TW491871B - Block oligomers containing l-hydrocarbyloxy-2,2,6,6-tetramethyl-4- piperidyl groups as stabilizers for lower polyolefin - Google Patents
Block oligomers containing l-hydrocarbyloxy-2,2,6,6-tetramethyl-4- piperidyl groups as stabilizers for lower polyolefin Download PDFInfo
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491871 A7 B7 五、發明説明(f ) 本發明闞於一種含有1 一碳氫氧基一 2,2,6 · 6 一四甲基一 4 -哌啶基之特定嵌段寡聚物,及其當作有機 物質光穩定劑、熱穩定劑和氧化穩定劑的應用,特別是合 成聚合物,及·關於Μ此穗定的有機物質。除此之外,本發 明進一步闞於一種中間產物。 合成聚合物M2,2,6,6 —四甲基哌啶衍生物的 穩定已揭示於,例如US — Α — 4,086,204, US-A — 4,331,586;US-A — 4,335 ,242 ; US - A - 4 * 234 * 707 ; US - A-4,459,395; US - A — 4,492,791 ; US - A-5,204,473 ; EP - A-53,77 5 ; EP - A-357,223 ; EP - A - 377,3 24 ; EP-A - 462 · 069 ; EP - A - 782, 994 和 GB - A - 2,301,106。 本發明特別是闞於一種產物,得自·· 1 ) 一式(α )化合物 (請先閱讀背面之注意事項再填寫本頁)491871 A7 B7 V. Description of the invention (f) The present invention is directed to a specific block oligomer containing 1-hydrocarbonoxy-2,2,6.6-tetramethyl-4-piperidinyl, and Applications as light stabilizers, thermal stabilizers and oxidation stabilizers for organic substances, especially synthetic polymers, and · Regarding organic substances for this purpose. In addition, the present invention is further limited to an intermediate product. The stability of synthetic polymers M2,2,6,6-tetramethylpiperidine derivatives has been disclosed in, for example, US-A-4,086,204, US-A-4,331,586; US-A-4 , 335, 242; US-A-4 * 234 * 707; US-A-4, 459, 395; US-A — 4,492,791; US-A-5, 204, 473; EP-A-53 , 77 5; EP-A-357, 223; EP-A-377, 3 24; EP-A-462.069; EP-A-782, 994; and GB-A-2, 301, 106. The present invention is particularly derived from a product obtained from ... 1) a compound of formula (α) (please read the precautions on the back before filling this page)
、1T §Γ. 經漓部中央標隼局與工消费合作社印製, 1T §Γ. Printed by the Central Bureau of Standards and the Ministry of Industry and Consumer Cooperatives
CI /CI /
CICI
N 應 反 物 合 化 \—/ /IV 式 1 和 本紙張尺度適用中國國家標率(rNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明(V ) - N——R I ΗN should be anti-physical compound \ — / / IV type 1 and this paper size applies Chinese national standard (rNS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of invention (V)-N——R I Η
5 是 2 別 • 特 ·, If) 地 1 1 ·· : 較43 , ♦ 3 1 1 ♦ : 至,1 4 1 如 • : 例 13, 至 · 1 11: :或 6 2 , 3 • 1 . 1:1 為4至 例 · 1 比 1 ·· 耳至 3 莫 1 · ( : 1 應 反 於 在 存 \1/ 2 基 端 終 \—/ 7 /f\ 式 之 中 物 產 應 反 (請先閱讀背面之注意事項再填寫本頁)5 is 2 Don't special, If) Ground 1 1 ··: Compared with 43, ♦ 3 1 1 ♦: To, 1 4 1 Such as •: Example 13, to · 1 11:: or 6 2, 3 • 1. 1: 1 is 4 to Example · 1 to 1 · Ear to 3 Mo 1 · (: 1 should be reversed from the existence of \ 1/2 base end \ — / 7 / f \ (Read the notes on the back and fill out this page)
NN
N 7N 7
CICI
N -巳 物 合 化 的 Η ) I δ A /IN 式 和 經濟部中央標^局兵工消费合作社印來 佳 行 較 } 進 ,4* 下 : 3 •在 基 :2 存 群 2 : 鹼 } } 至 2 機 〜I δ 7 至無 I ί · 2 及 G 1 : 中 ί :2 劑 式 } 是溶 之 基別機 中 端特有 物 終,一 產 ί 6 在 } 2 · 是 2 為 2 } 應 例 :2 反 比 2 和 於 耳至 } 在 莫 2 1 存 應:應 將 反 2 反及 } { 地 ; ; 3 8 本紙張尺度適用中國國家標嗥(CNS ) Λ4規格(210X 297公釐) 491871 A7 B7N-巳 物 合 化) I δ A / IN formula and the Central Standards Bureau of the Ministry of Economic Affairs, Bureau of Industrial and Military Consumer Cooperatives, Yin Lai Jia Xing}, 4 * Under: 3 • In the base: 2 Storage group 2: Alkali} } To 2 machines ~ I δ 7 to no I ί · 2 and G 1: middle ί: 2 agent type} is the end-of-line unique end product of the soluble base machine, one product ί 6 in} 2 · yes 2 is 2} Example: 2 inverse ratio 2 and Yu Erzhi} in Mo 2 1 deposit should: inverse 2 should be reversed} {地;; 3 8 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 491871 A7 B7
jlL 五、發明說明( Λ V, :滴:Ϊ.jlL V. Description of the invention (Λ V,: drop: Ϊ.
UiUi
(G-丨) 轉化為式(G — I I )群基(G- 丨) into group base of formula (G — I I)
(請先閱讀背面之注意事項再填寫本頁) (G-Π) 該轉換是由反應2 )產檄和一過氧化氫,在一碳氫化合物 溶劑中及一過氧化氫分解觸媒存在下進行;(Please read the notes on the back before filling in this page) (G-Π) The conversion is made by reaction 2) Tritium and hydrogen peroxide, in a hydrocarbon solvent and in the presence of a hydrogen peroxide decomposition catalyst get on;
Ri是烴基反應基或一 0 — Rt是氧基; R2 是 C2 — 烷撐,C4 一 Ci2 烯撐,C5 - C7環烷撐,C5 - C7環烷撐二(Ci 一 C4烷撐), Ci—C4烷撐二(C5 - C7環烷撐),苯撐二(Ci· 一 C4烷撐)或C4 一 Ci 2烷撐,其是由1 ,4 一褫嗪 二基,一 ◦一或>N — Xi所中斷的,Xi是Ci 一 Ci 2藤基或(Ci 一 Ci 2燒氧基)幾基,或具有下述 R4定義中之一者;或R2是一式(I 一 a) , (I 一 b )或(I 一 c )群基: 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 491871 A7 B7 五、發明説明(+Ri is a hydrocarbyl reactive group or a 0—Rt is an oxy group; R2 is a C2—alkylene, C4—Ci2 alkylene, C5—C7 cycloalkylene, C5—C7 cycloalkylene di (Ci—C4 alkylene), Ci —C4 alkylene di (C5-C7 cycloalkylene), phenylene di (Ci · C4 alkylene) or C4—Ci 2 alkylene, which is composed of 1, 4 monopyrazinediyl, 1◦one or> ; N — Xi interrupted, Xi is Ci-Ci 2 rattan or (Ci-Ci 2 alkoxy) several groups, or has one of the following definitions of R4; or R2 is a formula (I a a), (I-b) or (I-c) group basis: This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 491871 A7 B7 V. Description of the invention (+
(l-a) •CH^ —CH—CH«I 2〇 Ic=〇 I X2 (l-b)(l-a) • CH ^ —CH—CH «I 2〇 Ic = 〇 I X2 (l-b)
(l-c) m是2或 X2 是 Ci 一 Ci8 燒基,Cs —Ci2 經取代的或由1 ,2或3個Ci -C4烷基取代的;苯 苯基上由1 ,2或3個Ci —C 一 C 9苯基烷基 3 環烷基,其是未 基 *其是未經取代的或在 烷基或Ci —C4烷氧基取代的;C 其是未經取代的,或在苯基上由1 · 2或3個Ci —C 烷基取代的;及 4 (請先閱讀背面之注意事項再填寫本頁) 經滴部中央標準局貨工消费合作社印繁 2 R C ( 為 } 別 4 分 R 的 ί 關 Ν 相 I 不, 互 3 3 R X ο : 基 I 基 應是群 反 Α 的(lc) m is 2 or X2 is Ci-Ci8 alkyl, Cs-Ci2 is substituted or substituted by 1, 2 or 3 Ci-C4 alkyl; phenylphenyl is substituted by 1, 2 or 3 Ci — C-C 9 phenylalkyl 3 cycloalkyl, which is unsubstituted * which is unsubstituted or substituted in alkyl or Ci-C4 alkoxy; C which is unsubstituted, or in phenyl It is substituted by 1 · 2 or 3 Ci—C alkyl groups; and 4 (Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau, Cargo Workers and Consumers Cooperatives 2 RC R is divided into R, N, I, I, 3 3 RX ο: Radical I Radical should be group anti-A
ΗΗ
C 本紙張尺度適用中國國家標率((、NS ) Λ4規格(210X 297公釐)C This paper size applies to China's national standard ((, NS) Λ4 specifications (210X 297 mm)
C 撐式 烷一 2 或 \)/ /(\ 491871 A7 B7 R 3 ,;R4和R5 (相同或不同的)為Ci—CiS烷基 » C5 — Ci 2環烷基*其是未經取代的或由1 ,2或3 個Ci —C4烷基取代的;C3 — Cl8烯基,苯基,其 是未經取代的或由1 ,2或3個Ci 一 C4烷基或Ci _ C4烷氧基取代的·,C7 — C9苯基烷基,其是未經取 的或在苯基上由1 ,2或3個Ci 一〇4烷基取代的; 氫呋喃基或C2 — C4烷基*其在第2,3或4位置上 由一 OH,Ci —C8烷氧基,二(Ci 一〇4烷基) 基或一式(I I I)的群基取代的; 代 四 是 胺 (III) 經濟部中央標準局Μ X,消贽合作社印裝 Y 是一 0 —,一 CH2 -,一 CH2 ch2 -或 > N - C Η 3 •,及 R3另外是氫或一N(R4) (Rs)另外是一式( I I I )的群基; X 是一 0 — 或 >N — R6; 、 Rs 是 Ci 一 Ci8 焼基,C3 — C18 稀基,Cs — Ci 2環烷基,其是未經取代的或由1 ,2或3個Ci 一 C4烷基取代的;C7 — C9苯基烷基,其是未經取代的 -U- 本紙張尺度用中國國家標枣(rNS ) Λ4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁)C-butane-2 or \) // (\ 491871 A7 B7 R 3,; R4 and R5 (same or different) are Ci-CiS alkyl »C5 — Ci 2 cycloalkyl * which is unsubstituted Or substituted by 1, 2, or 3 Ci—C4 alkyl groups; C3-Cl8 alkenyl, phenyl, which are unsubstituted or substituted by 1, 2, or 3 Ci—C4 alkyl groups or Ci_C4 alkoxy groups -C7-C9phenylalkyl, which is unsubstituted or substituted with 1, 2 or 3 Ci-10 alkyl on phenyl; hydrofuryl or C2-C4 alkyl * It is substituted at the 2, 3, or 4 position by mono-OH, Ci-C8 alkoxy, di (Ci-104 alkyl) or a group of formula (III); substitution for tetra is an amine (III). Ministry of Central Standards Bureau MX, printed by cooperatives Y is a 0 —, a CH2 —, a CH2 ch2 — or> N-C Η 3 •, and R3 is also hydrogen or a N (R4) (Rs) In addition, it is a group group of formula (III); X is a 0 — or> N — R6 ;, Rs is Ci — Ci8 fluorenyl, C3 — C18 dilute, Cs — Ci 2 cycloalkyl, which is unsubstituted Or substituted by 1, 2 or 3 Ci-C4 alkyl; C7-C9 phenylalkyl, which is unsubstituted -U- This paper uses the Chinese national standard date (rNS) Λ4 size (210X297 mm) (Please read the precautions on the back before filling this page)
^1871 A7 B7 發明説明(b) (請先閱讀背面之注意事項再填寫本頁) 或在苯基上由1 ,2或3個Ci -C4烷基取代的;四氫 呋喃華,一式(G — I)的群基,或Cz — C4烷基•其 在第2,3或4位置上由一 〇H,Ci 烷氧基,二 (Ci _C4烷基)胺基或一式(I I I)的群基取代的^ 1871 A7 B7 Description of the Invention (b) (Please read the notes on the back before filling this page) or substituted with 1, 2, or 3 Ci-C4 alkyl groups on the phenyl group; tetrahydrofuran, a formula (G — I ), Or a Cz-C4 alkyl group, which is substituted at the 2, 3, or 4 position by a 10H, Ci alkoxy group, a di (Ci_C4 alkyl) amino group, or a group group of formula (III) of
I R具有如上Re定義中之一者,及 B具有如上A定義中之一者。 式(G — I)至式(G — I I)的轉換可Μ類似,如 描述於US — Α — 4,921 ,962的方法進行,在此 將其併入作為參考。I R has one of the definitions of Re above and B has one of the definitions of A above. The conversion from formula (G — I) to formula (G — I I) can be similar to that described in US — A — 4,921,962, which is incorporated herein by reference.
Ri的定義是依據反應3)所使用的碳氫化合物溶劑 而定,Ri較佳的是具有5至1 8個碳原子之烴基。 經滴部中央標擎爲另二消贽合作社印^The definition of Ri is based on the hydrocarbon solvent used in reaction 3). Ri is preferably a hydrocarbon group having 5 to 18 carbon atoms. The central standard of the Ministry of Economic Affairs is printed for another second consumer cooperative ^
Ri特別是Cs — Ci 8烷基,C5 —Ci 8烯基, C5 —Ci 8炔基,Cs — Ci 2環烷基,其是未經取代 的或由Ct _C4烷基取代的;Cs — Ci 2環烯基,其 是未經取代的或由Ci 一 C4烷基取代的;一雙環或三環 具有6至1 0個碳原子之烴基,或C7 — C9苯基烷基, 其是未經取代的或在苯基上由C i —C4烷基取代的;及 反應3)中的碳氫化合物溶劑是依據Ri ( C 5 ~ C 1 8 烷基,C5 —CiS 烯基,C5 — Ci8 炔基,— C i 2環烷基,其是未經取代的或由Ci 一 C4烷基取代的 ;C5 —Ci 2環烯基•其是未經取代的或由Ci 一 C4 烷基取代的;一雙環或三環具有6至10涸碳原子之烴基 -12- 本紙張尺度通用中國國家標令(CNS ) Λ4規格(210X 297公釐) 經濟部中央標枣局β-χ消贽合作社印繁 491871 A7 B7 五、發明説明(7 ) ,或c7 —c9苯基烷基》其是未經取代的或在苯基上由 C i 一; C 4烷基取代的)而定。 依據本發明另一較佳實施例,R i是庚基,辛基,環 己基,甲基環己基,環辛基,環己烯基* α —甲基苄基或 1,2,3,4一四氫環烷基,及 反應3)中的碳氫化合物溶劑是(依據Ri )庚烷,辛燒 ,環己烷,甲基環己烷,環辛烷,環己烯,乙基苯或四啉 (tetralin) 〇 依據最佳的實施例,Ri是辛基或環己基*及反應3 )的碳氫化合物溶劑(依據Ri)是辛烷或環己烷。 含有不超過1 8個碳原子烷基的例子為甲基,乙基, 丙基*異丙基,丁基,2 —丁基,異丁基,戊基,2 —戊 基,己基,庚基,辛基,2—乙基己基,叔一辛基,壬基 ,癸基,十一烷基,十二烷基,十三烷基,十四烷基,十 六烷基及十八烷基。Ri較佳的是C6 — Ci 2烷基,特 別是庚基或辛基。R4 ,Rs和Re較佳的是Ci —C8 烷基,特別是Ci-C*烷基。 經由一 0H取代的烷基例子為2 —羥基乙基。 經由Ci 一〇8烷氧基,較佳的由Ci 一 C4烷氧基 ,特別是甲氧基或乙氧基取代的C2 - C4(烷基之例子2 一甲氧基乙基,2 —乙氧基乙基,3 —甲氧基丙基,3 — 乙氧基丙基,3 — 丁氧基丙基,3 —辛氧基丙基和4 一甲 氧基丁基。 -13- 本紙張尺度適州中國國家標嘩((’NS ) Λ4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂 經^‘部中决標津局負工消费合作·社印來 491871 A7 B7 五、發明説明(2 ) 經由二(Ci一C4烷基)胺基,較佳的由二甲基胺 基或:;乙基胺基取代之C2 — C4烷基例子為2 —二甲基 胺基乙基,2 —乙基胺基乙基,3 —二甲基胺基丙基,3 一二乙基胺基丙基,3 —二丁基胺基丙基和4 一二乙基胺 基丁基。 /^\ 式(III)群基較佳的是 一 N 〇 〇 \^/ 經由式(I I I)群基取代的c2 —c4烷基之較佳 例子為 〇—(ch2)— 。下 式群基是特別佳的 /^\ ^-(CH2>2:— ο 未經取代或經由1 ,2或3個Ci —C4烷基取代之 C5 — Ci 2環烷基的例子為環戊基,甲基環戊基,二甲 基環戊基,環己基,甲基環己基,二甲基環己基,三甲基 環己基,叔一丁基環己基,環辛基,環癸基和環十一烷基 。未經取代的或經取代的環己基是較佳的。 -14- ~本紙張尺度用中國國家標率(CNS ) Λ4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 、11 經滴部中决標隼局只工消費合作社印製 491871 A7 B7 _ 五、發明说明(q ) 具有6至10個碳原子之雙環或三環烴基的較佳例子 為1 ,; 2,3,4 一四氫環烷基。 未經取代的或由Ci —C4烷基取代之C5 —Ci 2 環烯基的較佳例子為環己烯基。 含有不超過1 8個碳原子基的例子為烯丙基,2 —甲 基烯丙基,丁烯基,己烯基*十一烯基及十八烯基。其中 碳原子在第1個位置是飽和的烯基是較佳的,烯丙基是特 別佳的。 炔基的例子為戊炔基或辛炔基。 經1 ,2或3個Ci —C4燒基或Ci —C4烷氧基 取代之苯基的例子為甲基苯基,二甲基苯基*三甲基苯基 ,叔一丁基苯基,二一叔一丁基苯基,3,5 —二一叔一 丁基一 4 一甲基苯基,甲氧基苯基,乙氧基苯基及丁氧基 苯基。 未經取代的或在苯基上由1 ,2或3個Ci —C4烷 基取代之C7 — C9苯基烷基的例子為苄基,甲基苄基, 二甲基苄基,三甲基苄基,叔一丁基苄基,及2 —笨基乙 基。苄基是較佳的。 含有不超過1 2個碳原子醢基(脂肪系,環脂系或芳 香糸的)之例子為甲醢基,乙醯基,丙醃塞,丁醯基,戊 醯基,己醚基,庚醯基,辛醮基和苯甲醯基。(:! 一(:8 烷醢基和苯甲醯基是較佳的,乙醯基是特別佳的。 (Ci 2烷氧基)羰基的例子為甲氧基羰基, -15- 本紙張尺度適^中國國家標缚((:^ )八4規格(21(^ 297公楚) 一 (請先閲讀背面之注意事項再填寫本頁)Ri is especially Cs — Ci 8 alkyl, C5 — Ci 8 alkenyl, C5 — Ci 8 alkynyl, Cs — Ci 2 cycloalkyl, which are unsubstituted or substituted by Ct — C4 alkyl; Cs — Ci 2-cycloalkenyl, which is unsubstituted or substituted by Ci-C4 alkyl; a bicyclic or tricyclic hydrocarbon group having 6 to 10 carbon atoms, or C7-C9 phenylalkyl, which is unsubstituted Substituted or substituted by C i -C4 alkyl on phenyl; and the hydrocarbon solvents in reaction 3) are based on Ri (C 5 ~ C 1 8 alkyl, C5-CiS alkenyl, C5-Ci8 alkyne —C i 2 cycloalkyl, which is unsubstituted or substituted with Ci-C4 alkyl; C5 —Ci 2 cycloalkenyl, which is unsubstituted or substituted with Ci-C4 alkyl; A bicyclic or tricyclic hydrocarbon group with 6 to 10 涸 carbon atoms -12- This paper is based on the Chinese National Standard (CNS) Λ4 size (210X 297 mm) Central Standard Jujube Bureau of the Ministry of Economic Affairs 491871 A7 B7 V. Description of the invention (7), or c7-c9 phenylalkyl "is unsubstituted or substituted by C i-; C 4 alkyl on phenyl). According to another preferred embodiment of the present invention, R i is heptyl, octyl, cyclohexyl, methylcyclohexyl, cyclooctyl, cyclohexenyl * α -methylbenzyl or 1,2,3,4 Tetrahydrocycloalkyl, and the hydrocarbon solvent in reaction 3) is (according to Ri) heptane, octane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene, ethylbenzene or Tetralin. According to a preferred embodiment, Ri is octyl or cyclohexyl * and the hydrocarbon solvent of reaction 3) (according to Ri) is octane or cyclohexane. Examples of alkyl groups containing not more than 18 carbon atoms are methyl, ethyl, propyl * isopropyl, butyl, 2-butyl, isobutyl, pentyl, 2-pentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl . Ri is preferably C6-Ci 2 alkyl, especially heptyl or octyl. R4, Rs and Re are preferably Ci-C8 alkyl, especially Ci-C * alkyl. An example of an alkyl group substituted by -0H is 2-hydroxyethyl. Via Ci-10 alkoxy, preferably C2-C4 substituted by Ci-C4 alkoxy, especially methoxy or ethoxy (example of alkyl 2-methoxyethyl, 2-ethyl Oxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octyloxypropyl, and 4-monomethoxybutyl. -13- This paper Standards in China ("NS" Λ4 size (210X 297 mm)) (Please read the notes on the back before filling out this page.) 491871 A7 B7 V. Description of the invention (2) Via a bis (Ci-C4 alkyl) amino group, preferably a dimethylamino group or :; an example of a C2-C4 alkyl group substituted with an ethylamino group is 2-di Methylaminoethyl, 2-ethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethyl Amino group butyl. / ^ \ The group of formula (III) is preferably a N OO \ ^ / A preferred example of a c2-c4 alkyl group substituted by a group of formula (III) is 0- (ch2) —. The group base of the following formula is particularly good / ^ \ ^-(CH2 > 2 — Ο Examples of C5 —Ci 2 cycloalkyl groups which are unsubstituted or substituted via 1, 2 or 3 Ci —C4 alkyl groups are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, Methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cyclooctyl, cyclodecyl and cycloundecyl. Unsubstituted or substituted cyclohexyl are -14- ~ This paper uses China National Standards (CNS) Λ4 specifications (210X297 mm) (please read the precautions on the back before filling this page), and 11 will be awarded by the Ministry of Standards and Technology. Printed by the Consumer Cooperative 491871 A7 B7 _ V. Description of the Invention (q) A preferred example of a bicyclic or tricyclic hydrocarbon group having 6 to 10 carbon atoms is 1, 2, 3, 4 tetrahydrocycloalkyl. A preferred example of a C5 -Ci 2 cycloalkenyl substituted or substituted by Ci -C4 alkyl is cyclohexenyl. Examples containing no more than 18 carbon atoms are allyl, 2-methylallyl Alkenyl, butenyl, hexenyl * undecenyl and octadecenyl. Among them, alkenyl having a saturated carbon atom at the first position is preferred, and allyl is particularly preferred. Examples of alkynyl are pentynyl or octynyl. Examples of phenyl substituted with 1, 2 or 3 Ci-C4 alkyl or Ci-C4 alkoxy are methylphenyl, dimethylphenyl * Trimethylphenyl, tert-butylphenyl, di-tert-butylphenyl, 3,5-di-tert-butyl-4 4-methylphenyl, methoxyphenyl, ethoxybenzene And butoxyphenyl. Examples of C7-C9phenylalkyl which are unsubstituted or substituted with 1, 2 or 3 Ci-C4 alkyl groups are benzyl, methylbenzyl, di Methylbenzyl, trimethylbenzyl, tert-butylbenzyl, and 2-benzylethyl. Benzyl is preferred. Examples of fluorenyl groups (fatty, cycloaliphatic or aromatic fluorene) containing not more than 12 carbon atoms are methyl, ethyl, propyl, butyl, butyl, pentyl, hexyl, heptyl , Octyl and benzamyl. (:! A (: 8 alkylfluorenyl and benzamidine groups are preferred, ethenyl is particularly preferred. An example of a (Ci 2 alkoxy) carbonyl group is methoxycarbonyl, -15- this paper size Applicable ^ Chinese national standard binding ((: ^) 8 4 specifications (21 (^ 297)) (Please read the precautions on the back before filling this page)
