each R2 is a monovalent group, which includes, but is not limited to, a hydrocarbon group, a saturated hydrocarbon, an unsaturated hydrocarbon, or a cyano group. R2 is preferably a cycloalkyl group, an alkyl group (linear or branched), or an aralkyl group, which may include Heteroatoms, for example, oxygen, nitrogen, or sulfur. Examples of R2 include phenyl, phenethyl, 3-oxobutyl, or 2-methoxypropyl. R2 is methyl or ethyl. R3 is two. Valence bridging groups, including butylene, alkyl, aryl, or polyoxyalkylene, but not limited to this, but Ci-Ci2 alkylene is preferred, for example, propylene or butylene However, it may be branched, for example, neopentyl, a ring system, for example, dimethylene cyclohexane, or an unsaturated, for example, dimethylene cyclohexene. R3 may include heteroatom substitution Things, for example, 3 may include an amine group on or in the main chain or a side chain attached to the main chain. If R3 includes amine ear energy, each of the amines is a tertiary amine. A special example of R3 is propylene , N-butyl, phenyl, di (ethyl) ethylamine, and polyoxyethyl. X is a carboxyl group containing a monovalent group, for example, g homo, g, thio, or amine Based on the chemical formula (11) (R4) bZC (= 〇) CH (Q) CH (Q) y < Table is a preferred embodiment of X. Z is CH2, 0, S or N (which depends on whether 乂 is different It is the standard of ketone basic paper standard (CNSM4 specification ----- ^ __ (Please read the note on the back 3 and fill out this page)-· Packing 1243174 A7 B7 V. Description of the invention (3), ester group, Thioester or amido). Q is fluorene, alkyl, aryl, alkaryl or (R4) bZC (= 0)-. R4 is a hydrocarbon moiety of 1 to 20 carbon atoms, which may include heteroatoms, hydrogen, silyl, or organic polymers, such as polyester, polyurethane, polyether, polysulfide, or polyfluorene The amine itself may include one or several ZCeCOCHQCHQNtfSiR ^ JYCRib): groups. R4 is preferably an alkyl group (linear, cyclic or branched), an aryl group or an aryl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Q is preferably hydrogen. According to chemical formula 1, b 値 is based on the valence of Z, that is, Z = oxygen or sulfur, then b = 1, and Z = nitrogen, then b = 2 ° (Please read the notes on the back first; fill in this page ) 丨 special examples of equipment-X include: (CH3) 3C0C (= 0) CH2CHr, CH3QC (= 〇) CH (CH3) CHr, (CH3CH:) 0C (= 0) CH2CH (CH3)-.% (CH3 ) 2CHpC (= 0) CH2CH (C6H5)-, CH3〇C (= 0) CH2CH [CJ (= 0) OCH3]-, H: C = CH0C (= 0) CH2CH2-, C6H5CX: (= 0) CH2CH2- i C6H5CH2OC (= 0) CH2CH2-, CH3C (= 0) (CH2CH20) 5C (= 0) CH: CH2 CH3C (= 0) 0C6H40C (= 0) CH2CHr, CH30C (= 0) CH2CH (CN)-, C6Hu0C ( = 0) CH2CHr, H2NC (two 0) CH2CH factory, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (CH3) 2NC (= 0) CH2CHr, (CHACHNHChC ^ CHfHr, H2C = CHCH2NHC (= 0) CH2CH2-, CH3SC ( = 0) CH: CH2 'CH3 (CH2) 3SC (= 0) CH2CHr, C6H5SC (= 0) CH: CHrt CH3C (= 0) CH: CHr. C6H5C (= 0) CH2CHr, H2C = CHCH2C (= 0) CH2CH2 -, CF3C (= 〇) CH2CH2-, [(CH3〇) 3Si (CH2) 3] 2NCH: CH2C (= O) 〇 [CH2CH2OCi = O) (CH2) 4C (= O) O] 10C (= O) CH2CH :-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1243174 A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives 5. Description of the Invention (4) Specific examples of bis (silyl) amines useful in this development include: [(CH3〇) 3Si (CH2) 3] 2 NCH: CH: C ( = 0) 0C (CH3): [(CH30) 3SiCH: CH2CH2N (CH: CH2C (= 0; NH2) CH2-] 2. [(CH3): CH 0) 3SiCH2CH2 C6H4]: NCH: CH: C (= 0) CH · '[(CH30) 3Si0Si (0CH3) 2CH2CH2CH2N (CH: CH: C (= 0) NH:) CHr] :. [(CH3CH: 0) 2Si (CH3) CH2CH: C (CH3): CH: ] 2NCH2CH2C (= 0) SCH3, [(CH3) 2C = N0) 3SiCH2CH2C (CH3): CH2] 2NCH2CH2C (= 0) SCH3, [(CH30) 3Si (CH2) 3] 2NCH2CH2C (= 0) 0 [CH2CH20C (= 0) (CH:) 4C (= 0) 0] 10CH2CH2OC (= 0) C H2CH2N [(CH2) 3Si (OCH3) 3] 2. Manufacturing method self-corresponding bis-silyl secondary amine and α, β- Unsaturated carbonyl compounds (including ketones, vinegars, sulfur compounds, amidines, and containing at least one a, β-unsaturated amidines, such as unsaturated polyesters, unsaturated polyamides, or vinyl esters, but are not limited thereto ) Michael addition reaction chemistry to prepare the amines of the present invention. Contains α, β-unsaturated carbonyl groups of compounds, ie (R4) bZC (= 0) CQ = CHQ, where R4, Z, Q and b are the same as the above formula (II). Suitable ketones include alkyl vinyl ketones, allyl vinyl ketones, and phenyl vinyl ketones. Suitable esters include methyl, ethyl, propyl, butyl, phenyl and fluorenyl acrylates, methacrylates, crotonates, cinnamate, maleates, sorbates, itaconic acid Esters and fumarate. Contains compounds (please read the notes on the back first * ^ Fill this page) Packing.-_ Miscellaneous · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1243174 B7 V. Description of the invention (5 ) Corresponding to S and N also apply. Organic polymers include α, β-unsaturated carbonyl functional groups. The functional groups include unsaturated polyacetates made by the concentration of glycols and diacids. Some of the diacids include α, β-unsaturated polymers. For example, succinic acid or maleic acid, acetic acid acetic acid, and polyethers, polyamines, and polysulfide polymers whose end groups are propionic acid g. The bis-silylamine used in the Mike reaction has the chemical formula IIItGK ^ bYXR ^ .aSiRlNH, where R1, R2, R3, a, b, and Y are the same as Chemical Formula I. Specific examples of these silanes are bis- (3-trimethoxysilylpropyl) amine, bis- (3-triethoxysilylpropyl) amine, N- (3-trimethoxysilyl) Propyl) -N- (4-trimethoxysilylpropyl) amine and bis- (3-triisopropoxysilylpropyl) amine. These bis-silylamines can be obtained from Witco's bis- (3-trimethoxysilylpropyl) amine under the trademark SILQUEST® A-1170. Moreover, diamines can also be used, each of which can react with an acrylate. For example, ((R1) bY) aR23_aSi-(< 3Η2) η-ΝΗ- (ί: Η2) η-ΝΗ-(< 3Η2) η-8ίΙ123_3 (Υ (Κ \)) 3, each of which "Η, 'are each 1 to 10. Moreover, these amines can be prepared in accordance with the guidance of U.S. Patent Application No. 4,526,996 in the art. According