,1T 491871 A7 B7 五、發明説明() 乙氧基羰基,丙氧基羰基* 丁氧基羰基•戊氧基羰基,己 氧基璨基,庚氧基羰基,辛氧基羰基’壬氧基羰基*癸氧 基羰基,十一烷氧基羰基及十二烷氧基羰基。 含有不超過1 2個碳原子烷撐的例子為乙撐,丙撐, 三甲撐,四甲撐,五甲撐,六甲撐,八甲撐•十甲撐及十 二甲撐。R2的例子為C2 — C8烷撐或C4 一 Cs烷撐 ,特別是C2 — c6烷撐’較佳的是六甲撐。 C4 一 C: 2烯撐的例子為3 —己烯撐。 Cs — C7環烷撐的例子為環己撐。 由1 ,4 一哌嗪二基所中斷C4 烷撐的例 子 ---·------0 II (請先閱讀背面之注意事項再填寫本頁) 為 —N N一CH2CH2, 1T 491871 A7 B7 V. Description of the invention () Ethoxycarbonyl, propoxycarbonyl * Butoxycarbonyl • pentoxycarbonyl, hexyloxycanyl, heptyloxycarbonyl, octyloxycarbonyl'nonoxy Carbonyl * decyloxycarbonyl, undecyloxycarbonyl and dodecyloxycarbonyl. Examples of alkylenes containing not more than 12 carbon atoms are ethylene, propylene, trimethyl, tetramethyl, pentamethyl, hexamethyl, octadecane, tenmethyl and twelve methyl. Examples of R2 are C2-C8 alkylene or C4-Cs alkylene, and especially C2-c6 alkylene 'is preferably hexamethylene. An example of C4-C: 2 olefin is 3-hexene. An example of Cs-C7 cycloalkylene is cyclohexylene. Example of C4 alkylene interrupted by 1,4-piperazinediyl --- · ------ 0 II (Please read the precautions on the back before filling this page) as --N N-CH2CH2
,1T 或 -CH2CH2CH2— N N ——CH2CH2CH2- 經滴部中次標率局Μ工消费合作社印1?- 由一 0 —,如1 ,2或3個一 0 —所中斷— Ci 2烷撐的例子為3 —氧雜戊烷一 1 ’ 5 —二基,4 一 氧雜庚燒一 1 ,7 —二基,3,6 —氧雜辛烧一 1 ,8 一 二基,4, 7 - 二氧雜癸烷一 1 ,1〇 一 二基,4,9 一 -1 6 - 本紙張尺度適州中國國家標率(CNS ) Λ4規格(210X 297公釐), 1T or -CH2CH2CH2— NN ——CH2CH2CH2- Printed by the Ministry of Substandard Standards Bureau M Industrial Consumption Cooperatives 1—- interrupted by a 0—such as 1, 2 or 3—0—Ci 2 alkylene Examples are 3-oxapentane-1'5-diyl, 4-oxaheptane-1,7-diyl, 3,6-oxaoctane-1,8-diyl, 4, 7- Dioxadecane-1, 110-diyl, 4, 9-1-6-The paper size is suitable for China National Standards (CNS) Λ4 specification (210X 297 mm)
i'發明説明u ) 二氡雜十二烷一 1,12 -二基,3,6,9 一三氧雜十 〜烷-?1 ,1 1 一二基及4,7,10 —三氧雜十三烷一 1,1 3 - 二基0 由>N — Xi所中斷C4 一 Ci 2烷撐的例子為: ^ C Η 2 C Η 2 C Η 2 一 Ν ( X 1 ) - C Η 2 C Η ζ 一 Ν (X ι ) 一 CHz CH2 CH2 — ,特別是 〜CHz C Η 2 C Η 2 - Ν ( C Η 3 ) 一 CH2 C Η 2 一 N(CH3) - CH2CH2CH2-0i 'Description of the Invention u) Dioxadodecane-1,12-diyl, 3,6,9-trioxadeca ~? -1,1 1-diyl and 4,7,10-trioxy Examples of heterotridecane-1,1 3 -diyl0 interrupted by > N — Xi C4 -Ci 2 alkylene are: ^ C Η 2 C Η 2 C Η 2 -N (X 1)-C Η 2 C Η ζ-Ν (X ι)-CHz CH2 CH2 —, especially ~ CHz C Η 2 C Η 2-Ν (C Η 3)-CH2 C Η 2-N (CH3)-CH2CH2CH2-0
Cs — C7環烷撐二(Ci—C*烷撐)的例子為環 己撐二甲撐。 (請先閲讀背面之注意事項再填寫本頁)An example of Cs—C7 cycloalkylene di (Ci—C * alkylene) is cyclohexyl dimethylene. (Please read the notes on the back before filling this page)
C 撐 己 ί 環 二 二 撐撐 燒丙 4 異 C 和 I 撐 1 己 C 環 二 撐C supports two rings, two supports, and 4 iso-C and I supports one, two rings, and two supports.
甲 為 子 例 的 V)/ 撐 烷 環 7 C -訂 (θ. 二{ 撐式 苯在A is a sub-example of V) / alkylene ring 7 C-order (θ. Di {
CC
撐 烷 4 C R 中 物 合 化 的 ο ) 撐 I 甲 I 二 G 撐 ί 苯式 為一 子是 例的 的佳 } 較 基 群 經濟部中央標準局Μ τ-消费合作社印製Compounds in alkylene 4 C R ο) I, I, I, G, and Benzene as an example are better.} Compared with the basic group printed by the Central Standards Bureau of the Ministry of Economic Affairs τ-Consumer Cooperative
為 物 產 I 的 2 佳 C 較是 2 RThe 2 best C for property I is 2 R
C : 撐 中烷 其C: alkylene
CC
C 撐 烷 環 7 CC alkylene ring 7 C
C 撐 ί烷 二環 撐 7 烷 C 環 I 7 5 c C )C 撐 ί 烷二 4 撐 C 苯C-supported alkane bicyclo-supported 7-alkane C-ring I 7 5 c C
CC
XX
C Ν I > 1 或C I ( ο 或 1 基 由醯 是 2 其 1 , C 撐 | 烷 1 2 C 1 是C Ν I > 1 or C I (ο or 1 group is from 醯 is 2 its 1, C 1 | alkane 1 2 C 1 is
C X 4 二 C 撐或 烷 } 4 撐 C 烷C X 4 di-C-alkylene or alkane} 4-alkylene C-alkane
C 2 基 ’ 羰 的 } 斷基 中氧 所烷 式1 是 2 R 或 者1 之 中 義 定 4 R 述 如基 有群 具的 或 } 本紙張尺度適用中國國家標枣(CNS ) Λ4規格(210X297公釐) 經濟部中次標準局兑工消费合竹社印製 491871 A7 B7 五、發明説明() R 3 ,R4和R5 (相同或不同的)是(:! 一Ci 8烷基 ,(:5 — Ci 2環烷基,其是未經取代的或經由1 * 2或 3個Ci 一 c4烷基取代的;苯基*其是未經取代的或經 由1 ,2或3個Ci —C4烷基或Ci 一 C4烷氧基取代 的;C7 — C9苯基烷基,其是未經取代的或在苯基上由 1 ,2或3個Ci -C4烷基取代的;及 R3另外是氫或一 N(R4) (Rs)另外是一式( I I I )的群基; R6是(:1 —Ci 8烷基,C5 — Ci 2環烷基其是未經 取代的,或是由1 ,2或3個Ci 一 C4烷基取代的;C 2 radical 'carbonyl's oxygen radical in the radical group is 2 R or 1 in the definition of 4 R as described in the above, or} This paper size applies Chinese National Standard Date (CNS) Λ4 specification (210X297) (%) Printed by the Intermediate Standards Bureau of the Ministry of Economic Affairs and printed by Hezhu News Agency 491871 A7 B7 V. Description of the invention () R 3, R 4 and R 5 (same or different) are (:! Ci 8 alkyl, (: 5 — Ci 2 cycloalkyl, which is unsubstituted or substituted via 1 * 2 or 3 Ci-c4 alkyl; phenyl * which is unsubstituted or via 1, 2 or 3 Ci-C4 alkyl Or Ci-C4 alkoxy substituted; C7-C9 phenylalkyl, which is unsubstituted or substituted on the phenyl with 1, 2, or 3 Ci-C4 alkyl; and R3 is additionally hydrogen Or one N (R4) (Rs) is another group group of formula (III); R6 is (: 1-Ci 8 alkyl group, C5—Ci 2 cycloalkyl group which is unsubstituted, or consists of 1, 2 Or 3 Ci-C4 alkyl substituted;
C7 _C9苯基烷基,其是未經取代的*或是在苯基上由 1 ,2或3個Ci —C4烷基取代的;或是一式(G - I )的群基。 也是較佳的產物為其中: R2是C2 —C1〇烷撐,環己撐,環己撐二(Ci 一 C4)烷撐),Ci 一 C4烷撐二環己撐或苯撐二(Ci 一 C 4烷撐); R 3 ,R4和Rs (相同或不同的)是Ci—Ciz烷基 ,C5 — C7環烷基,其是未經取代的,或是由1 * 2或 3個C i 一 C 4烷基取代的;苯基,其是x未經取代的,或 是由1 ,2或3個Ci 一 C4烷基取代的;苄基·其是未 經取代的,或是在苯基上由Ci 一 C4烷基取代的;或一 N ( R 4 ) (Rs)另外是一式(III)的群基;及 -1 8 - 本紙張尺度適州中國國家標卒(CNS〉Λ4規格(2丨0X 297公釐) ——"------·! (請先閲讀背面之注意事項再填寫本頁) 訂 491871 A7 _B7__ 五、發明説明(4) R 6是Ci 一 Ci2烷基,C5 — C7環烷基,其是未經 取代的,或是由1,2或3個Ci 一 C4烷基取代的;苄 基,其是未經取代的,或是由1 ,2或3個Ci —C4烷 基取代的;或是一式(G — I)的群基。 更佳的產物為其中: R2是C2 —C8烷撐; R 3 ,R4和Rs (相同或不同的)是Ci 一 C8烷基· 環己基*其是未經取代的,或是由甲基取代的;笨基•其 是未經取代的,或是由甲基取代的;苄基或一 N (R4 ) (Rs)另外是4 一嗎啉基;及 R6是(:1 -C3烷基,環己基,其是未經取代的,或是 由甲基取代的;苄基或一式(G — I)的群基。 特別佳的產物為其中:C7-C9 phenylalkyl, which is unsubstituted * or substituted with 1, 2, or 3 Ci-C4 alkyl groups on the phenyl group; or a group group of the formula (G-I). Also preferred products are among them: R2 is C2-C10 alkylene, cyclohexyl, cyclohexylene (Ci-C4) alkylene), Ci-C4 alkylene dicyclohexylene or phenylene (Ci- C 4 alkylene); R 3, R 4 and Rs (same or different) are Ci-Ciz alkyl, C 5-C 7 cycloalkyl, which are unsubstituted or consist of 1 * 2 or 3 C i -C 4 alkyl substituted; phenyl, which is unsubstituted or substituted by 1, 2 or 3 Ci-C 4 alkyl; benzyl · which is unsubstituted or benzene Ci-C4 alkyl substituted on the base; or N (R 4) (Rs) is additionally a group base of formula (III); and -1 8-this paper is suitable for China National Standard (CNS> Λ4 specification) (2 丨 0X 297mm) —— " ------ ·! (Please read the notes on the back before filling in this page) Order 491871 A7 _B7__ 5. Description of the invention (4) R 6 is Ci-Ci2 Alkyl, C5-C7 cycloalkyl, which is unsubstituted, or substituted by 1, 2 or 3 Ci-C4 alkyls; benzyl, which is unsubstituted, or by 1, 2 Or 3 Ci-C4 alkyl substituted; or a group group of the formula (G-I). The products are: R2 is C2-C8 alkylene; R3, R4 and Rs (same or different) are Ci-C8 alkyl · cyclohexyl * which is unsubstituted or substituted by methyl; stupid Is unsubstituted or substituted by methyl; benzyl or -N (R4) (Rs) is additionally 4-morpholinyl; and R6 is (: 1-C3 alkyl, cyclohexyl, It is unsubstituted or substituted by methyl; benzyl or a group of formula (G-I). Particularly preferred products are:
Ri是辛基或環己基,及 在反應3)中的碳氫化合物溶劑是(依據Ri而定)辛烷 或環己烷;Ri is octyl or cyclohexyl, and the hydrocarbon solvent in reaction 3) is (depending on Ri) octane or cyclohexane;
Rz是Cz — C6燒撐; 經湳部中央樣準局員工消费合作社印欠 (請先閲讀背面之注意事項再填寫本頁) A是一 N(R4) (Rs)或一式(II)的群基; R4和R5 (相同或不同的)是Ci—Cs烷棊; 或一N(R4) (R5)另外是4 一嗎啉'基; X 是 > N - R s ;Rz is Cz — C6 burner; the debt is owed by the Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) A is a group of N (R4) (Rs) or formula (II) R4 and R5 (same or different) are Ci-Cs alkane groups; or one N (R4) (R5) is another 4-morpholine 'group; X is > N-R s;
Re是Ci-Cs烷基;及 B具有如A定義中之一者。 __ -19- 本紙张尺度適用中國囤家標蟬((:奶)八4規格(210 / 297公釐〉 一 ^1871 R_____ 經濟部中央標準局兵τ-消f合作社印製 A7 B7 發明説明(θ) 也是特 R 1燁辛基 在反應3) 或環己烷; R2是c2 — c6烷撐 別佳的產物為其中: 或環己基*及 中的碳氫化合物溶劑是(依據Ri而定)辛烷 R是一式( A 是一 N ( R 4 和 R 5 B是式(I X 是 > N -R 6 是 C 1 用於反 合物或脂肪 芳香糸 異丙基苯, 脂肪系 丁基嗣*甲 基己基酮和 G — I )的群基; R 4 ) ( R 5 ); (相同或不同的)是Ci 一 C8烷基; I )的群基; R 6 > 一 C 8燒基。 應1)和2)的有機溶劑特別是芳香系碳氫化 条嗣。 碳氫化合物的例子為甲苯,二甲苯,三甲苯, 二異丙基苯和叔一丁基苯。 酮的例子為甲基乙基酮,甲基丁基酮*甲基異 基戊基嗣,乙基丁基酮,二一正一丙基酮,甲 乙基戊基酮。特別是水不可溶的酮類是較佳的 (請先閱讀背面之注意事項再填寫本頁) 訂 基酮 較佳的溶劑是甲苯,二甲苯,甲基丁基酮及甲基異丁 〇 二甲苯及甲基異丁基酮是特別佳的。 用於本發明方法的無機鹸例子為氫氧化納,氫氧化鉀 20 本紙張尺度適川中國國家標淨((、NS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明() ,碳酸納及碳酸鉀。氪氧化納是較佳的。 反應1)和2)較佳的是在一惰性氣體中,特別是在 氮氣中進行。 式(cx)和(々)的反應劑是彼此互相加入至一反應 器中,溫度為1 ου至6〇υ。依據所使用的溶劑,溫度 為,例如可增加至80至85¾,然後在關閉反應器後, 溫度可進一步增加至,例如1 1 0¾至220它,較佳地 是1501至16〇υ。因為此反應是在一密閉系統中進 行*所以壓力随著溫度上升而增加,一般而言,在反應器 中可測得3至8bar ,如4至6bar。 因為所使用溶劑的低沸點*反應2)也可方便的在一 密閉系統中進行。依據所使用的溶劑,反應2)可在溫度 ,例如11 0¾至1 8〇υ間進行,較佳地1 30¾至 1 7〇υ,特別是1 40¾至1 60¾間進行。因為反應 溫度高,所Μ—般在反應器中所測得的壓力為3至8 bar,如 4 至 6bar。 經滴部中央標準局Μ工消贽合作社印製 (請先閲讀背面之注意事項再填寫本頁) 假使需要,在反應2)完成後*式(δ)化合物及最 後未反應的起始物質可蒸鲡法,或使用一般的純化技藝由 最終混合物中排除。 反應2)的產物可方便的在反應3) 4進行前分離出。 反應3)中所使用的過氧化物分解觸媒為•例如金屬 羰基化物,金屬氧化物*金屬乙醯丙酮酸鹽或金靨烷氧化 物,其中金屬是選自週期表第IVb ,Vb,VIb, -2卜 本紙張尺度適用ϋ國家標枣((,奶)八4規格(210、/297公釐〉 491871 A7 __B7_五、發明説明(山) VI lb及VI I I的金靥,較佳的是釩(I I I)乙醯 丙酮酸鹽,羰基鈷,氧化铬(VI),異丙氧化鈦(IV ),四丁氧化钛,六羰基鉬,三氧化鉬及類似物。最佳的 觸媒是Μ 〇 0 3 。 合適的過氧化氫是叔一丁基過氧化氫,叔一戊基過氧 化氫,叔一己基過氧化氫,叔一辛基過氧化氫,乙基苯過 氧化氫*四琳過氧化氫或枯烯(=異丙基苯)過氧化氬。 最佳的過氧化氫是叔一丁基過氧化氬。 在反應3)中,對於每1莫耳存在於反應2)產物中 的式(G — I)位阻胺,使用2至8莫耳*較佳地3至6 莫耳的過氧化氫,0 · 001至〇 · 1莫耳,較佳地 〇 · 005至0 · 05莫耳的過氧化氫分解觸媒及5至 30莫耳,較佳地1 〇至20莫耳的碳氫化合物溶劑: (請先閲讀背面之注意事項再填寫本頁) 、1Τ 經滴部中央標率局贤工消费合作社印掣Re is Ci-Cs alkyl; and B has one of the definitions of A. __ -19- This paper size is applicable to Chinese storehouse standard cicada ((: milk) 8 4 size (210/297 mm) 1 ^ 1871 R_____ Printed by the Central Standards Bureau of the Ministry of Economic Affairs, τ- 消 f Cooperative, printed A7 B7 Invention Description ( θ) is also R 1 烨 octyl in reaction 3) or cyclohexane; R 2 is c2-c6 alkylidene. The best products are: or cyclohexyl * and the hydrocarbon solvent is (depending on Ri) Octane R is a formula (A is a N (R 4 and R 5 B are formulas (IX is > N -R 6 is C 1) for the reactant or fatty aromatic cumene cumene, fatty butyl hydrazone * Groups of methylhexyl ketone and G — I); R 4) (R 5); (same or different) is Ci-C8 alkyl; I); R 6 >-C 8 alkyl. The organic solvents of 1) and 2) are particularly aromatic hydrocarbons. Examples of hydrocarbons are toluene, xylene, trimethylbenzene, diisopropylbenzene and tert-butylbenzene. Examples of ketones are methyl ethyl ketone, methyl butyl ketone * methyl isopentyl hydrazone, ethyl butyl ketone, di-n-propyl ketone, methyl ethyl pentyl ketone. In particular, water-insoluble ketones are preferred (please read the notes on the back before filling this page). The preferred solvents for ketones are toluene, xylene, methylbutyl ketone, and methyl isobutane. Toluene and methyl isobutyl ketone are particularly preferred. Examples of inorganic rhenium used in the method of the present invention are sodium hydroxide, potassium hydroxide 20 This paper is suitable for Sichuan National Standard ((, NS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention (), Sodium carbonate and potassium carbonate. Sodium oxide is preferred. Reactions 1) and 2) are preferably carried out in an inert gas, especially under nitrogen. The reactants of the formulae (cx) and (ii) are added to each other into a reactor at a temperature of 1 to 6o. Depending on the solvent used, the temperature may be, for example, increased to 80 to 85¾, and then after the reactor is closed, the temperature may be further increased to, for example, 1102 to 220, preferably 1501 to 160. Because this reaction is performed in a closed system *, the pressure increases with increasing temperature. Generally speaking, 3 to 8 bar, such as 4 to 6 bar, can be measured in the reactor. Because of the low boiling point of the solvent used * reaction 2) can also be conveniently performed in a closed system. Depending on the solvent used, the reaction 2) can be carried out at a temperature of, for example, 110 2 to 1 800, preferably 1 30¾ to 1700, especially 1 40¾ to 1 60¾. Because of the high reaction temperature, the pressure measured in the reactor is usually 3 to 8 bar, such as 4 to 6 bar. Printed by the Ministry of Standards, Mie Cooperative Cooperative (please read the precautions on the back before filling out this page) If necessary, after the reaction 2) is completed, the compound of formula (δ) and the final unreacted starting material may be Distillation is eliminated from the final mixture, or using general purification techniques. The product of reaction 2) can be conveniently isolated before reaction 3) 4 is performed. The peroxide decomposition catalysts used in reaction 3) are, for example, metal carbonyls, metal oxides * metal acetamidine pyruvate or amidoxane oxide, where the metal is selected from the group consisting of Period IVb, Vb, VIb , -2 The size of the paper is applicable to the national standard date ((, milk) 8 4 specifications (210, / 297 mm) 491871 A7 __B7_ V. Description of the invention (mountain) VI lb and VI II gold, preferably Vanadium (III) acetamidine pyruvate, cobalt carbonyl, chromium (VI) oxide, titanium isopropoxide (IV), titanium tetrabutoxide, molybdenum hexacarbonyl, molybdenum trioxide and the like. Best catalysts Is M 03. Suitable hydrogen peroxide is tert-butyl hydroperoxide, tert-pentyl hydroperoxide, tert-hexyl hydroperoxide, tert-octyl hydrogen peroxide, ethylbenzene hydroperoxide * Si Lin hydrogen peroxide or cumene (= cumene) argon peroxide. The best hydrogen peroxide is tert-butyl argon peroxide. In reaction 3), for every 1 mole present in reaction 2) Hindered amines of formula (G-I) in the product, using 2 to 8 moles * preferably 3 to 6 moles of hydrogen peroxide, 0. 001 to 0.1 moles, preferably 〇 · 005 to 0 · 05 mol of hydrogen peroxide decomposition catalyst and 5 to 30 mol, preferably 10 to 20 mol of hydrocarbon solvent: (Please read the precautions on the back before filling this page ) 、 1Τ Printed by the Consumer Standards Cooperative of the Central Standards Bureau of Didi Ministry