to the disclosure in U.S. Patent Application No. 4,122,074, a known Mack addition reaction Chemistry, which is incorporated herein by reference. The reaction is preferably performed with an excess of amine to avoid the presence of unreacted acrylate in the final product. The catalyst can be concentrated to carry out this method. The reaction temperature is 6 5 ° C To 140 ° C and the reaction time is typically 6 to 100 hours. The product is purified by steaming or filtering. Use -8-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ( Please read the notes on the back first and fill in this page).
經濟部智慧財產局員工消費合作社印製 五、發明說明（6) 雙-甲石夕坑基三級胺在氮上不具有活性氫及因此可在一級 及一級胺以其它方式傾向於進行不期望的副反應之任何反 應中使用。但是，三級胺適合當成增加矽烷水解作用及交 聯反應速度與及催化含有可水解基之甲矽烷基或水解之後 的矽烷醇與無機物質反應之觸媒。雙-矽烷具有數個可水解 基（例如，烷氧基）。兩個甲矽烷基為數個附著物提供強且 安足鍵之我機表面及形成具有少量未鍵結聚矽氧烷之膜， 例如，立體結構。以實例說明的應用包括膜、以溶劑及水 係王成份之塗料、黏著劑、黏結劑、底漆、纖維玻璃膠水 、downhole fine固著物、鑄造物、油漆及任何其它迄今已使 用胺基矽烷之應用。 可將本發明的胺基矽烷與已知的添加劑結合，如抗靜電 劑、無機聚合物、甲矽烷基化聚合物、矽氧烷、潤滑劑、 頒料、填孔劑（纖維狀及非纖維狀）、抑制劑、乳化劑及其 它秒燒。 實施例 簠Ο -二甲氧基甲石@基丙基）胺輿丙烯酸甲酯之麥克加成 物 將雙-(3-三甲氧基甲矽烷基丙基）胺（9〇1·3公克，2 64莫耳 ，1 . 1 *量）及甲醉（479.2公克）加至配備加料漏斗、維格羅 (Vigreux)分餾柱、溫度計、氣體入口、磁攪拌棒及加熱罩 足3公升的三頸燒杯中。將燒杯放置在利用室内氮氣及起泡 線之氮氣下。將燒杯加熱至5 〇它，並將丙烯酸甲酯（2〇7公 克，2.4莫耳，1 · 〇當量）經由加料漏斗以丨5小時加入。在 本纸張尺度適用中國國豕標準（CNS)A4規格（21〇 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) « 裝 ·. 羲 1243174 A7 B7 五、發明說明（7 ) 室溫下2天之後，G C分析顯示未殘留任何丙烯酸甲酯。在 減壓下除去甲醇（60°C，〇. 1毫米汞柱）。 (請先閱讀背面之注意事$填寫本頁) K 3 -三甲氧基甲矽烷基丙某）胺與丙烯酸特丁酯之麥克& 成物 將雙-(3-三甲氧基甲矽烷基丙基）胺（751.3公克，2.2莫耳 ，1當量）及甲醇（402公克）裝入配備Freidrich濃縮器、加料 漏斗、加熱罩、溫度計、以PTFE塗覆之攪拌棒及氣體入口 之2公升的三頸燒杯中。將燒杯加熱至4 〇，並放置在利 用室内氮氣及起泡線之氮氣下。將丙烯酸特丁酯（253.8公克 ’ 2 · 0莫耳，〇 · 9當量）經由加料漏斗以4 0分鐘加入。將熱 增加至回流，並維持約6小時。在大氣壓力下汽提甲醇，在 以汽提之後，在高眞空下除去最後少量的甲醇及丙烯酸酯 。將產物經由0 . 1 μ之Abestocel墊過濾。G C - M S分析顯示麥 克加成物成爲主要產物（約9 〇 %)。以過量的胺進行反應， 使其成爲殘留的1 〇 %產物。將該產物稱爲胺Α。 基甲矽烷基丙基）胺與丙烯酸正丁酯之麥克加 成物 經濟部智慧財產局員工消費合作社印製 將雙-(3-三甲氧基甲矽烷基丙基）胺（751 3公克，2 2莫耳 ’ 1當量）裝入配備Freidrich濃縮器、加料漏斗、加熱罩、溫 度計、以PTFE塗覆之攪拌棒及氣體入口之2公升的三頸燒 杯中。將燒杯加熱至4 0 °C，並放置在利用室内氮氣及起泡 線之氮氣下。將丙烯酸正丁酯（253.8公克，2.0莫耳，0.9 ▲里）、纟k由加料漏斗以2 5分鐘加入。將熱增加至5 0 °C，並 、’隹持1小時’接著以7 0 °C維持4小時。G C顯示出低的轉換 -10 - 本紙張尺度細中_家標準（CNS)A4規格⑵Q χ 297公髮） 1243174 A7 B7 經濟部智慧財產局員工消費合作社印制农 五、發明說明（8 ) 率。將溫度增加至100°C，並維持42小時，以12(TC維持18 小時，接著以140°C維持4 2小時。在減壓下利用短路後蒸餘 頭汽提輕餾份。利用降膜分子蒸餾設備蒸餾產物。利用回 '成的1 -辛醇當成熱源。將粗產物送入在〇 3毫米汞柱下以 5 〇滴/分鐘之蒸餾設備中。g C - M S分析顯示麥克加成物成 爲主要產物（約9 0 % )。以過量的胺進行反應，使其成爲殘 留的1 0 %產物。將該產物稱爲胺Α。 藍_的製備及物理測試（抗溶劑性1 利用含有6 %結合劑（二乙二醇單丁基醚之苯乙烯丙締酸 系樹膠（SCX2500，S.C.Johnson&Son)評估丙烯酸系聚合物。 將混合物（當控制品使用）塗覆在4英吋X 1 2英吋之鋁板上 及在室溫下經7天固化。利用ASTM D 4752-87 MEK磨擦試 驗評估膜。控制膜在10次磨擦之後失敗。將3 %胺A加至控 制品混合物中，並塗覆在鋁基板上。將在相同條件下固化 之膜當成控制品。含有胺A之膜在MEK磨擦試驗的2 4次磨 擦之後失敗（比控制品增加240% )。 利用胺基甲酸酯混合乳液（Hexane 620，空氣產物及化學 品公司（Air Products and Chemicals，Inc·))評估胺基甲酸酯/丙 烯酸系混合聚合物。將當控制品使用的純乳液塗覆在鋁板 上及在6 6 °C下經1 5分鐘及接著在室溫下經7天固化。利用 異丙醇鐘式磨擦（1碌的鐘）評估膜。控制品在8 〇次磨擦之 後失敗。將含有3 %胺A之Flexane 620塗覆在鋁板上，並在 相同條件下固化，將其當成控制品。該膜在3 4 〇次的異丙 醇鐘式磨擦之後失敗（比控制品增加425%)。 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注音？