式(G — I)的位阻胺群基至下式群基的轉化: 嫌22- 本紙張尺度適用中國國家榡率(CNS ) Λ4規格(210X 297公釐) 491871 A7 B7 經斌部中*標導扃Μ,χ消費合作社印$ 五、發明説明(β )Conversion of sterically hindered amine group group of formula (G — I) to the following group group: Suspect 22- This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 491871 A7 B7 Jing Bin Department * Marked by 扃 Μ, χ consumer cooperative printed $ 5. Invention Description (β)
是在,例如75¾至1 60¾,較佳地lOOt:至1 50 υ間進行。 在反應3)中,當式(G — I)的位阻胺群基首先Μ 過氧化氫水溶液,在過氧化氫分解觸媒存在下及於一惰性 溶劑中處理時(例如類似描述於US — Α - 4,69 1 , 015的方法)*在非常短的時間内所得的起始反應產物 相當於N —氧基中間物(一 〇Ri=氧基),其是高度染 色的,且可獨自分離出來。 因此,本發明的其它較佳實施例為關於一種得自上述 反應1)至3)的產物,其中反應基一 0 -只^是氧基, 及反應3)中所使用的碳氫化合物溶劑是惰性有機溶劑* 較佳的是甲苯或1 ,2 —二氯乙烷。 當反應3)的有機溶劑是具有不安定氫原子之碳氫化 合物時,當保留有遠超過胺基轉化成相對N -氧基衍生物 所需莫耳量之過氧化氫時,且當反應混合'物是另外加熱至 適當溫度(較佳的在lOOt:至150*0時)一般時間時 ,則Ν —氧基化合物(可為由原來的胺製備而得,或在此 反應過程中用作起始中間物者)和碳氫化合物溶劑會進一 -23- 度i州中國國家榡嘩((’奶)八4規格(210'/ 297公釐) ---:——J----Φ------1T------Φ— (請先閱讀背面之注意事項再填寫本頁) 491871 A7 B7 五、發明説明(β ) 步反應,而形成相對應的N —烴氧基衍生物。 在反應3)中,原先的反應混合物是無色的•但當N 一氧基中間物形成時則變為高度染色的。當此N -氧基化 合物轉化為無色的N -烴氧基產物時*則顔色消失。因此 ,此方法重要的是必須有一內鍵的顔色指示劑Μ顯示反應 的程度。當反應混合物變為無色時,則代表有色的Ν —氧 基中間物已完全轉化為Ν—烴氧基產物。 本發明的一個實施例也關於一種得自氫化反應3)產 物(其中在式(G — I I)中,一 ORi是氧基)而獲致 具有一式(G - III)群基的產物 (請先閱讀背面之注意事項再填寫本頁) 訂It is carried out, for example, at 75¾ to 1 60¾, preferably 100t: to 1 50 υ. In reaction 3), when a sterically hindered amine group of the formula (G-1) is first treated with an aqueous hydrogen peroxide solution, treated in the presence of a hydrogen peroxide decomposition catalyst and in an inert solvent (such as described in US- Method A-4,69 1, 015) * The initial reaction product obtained in a very short time is equivalent to the N-oxy intermediate (-10Ri = oxy), which is highly dyed and can be used alone separate from. Therefore, other preferred embodiments of the present invention pertain to a product obtained from the above reactions 1) to 3), wherein the reactive group is 0 to ^ is an oxy group, and the hydrocarbon solvent used in the reaction 3) is The inert organic solvent * is preferably toluene or 1,2-dichloroethane. When the organic solvent of reaction 3) is a hydrocarbon having a labile hydrogen atom, when a hydrogen peroxide which is far more than the molar amount required for the conversion of the amine group to the relative N-oxy derivative is retained, and when the reaction is mixed If the substance is additionally heated to an appropriate temperature (preferably at 100t: to 150 * 0 hours) for a normal time, then the N-oxyl compound (which can be prepared from the original amine or used in this reaction process) Those who start the intermediate) and hydrocarbon solvents will advance to -23-degree. State of China (('Milk) 8 4 size (210' / 297 mm)) ---: --J ---- Φ ------ 1T ------ Φ— (Please read the notes on the back before filling in this page) 491871 A7 B7 V. Description of the invention (β) Step reaction to form the corresponding N-hydrocarbon Oxygen derivatives. In reaction 3), the original reaction mixture was colorless, but became highly dyed when the N-oxyl intermediate was formed. When this N-oxyl compound is converted to a colorless N-alkoxy product *, the color disappears. Therefore, it is important for this method that the color indicator M having an internal bond shows the degree of the reaction. When the reaction mixture becomes colorless, it means that the colored N-oxy intermediate is completely converted to the N-alkoxy product. An embodiment of the present invention also relates to a product obtained from the hydrogenation reaction 3) (wherein ORi is an oxygen group in the formula (G-II)) to obtain a product having the group (G-III) group (please read first (Notes on the back then fill out this page)
^1. 經消部中央標卒局负JT-消费合竹社印繁 此氫化反應是依據習知的方法進行,例如在一有機溶 劑中,如甲酵或乙醇中,且在一氫化觸媒存在下,較佳的 是碳上的鈀或?1:〇2,如描述於113-八一4,691 ,0 1 5。 、 假使需要,反應3 )所得的產物能Μ下述方法之一純 化: a)分解殘留的過氧化物,且蒸發溶劑而獲得一粗固體產 -24- 本紙張尺度適州中國國家標枣(rNS ) Λ4規格(210X 297公釐) 經滴部中央標準局吳工消费合作社印f 491871 A7 B7 i、發明説明(4 ) 物。此固體產物和一惰性溶劑攪拌,如環己烷*辛烷,己 烷,石油醚,二甲苯,甲苯,丙酮,甲基乙基酮*乙酸乙 酯*乙酸丁酯,叔- 丁基醇,叔一戊基醇,異丙基酵*乙 酵,甲酵,氛仿,二氯甲烷,乙腈,二乙醚,二丁基醚及 /或水。此混合物可加熱時攪拌,攪拌後*冷却混合物, 過漶收集固體產物*然後乾燥。 b) 分解殘留過氧化物,溶劑部份蒸發掉*過滅殘留物, 可得一固體,其Μ—惰性溶劑洗濯,像上述溶劑之一,且 可淬冷所得固體產物,然後乾燥。 c) 分解殘留過氧化物,溶劑在高溫下蒸發,可得一熔融 物。將熱的熔融物和一惰性溶劑混合,像上述溶劑之一( 可淬冷),過滹收集沈澱物,然後乾燥。此步驟的變異方 式包括混合熱的熔融物和溶劑*然後冷却混合物,而獲致 一沈澱物,或混合熱的熔融物和溶劑,接著加熱,使得任 何的固體溶於溶液中,然後冷却獲得沈澱物。 d) 分解殘留過氧化物,溶劑在高溫下蒸發,而獲得一熔 融物。此熔融物溶於一惰性溶劑中*像上述溶劑之一(可 加熱或不加熱),然後蒸餾出一些過量的溶劑而濃縮结果 溶液,然後此溶液和一第二溶劑在高溫下混合,像上述溶 劑之一,如此產物沈澱出。過漶收集固體產物,及乾燥。 更特別的是反應3)的產物較佳的是Μ下述方法純化 在反應3)完成後,粗反應混合物冷_至50C,且 -25- 本紙张尺度適州中國囤家標碑(CNS ) AAim ( 210X 297/>t ) 一 ---.-----ΦΙ — (請先閲讀背面之注意事項再填寫本頁) 訂 ^1. 經滴部中央標沭局貝工消费合作社印製 491871 A7 B7 五、發明説明(,) 以2 0%的亞硫酸納水溶液處理直至殘留遇氧化物的濃度 降低至0 · 下。分離出水溶液層,在減壓下加熱產 物濃縮有機層。粗產物溶於過量的叔-丁基醇中,在減壓 下加熱溶液而移去溶劑,直至固體的濃度是5 0%為止。 慢慢的將此溶液加至冷甲酵中,遇滤结果沈澱物,Μ甲醇 洗濯,和在真空下加熱乾燥。 一般而言,上述方法所使用的起始物質是習知的。在 其不是商業化生產的情況下*他們也可類似習知的方法製 備而得。 式(cx)的化合物可由,例如一氰尿醯氯和一式Β — Η的化合物反應製備而得,反應是Μ化學計量比例》且在 一有機溶劑和一無機鹼的存在下進行。使用上述反應1 ) 和2)的相同溶劑和無機鹼製備式(《)化合物也是適當 的0 假使需要*在製備式(a)起始物質後,反應1)可 立刻接著進行,而沒有分離出式(α)化合物。 一些式(/3)起始物質描述於,例如W0 — Α — 95 /21,157; US - A - 4,316,837 和 US 一 A — 4,743,688 號中。 本發明的其它實施例是一得自上述反應1)和2)的 產物。 其中在下式群基中的氮原子 -26- 本紙張尺度適用中國國家標枣((、NS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 491871 A7 B7 五、發明説明(yj )^ 1. The Ministry of Economic Affairs and the Central Bureau of the Ministry of Justice of the People's Republic of China, the negative JT-consumer Hezhu company printed the hydrogenation reaction according to conventional methods, such as in an organic solvent, such as formazan or ethanol, and a hydrogenation catalyst In the presence, palladium or carbon on carbon is preferred 1: 02, as described in 113-Aug 4,691, 0 1 5. 3. If necessary, reaction 3) The product obtained can be purified by one of the following methods: a) Decomposing the remaining peroxide and evaporating the solvent to obtain a crude solid product. rNS) Λ4 specification (210X 297 mm) Printed by Wu Gong Consumer Cooperative of the Central Standards Bureau of the Ministry of Industry, F 491871 A7 B7 i. Description of the invention (4). This solid product is stirred with an inert solvent such as cyclohexane * octane, hexane, petroleum ether, xylene, toluene, acetone, methyl ethyl ketone * ethyl acetate * butyl acetate, tert-butyl alcohol, Tert-amyl alcohol, isopropyl *, ethyl acetate, formazan, chloroform, dichloromethane, acetonitrile, diethyl ether, dibutyl ether and / or water. This mixture can be stirred while heating. After stirring * the mixture is cooled, the solid product is collected over time and then dried. b) The residual peroxide is decomposed, and the solvent is partially evaporated to eliminate the residue. A solid can be obtained, which is washed with an M-inert solvent, like one of the above solvents, and the obtained solid product can be quenched and then dried. c) The residual peroxide is decomposed, and the solvent is evaporated at a high temperature to obtain a melt. The hot melt is mixed with an inert solvent, like one of the solvents mentioned above (quenchable), and the precipitate is collected over time and then dried. Variations of this step include mixing hot melt and solvent * and then cooling the mixture to obtain a precipitate, or mixing the hot melt and solvent, followed by heating to dissolve any solids in solution, and then cooling to obtain a precipitate. . d) The residual peroxide is decomposed, and the solvent is evaporated at a high temperature to obtain a melt. This melt is dissolved in an inert solvent * like one of the above solvents (with or without heating), and then the excess solution is distilled off to concentrate the resulting solution. Then the solution and a second solvent are mixed at a high temperature, as described above. One of the solvents, so that the product precipitated. The solid product was collected by centrifugation and dried. More specifically, the product of reaction 3) is preferably purified by the following method. After reaction 3) is completed, the crude reaction mixture is cooled to 50C, and -25- this paper size Shizhou China Storehouse Mark (CNS) AAim (210X 297 / > t) I ---.----- ΦΙ — (Please read the notes on the back before filling out this page) Order ^ 1. Printed by the Shell Department Consumers Cooperative of the Central Bureau of Standards Preparation 491871 A7 B7 V. Description of the invention (,) Treat with 20% sodium sulfite aqueous solution until the concentration of residual oxides is reduced to below 0 ·. The aqueous layer was separated, and the product was concentrated under reduced pressure to concentrate the organic layer. The crude product was dissolved in an excess of t-butyl alcohol, and the solvent was removed by heating the solution under reduced pressure until the solid concentration was 50%. This solution was slowly added to cold formazan, and the precipitate was filtered, washed with methanol, and dried under vacuum in the presence of filtration. In general, the starting materials used in the above methods are conventional. Where they are not commercially produced * they can also be prepared in a similar way. The compound of formula (cx) can be prepared, for example, by reacting monocyanuric chloride with a compound of formula B-fluorene. The reaction is in a stoichiometric ratio and is carried out in the presence of an organic solvent and an inorganic base. It is also appropriate to prepare the compound of formula (") using the same solvents and inorganic bases of the above reactions 1) and 2). If required * After preparing the starting material of formula (a), reaction 1) can be carried out immediately without isolation. Compound of formula (α). Some starting materials of formula (/ 3) are described in, for example, WO-A-95 / 21,157; US-A-4,316,837 and US-A-4,743,688. Other embodiments of the present invention are a product obtained from the above reactions 1) and 2). Among them, the nitrogen atom in the group formula below -26- This paper size applies to the Chinese national standard date ((, NS) Λ4 size (210X 297 mm) (Please read the precautions on the back before filling this page) Order 491871 A7 B7 V. Description of the invention (yj)
是由Ci —C8烷基* C2 — C8羥基烷基,0,一 OH ,Ct 一 Ci 8烴氧基(如Ci 一 Ci 8烷氧基或Cs -c!2環烷氧基),一CH2CN,C3 —ce烯基, C3 — c6炔基,C7 — C9苯基烷基(其可是未經取代 的或在苯基上由1,2或3個Ci—Ci烷基取代的); 或Ci —C8醢基取代之產物可由類似上述反應1)和2 )的方法,使用適當的起始物質製備而得。氮原子較佳的 是由Ci —C4烷基取代的,特別是甲基。 那些含有下式群基之起始物質, (請先閲讀背面之注意事項再填寫本頁) 經消部中央標準局负JT.消费合作社印製Ci—C8 alkyl * C2—C8 hydroxyalkyl, 0, 1 OH, Ct—Ci 8 alkoxy (such as Ci—Ci 8 alkoxy or Cs—c! 2 cycloalkoxy), 1 CH2CN , C3-cealkenyl, C3-c6 alkynyl, C7-C9 phenylalkyl (which may be unsubstituted or substituted with 1,2 or 3 Ci-Ci alkyl groups on the phenyl group); or Ci —C8 fluorenyl substituted products can be prepared by methods similar to the above reactions 1) and 2), using appropriate starting materials. The nitrogen atom is preferably substituted by a Ci-C4 alkyl group, especially a methyl group. Those starting materials containing the following group bases (please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Consumer Affairs, JT. Consumer Cooperative
-27- 本紙張尺度適川中國國家標搫(CNS ) Λ4規格(210X 297公釐) 491871 Α7 Β7 五、發明説明(Ί 可由,例如類似描述於US — Α - 4,921 ,962; US4A 一 5,021,5 77 和 US - A - 5,204 *473的方法製備而得。 反應2)的產物不是單一特定的化合物,而是具有分 子量分佈的化合物。 聚分散度(polydispersity)指示聚合化合物分子量 的分佈。在本發明中,聚分散度是重量平均分子董(Mw )和數量平均分子量(Μη)的比例,Mw/Mn值愈接 近1 ,代表該化合物是單分散的,且只有一種分子量’而 沒有分子量分佈。窄的分子量分佈的特徵是聚分散度( Mw/Mn)接近 1。 反應2)的較佳產物之聚分散度1 至1 ’ 7 ’例 如1 · 1至1 ·6或1 .3至1 ·7,特別是1 .3至 1 · 6 ° 需注意的是反應2)產物包括,例如少於5冥耳%’ 特別是少於2莫耳%或少於1莫耳炻的終端不是由下群基 (請先閱讀背面之注意事項再填寫本頁) 訂 性 線 的 蓋 覆 端 終 經滴部中央標if局员工消费合作社印裝-27- The size of this paper is suitable for Sichuan National Standard (CNS) Λ4 specification (210X 297 mm) 491871 Α7 Β7 5. Description of the invention (Ί can be, for example, similarly described in US — Α-4,921,962; US4A 1 5,021,5 77 and US-A-5,204 * 473. The product of reaction 2) is not a single specific compound, but a compound having a molecular weight distribution. Polydispersity indicates the molecular weight distribution of the polymerized compound. In the present invention, the degree of polydispersity is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mη). The closer the Mw / Mn value is to 1, the compound is monodispersed and has only one molecular weight, and no molecular weight. distributed. The narrow molecular weight distribution is characterized by a polydispersity (Mw / Mn) close to one. The degree of polydispersity of the preferred product of reaction 2) is 1 to 1'7 ', for example, 1.1 to 1.6, or 1.3 to 1.7, especially 1.3 to 1.6. Note that reaction 2 ) The products include, for example, less than 5 mole% ', especially less than 2 mole% or less than 1 mole, the terminal is not made by Xunquji (please read the precautions on the back before filling this page) The end of the cover is printed by the employee ’s consumer cooperative of the Central Standard Bureau of Dibu
A 本紙張尺度適州中國國家標冷·( CNS ) Λ4規格(210X 297公釐) 491871 A7 _ B7__五、發明説明(v1)) 反應1 )進行時,可形成一下式的環形結構化合物之副產 物1 ΗA This paper size is suitable for China National Standard Cold (CNS) Λ4 specification (210X 297 mm) 491871 A7 _ B7__ V. Description of the invention (v1)) Reaction 1) When performed, it can form a ring structure compound of the following formula 1 byproduct
(請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標年局Μ Η消费合作社印來 由US — Α — 4,442,250可知,此化合物是習知 的,且可以少於8莫耳%的量存在於反應2)的產物中。 反應2)的產物較佳地是包含一式(M - I)單分散 體化合物,一式(M - I I)單分散體化合物’一式(M 一 I I I)單分散體化合物,及一式(M - IV)單分散 體化合物的混合物,這些化合物不同之處只在於重覆單元 \ 數的不同, 本紙張尺度適州中國國家標苹(rNS ) Λ4規格(210X 297公釐) 491871(Please read the precautions on the back before filling this page.) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, MΗConsumer Cooperative, and printed from US — Α — 4,442,250. This compound is known and can be less than 8 Mole% is present in the product of reaction 2). The product of reaction 2) preferably comprises a monodisperse compound of formula (M-I), a monodisperse compound of formula (M-II) ', a monodisperse compound of formula (M-III), and a formula of (M-IV) A mixture of monodisperse compounds. These compounds differ only in the number of repeating units. This paper is suitable for the Chinese national standard (rNS) Λ4 size (210X 297 mm) 491871.
A 説明發五A description of five
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\\ A rN, /丫 (Μ (請先閲讀背面之注意事項再填寫本頁) ΤΝ τ ΝΝ. /丫 經濟部中央標皁局貨Τ-消费合作社印製 Β\\ A rN, / Ya (M (Please read the notes on the back before filling in this page) ΤΝ τ ΝΝ. / Ya Printed by the Central Standard Soap Bureau of the Ministry of Economic Affairs T-Consumer Cooperative Β
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(M Μ } 至 (V ο 式 I 5 且 I 是 ,Μ 別 者 ί 特 義及, 定}% 所 I 耳 上 I 莫 如 I ο 是 I 7 2 Μ 至 R ( ο 和 ,4 R } 是 , I 量在存共 總 的 物合 化 -30- 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明( | 為 ·· Μ 例 4 ί 比 · 和之 1 丨物至 I 合 1 I 化 : Μ ) 6 (V . ο * I ο } } I 或 物 I Μ 1 合 I { : 混 I 和 6 共 Μ > · 總 { I 1 於和 I 至 對 } Μ 1 相 I ί : { I 及 6 % Μ , · 耳 ί 莫式 5 6* )ο I 如 I 例 〇 I—- > 1 物 1 合 Μ 混 { 之 , 物 ) 合 I 化 I ) Μ V ( I 式 I 有 Μ 含 { 於 和 在 }: 存 I 基 於 I 群 0 1) 係 一 I )Μ I 3 ( G 應 ,ί 反} 式 I 之 I 中(M Μ) to (V ο Formula I 5 and I is, Μ and other special, and definite)% So I on the ear is like I ο is I 7 2 Μ to R (ο and, 4 R) Yes, I The total amount of physical compounds in existence -30- This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention (| is ·· Μ Example 4 ί ratio and and No. 1 丨 matter to I in 1 I: Μ) 6 (V. Ο * I ο}} I or matter I Μ 1 in I {: mixed I and 6 in total > · total {I 1 于 和 I 至Pair} Μ 1 phase I ί: {I and 6% Μ, · ear 莫 Mo formula 5 6 *) ο I like I Example 〇I—- > 1 thing 1 and M mixed {of, matter) compound I ) MV (I formula I has Μ containing {于 和 在}: Preserve I based on I group 0 1) is a I) Μ I 3 (G shall, ί trans} in I of formula I
(G (請先閲讀背面之注意事項再填寫本頁) 訂 G /V 式 為 化 轉 基 群 ,· 經濟部中央標準局貝工消费合作社印袈(G (please read the precautions on the back before filling this page) Set G / V format to be the base group.
(G- 式 的 中 物 產 3 應 反 述 下 後 化 轉 本紙張尺度適用中國國家標率(rNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明(> ) Ρ } 物 I 合 I 化 Μ ) (V 式 I 始 I 起 Μ 述 { 上 和 和 Μ 於 當 相 物 合 化 > 反 I 在 I 幹 I 主 I 的 Μ 物 } ί 合 V , 化 I } 些 1 I 這 Ρ I 為 (I 因 是 這 式 有 含 1 種 1 於 0 是 例 施 實 它 〇 其 響的 影 明 到發 受本 有, 沒此 並因 時 應 , 分 物單 合 } 化 V 體.I 散 I 分 P 單 ί > 式 I 及 I 物 I 合 Ρ 化 ί 體 式散 , 分 物單 合 > 化 I 體 I 散 I 分 I 單 Ρ ✓fv VI/ I 式 覆 ί 3 於 在 只 處 之 同 不 的 物 合 化 些 這 物 合 混 , 的同 物不 合的 化數 體元 散單 (請先閲讀背面之注意事項再填寫本頁)(G-type Chinese products 3 should be reversed. The paper size shall be reversed. The paper standard shall apply the Chinese national standard (rNS) Λ4 specification (210X 297 mm). 491871 A7 B7. 5. Description of the invention (>)) P} I Μ) (V formula I from the beginning of the description {the above and MH are combined with the current phase > the reverse ions in the I stem I main I} ί combined V, chemistry I} some 1 I this P I is (I because this formula contains 1 kind of 1 and 0 is an example to implement it. The effect of the effect is to receive it. If it does not respond to the situation, the separate items are combined.} Form V I points P single > Formula I and I matter I combine to form 散, form separate form > I form I separate I point I to form single ✓ ✓vv VI / I form cover 3 The same thing is compounded, some of this thing is mixed, and the same thing is not the same as the number of voxels (please read the precautions on the back before filling this page)
Α* (Ρ- 經濟部中央標攀局賀工消费合作社印製Α * (Ρ- Printed by the Hegong Consumer Cooperative of the Central Bureau of Standardization of the Ministry of Economic Affairs
•Α (Ρ 本紙張尺度適州中國國家標嗥((:奶)八4規格(2丨0、/297公釐) 491871 五、發明説明(4 ) A··• Α (Ρ This paper is in the state of Shizhou, China's national standard ((: milk) 8 4 size (2 丨 0, / 297 mm) 491871 V. Description of the invention (4) A ··
N丫 N B* 經濟部中央標準局货工消贽合作社印來 A7 B7 (p-m)N YA N B * Printed by the Consumer Goods Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 (p-m)
式(P — I) · (P — II) , (P — III)和( P — IV)化合物的總共量為40至70莫耳%,特別是 50至65莫耳% (相對於總共混合物的量)·,及 Ri是氫,烴基反應基,或一 0 — Ri是氧基;The total amount of compounds of formula (P — I) · (P — II), (P — III) and (P — IV) is 40 to 70 mole%, especially 50 to 65 mole% (relative to the total mixture Amount) ·, and Ri is hydrogen, a hydrocarbyl reactive group, or 0—Ri is an oxygen group;
Rz 是 Cz — Ci2 焼撐,C4 一 Ci2 嫌撐,C 5 — C7環烷撐,c5 — C7環烷撐二(Ci—C4烷撐), Ci —C4烷撐二(c5 —C7環烷撐),苯撐二(Ci 一 C4烷撐)或C4 一 Ci 2烷撐,其是由1 ,4 一呢嗪 -33- 本紙張尺度適用中國國家標蜂(CNS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁)Rz is Cz—Ci2, C4—Ci2, C5—C7 cycloalkylene, c5—C7 cycloalkylene (Ci—C4 alkylene), Ci—C4 alkylene di (c5—C7 cycloalkylene) ), Phenylene di (Ci-C4 alkylene) or C4-Ci 2 alkylene, which is composed of 1, 4 monomorphazine-33- This paper size applies to the Chinese National Standard Bee (CNS) Λ4 specification (210X 297 mm ) (Please read the notes on the back before filling this page)
491871 A7 B7 五、發明说明(4 ) 二基,一 0 —或〉N — Xi所中斷的,X!是Ci 一 Ci 2醯基或(Ci — Ci 2烷氧基)羰基,或具有以下 R4定義中之一者;或R2是一式(I 一 a) ,(I—b )或(I 一 c )的群基491871 A7 B7 V. Description of the invention (4) Diyl radical, interrupted by 0—or> N—Xi, X! Is Ci—Ci 2fluorenyl or (Ci—Ci 2 alkoxy) carbonyl, or has the following R4 One of the definitions; or R2 is a group basis of the formula (I aa), (I-b) or (I-c)
(卜a) •CH2—CH—CH^ I 2 ο Ic=〇 (l-b)(Bua) • CH2—CH—CH ^ I 2 ο Ic = 〇 (l-b)
(l-c) 經濟部中央標革局工消资合作社印^ m是2或3, Xz是Ci —Ci 8烷基,C5 — Ci 環烷基,其是未 經取代的或由1 ,2或3個Ci 一〇4烷基取代的;苯基 ,其是未經取代的或由1 ,2或3個Ci 一 C4烷基或 Ci 一 C4烷氧基取代的;C7 — C9苯基烷基,其是未 -34- (請先閲讀背面之注意事項再填寫本頁)(lc) Seal of the Industrial and Consumer Cooperatives of the Central Standardization Bureau of the Ministry of Economic Affairs m is 2 or 3, Xz is Ci—Ci 8 alkyl, and C5—Ci cycloalkyl, which are unsubstituted or composed of 1, 2 or 3 Ci Ci04 alkyl substituted; phenyl, which is unsubstituted or substituted with 1, 2 or 3 Ci Ci4 alkyl or Ci Ci4 alkoxy; C7-C9 phenylalkyl, It is Wei-34- (Please read the notes on the back before filling this page)
本紙張尺度適用中國國家標缚(CNS ) Λ4規格(210X29*7公釐) ^1871 A7 B7 五、 發明説明(Vj 經取代的或在苯基上由1 ,2或3個C! _C4烷基取代 的;及 反應基X3互不相關的分別為C2 — Ci 2烷撐; A 来是一 OR3 ,一 N ( R 4 ) ( R $ ),或一式(G — I V )的群基:This paper size is applicable to China National Standards (CNS) Λ4 specifications (210X29 * 7 mm) ^ 1871 A7 B7 V. Description of the invention (Vj substituted or 1,2 or 3 C on phenyl! C__C4 alkyl Substituted; and the reactive groups X3 are independent of each other C2 — Ci 2 alkylene; A is an OR3, an N (R 4) (R $), or a group group of the formula (G-IV):
(G-IV) (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標革局员Η消贽合作i印到木 R 3 ,R4和Rs (相同或不同的)為Ci 一 Ci8烷基 ,C5 - Ci 2環烷基,其是未經取代的或由1 » 2或3 個Ci 一 C4烷基取代的;C3 —Ci 8烯基,苯基,其 是未經取代的或由1 ,2或3個Ci —C4烷基或Ci 一 C4烷氧基取代的;C7 — C9苯基烷基,其是未經取代 的或在苯基上由1 ,2或3個Ci 一 C4烷基取代的;四 氫呋喃基或C2 _C4烷基,其在第2,3或4位置上是 由一 OH,Ct —C8烷氧基,二(Ci、一 C4烷基)胺 基或一式(I I I)的群基取代的; -35 本紙張尺度適州中國國家標冷(CNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明(v> (III) Y 是一 0 -,一 CH2 —,一 CH2 CHz — 或 > N - C Η 3 ;及 R3另外是氫或一 N(R4) (Rs)另外是一式( I I I )的群基; X 来是一 0 — 或 >N_R6 ; R6来是Ci—Cis烷基,C3 —Cl8烯基,C5 Ci 2環烷基,其是未經取代的或由1 * 2或3個(:1 C4烷基取代的;C7 — C9苯基烷基*其是未經取代 或在苯基上由1 ,2或3個Ci —C4烷基取代的;四 呋喃基,一式(G - I I)的群基, 的 氫 (請先閱讀背面之注意事項再填寫本頁) 訂 經滴部中夾標準局貞-T-消费合作社印f(G-IV) (Please read the precautions on the back before filling out this page) Member of the Central Standardization Bureau of the Ministry of Economic Affairs and Cooperation i printed to wood R 3, R 4 and Rs (same or different) are Ci-Ci8 alkane , C5-Ci 2 cycloalkyl, which is unsubstituted or substituted with 1 »2 or 3 Ci-C4 alkyl; C3-Ci 8 alkenyl, phenyl, which is unsubstituted or substituted by 1, 2 or 3 Ci-C4 alkyl or Ci-C4 alkoxy substituted; C7-C9 phenylalkyl, which is unsubstituted or substituted by 1, 2 or 3 Ci-C4 on phenyl Alkyl-substituted; tetrahydrofuranyl or C2-C4 alkyl, which is at the 2, 3, or 4 position by mono-OH, Ct-C8 alkoxy, di (Ci, mono-C4 alkyl) amine, or a formula (III ) Group replacement; -35 This paper size is suitable for China National Standard Cold (CNS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention (v > (III) Y is a 0-, a CH2 —, A CH2 CHz — or> N-C Η 3; and R3 is additionally hydrogen or a N (R4) (Rs) is also a group group of formula (III); X is a 0 — or> N_R6; R6 is Ci-Cis alkyl, C3-Cl8 alkenyl, C5 Ci 2 Cycloalkyl, which is unsubstituted or substituted by 1 * 2 or 3 (: 1 C4 alkyl; C7-C9 phenylalkyl * which is unsubstituted or substituted by 1, 2 or 3 Ci-C4 alkyl substituted; tetrafuranyl, a group of formula (G-II), hydrogen (please read the precautions on the back before filling this page). -Consumer cooperative print
(G-II) 或C2 —C4烷基,其在第2,3或4位置上由一 0H* C! —C8烷氧基,二(Ci _C4烷基)胺基或一式( I I I )的群基取代的; R来具有如上R6来定義中之一者,及 -3 6 - 本紙張尺度適州中國國家標净((、NS ) Λ4規格(210X 297公釐) 491871 A7 B7 — —— _ 五、發明説明(W ) B来具有如上A来定義中之一者0 較佳的混合物為其中:(G-II) or C2-C4 alkyl, which is at the 2, 3 or 4 position by a 0H * C! -C8 alkoxy group, a di (Ci_C4 alkyl) amino group or a group of formula (III) Base substitution; R has one of the above definitions of R6, and -3 6-This paper size is suitable for China National Standard Net ((, NS)) Λ4 specifications (210X 297 mm) 491871 A7 B7 — —— _ V. Description of the Invention (W) B has one of the definitions of A above. 0 The preferred mixture is:
Ri是辛基或環己基;Ri is octyl or cyclohexyl;
Rz是_C6烷撐; R来是一式(G—I I)的群基; A 来是一 N (R4) ( R 5 ); R4和Rs (相同或不同的)為Ci一C8烷基; B来是一式(G — IV)的群基; X来是〉NRe来;及 R6米是Ci 一 C8焼基0 在本發明的混合物中,反應基Ri能當作兩個或多個 式(P — I) , (P - II) , (P—III)及 / 或( P-IV)化合物間的連结基,在此情況下,於是在上述 化合物間形成式(L一I)的架橋基: (請先閲讀背面之注意事項再填寫本頁) 經滴部中央標準局負工消费合作社印來Rz is _C6 alkylene; R is a group group of the formula (G-II); A is a N (R4) (R 5); R4 and Rs (same or different) are Ci-C8 alkyl; B Is a group group of formula (G-IV); X is> NRe; and R6 is Ci—C8 焼 group 0 In the mixture of the present invention, the reactive group Ri can be regarded as two or more formulas (P — I), (P-II), (P-III) and / or (P-IV) linking group between the compounds, in which case a bridging group of formula (L-I) is then formed between the above compounds : (Please read the notes on the back before filling out this page)
(L-l)(L-l)
Ri ¥的意義能由Ri的定義推衍而得,這兩個反應 -37- 本紙張尺度適用中國國家標埤(rNS ) Λ4規格(210X 297公釐) 經滴部中夾標率局兵工消费合竹社印裝 491871 A7 B7 五、發明説明卜:) 基的差別在於R i米具有一個或兩個其它架橋價,因此, R i為環己基時相當於R i来為環己烷二基或環己烷三基 ,Ri為辛基時相當於Ri来為辛烷二基或辛烷三基。 本發明的產物,及上述的混合物可有效的改善有機物 質的光、熱及氧化阻抗性,尤其是合成聚合物和共聚物。 特別是,在聚丙烯上可觀察到低的顔色交互作用及良好的 色澤,尤其是聚丙烯纖維,特別是在火焰延遲劑存在下的 聚丙烯孅維及用於農業用的低密度聚乙烯(LDPE)膜 。其它特特別值得注意的是本發明產物及上述混合物本身 是火焰阻抗劑。 能被穩定的有機物質例子為: 1·軍烯烴和二烯烴的聚合物,例如,聚丙烯*聚異丁烯 ,聚丁一 1 一烯,聚一 4 一甲基戊一 1 一烯,聚異戊烯或 聚丁二烯,及環烯烴的聚合物,例如環戊烯或原冰片烯( norbornene),其它聚乙烯(假使需,其可是交聯的), 例如高密度聚乙烯(HDPE),高密度和高分子量聚乙 烯(HDPE—HMW),高密度超高分子量聚乙烯(H DPE-UHMW),中密度聚乙烯(MDPE),低密 度聚乙烯(LDPE),線性低密度聚乙烯(LLDPE ),(VLDPE)和(ULDPE) 〇' 聚烯烴,亦即,單烯烴的聚合物,像前述一段中所舉 例之單烯烴聚合物,特別是聚乙烯和聚丙烯能由不同的方 法製備而得,特別是下述的方法: -3 8 _ 本紙張尺度適川中國國家標率((、NS ) Λ4規格(210 X 297公釐) (請先聞讀背面之注意事項再填寫本頁) 訂 經滴部中央標嗥局贷工消费合作社印 491871 A7 B7 五、發明説明(4 ) a )游雛反應基聚合化(通常是在高壓和高溫下)。 b)使用一觸媒之觸媒聚合反應,此觸媒通常包含一種或 超過一種週期表上IVb · Vb,VI b或VI I I族的 金屬,這些金靥通常具有一種或多種型式,典型的為氧化 物,鹵化物,醇酯,酯,醚,胺,烷基化物,烯基化物及 /或芳基化物,其可是π —或σ—共價的。這些金饜複合 物可是游離狀態或固定在基質上*典型上是在活化氯化鎂 ,氯化鈦(III),鋁或矽氧化物。這些觸媒可溶於或 不溶於聚合界質中,且這些觸媒可其自己在聚合反應中使 用,或可使用活化劑,典型的為金羼烷基化物,金靥氫化 物,金靥烷基齒化物,金屬烷基氧化物或金屬烷基噁烷, 該金屬可是週期表之I a,I I a,和/或I I ΙΑ族的 元素,活化劑可進一步用酯,醚*胺或矽烷基醚方便的改 質,這些觸媒系統通常稱作Phillips, Standard Oil Indiana, Ziegler ( -N a 11 a) , T N Z (DuPont), metallocene 或單邊觸媒(SSC)。 2·在1)中所提聚合物的混合物,例如,聚丙烯和聚異 丁烯的混合物,聚丙烯和聚乙烯的混合物(例如,P P/ HDPE,PP/LDPPE),和不同型式聚乙烯混合 物(例如 LDPE/HDPE)。 、 3 ·單烯烴和二烯烴的共聚物,或和其他乙烯單體之共聚 物,例如,乙烯/丙烯共聚物,線性低強度聚乙烯(LL DPE)和其混合物及低強度聚乙烯(LDPE),丙烯 -39- 本紙張尺度適川中國國家標卒(rNS ) Λ4規格(210X 297公釐) * ---------P! (請先閲讀背面之注意事項再填寫本頁) 訂 經滴部中央標準局炅-Τ-消费合作社印製 491871 A7 B7 五、發明説明(vV ) /丁一 1 一烯共聚物•丙烯/異丁烯共聚物,乙烯/丁一 1一烯共聚物,乙烯/己烯共聚物•乙烯/甲基戊烯共聚 物,乙烯/庚烯共聚物》乙烯/辛烯共聚物,丙烯/丁二 烯共聚物,異丁烯/異戊間二烯共聚物,乙烯/烷基丙烯 酸酯共聚物,及其和碳單氧化物形成的共聚物,或乙烯/ 丙烯酸共聚物,及其鹽類(離子化物)及乙烯和丙烯和一 二烯所形成的三聚物,像己二烯,二環戊二烯或乙二烯一 原冰Η烯;及該共聚物間的混合物及上述1)所提聚合物 的混合物,例如,聚丙烯/乙烯/丙烯共聚物,LDPE /乙烯一乙烯醋酸酯共聚物(EVA) ,LDPE/乙烯 一丙烯酸共聚物(EAA) ,LLDPE/EVA,LL D P E/E AA及具有一交錯或散亂结構之聚烷撐一單氧 化碳共聚物,及和其它聚合物之混合物*例如聚醢胺。 4·碳氫化物的樹脂(例如Cs — C9) ’包括其氫化改 質者(如,膠黏劑),及聚烯烴和澱粉的混合物。 5·聚苯乙烯,聚(P —甲基苯乙烯)’聚(α —甲基苯 乙烯)。 