事^^填寫本頁〕 li5 裝 0Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention. (6) Bis-methyl stone pit-based tertiary amines do not have active hydrogen on nitrogen and therefore may be undesired in primary and primary amines in other ways. Side reactions are used in any reaction. However, tertiary amines are suitable as catalysts that increase the hydrolysis of silanes and the rate of cross-linking reactions and catalyze the reaction of silyl groups containing hydrolyzable groups or silanols after hydrolysis with inorganic substances. Bi-silane has several hydrolyzable groups (for example, alkoxy). Two silyl groups provide strong and well-bonded surfaces to several attachments and form a film with a small amount of unbonded polysiloxane, for example, a three-dimensional structure. Illustrative applications include films, coatings with solvents and water based ingredients, adhesives, adhesives, primers, fiberglass glues, downhole fine fixtures, castings, paints, and any other amine silanes that have been used to date Its application. The amine silanes of the present invention can be combined with known additives such as antistatic agents, inorganic polymers, silylated polymers, silicones, lubricants, materials, fillers (fibrous and non-fibrous) Like), inhibitors, emulsifiers and other seconds. Example 簠 -Dimethoxymethyst @ ylpropyl) amine methyl adduct of methyl acrylate The bis- (3-trimethoxysilylpropyl) amine (90.3 g, 2 64 mol, 1.1 * amount) and nail drunk (479.2 g) are added to the three-necked three-liter three-liter foot equipped with an addition funnel, a Vigreux fractionation column, a thermometer, a gas inlet, a magnetic stirrer, and a heating mantle In the beaker. Place the beaker under nitrogen using a chamber nitrogen and bubble line. The beaker was heated to 50 ° C, and methyl acrylate (207 g, 2.4 moles, 1.0 equivalent) was added via an addition funnel over 5 hours. In this paper standard, China National Standard (CNS) A4 specification (21〇X 297 public love) is applied (please read the precautions on the back before filling this page) «Installation · .1243174 A7 B7 V. Description of the invention (7 ) After 2 days at room temperature, GC analysis showed that no methyl acrylate remained. The methanol was removed under reduced pressure (60 ° C, 0.1 mmHg). (Please read the note on the back of this page to fill in this page first.) K 3 -Trimethoxysilylpropane) Mike & butyl acrylate & product will be bis- (3-trimethoxysilylpropane) Base) amine (751.3 g, 2.2 mol, 1 eq.) And methanol (402 g) are charged into a 2 liter three-equipment equipped with a Freidrich concentrator, an addition funnel, a heating mantle, a thermometer, a PTFE-coated stirring rod, and a gas inlet Neck beaker. The beaker was heated to 40 and placed under nitrogen in a chamber using nitrogen and a bubble line. Tert-butyl acrylate (253.8 g '2. 