6 ·苯乙烯或ex -甲基苯乙烯和二烯或丙烯酸衍生物之共 聚物,例如,苯乙烯/ 丁二烯,苯乙烯/丙烯腈,苯乙烯 /烷基甲丙烯酸酯,笨乙烯/ 丁二烯/燒基丙烯酸酯’苯 乙烯/ 丁二烯/烷基甲丙烯酸酯,笨乙烯/順丁烯二酸酐 ,苯乙烯/丙烯腈/甲基丙烯酸酯·,苯乙烯共聚物的高衝 擊強度混合物,及另一種聚合物,例如,聚丙烯酸酯,一 -40- 本紙張尺度適用中國國家標肀(rNS ) Λ4規格(210X29*7公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 線 ^1871 五 _^^__ 經滴部中次標卑局另工消贽合竹社印繁 A7 B7 發明説明(6) 二烯聚合物或一乙烯/丙烯/二烯三聚合物;和苯乙烯的 嵌段共聚物,像笨乙烯/丁二烯/苯乙烯*苯乙烯/異戊 間二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯 /乙烯/丙烯/苯乙烯。 7 ·笨乙烯或α —甲基苯乙烯的接枝共聚物*例如*在聚 丁二烯上的苯乙烯,在聚丁二烯一苯乙烯上或在聚丁二烯 一丙烯腈共聚物上的苯乙烯;在聚丁二烯上的苯乙烯及丙 烯腈(或甲丙烯膳);在聚丁二烯上的苯乙烯,丙烯腈和 甲基甲丙烯酸酯;在聚丁二烯上的苯乙烯和順丁烯二酸酐 ;在聚丁二烯上的苯乙烯,丙烯腈和順丁烯二酸酐或順丁 烯二醯亞胺;在聚丁二烯上的苯乙烯和順丁烯二醯亞胺; 在聚丁二烯上的苯乙烯和烷基丙烯酸酯或甲丙烯酸酯;在 乙烯/丙烯/二烯三聚物上的笨乙烯和丙烯腈;在聚烷基 丙烯酸酯或聚烷基甲丙烯酸酯上的苯乙烯和丙烯腈;在丙 烯酸酯/ 丁二烯共聚物上的苯乙烯和丙烯購,及和列於6 )項共聚物之混合物,例如,習知ABS,MBS,AS A或AE S聚合物的共聚物混合物。 8 ·包含鹵素的聚合物,像聚氯化戊間二烯,氯化橡膠, 氯化或硫化氯化聚乙烯,乙烯和氯化乙烯共聚物,表氯醇 均-及共聚物,特別是含鹵素乙烯化合物的聚合物,例如 ,聚乙烯氯化物,聚乙二烯氯化物,聚乙烯氟化物,聚乙 二烯氟化物,及其共聚物’像乙烯氯化物/乙二烯氯化物 ,乙烯氯化物/乙烯醋酸酯或乙二烯氛化物/乙烯醋酸酯 -4 1- 本紙張尺度適用中國國家標率(CNS ) Λ4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 491871 A7 B7 五、發明説明(沙) 共聚物。 9 ♦由α,—未飽和酸和其衍生物製備而得的聚合物, 像聚丙烯酸酯和聚甲丙烯酸酯;聚甲基甲丙烯酸酯,聚丙 醯胺和聚丙烯腈* Κ丙烯酸丁酯成衝擊改質者。 1 0 ·上述9 )之單體之間和其他未飽和單體所形成的共 聚物,例如丙烯膳/ 丁二烯共聚物,丙烯腈/烷基丙烯酸 酯共聚物,丙烯腈/烷氧烷基丙烯酸酯或丙烯腈/乙烯鹵 化物之共聚物或丙烯腈/烷基甲丙烯酯/丁二烯三聚物。 11·由未飽和醇和胺衍生而得的聚合物或其醢化衍生物 或其縮醛,例如,聚乙烯醇,聚乙烯乙酸酯,聚乙稀硬脂 酸酯,聚乙烯苯甲酸酯,聚乙烯順丁烯二酸酿,聚乙丁縮 醛,聚烯丙基酞酸酯或聚烯丙基密胺;及其和上述第1點 中所提之烯烴的共聚物。 1 2 ·環醚的均聚物和共聚物,像聚烯烴二醇,聚乙烯氧 化物,聚丙烯氧化物或其和雙氧丙環基醚的共聚物。 經滴部中央榡卑局只-T-消费合作社印製 (請先閱讀背面之注意事項再填寫本頁) 13·聚縮醛,像聚氧甲撐和那些聚氧甲撐類*其包含乙 烯氧化物當作共單體,Κ熱塑性聚尿烷,丙烯酸酯或MB S改質的聚縮醛。 1 4 ·聚苯撐氧化物和硫化物*及聚苯烯氧化物和苯乙烯 聚合物或聚醯胺的混合物。 ' 1 5 ♦由羥基終端的聚醚衍生而得的聚尿烷,聚酿或聚丁 二烯在一邊,且脂肪族或芳香族聚異氰酸酿在另一邊’及 其先質。 -42- 本紙張尺度適用中國國家標瑋(ms ) Λ4規格(210X 297公釐) 經滴部中央標準局货工消费合作社印製 491871 A7 _ B7 五、發明説明() 16 ·聚醢胺和由二胺和二羧酸及/或由胺基羧酸或對等 內醃胺衍生而得的共聚物,例如,聚醢胺4,聚醯胺6, 聚醚胺 6/6 · 6/10 * 6/9 · 6/12,4/6 , 1 2/1 2,聚醯胺1 1»聚醯胺1 2 ·由m —二甲苯二 胺和己二酸起始的芳香族聚醯胺;由六甲撐二胺和異酞酸 或/及對酞酸衍生而得的聚醢胺*其具有或不具有彈性體 當作改質劑,例如,聚一 2,4,4 一三甲基六甲撐對酞 醯胺或聚一m-苯烯異肽醯胺;及上述聚醯胺和聚烯烴, 烯烴共聚物,離子化物,或化學鍵结或接枝弾性體;或和 聚醚,如和聚乙烯二醇,聚丙烯二醇或聚四甲撐二酵的嵌 段共聚物;及KEPDM或ABS改質的聚_胺或共聚醯 胺;及在製備過程(RI Μ聚醯胺系統)中濃縮的聚醢胺 Ο 1 7 ·聚尿素,聚醯亞胺,聚醣胺一醯亞胺及聚苯眯唑。 18·由二羧酸和二醇及/或由羥基羧酸或對等的內酯衍 生而得的聚酯,例如,聚乙烯對肽酸酯,聚丁烯對肽酸酯 ,綠一 1 ,4 一二甲酵環己烷對肽酸酯及聚羥基苯甲酸酯 ,及由羥基終端之聚醚衍生而得的嵌段共聚醚酯;和Κ聚 碳酸酯改質或MB S改質之聚酯。 19·聚碳酸酯和聚酯碳酸酯。 \ 20·聚碾,聚醚碾和聚醚嗣。 21·由醛在一邊,酚,尿素和密胺在另一邊所衍生而得 的交聯聚合物,像酚/甲醛樹脂,尿素/甲醛樹脂,和蜜 -4 3 - 本紙張尺度適州中國國家標肀(CNS ) Λ4規格(210X 297公釐) ---------f, (請先閲讀背面之注意事項再填寫本頁) 訂 線- 491871 A7 B7 五、發明説明(J ) 胺/甲醛樹脂。 2 2 ;•乾燥和非乾燥醇酸樹脂。 23 ·由飽和和未飽和二狻酸和聚氫酵及以乙烯化合物當 作交聯劑衍生而得的未飽和聚酯樹脂,及其低可燃性的含 鹵素改質物。 24 ·由經取代的丙烯酸酯衍生而得的交聯丙烯酸樹脂* 例如,環氧丙烯酸樹脂,尿烷丙烯酸樹脂或聚酯丙烯酸酯 0 2 5 ·醇酸樹脂,聚酯樹脂和密胺樹脂交聯的丙烯酸樹脂 ,尿素樹脂,聚異氰酸酯或環氧樹脂。 26·由脂肪族,環脂肪族,雜環或芳香糸氧丙環基化合 物衍生而得的交聯環氧樹脂,例如由雙酚A和雙酚F之雙 氧丙環基醚所得的產物,其可以傳統硬化劑交職,像酐或 胺(可在促進劑的存在或不存在下)。 27·天然聚合物,例如,纖維素,橡膠,明膠和其Μ化 學方法改質之同系衍生物,例如纖維素醋酸酯,纖維素丙 酸酯和纖維素丁酸酯*或纖維素醚,像甲基纖維素;及松 經濟部中央標Φ局貞工消费合作社印製 ---------f (請先閲讀背面之注意事項再填寫本頁) 脂及其衍生物。 28 ♦上述聚合物的混合物(聚混合物),例如ΡΡ/Ε PDM,聚醯胺 /EPDM 或 ABS,PVC/EVA , PVC/ABS,PVC/MBS,PC/ABS,ΡΒ TP/ABS,PC/ASA,PC/PBT,PVC/ CPE · PVC/丙烯酸酯,ΡΟΜ/熱塑性PUR,Ρ -44- 本紙張尺度適用中國國家標卒(CNS ) Λ4規格(210X 297公釐) 外 1871The meaning of Ri ¥ can be derived from the definition of Ri. These two reactions -37- This paper size is applicable to the Chinese national standard (rNS) Λ4 specification (210X 297 mm). Consumption of Hezhusha Printing Co., Ltd. 491871 A7 B7 V. Description of the invention: The difference in base is that Ri rice has one or two other bridge valences. Therefore, when Ri is cyclohexyl, it is equivalent to Ri to cyclohexane. Or cyclohexanetriyl, when Ri is octyl, it is equivalent to Ri to be octanediyl or octanetriyl. The product of the present invention and the above-mentioned mixture can effectively improve the light, heat and oxidation resistance of organic substances, especially synthetic polymers and copolymers. In particular, low color interaction and good color are observed on polypropylene, especially polypropylene fibers, especially polypropylene in the presence of flame retarders, and low-density polyethylene for agricultural use ( LDPE) film. It is particularly noteworthy that the products of the present invention and the above-mentioned mixtures themselves are flame resistance agents. Examples of organic substances that can be stabilized are: 1. Polymers of military olefins and diolefins, for example, polypropylene * polyisobutylene, polybutadiene-1ene, poly-4-methylpentyl-1ene, polyisoprene Olefins or polybutadienes, and polymers of cycloolefins, such as cyclopentene or norbornene, other polyethylenes (if required, they can be crosslinked), such as high density polyethylene (HDPE), high Density and high molecular weight polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (H DPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) (VLDPE) and (ULDPE) olefins, that is, polymers of monoolefins, such as the monoolefin polymers exemplified in the previous paragraph, especially polyethylene and polypropylene can be prepared by different methods, In particular, the following methods: -3 8 _ This paper is suitable for China National Standard ((, NS) Λ4 size (210 X 297 mm) (please read the notes on the back before filling this page). Printed by the Central Ministry of Standards, Loan Workers, Consumer Cooperatives 491871 A7 B7 Explain (4) a) Reactive radical polymerization (usually under high pressure and high temperature). b) A catalyst polymerization reaction using a catalyst. The catalyst usually contains one or more metals of Group IVb · Vb, VI b or VI II on the periodic table. These gold tinctures usually have one or more types, typically: Oxides, halides, alcohol esters, esters, ethers, amines, alkylates, alkenylates and / or arylates, which may be π- or σ-covalent. These gold dysprosium compounds can be free or immobilized on a substrate * typically in activated magnesium chloride, titanium (III) chloride, aluminum or silicon oxide. These catalysts can be soluble or insoluble in the polymer matrix, and these catalysts can be used by themselves in the polymerization reaction, or an activator can be used, typically gold amidate, amidate hydride, aureate Base halide, metal alkyl oxide or metal alkyl oxane, the metal may be an element of group I a, II a, and / or II IA of the periodic table, and the activator may further be ester, ether * amine or silane Convenient modification of ethers. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-N a 11 a), TNZ (DuPont), metallocene or single-sided catalyst (SSC). 2. A mixture of polymers mentioned in 1), for example, a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (for example, PP / HDPE, PP / LDPPE), and a mixture of different types of polyethylene (for example, LDPE / HDPE). 3. Copolymers of mono- and diolefins, or copolymers with other ethylene monomers, such as ethylene / propylene copolymers, linear low-strength polyethylene (LL DPE) and mixtures thereof, and low-strength polyethylene (LDPE) , Acrylic-39- This paper is suitable for Sichuan National Standard (rNS) Λ4 specification (210X 297mm) * --------- P! (Please read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Printing, printed by --T-Consumer Cooperatives 491871 A7 B7 V. Description of the invention (vV) / butadiene-1 copolymer • propylene / isobutylene copolymer, ethylene / butadiene-1 copolymer, Ethylene / hexene copolymer • ethylene / methylpentene copolymer, ethylene / heptene copolymer》 ethylene / octene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / Alkyl acrylate copolymers, and their copolymers with carbon monoxide, or ethylene / acrylic acid copolymers, and their salts (ions), and terpolymers of ethylene, propylene, and diene, like Hexadiene, dicyclopentadiene or ethylene di-orbornene; and mixing between the copolymers And the mixture of polymers mentioned in 1) above, for example, polypropylene / ethylene / propylene copolymer, LDPE / ethylene-ethylene acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LL DPE / E AA and polyalkylene-carbon monoxide copolymers with a staggered or scattered structure, and mixtures with other polymers * such as polyamides. 4. Hydrocarbon resins (e.g., Cs-C9) 'include their hydrogenated modifiers (e.g., adhesives), and mixtures of polyolefins and starch. 5. Polystyrene, poly (P-methylstyrene) 'poly (α-methylstyrene). 6. Copolymers of styrene or ex-methylstyrene and diene or acrylic acid derivatives, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene Diene / Alkyd Acrylate's Styrene / Butadiene / Alkyl Methacrylate, Styrene / Maleic Anhydride, Styrene / Acrylonitrile / Methacrylate ·, High Impact Strength of Styrene Copolymer Mixture, and another polymer, for example, polyacrylate, -40- This paper size is applicable to Chinese national standard (rNS) Λ4 size (210X29 * 7 mm) (Please read the precautions on the back before filling this page ) Ordering line ^ 1871 Five _ ^^ __ The Ministry of Standards and Disposal of the Ministry of Economics and Industry separates and eliminates Hezhu News Agency A7 B7 Description of the invention (6) Diene polymer or monoethylene / propylene / diene terpolymer; Block copolymers with styrene, like stupid ethylene / butadiene / styrene * styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / Styrene. 7. Graft copolymers of stupid ethylene or α-methylstyrene * For example * styrene on polybutadiene, on polybutadiene-styrene or on polybutadiene-acrylonitrile copolymer Styrene on polybutadiene and acrylonitrile (or methacrylic); styrene, acrylonitrile and methacrylic acid on polybutadiene; benzene on polybutadiene Ethylene and maleic anhydride; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene Imines; styrene and alkyl acrylates or methacrylates on polybutadiene; ethylene and acrylonitrile on ethylene / propylene / diene terpolymers; polyalkyl acrylates or polyalkylenes Styrene and acrylonitrile on methacrylate; styrene and propylene on acrylate / butadiene copolymers, and mixtures with copolymers listed in item 6), for example, the conventional ABS, MBS, AS A Or copolymer blends of AES polymers. 8 · Halogen-containing polymers like polychlorinated pentadiene, chlorinated rubber, chlorinated or vulcanized chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially those containing Polymers of halogenated ethylene compounds, for example, polyvinyl chloride, polyethylene chloride, polyethylene fluoride, polyethylene fluoride, and copolymers thereof 'like ethylene chloride / ethylene dichloride, ethylene Chloride / Ethylene Acetate or Ethylene Diene / Ethylene Acetate-4 1- This paper size applies to China National Standard (CNS) Λ4 specification (210X 297 mm) (Please read the precautions on the back before filling in this Page) 491871 A7 B7 V. Description of the invention (sand) Copolymer. 9 ♦ Polymers prepared from α, -unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethacrylates, polyamidamine and polyacrylonitrile * κ acrylate Impact reformers. 1 0 · 9) The copolymer formed between the monomers and other unsaturated monomers, such as acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl Acrylate or acrylonitrile / ethylene halide copolymer or acrylonitrile / alkylmethacrylate / butadiene terpolymer. 11. Polymers derived from unsaturated alcohols and amines or their halogenated derivatives or acetals, for example, polyvinyl alcohol, polyvinyl acetate, polyethylene stearate, polyvinyl benzoate , Polyethylene maleate, polybutylene acetal, polyallyl phthalate or polyallyl melamine; and copolymers thereof with the olefins mentioned in point 1 above. 1 2 · Homopolymers and copolymers of cyclic ethers, such as polyolefin diols, polyethylene oxides, polypropylene oxides, or copolymers with dioxypropylene ethers. Printed by the Central Government Bureau of Dibei-T-Consumer Cooperative (please read the precautions on the back before filling this page) 13. Polyacetal, like polyoxymethylene and those polyoxymethylenes * which contain ethylene The oxide is treated as a comonomer, K thermoplastic polyurethane, acrylate or MB S modified polyacetal. 1 4 · Mixtures of polyphenylene oxide and sulfide * and polystyrene oxide and styrene polymer or polyamide. '1 5 ♦ Polyurethane derived from hydroxyl-terminated polyether, with poly or polybutadiene on one side, and aliphatic or aromatic polyisocyanate on the other side' and its precursors. -42- This paper size applies to Chinese national standard Wei (ms) Λ4 specifications (210X 297 mm) Printed by the Central Bureau of Standards of the Ministry of Freight and Consumers' Cooperatives 491871 A7 _ B7 V. Description of the invention () 16 · Polyamide and Copolymers derived from diamines and dicarboxylic acids and / or amine carboxylic acids or equivalent internally salted amines, for example, polyamine 4, polyamine 6, polyetheramine 6/6 · 6/10 * 6/9 · 6/12, 4/6, 1 2/1 2, polyamine 1 1 »polyamine 1 2 · aromatic polyamines starting from m-xylenediamine and adipic acid; Polyamines derived from hexamethylene diamine and isophthalic acid or / and terephthalic acid * with or without elastomers as modifiers, for example, poly-2,4,4-trimethylhexamethyl P-phthalamide or poly (m-phenylene isopeptide) amine; and the above-mentioned polyamines and polyolefins, olefin copolymers, ionized compounds, or chemically bonded or grafted amidines; or polyethers, such as Block copolymers of ethylene glycol, polypropylene glycol or polytetramethylene dienzyme; and KEPDM or ABS modified polyamines or copolyamides; and concentrated during the preparation process (RI M polyamine system) Polyamide 0 1 7 Polyurea, polyimide, polysaccharideamine and imidazole. 18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or equivalent lactones, for example, polyethylene peptidate, polybutene peptidate, green-1, 4 Dimesylated cyclohexane para-peptides and polyhydroxybenzoates, and block copolyether esters derived from hydroxyl terminated polyethers; and K polycarbonate modified or MB S modified Polyester. 19. Polycarbonate and polyester carbonate. \ 20 · polymill, polyether mill and polyether 嗣. 21 · Crosslinked polymers derived from aldehyde on one side, phenol, urea and melamine on the other side, such as phenol / formaldehyde resin, urea / formaldehyde resin, and honey-4 3-This paper is suitable for China in China Standard (CNS) Λ4 specification (210X 297 mm) --------- f, (Please read the precautions on the back before filling this page) Thread-491871 A7 B7 V. Description of the invention (J) Amine / formaldehyde resin. 2 2; • Dry and non-drying alkyd resins. 23 · Unsaturated polyester resins derived from saturated and unsaturated dibasic acid and polyhydrogenase and ethylene compounds as crosslinking agents, and their low-flammability halogen-containing modifiers. 24 Crosslinked acrylic resins derived from substituted acrylates * For example, epoxy acrylic resins, urethane acrylic resins or polyester acrylates 0 2 5 Alkyd resins, polyester resins and melamine resins are crosslinked Acrylic resin, urea resin, polyisocyanate or epoxy resin. 26. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic oxopropionyl compounds, such as products obtained from bisphenol A and bisphenol F bisoxypropyl ethers, It can work with traditional hardeners, like anhydrides or amines (either in the presence or absence of accelerators). 27. Natural polymers, such as cellulose, rubber, gelatin and their homologous derivatives modified chemically, such as cellulose acetate, cellulose propionate and cellulose butyrate * or cellulose ethers, like Methylcellulose; and printed by Zhengong Consumer Cooperative, Central Bureau of the Ministry of Economic Affairs, -------- f (please read the precautions on the back before filling this page) and their derivatives. 28 ♦ Blends (Polyblends) of the above polymers, such as PP / E PDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PP TP / ABS, PC / ASA , PC / PBT, PVC / CPE · PVC / Acrylic, POM / Thermoplastic PUR, P -44- This paper size applies to China National Standards (CNS) Λ4 specifications (210X 297 mm) outside 1871
經滴部中央標準局兵工消费合作社印製 i、發明説明(β) 〇/熱塑性?111^*?01^/丙烯酸酯,?0^4/“88 ,PPO/HIPS,PP0/PA6 · 6 和共聚物,P A/HDPE,PA/PP,PA/PPO,PBT/ PC/ABS 或 PBT/PET/PC。 29 ·天然發生及合成的有機物質,其是純化合物或該化 合物的混合物,例如,礦物油,動物和椬物脂肪,油和蠟 ,或Μ合成酯為基礎之油,脂肪和蠟(如,酞酸酯,己二 酸酯,磷酸酯,三苯六酸酯)及合成酯和礦物油Μ任何重 量比例混合之混合物,典型上是那些用作旋轉組成物,及 該物質的水溶液乳化物。 3 0 ·天然或合成橡膠的水溶液乳化物,如羧酸苯乙烯/ 丁二烯共聚物之天然膠乳或乳液。 因此本發明也關於一種組成物,包括一對於因光、熱 或氧化導致的降解是敏感的有機物質及本發明的產物或混 合物。 有機物質較佳的是合成聚合物,更佳地是一種選自前 述族群的聚合物。聚烯烴是較佳的,且聚乙烯及聚丙烯是 特別佳的。 本發明的其它賁施例是一種穗定有機物質抵抗因光、 熱或氧化導致降解的方法,包括在該有機物質中加入本發 明的產物或混合物。 依據被穩定物質的性質,最終用途及其它添加劑是否 存在,本發明的產物或混合物可Κ各種量使用。 -45- 本紙張尺度ϋΐ中國國家標缚((、奶)八4規格(210\ 297公釐) (請先閲讀背面之注意事項再填寫本頁) 、11 % 經滴部中*梂準局只工消费合作社印褽 491871 A7 B7 一丨•'丨 ‘一 _ 五、發明説明) 一般而言*適當的是使用,例如0 · 01至5%重量 百分比的本發明產物或混合物(相對於被稱定物質的重量 而定)•較佳地是0·05至2%*特別是0·05至1 本發明產物或其混合物可在,例如聚合化或該物質交 聯前,當時或之後加入至聚合物質中•除此之外*他們可 以純物質的型式或包覆於櫬,油或聚合物中的型式加入至 聚合物質中。 一般而言,本發明產物或混合物可Κ各種的方法加入 至聚合物質中,像粉末型式的乾式混合,或溶液或懸浮液 型式的溼式混合,也可Μ含有濃度從2 · 5至25%重量 百分比本發明產物或混合物的母體型式加入;在這些操作 中,所使用的聚合物能是粉末狀,粒狀,溶液狀,懸浮液 狀,或Κ膠乳型式應用。 Μ本發明產物或混合物穩定的物質能用於生產模製物 ,薄膜,帶狀物,單絲,纗維,表面塗覆物和類似物。 假使需要,可加入其它適用於合成聚合物的傳統添加 劑至含有本發明產物或混合物的有機物質中,像抗氧化劑 ,UV吸收劑,鎳穩定劑,顔料,填充劑·增塑劑*腐蝕 抑制劑和金屬去活性劑。 ' 該傳統添加劑的特殊例子為: 1 ·抗氧化劑f 1 · 1 ·烷基化單酚·例如,2,6 —二一叔一 丁基一 4 -4 6 - 本紙張尺度適川中國國家標彳((、NS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁)Printed by the Ordnance Industry Consumer Cooperative of the Central Bureau of Standards of the Ministry of Discharge i. Invention Description (β) 〇 / Thermoplastic? 111 ^ *? 01 ^ / acrylate,? 0 ^ 4 / "88, PPO / HIPS, PP0 / PA6 · 6 and copolymer, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC. 29 · Naturally occurring and synthetic Organic substances, which are pure compounds or mixtures of such compounds, for example, mineral oils, animal and animal fats, oils and waxes, or synthetic ester-based oils, fats and waxes (eg, phthalates, adipates Acid esters, phosphate esters, trimelates) and mixtures of synthetic esters and mineral oils in any weight ratio, typically those used as spinning compositions and aqueous emulsions of the substances. 3 0 · Natural or synthetic An aqueous emulsion of a rubber, such as a natural latex or emulsion of a carboxylic acid styrene / butadiene copolymer. The present invention also relates to a composition including an organic substance that is sensitive to degradation by light, heat, or oxidation, and The product or mixture of the present invention. The organic substance is preferably a synthetic polymer, more preferably a polymer selected from the aforementioned groups. Polyolefins are preferred, and polyethylene and polypropylene are particularly preferred. The present invention The other example of cricket is A method for a substance to resist degradation caused by light, heat or oxidation, including adding the product or mixture of the present invention to the organic substance. Depending on the nature of the stabilized substance, the end use and other additives, the product or mixture of the present invention may be Used in various quantities. -45- This paper size is ϋΐ Chinese national standard ((, milk) 8 4 size (210 \ 297 mm) (Please read the precautions on the back before filling this page), 11% * 梂 Quasi-Bureau Consumer Cooperatives Co., Ltd. Seal 491871 A7 B7 A 丨 • '丨' 一 _ V. Description of the invention) Generally speaking * It is appropriate to use, for example, 0.01 to 5% by weight of the product or mixture of the present invention (Relative to the weight of the substance to be weighed) • Preferably 0. 05 to 2% * especially 0. 05 to 1. The product of the present invention or a mixture thereof may be, for example, polymerized or cross-linked, Added to the polymeric substance at the time or later • In addition * they can be added to the polymeric substance in the form of pure substances or coated in rhenium, oil or polymer. In general, the products or mixtures of the invention can be Various party Addition to polymer materials, such as powder type dry mixing, or solution or suspension type wet mixing, can also be added in the form of a matrix containing the product or mixture of the present invention at a concentration of 2.5 to 25% by weight; in these In operation, the polymer used can be applied in the form of powder, granule, solution, suspension, or K latex. Μ The product or mixture-stabilized substance of the present invention can be used to produce moldings, films, and ribbons. Materials, monofilaments, fibers, surface coatings and the like. If necessary, other conventional additives suitable for synthetic polymers can be added to organic substances containing products or mixtures of the present invention, such as antioxidants, UV absorbers, Nickel stabilizers, pigments, fillers, plasticizers * corrosion inhibitors and metal deactivators. 'Specific examples of this traditional additive are: 1 · Antioxidant f 1 · 1 · Alkylated Monophenols · For example, 2,6-di-tert-butyl-1 4 -4 6-This paper is suitable for the Sichuan National Standard彳 ((, NS) Λ4 size (210X 297mm) (Please read the precautions on the back before filling in this page)
、1T % 491871 A7 B7__ 五、發明説明(Μ ) —甲基酚,2 — 丁基一 4,6 —二甲基酚,2,6 —二一 叔一 丁基一 4 一正一丁基紛,2,6 —二一叔一 丁基一 4 一乙基酚,2,6 —二一叔一 丁基一 4 一異丁基酚,2, 6 —二環戊基一 4 一甲基酚,2 — (α —甲基環己基)一 4,6 —二甲基酚,2,6 —二十八烷基一 4 一甲基酚, 2,4,6 —三環己基酚,2,6 —二一叔一 丁基一 4 一 甲氧基甲基酚,2,6 —二一壬基一 4 一甲基酚· 2,4 一二甲基一 6 — (1,一甲基十一烷一 1 一基)酚,2, 4 一二甲基一 6 — (1, 一甲基十七烷一 1 一基)酚,2 ,4 一二一甲基一 6 — (1, 一甲基十三烷一 1, 一基) 酚和其混合物。 1 ,2 ·烷硫基甲基酚,例如,2,4 一二辛基硫甲基一 6 —叔一丁基齡,2,4 一二辛基硫甲基一 6 —甲基酚, 2,4 一二辛基硫甲基一 6 —乙基酚,2,6 —二一十二 烷基硫甲基一4一壬基酚。 經满部中决標準局貞工消费合竹社印製 ---------f, (請先閱讀背面之注意事項再填寫本頁) 線一 1 · 3 ·對苯二酚和其烷基化對苯二酚,例如,2,6 — 二一叔一 丁基一 4 一甲氧基酚,2,5 —二一叔一 丁基對 苯二酚,2,5 -二一叔一戊基對苯二酚,2,6 —二一 苯基一 4 一十八燒氧基齡,2,6 -二一叔一丁基對苯二 齡,2,5 -二—叔一 丁基一 4 一經基茵香酸’ 3 ’ 5 — 二一叔一 丁基一 4 一羥基茴香醚,3,5 —二一叔一丁基 一 4 一羥基苯基硬脂酸酯,雙一 (3,5 —二一叔一丁基 一4一羥苯基)己二酸酯。 -47- 本紙張尺度用中國國家標卒((、NS ) Λ4規格(210X 297公釐) 經湞部中夾標卑局兵.T消费合作社印$ 491871 Α7 Β7 五、發明説明(wV) 1·4 ·生育酚,例如,α -生育酚,yS —生育酚,7 -生育酚,S —生育酚及其混合物(維他命E)。 1·5·羥基化硫二苯基醚,例如*2*2’ 一硫雙(6 一叔一 丁基一 4 一甲基酚),2,2’ 一硫雙(4 一辛基 酚),4,4’ 一硫雙(6—叔一丁基一3—甲基酚), 4,4' 一硫雙(6 —叔一 2 —甲基酚),4,4’ 一硫 雙(3,6-二一仲-戊基酚),4,4’一雙(2,6 一二甲基一4一羥苯基)二硫化物。 1 ·6·烷叉雙酚,例如,2,2^ —甲撐雙(6 —叔一 丁基一 4 一甲基酚),2,2’ 一甲撐雙(6 —叔一丁基 一 4 一乙基酚)、2、2Τ 一甲撐雙〔4 一甲基一 6 — ( « —甲基環己基)酚〕,2,2' —甲撐雙(4 一甲基一 6 —環己基酚),2,2, 一甲撐雙(6 —壬基一 4 一甲 基酚),2,2, 一甲撐雙(4,6 —二一叔一丁基酚) ,2,2’ 一乙叉雙(4,6—二一叔一丁基酚),2, 2’ 一乙叉雙(6 —叔一 丁基一 4 一異丁基酚)* 2,2 ,一甲撐雙〔6 — (c(一甲基苄基)一 4 一壬基酚〕,2 ,2’ 一甲撐雙〔6 — (α,α —二甲基苄基)一 4 一壬 基酚〕,4,4’ 一甲撐雙(2,6 —二一叔一丁基酚) ,4,4> 一甲撐雙(6 —叔一 丁基一 2'—甲基酚),1 ,:L 一雙(5 —叔一 丁基一 4 一羥基一 2 —甲基苯基)丁 烷,2,6 —雙(3 —叔一 丁基一 5 —甲基一 2 —羥基苄 基)一 4 一甲基酿,1 ,1 ,3 —三(5 —叔一 丁基一 4 ~48- 本紙張尺度適州中阈國家標嘩((、NS ) Λ4規格(210X 297公釐) ---------f (請先閲讀背面之注意事項再填寫本頁) 訂 線 經滴部中决標準局兵Η消費合作社印製 491871 A7 B7 五、發明説明(…) 一羥基一 2 -甲基苯基)丁烷* 1 · 1 一雙(5 —叔一丁 基一4一羥基一2—甲基苯基)一3—η—十二烷基氫硫 基丁烷,乙烯二醚雙〔3,3 —雙(3# —叔一 丁基一 4 ’ 一羥基苯基)丁酸_〕,雙(3 —叔一 丁基一 4 一羥基 一 5 —甲基一苯基)二環戊叉,雙〔2 — ( 3 # 一叔一丁 基一2’ 一羥基一5’ 一甲基苄基)一6—叔一丁基一4 一甲基苯基)對肽酸酯,1 »1 —雙一 (3,5 —二甲基 一 2 -羥基苯基·)丁烷,2,2 —雙一 (3,5 —二一叔 一 丁基一 4 一經基苯基)丙烧,2,2 —雙一 (5 —叔一 丁基一4一經基一2—甲基苯基)一4一η—十二焼基氫 硫基 丁烷,1 ,1 ,5,5 —四一 (5 —叔一 丁基一 4 一 羥基一 2 —甲基苯基)戊烷。 1 · 7 · 0 — · Ν —和S —苯甲基化合物,例如3,5, 3, ,(3,一四一叔一 丁基一 4,4, 一二羥基一二苯甲 基醚,十八烷基一 4 一羥基一 3,5 —二甲基苯甲基氫硫 基乙酸酯,三一 (3,5—二一叔一丁基一4一羥基苯甲 基)胺,雙(4 一叔一 丁基一 3 —羥基一 2,6 —二甲基 苯甲基)二硫代一對肽酸酯,雙(3,5 —二一叔一丁基 一 4 一羥基苯甲基)硫化物,異辛基一 3,5二一叔一丁 基一4一羥基苯甲基氫硫基乙酸酯。 ' 1·8·羥基苯甲基化的丙二酸酯,例如二(十八烷基) 一 2,2 -雙一 (3,5 —二一叔一 丁基一 2 —經基苯甲 基)一丙二酸酯,二一十八烷基一 2 一 (3 一叔一 丁基一 -49- 本紙張尺度適州中國國家標導((、NS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁) f、 1T% 491871 A7 B7__ V. Description of the invention (M)-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4, n-butylbutyl , 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol , 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-octacosyl-4 monomethylphenol, 2,4,6-tricyclohexylphenol, 2, 6-Di-tert-butyl-4 4-methoxymethylphenol, 2,6-di-nononyl-4 4-methylphenol · 2,4-dimethyl-2-6- (1,1-methyldeca 1-alkane- 1-yl) phenol, 2, 4-dimethyl- 6- (1,1-methylheptadecanyl- 1-yl) phenol, 2,4-di-methyl- 6- (1, 1 Methyltridecane-1,1-yl) phenol and mixtures thereof. 