0 Mol, 0.9 equivalent) was added via an addition funnel over 40 minutes. Heat was increased to reflux and maintained for about 6 hours. Methanol is stripped at atmospheric pressure. After stripping, the last small amounts of methanol and acrylate are removed under high headspace. The product was filtered through a 0.1 μm Abestocel pad. G C-MS analysis showed that the Michael adduct was the main product (about 90%). The reaction was carried out with an excess of amine to make it a residual 10% product. This product is called amine A. Dimethylsilylpropyl) amine and n-Butyl Acrylate Printed by Bis- (3-trimethoxysilylpropyl) amine (751 3 g, 2 2 mol '1 equivalent) into a 2-liter three-necked beaker equipped with a Freidrich concentrator, an addition funnel, a heating mantle, a thermometer, a PTFE-coated stir bar, and a gas inlet. Heat the beaker to 40 ° C and place under nitrogen using a chamber nitrogen and a bubble line. Add n-butyl acrylate (253.8 g, 2.0 mol, 0.9 ▲ li) and 纟 k from the addition funnel over 25 minutes. The heat was increased to 50 ° C, and 'hold for 1 hour' and then maintained at 70 ° C for 4 hours. The GC shows a low conversion -10-This paper is fine-sized _ Home Standard (CNS) A4 size ⑵Q χ 297 issued) 1243174 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of inventions (8) rate . The temperature was increased to 100 ° C, and maintained for 42 hours, maintained at 12 ° C for 18 hours, and then maintained at 140 ° C for 4 2 hours. The light ends were stripped of the light ends by short-circuiting under reduced pressure. Using a falling film Molecular distillation equipment distills the product. The recovered 1-octanol is used as the heat source. The crude product is sent to a distillation equipment at 50 drops / minute under 0.3 mm Hg. G-MS analysis shows the addition of Mike The product becomes the main product (about 90%). The excess amine is reacted to make it a residual 10% product. This product is called amine A. Preparation and physical testing of blue_ 6% binder (Diethylene glycol monobutyl ether, styrene-acrylic acid gum (SCX2500, SCJohnson & Son)) Evaluation of acrylic polymers. The mixture (used as a control product) was coated on 4 inches X 12-inch aluminum plate and cured at room temperature for 7 days. The film was evaluated using the ASTM D 4752-87 MEK rub test. The control film failed after 10 rubs. 3% Amine A was added to the control mixture, And coated on an aluminum substrate. The film cured under the same conditions was used as a control product. Films with amine A failed after 24 rubs in the MEK friction test (240% increase over control products). Utilized urethane hybrid emulsion (Hexane 620, Air Products and Chemicals, Inc. ·)) Evaluate urethane / acrylic hybrid polymers. Pure emulsions used as control products are coated on aluminum plates and cured at 66 ° C for 15 minutes and then at room temperature for 7 days The film was evaluated using isopropanol bell rubbing (1 bell). The control failed after 80 rubbings. Flexane 620 containing 3% amine A was coated on an aluminum plate and cured under the same conditions. It was used as a control product. The film failed after 3,400 isopropyl alcohol bell frictions (a 425% increase over the control product). -11-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297) Li) (Please read the Zhuyin on the back? Matt ^^ Fill in this page] li5 Pack 0