1,2 · Alkylthiomethylphenol, for example, 2,4-dioctylthiomethyl-6-tert-butyl age, 2,4-dioctylthiomethyl-6-methylphenol, 2,4 Dioctylthiomethyl-6-ethylphenol, 2,6-dodecanylthiomethyl 4-nonylphenol. Printed by the Ministry of Justice, Bureau of Standards and Consumption, Hezhu Co., Ltd .--------- f, (Please read the precautions on the back before filling out this page) Line 1 · 3 · Hydroquinone and Its alkylated hydroquinone, for example, 2,6-di-tert-butyl-4, methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-dione Tert-pentylhydroquinone, 2,6-diphenylphenyl-4 octadecyloxy, 2,6-di-tert-butylparaphenylene, 2,5-di-tertiary Butyl-1, 4-butyl-tert-butyl-1, 4-mono-hydroxyanisole, 3,5-di-tert-butyl-1, 4-hydroxyphenylstearate, di-1 (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. -47- This paper uses the Chinese national standard ((, NS) Λ4 size (210X 297 mm) in the Ministry of Economic Affairs. T consumer cooperatives printed $ 491871 Α7 Β7 V. Description of invention (wV) 1 · 4 · Tocopherols, such as α-tocopherol, yS—tocopherol, 7-tocopherol, S—tocopherol and mixtures thereof (vitamin E). 1.5 · hydroxylated thiodiphenyl ether, such as * 2 * 2 'monothiobis (6-t-butyl-4-methylol), 2,2' monothiobis (4-octylphenol), 4,4 'monothiobis (6-tert-butyl) -3-methylphenol), 4,4 'monothiobis (6-tert-2-methylphenol), 4,4' monothiobis (3,6-di-sec-pentylphenol), 4, 4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide. 1 · 6 · alkylidene bisphenols, for example, 2,2 ^ -methylenebis (6-tert-butyl-1 4 monomethylphenol), 2,2 'monomethylbis (6-tert-butyl-4 monoethylphenol), 2,2T monomethylbis [4 monomethyl-6 — («—methyl Cyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2, monomethylbis (6 —Nonyl-4 monomethylphenol), 2,2,1-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butyl) Butylphenol), 2, 2'-ethylidenebis (6-tert-butyl-1, 4-isobutylphenol) * 2, 2, methylidene [6 — (c (monomethylbenzyl) -1 4 monononylphenol], 2, 2 'monomethylbis [6 — (α, α —dimethylbenzyl) 4 monononylphenol], 4, 4 ′ monomethylbis (2,6 — Di-tert-butyl phenol), 4,4 > Monomethylbis (6-tert-butyl-2'-methylphenol), 1,: L-bis (5-tert-butyl-4-hydroxyl One 2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4 methyl, 1,1,3-tri ( 5 —tert-butyl-1 4 ~ 48- This paper is suitable for the middle threshold national standard of the state ((, NS) Λ4 specification (210X 297mm) --------- f (Please read the Please fill in this page for the matters needing attention) Printed by Didi Zhongxing Standard Bureau, Soldier Cooperative Co., Ltd. 491871 A7 B7 5. Description of the invention (…) 2-methylphenyl) butane * 1 · 1 bis (5-tert-butyl-4, hydroxy-1,2-methylphenyl) -3-n-dodecylhydrothiobutane, ethylene Diether bis [3,3-bis (3 # -tert-butyl-4'-hydroxyphenyl) butanoic acid]], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl ) Dicyclopentanyl, bis [2 — (3 # mono-t-butyl- 2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4 4-methylphenyl) p-peptidic acid Esters, 1 »1-bis (3,5-dimethyl-2-hydroxyphenyl ·) butane, 2,2-bis- (3,5-di-tert-butyl-1, 4-merylphenyl) ) Benzene, 2,2-bis (5-tert-butyl-4, meridyl, 2-methylphenyl), 4-n-dodecylhydrothiobutane, 1, 1, 5, 5-tetrakis (5-tert-butyl-4, hydroxy-1,2-methylphenyl) pentane. 1 · 7 · 0 — · Ν — and S — benzyl compounds, such as 3,5,3,, (3,4-tetra-t-butyl-4,4, -dihydroxy-diphenylmethyl ether, Octadecyl-4 monohydroxy-3,5-dimethylbenzyl hydrothioacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-t-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithio-peptide, bis (3,5-di-t-butyl-4-4-hydroxybenzoate Group) sulfide, isooctyl-3,5-di-tert-butyl-1, 4-hydroxybenzyl hydrothioacetate. '1.8 · hydroxybenzyl malonate, such as di (Octadecyl) 2,2-bis- (3,5-di-tert-butyl-2-transylbenzyl) monomalonate, dioctadecyl-2 1 (3 1-tert-butyl-1-49- This paper size is suitable for China National Standard ((, NS) Λ4 size (210X 297 mm) (Please read the precautions on the back before filling this page) f
、1T 經滴部中央標準局貝工消费合作社印製 491871 A7 B7 五、發明説明(4 ) 4一羥基一5—甲基苯甲基)一丙二酸酯,二一十二烷基 氫硫基乙基一 2,2 —雙一 (3,5 —二一叔一 丁基一 4 一羥基苯甲基)丙二酸_,雙一〔4一 (1,1,3,3 一四甲基丁基)苯基〕一 2,2 —雙(3,5 —二一叔一 丁基一4一羥基苯甲基)丙二酸酯。 1 · 9 ·芳香族的羥苯甲基化合物·例如1 ,3,5 —三 一 (3,5 — 二一叔一 丁基一 4 一羥苯甲基)一 2,4, 6 —三甲基苯,1 ,4 一雙(3,5 —二一叔一 丁基一 4 一羥基苯甲基)一2,3,5,6—四甲基苯,2,4» 6 —三一 (3,5 —二一叔一 丁基一 4 一羥基苯甲基)酚 〇 1 · 10·三嗪化合物,例如2,4 一雙(辛基氫硫基) 一6— (3,5—二一叔一丁基一4一羥基苯胺基)一1 ,3,5 —三嗪,2 —辛基氫硫基一 4,6 —雙(3,5 一二一叔一 丁基一 4 一羥基一苯胺基)一 1 ,3,5 —三 嗪,2 —辛基氫硫基一 4,6 -雙(3,5 —二一叔一丁 基一 4 一羥基苯氧基)一 1,3,5 -三嗪,2,4,6 一三(3,5 —二一叔一 丁基一 4 一羥基苯氧基)一 1 , 2,3 — 三嗪,1 ,3,5 -三一 (3,5 — 二一叔一丁 基一 4 一羥基苯甲基)異氰尿酸酯,1 ,3,5 —三一( 4 一叔一 丁基一 3 —羥基一 2,6 —二一甲基苯甲基)異 氰尿酸酯,2,4,6 —三(3,5 —二一叔一 丁基一 4 一羥基苯基乙基)一 1 ,3,5 —三嗪,1 ,3,5 —三 -50- 本紙張尺度適用中國國家標卒(CNS ) Λ4規格(210X 297公釐) ---------f, (請先閱讀背面之注意事項再填寫本頁)1, 1T printed by the Central Bureau of Standards of the Ministry of Standards, Shellfish Consumer Cooperative, 491871 A7 B7 V. Description of the invention (4) 4-hydroxy-1,5-methylbenzyl) malonate, didodecyl hydrosulfide Ethylethyl-2,2-bis (3,5-di-tert-butyl-1, 4-hydroxybenzyl) malonate, bis- [4-a (1,1,3,3, tetramethyl) Butyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4 4-hydroxybenzyl) malonate. 1 · 9 · Aromatic hydroxybenzyl compounds · For example 1,3,5-tris (3,5-di-tert-butyl-4 4-hydroxybenzyl) -2,4,6-trimethyl Phenylbenzene, 1,4 bis (3,5-di-tert-butyl-1, 4-hydroxybenzyl), 2,3,5,6-tetramethylbenzene, 2,4 »6-trione ( 3,5-di-tert-butyl-4 4-hydroxybenzyl) phenol 0 · 10 · triazine compounds, such as 2,4-bis (octylhydrothio) -6- (3,5-di 1-tert-butyl-4 4-hydroxyaniline) -1,3,5-triazine, 2-octylhydrosulfanyl-4,6-bis (3,5-di-tert-butyl-4-hydroxy (Monoaniline)-1,3,5-triazine, 2-octylhydrothio- 4,6-bis (3,5-di-tert-butyl- 4 -hydroxyphenoxy)-1,3 , 5 -triazine, 2,4,6 -tris (3,5-di-tert-butyl-4 -hydroxyphenoxy) -1,2,3-triazine, 1,3,5 -trin (3,5-di-tert-butyl-4 4-hydroxybenzyl) isocyanurate, 1,3,5-tri- (4-tert-butyl-3- Phenyl-2,6-di-methylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4, 4-hydroxyphenylethyl) -1, 3,5 —triazine, 1, 3,5 —tri-50 — This paper size is applicable to China National Standard Soldier (CNS) Λ4 specification (210X 297 mm) --------- f, (please first (Read the notes on the back and fill out this page)
*1T 491871 經濟部中央標隼局貨Η消費合作社印製 A7 B7五、發明説明(〆) 一 (3,5 -二一叔一 丁基一 4 一羥基苯基丙醯)一六氳 一 1 ,3 ,5 — 三嗪,1 ,3 ,5 —三一 (3 ,5 —二環 己基一4一羥基苯甲基)異氰尿酸酯。 1 · 1 1 ·苯甲基膦酸酯,例如,二甲基一 2,5 —二一 叔一 丁基一 4 一羥基苯甲基膦酸酯,二乙基一 3,5 —二 一叔一 丁基一 4 一羥基苯甲基膦酸酯*二十八烷基3,5 一二一叔一 丁基一 4 一羥基苯甲基膦酸酯,二十八烷基一 5 —叔一 丁基一 4 一羥基3 —甲基苯甲基一膦酸酯,3, 5—二一叔一丁基一4一羥基苯甲基一膦酸的單乙基酯之 鈣鹽。 1·12·醯基氨基酚,例如,4一羥基醯月桂基替苯胺 ,4 一羥基硬脂酸醯替苯胺,辛基一 N — (3,5 —二 一叔一 丁基一 4 一羥基苯基)氨基甲酸酯。 1 · 13·/3 - (3,5 — 二一叔一 丁基一 4 一羥基苯基 )丙酸和單一或聚一氫醇的酯,如和甲醇,乙醇,十八烷 醇,1 ,6 —己烷二醇,1 ,9 一壬烷二醇,乙烯二醇, 1 ,2 —丙烷二醇,新戊基二醇,硫代二乙烯二醇,二乙 烯二醇,三乙烯二醇,季戊四醇,三一(羥基乙基)異氰 尿酸酯,Ν,Ν’ 一雙(羥乙基)乙二醯二胺,3 -噻十 一烷醇,3 —噻五癸醇,三甲基己烷二醴,三一甲基酵丙 烷,4 一羥基甲基一 1 一磷一 2 · 6,7 —三氧雙環〔2 • 2 · 2〕辛烷。 1 · 14· /9 一 (5 —叔一 丁基一 4 一羥基一 3 —甲基苯 -51- 本紙張尺度適用中國國家標卑(rNS ) Λ4規格(210X 297公釐) (請先閱讀背面之注意事項再填寫本頁) #-·* 1T 491871 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and the Consumer Goods Cooperative of A7 B7 V. Description of the invention , 3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4 4-hydroxybenzyl) isocyanurate. 1 · 1 1 · benzylphosphonates, for example, dimethyl-2,5-di-tert-butylbutyl-4 monohydroxybenzylphosphonate, diethyl-3,5-ditert Monobutyl-4 monohydroxybenzyl phosphonate * octacosyl 3,5 di-tert-butyl mono-4 monohydroxy-benzyl phosphonate, octacosyl 5-tert-one Calcium salt of monoethyl 4-butyl-hydroxy 3-methylbenzyl monophosphonate, monoethyl ester of 3, 5-di-tert-butyl 4-hydroxybenzyl monophosphonic acid. 1 · 12 · fluorenylaminophenol, for example, 4-monohydroxy 醯 lauryl aniline, 4-monohydroxystearyl tetanil, octyl-N— (3,5-di-tert-butyl-4-hydroxy Phenyl) carbamate. 1 · 13 · / 3-(3,5-Di-tert-butyl-4 4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohol esters, such as and methanol, ethanol, stearyl alcohol, 1, 6-hexanediol, 1,9 monononanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol , Pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N 'bis (hydroxyethyl) ethylenediamine diamine, 3-thiaundecanol, 3-thiopentadecanol, trimethyl Hexane diamidine, tris-methyl-propane, 4-hydroxymethyl- 1-phosphorus 2 · 6,7-trioxabicyclo [2 • 2 · 2] octane. 1 · 14 · / 9 Mono (5-tert-butyl-1, 4-hydroxy-1, 3-methylbenzene-51- This paper size applies to Chinese National Standard (rNS) Λ4 specification (210X 297 mm) (Please read first Note on the back then fill out this page) #-·
、1T 線一 491871 A7 __B7__ 五、發明説明(4) 基)丙酸和單一或聚氫酵的酯•如》和甲酵*乙醇*十八 烷醇,1 ,6 —己烷二酵,1 ,9 一壬烷一二醇,乙烯二 酵,1 ,2 -丙烷二酵,新戊基二酵,硫代二乙烯二酵, 二乙烯二醇,三乙烯二酵,季戊四酵,三一(羥基乙基) 異氰尿酸酯,N,N> —雙一(羥基乙基)乙二醢二胺, 3 —暖十一烷醇,3 —噻十五烷醇,三甲基己烷二酵,三 一甲基醇丙烷,4 一羥基甲基一 1 一磷一 2,6,7 —三 氧雙環〔2·2·2〕辛烷。 1 * 1 5 · >3 — (3,5 —二環己基一 4 一經基苯基)丙 酸和單一或聚一氫醇的酯,如和甲醇,乙醇,十八烷醇, 1 ,6 —己烷二酵,1 ,9 一壬烷二醇,乙烯二醇,1 , 2 —丙烷二醇,新戊基二醇,硫代二乙烯二醇,二乙烯二 醇,三乙烯二醇,季戊四醇,三一(羥基乙基)異氰尿酸 酯,Ν,Ν’ 一雙(羥乙基)乙二醯二胺,3 —噻十一烷 醇,3 —噻十五烷醇,三甲基己烷二醇,三一甲基醇丙烷 ,4 一羥基甲基一 1 一磷一 2,6,7 —三氧雙環〔2 · 2 ♦ 2〕辛烷。 經濟部中央標苹局只工消贽合作社印f (請先閲讀背面之注意事項再填寫本頁) 1 · 1 6 . 3,5 —二一叔.一 丁基一 4 一羥基苯基醋酸 和單一或聚氫醇的酯,如和甲醇,乙醇,十八烷醇,1 , 6 -己烷二酵,1 ,9 一壬烷二醇,乙烯二醇,1 ,2 - 丙烷二酵,新戊基二醇,硫代二乙烯二醇,二乙烯二醇, 三乙烯二酵,季戊四醇,三一(羥基乙基)異氰尿酸酯, Ν,Ν, 一雙(羥基一乙基)乙二醢二胺,3 —噻十一烷 -52- 本紙張尺度適用中國國家標卒(CNS ) Λ4規格(210X 297公釐) 491871 Α7 Β7 經Μ部中央標準局兑工消贽合作社印來 五、發明説明(叫) 酵,3 —噻十五烷醇•三甲基己烷二酵,三甲基醇丙烷, 4 一羥基甲基一 1 一磷一 2,6,7 —三氧雙環〔2 · 2 • 2〕辛烷。 1 · 17·/? — (3,5 — 二一叔一 丁基一 4 一羥基苯基 )丙酸的醯胺,如,N,Ν’ 一雙(3,5 -二一叔一丁 基一4一羥基苯基丙醯)六甲撐二胺,一雙(3 ,5 —二一叔一 丁基一 4 一羥基苯基丙醯)三甲撐二胺, Ν,Ν’ 一雙(3,5 -二一叔一 丁基一 4 一羥基一苯基 丙醯)肼,Ν,Ν' - 雙〔2 — (3 - 〔3,5 — 二一叔 一 丁基一 4 一羥基苯基〕丙醯)乙基〕氧醯胺。 1*18*抗壞血酸(維他命(:) 1·19·胺抗氧化劑,例如,Ν,Ν/ —二一異丙基一 ρ—苯撐二胺,Ν,Ν, 一二一仲一丁基一ρ-苯撐二胺 ,Ν,Ν< —雙(1 ,4 一二甲基戊基)一 ρ —苯撐二胺 ,Ν,ΝΧ —雙(1 一乙基一 3 —甲基戊基)一 ρ —苯撐 二肢,Ν,Ν' —雙(1 一甲基庚基)一 ρ —苯撐二胺, Ν * Ν / 一二環己基一 ρ —苯撐二胺,Ν,Ν’ 一二苯基 —ρ -苯撐二胺,Ν,Ν / —雙(2 -萘基)一 ρ —苯撐 二胺,Ν —異丙基一 Ν,一笨基一 ρ —笨撐二胺,Ν — ( 1 ,3 —二甲基丁基)一 Ν' —苯基一 ρ'—苯撐二胺,Ν 一 (1 一甲基庚基)一 Ν' —苯基一 ρ —苯撐二胺,Ν — 環己基一 Ν' —苯基一 ρ —苯撐二胺,4 一 (ρ —甲苯碌 醯)一二苯基胺,Ν,Ν,一二甲基一 Ν,!^^ 一二一仲 -53- (請先閱讀背面之注意事項再填寫本頁) 、11 本紙張尺度適;fl中國國家標缚(rNS ) Λ4規格(210X 297公釐) 經漓部中央標革局MJ-消费合作社印製 491871 A7 B7 五、發明説明(# ) 一 丁基一 p —苯撐二胺,二苯基胺,N —烯丙基二苯基胺 ,4τ~異丙氧基二苯基胺,N —苯基一 1 一第基胺,N — (4一叔一辛苯基)一1一萘基胺,Ν—苯基一2—萘基 胺,辛基化的二苯基胺,例如Ρ,Ρ,一二一叔一辛基二 苯基胺,4 一 η — 丁基胺基酚,4 一丁醢基胺基酚,4 一 壬醯胺基酚,4 一十二醯基胺基酚,4 一十八醯胺基酚, 雙(4 一甲氧基苯基)胺,2,6 —二一叔一 丁基一 4 一 二甲基胺基甲基酚,2,4' 一二一胺基二苯基甲烷,4 ,4, 一二胺基二苯基甲烷,Ν,Ν,Ν' ,Ν,一四甲 基一 4,4,一二胺基二苯基甲烷,1 ,2 —雙〔(2 — 甲基苯基)胺基〕乙烷,1 ,2 —雙(苯基胺基)丙烷, (〇 —甲苯基)縮二胍,雙〔4 一 ( 1 ^ ^ 3 , 一二甲基 丁基)苯基〕胺,叔一辛基化的Ν —苯基一 1 一萘基胺, 單一及二烷基化的叔一丁基/叔-辛基二苯基胺的混合物 ,單一及二烷基化的壬基二苯基胺混合物,單一及二烷基 化的十二烷基二苯基胺混合物,單-及二烷基化的異丙基 /異己基二苯基胺混合物,單一及二烷基化的叔一 丁基二 苯基胺混合物,2,3 —二氫一 3,3 —二甲基一 4Η — 1 ,4 一苯並噬嗪,吩噻嗪,單一及二烷基化的叔一丁基 /叔-辛基吩噻嗪混合物,單-及二烷基~化的叔-辛基吩 噻嗪混合物,Ν —烯丙基吩噻嗪,N,N,N< » N / - 四苯基一 1 ,4 一二胺基丁一 2 —烯,Ν,N —雙(2, 2,6,6 —四甲基一哌啶一 4 一基一六甲撐二胺,雙( -54- ---------Φ— (請先閲讀背面之注意事項再填寫本頁)1. 1T line 491871 A7 __B7__ 5. Description of the invention (4) Group) Propionic acid and mono- or polyhydrogenated esters • Such as "and formazan * ethanol * stearyl alcohol, 1, 6-hexanediase, 1 , 9 monononane monodiol, ethylene dienzyme, 1, 2-propane dienzyme, neopentyl dienzyme, thiodiethylene dienzyme, diethylene glycol, triethylene dienzyme, pentaerythritol, three Mono (hydroxyethyl) isocyanurate, N, N > —Bis (hydroxyethyl) ethylenedifluorene diamine, 3- warm undecanol, 3-thiapentadecanyl alcohol, trimethylhexyl Dioxan, trimethylolpropane, 4-monomethylol-1, 1-phospho-2,6,7-trioxabicyclo [2 · 2 · 2] octane. 1 * 1 5 · > 3-(3,5-dicyclohexyl-4 acylphenyl) propionic acid and mono- or polyhydric alcohol esters, such as with methanol, ethanol, stearyl alcohol, 1, 6 —Hexanediase, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, Pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) ethylenediamine diamine, 3-thiaundecanol, 3-thiapentadecanol, trimethyl Hexanediol, trimethylolpropane, 4 monohydroxymethyl-1 monophosphoryl 2,6,7-trioxabicyclo [2 · 2 ♦ 2] octane. The Central Bureau of Standards of the Ministry of Economic Affairs only eliminates the seal of the cooperative (please read the precautions on the back before filling out this page) 1 · 1 6. 3, 5 —di-tert. 1-butyl-4 4-hydroxyphenylacetic acid and Esters of mono- or polyhydric alcohols such as and methanol, ethanol, stearyl alcohol, 1,6-hexanedienyl, 1,9 monononanediol, ethylene glycol, 1,2-propanedial, new Amyl glycol, thiodiethylene glycol, diethylene glycol, triethylene dienzyme, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν, bis (hydroxymonoethyl) ethyl Dimethyldiamine, 3-thiaundecane-52- This paper size applies to the Chinese National Standards (CNS) Λ4 specification (210X 297 mm) 491871 Α7 Β7 printed by the Central Standards Bureau of the Ministry of M Description of the invention (called) Fermentation, 3-thiapentadecanol • trimethylhexanediase, trimethyl alcohol propane, 4-monohydroxymethyl-1, 1-phospho-2, 6, 7-trioxabicyclo [ 2 · 2 • 2] octane. 1 · 17 · /? — (3,5 —di-tert-butyl-4 4-hydroxyphenyl) propionate, such as N, N'-bis (3,5-di-tert-butyl) One 4-hydroxyphenylpropanyl) hexamethylene diamine, one bis (3,5-di-tert-butylbutyl-4 4-hydroxyphenylpropanyl) trimethylenediamine, Ν, Ν 'one bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropanyl) hydrazine, N, N'-bis [2- — (3-[3,5-di-tert-butyl-4-hydroxyphenyl]] Propyl) ethyl] oxamine. 1 * 18 * ascorbic acid (vitamin (:) 1.19 · amine antioxidants, for example, N, N / -diisopropyl-ρ-phenylene diamine, N, N, 1,2 sec-butyl-1 ρ-phenylenediamine, N, N < -bis (1,4-dimethylpentyl) -ρ, phenylene diamine, Ν, Νχ-bis (1-ethyl-3, methylpentyl) One ρ —phenylene limb, Ν, Ν ′ — bis (1 monomethylheptyl) — ρ —phenylene diamine, Ν * Ν / one dicyclohexyl—ρ — phenylene diamine, Ν, Ν ' Monodiphenyl-ρ-phenylenediamine, N, N /-bis (2-naphthyl) -ρ-phenylenediamine, N-isopropyl-N, one benzyl-ρ-benzyl diamine , Ν— (1,3-dimethylbutyl) -N′-phenyl-ρ′-phenylene diamine, N— (1-methylheptyl) -N ′ —phenyl-ρ —phenylene Diamine, N-cyclohexyl-N'-phenyl-ρ-phenylene diamine, 4-((p-toluidine) -diphenylamine, N, N, dimethyl-N, ^^ One Two One Two -53- (Please read the precautions on the back before filling out this page), 11 paper size; f l Chinese National Standard Binding (rNS) Λ4 specification (210X 297 mm) Printed by MJ-Consumer Cooperative of the Central Standardization Bureau of the Ministry of Justice 491871 A7 B7 V. Description of the invention (#) monobutyl-p-phenylenediamine, Diphenylamine, N-allyldiphenylamine, 4τ ~ isopropoxydiphenylamine, N-phenyl-1, 1-diylamine, N- (4-tert-octylphenyl) -1 Mononaphthylamine, N-phenyl-2naphthylamine, octylated diphenylamine, such as P, P, 1,2 tert-octyldiphenylamine, 4 η-butylamino Phenol, 4 monobutylaminoamino phenol, 4 monononylaminophenol, 4 dodecylaminophenol, 4 octamethylaminophenol, bis (4-methoxyphenyl) amine, 2, 6-Di-tert-butyl-1, 4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4, diaminodiphenylmethane, N, N , N ', N, tetramethyl-4,4, -diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis ( Phenylamino) propane, (0-tolyl) biguanide, bis [4 a (1 ^ ^ 3, a Methylbutyl) phenyl] amine, tert-octyl N-phenyl-1naphthylamine, single and dialkylated tert-butyl / tert-octyldiphenylamine mixtures, Single and dialkylated nonyldiphenylamine mixtures, single and dialkylated dodecyldiphenylamine mixtures, mono- and dialkylated isopropyl / isohexyldiphenylamine mixtures Mixtures, single and dialkylated tert-butyldiphenylamine mixtures, 2,3-dihydro-3,3-dimethyl-1,4Η-1,4,1-benzothiazine, phenothiazine, single And dialkylated tert-butyl / t-octylphenothiazine mixture, mono- and dialkylated tert-octylphenothiazine mixture, N-allylphenothiazine, N, N , N < »N /-Tetraphenyl-1,4-diaminobutane-2-ene, N, N-bis (2, 2, 6, 6, 6-tetramethylmonopiperidine-4 4-yl-6 Methylene diamine, double (-54- --------- Φ— (Please read the precautions on the back before filling this page)
、1T 線一 本紙張尺度適用中國國家標冷(CNS ) Λ4規格(210X 297公釐) _ 491871 Α7 Β7 五、發明説明(β) 2,2,6,6 -四甲基锨啶一 4 一基)癸二酸酯,2, 2,6,6—四甲基呢啶一4一酮,2,2,6,6—四 甲基呢唾一4一醇。 s 2 · UV吸收劑和光穩定劑 2 ·1 · 2 — ( 2 # 一羥苯基)苯並三唑基,例如,2 —(2 # 一羥基一 5, 一甲基苯基)一苯並三唑基,2 — (3’ » 5 # 一二一叔一 丁基一 一羥基苯基)苯並三 唑基,2- (5’ 一叔一丁基一2, 一羥基苯基)苯並三 唑基,2- (2, 一羥基一5’ 一 (1,1,3,3—四 甲基丁基)苯基)苯並一三唑基,2 — (3’ *5’ 一二 一叔一丁基一2’ 一羥基苯基)一5—氯代一苯並三唑基 ,2— (3’ 一叔一丁基一2’ 一羥基一5, 一甲基苯基 )一5—氯代一苯並三唾基,2— (3’ 一仲一丁基一5 ,一叔一丁基一2’ 一羥基苯基)苯並三唑基,2- (2 ’ 一羥基一4’ 一辛氧苯基)苯並三唑基,2- (3’ , 5’ 一二一叔一戊基一 2,一羥基苯基)苯並三唑基,2 一 (3, ,5, 一雙一 (《,《—二甲基笨甲基)一 Ζ, 經淖部中央標枣局貞.T消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) 一羥基苯基)苯並三唑基,2 — (3' —叔一 丁基一 2’ 一羥基一5’ 一 (2—辛基氧羰基乙基)苯基)一5—氯 代一苯並三唑基,2- (3’ 一叔一丁基一5’ 一 〔2- (2 —乙基己基氧)一乙基〕一 2Τ 一羥基苯基)一 5 — 氯代一苯並三唑基,2— (3’ 一叔一丁基一2’ 一羥基 ~ 5 , 一 (2 —甲氧基羰基乙基)苯基)一 5 —氯代一苯 -55- 本紙張尺度適州中國國家標缚(厂奶)八4規格(210'/297公釐) 經漭部中央標枣局貝工消費合作社印黧 491871 A7 B7 五、發明说明(θ ) 並三唾基,2— (3’ 一叔一丁基一2’ 一翔基一5, 一 (2r甲氧基羰基乙基)苯基)苯並三唑基,2— (3, 一叔一 丁基一 —羥基一 5, — (2 —辛基一氧羰基乙 基)笨基)苯並三唑基,2 — (3,一叔一 丁基一 5,一 〔2— (2—乙基己基氧)羰基乙基〕一2’ 一羥基苯基 )苯並三唑基,2— (3, 一十二烷基一2, 一羥基一5 ,一甲基苯基)苯並一三唑基,和2— (3, 一叔一丁基 一2’ 一羥基一5# — (2—異辛基氧羰基乙基)苯基苯 並三唑基2,2, 一甲撐一雙〔4 一 (1 ,1 ,3,3 — 四甲基丁基)一 6 -苯並三唾基一 2 -基酿〕的混合物; 2一 〔3’ 一叔一丁基一5’ 一 (2—甲氧基羰基乙基) 一2’ 一羥基一苯基〕一2H—苯並三唑基和聚乙烯二醇 300 的酯化產物,〔R 一 CH2 CH2 — COO ( C Η 2 )3 〕2 — 其中 R = 3, 一叔一 丁基一 4’ 一 羥基一 5, 一2H-苯並三唑基一2—基苯基,2— 〔2' —羥基一 3 / 一 (oc,oc — 二甲基苄基)一 5' — (1 ,1 ,3, 3 —四甲基丁基)一苯基〕苯並三唑;2 — 〔2' —羥基 一 3' — (1,1,3,3—四甲基丁基)一 5, 一 ( α ,α —二甲基苄基)一苯基〕苯並三唑。 2 ♦ 2 · 2 —羥基苯並苯酮,例如,4 一羥基,4 一甲氧 基,4 一辛基氧基,4 一癸氧基,4 一十二烧氧基’ 4 一 苄氧基,4,2, ,4, 一三羥基和2’ 一羥基一 4, 4’ 一二甲氧基衍生物。 -56- ^紙張尺度中國國家標绛>:(:奶)八4規格(210、/ 297公釐) (請先閲讀背面之注意事項再填寫本頁) f 訂 經漓部中央標導局贸.X消费合作社印製 491871 A7 B7 五、發明説明(4 ) 2 · 3 ·經取代或未經取代之苯甲酸的酯,例如4 一叔丁 基一苯基水楊酸酯*苯基水楊酸酯,辛基苯基水揚酸酿, 二苯甲醢間笨二酚,雙(4 一叔一 丁基苯甲醯)間苯二酚 ,苯甲醯間苯二酚,2,4 一二一叔丁基笨基3,5 —二 一叔一 丁基一 4 一羥基苯甲酸酯,十六烷基3,5 —二一 叔一 丁基一 4 一羥基苯甲酸酯·十八烷基3,5 —二一叔 一 丁基一 4 一羥基苯甲酸酯,2 —甲基一 4,6 —二一叔 一丁基苯基3,5 —二一叔一 丁基一 4 一羥基一苯甲酸酯 0 2 ·4 ♦芳族酯,例如乙基α —氰基一 /3,/3 —二苯基丙 烯酸酷*異辛基α —氰基一 /3,二一苯基丙烯酸酯, 甲基oc —碳甲氧基肉桂酸酯,甲基α —氰基一々,/3 —甲 基一 ρ —甲氧基一肉桂酸酯,丁基α —氰基点,>9 一甲基 一Ρ—甲氧基一肉桂酸酯,甲基α—碳甲氧基一ρ—甲氧 基肉桂酸酯和Ν - ( >9 一碳甲氧基一 /9 一氰基乙烯基)一 2 —甲基吲_ 〇 2· 5 ♦鎳化合物·例如2,2’ 一硫代一雙一 〔4 一 ( 1 ,1 ,3,3 —四一甲基丁基)酚〕的鎳複合物,如1 ·· 1或1 : 2的複合物,具有或不具有額外的反應基*像 η — 丁基胺,三乙醇胺或η —環己基二乙'酵胺,鎳二丁基 二一硫代氨基甲酸酯,4 一羥基一 3,5 —二一叔一丁基 苄基膦酸的單烷基酯的鎳鹽,如甲基或乙基酯,嗣肟的鎳 複合物,如2 -羥基一 4 一甲基苯基十一烷基酮肟,1 一 -57- 本紙張尺度適用中國囤家標嘩(CNS ) Λ4規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 線 491871 A7 B7 五、發明説明(β) 經濟部中央標嗥局兵工消费合作社印製 苯 基 一 4 一 月 桂 醯 一 5 一 羥 基 吡 唑 基 的 鎳 複 合 物 > 具 有 或 不 具 有 額 外 之 反 應 基 〇 2 6 • 位 阻 胺 ( St e r i C ally hind er e d ami ne S) • 例如 雙 ( 2 9 2 % 6 » 6 一 四 甲 基 一 哌 啶 基 ) 癸 二 酸 酯 > 雙 ( 2 2 1 6 $ 6 一 四 甲 基 — 锨 啶 基 ) 丁 二 酸 酯 > 雙 ( 1 % 2 f 2 1 6 6 一 五 甲 基 啶 基 ) 癸 二 酸 酯 > 雙 ( 1 9 2 $ 2 $ 6 $ 6 一 五 甲 基 哌 啶 基 ) η 一 丁 基 一 3 $ 5 一 二 一 叔 一 丁 基 一 4 一 羥 基 苯 甲 基 丙 二 酸 酯 t 1 一 ( 2 一 羥 基 乙 基 ) 一 2 f 2 , 6 » 6 一 四 甲 基 一 4 一 羥 基 哌 啶 丁 二 酸 的 濃 縮 物 $ N $ N f 一 雙 ( 2 > 2 f 6 $ 6 一 四 甲 基 一 4 — 哌 啶 基 ) 甲 撐 二 一 胺 和 4 一 叔 一 辛 基 氨 基 一 2 $ 6 — 二 氯 代 — 1 > 3 t 5 一 三 嗪 9 三 — ( 2 $ 2 > 6 9 6 一 四 甲 基 一 4 一 派 啶 基 ) > 四 個 ( 2 f 2 $ 6 $ 6 一 四 甲 基 一 4 一 哌 啶 基 ) 一 1 2 9 3 f 4 一 丁 烷 — 四 羧 酸 酯 $ 1 9 1 t — ( 1 $ 2 一 乙 烷 二 基 ) 雙 ( 3 3 9 5 $ 5 一 四 甲 基 哌 嗪 酮 ) 4 一 苯 甲 醒 — 2 $ 2 % 6 > 6 一 四 甲 基 哌 啶 5 4 — 硬 脂 醯 氧 基 一 2 $ 2 f 6 9 6 一 四 甲 基 呢 啶 9 雙 ( 1 2 t 2 6 f 6 一 五 — 甲 基 啶 基 ) 一 2 — η — 丁 基 一 2 一 ( 2 一 羥 基 一 3 9 5 — 二 — 叔 一 丁 基 苯 甲 基 ) 丙 二 酸 酷 9 3 — η 一 辛 基 一 7 > 7 $ 9 9 9 一 四 (甲 基 一 1 9 3 梦 8 — 二 氮 雜 螺 C 4 • 5 ] 癸 燒 一 2 t 4 — 二 酮 9 雙 ( 1 一 辛 基 氧 基 一 2 9 2 V 6 > 6 — 四 一 甲 基 啶 基 ) 癸 二 酸 酯 9 雙 ( 1 一 辛 基 氧 基 一 2 $ 2 9 6 $ 6 一 四 甲 基 派 啶 基 ) -58- ---------P, (請先閱讀背面之注意事項再填寫本I) ,ιτ -線 本紙張尺度適用中國國家標净(rNS ) Λ4規格(210X 297公釐) 491871 A7 B7 經滴部中央標準局貝工消費合作社印製 五、發明説明(A) 丁二酸酯的濃縮物,Ν,Ν’ 一雙一 (2,2,6,6 — 四甲基一 4 一锨啶基)六甲撐二胺和4 一嗎啉代一 2,6 一二氯代一 1 ,3,5 —三嗪的濃縮物,2 -氯代一 4, 6 —雙(4 一 η — 丁基一氨基一 2,2,6,6 —四甲基 锨啶基)一 1 ,3,5 —三嗪和1 ,2 —雙(3 —氨基丙 基氨基)一乙烷的濃縮物,2 —氯代—4 * 6 —二一 (4 一 η —丁基氨基一 1 ,2,2,6,6 —五甲基锨啶基) 一 1 ,3,5 -三嗪和1 ,2 —雙一 (3 —氨基丙基胺基 )乙燒,8 —乙驢基一 3 —十二焼基一 7,7,9,9一 四甲基一1,3,8—三氮雜嫘〔4*5〕癸烷一2,4 一二酮,3—十二烷基一1一 (2,2,6,6—四甲基 一 4 一呢啶基)吡咯烷一 2,5 —二酮,3 -十二烷基一 1 一 (1 ,2,2,6,6 —五甲基一 4 一哌啶基)吡咯 烷一 2,5 -二酮,4 一十六烷氧基及4 一十八烷氧基一 2,2,6,6—四甲基呢啶的混合物,1^,1^/一雙一 (2 ,2,6,6 —四甲基一 4 一哌啶基)六甲撐二胺及 4 一環己基胺基一 2,6 -二一氯一 1 ,3,5 —三嗪的 縮合產物,1 ,2 —雙(3 —胺基丙基胺基)乙烷和2, 4,6-三氯一 1 ,3,5 —三嗪及4 一丁基胺基一 2, 2,6,6— 四甲基锨啶(CAS Reg.'No.[ 1 3 6 5 0 4 - 9 6 -6 ])的縮合產物;N — (2,2,6,6 —四甲基一 4 一派 啶基)一正一十二烷基丁二醯亞胺,N — (1 ,2,2, 6,6 —五甲基一 4 一锨啶基)一正一十二烷基丁二醚亞 -59 - _________-- (請先閲讀背面之注意事項再填寫本頁)、 1T line A paper size applies to China National Standard Cold (CNS) Λ4 specification (210X 297 mm) _ 491871 Α7 Β7 V. Description of the invention (β) 2, 2, 6, 6-tetramethylpyridine 1 4 1 Group) sebacate, 2,2,6,6-tetramethylnesidine-4 monoone, 2,2,6,6-tetramethylnesiala 4-monool. s 2 · UV absorber and light stabilizer 2 · 1 · 2 — (2 # monohydroxyphenyl) benzotriazolyl, for example, 2 — (2 # monohydroxy-5, monomethylphenyl) -benzo Triazolyl, 2 — (3 '»5 # 1,2-tert-butyl-monohydroxyphenyl) benzotriazolyl, 2- (5'-tert-butyl-2, monohydroxyphenyl) benzene Benzotriazolyl, 2- (2, monohydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzo-triazolyl, 2- (3' * 5'-1 Di-tert-butyl- 2'-hydroxyphenyl) -5-chloro-benzotriazolyl, 2- (3'-tert-butyl- 2'-hydroxy-5,1-methylphenyl) 5-chloro-benzotrisalyl, 2- (3'-sec-monobutyl-5, 1-tert-butyl-2'-hydroxyphenyl) benzotriazolyl, 2- (2'- Hydroxy-4'-octyloxyphenyl) benzotriazolyl, 2- (3 ', 5'-1,2-tert-pentyl-2, monohydroxyphenyl) benzotriazolyl, 2-a (3, , 5, One pair one ("," -dimethylbenzylmethyl) -Z, printed by the Ministry of Justice Central Standard Jujube Bureau Zhen.T Consumer Cooperatives ( Read the notes on the back before filling out this page) Monohydroxyphenyl) benzotriazolyl, 2 — (3′-tert-butyl- 2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) ) Phenyl) 5-chloro-benzotriazolyl, 2- (3'-tert-butyl- 5 '-[2- (2-ethylhexyloxy) -ethyl]-2T-hydroxybenzene A) 5-chloro-benzotriazolyl, 2- (3'-tert-butyl- 2'-hydroxy ~ 5, 1 (2-methoxycarbonylethyl) phenyl) -5-chloro Daiichiben-55- This paper is in the size of Shizhou China National Standard (Factory Milk) 8 4 specifications (210 '/ 297 mm) Ministry of Economic Affairs Central Standard Date Bureau Shellfish Consumer Cooperatives Seal 491871 A7 B7 V. Description of the invention (Θ) bistrisalyl, 2- (3'-tert-butyl- 2'-yenyl-5,-(2rmethoxycarbonylethyl) phenyl) benzotriazolyl, 2- (3 , 1-tert-butyl-1 -hydroxy-5,-(2-octyl-oxycarbonylethyl) benzyl) benzotriazolyl, 2-(3, 1-tert-butyl-5, 1-2- (2-ethylhexyloxy) carbonylethyl]-2 '- Phenyl) benzotriazolyl, 2- (3, dodecyl-2,1-hydroxy-5, monomethylphenyl) benzo-triazolyl, and 2- (3,1-tert- Butyl-1 2'-hydroxy-5 # — (2-isooctyloxycarbonylethyl) phenylbenzotriazolyl 2,2, 1-methylene-bis [4 1 (1, 1, 3, 3 — A mixture of tetramethylbutyl) -6-benzotrisialyl-2-yl]; 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl)-2' Mono-hydroxy-phenyl]-2H-benzotriazolyl and the esterification product of polyethylene glycol 300, [R -CH2 CH2 — COO (C Η 2) 3] 2 — where R = 3, mono-tert-butyl -4'-hydroxy-5, 2H-benzotriazolyl-2-ylphenyl, 2- [2'-hydroxy-3 / 3-(oc, oc-dimethylbenzyl)-5 '- (1,1,3,3-tetramethylbutyl) monophenyl] benzotriazole; 2-[2 '-hydroxyl-3'-(1,1,3,3-tetramethylbutyl) -5, ((α, α-dimethylbenzyl) -phenyl] benzotriazole. 2 ♦ 2 · 2-Hydroxybenzophenone, for example, 4-monohydroxy, 4-monomethoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy '4-benzyloxy , 4,2,4,4-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. -56- ^ Paper size Chinese national standard >: (: milk) 8 4 size (210, / 297 mm) (Please read the precautions on the back before filling this page) Printed by Trade.X Consumer Cooperative 491871 A7 B7 V. Description of the Invention (4) 2 · 3 · Ester of substituted or unsubstituted benzoic acid, such as 4-t-butyl-phenylsalicylate * phenyl water Salicylate, octylphenyl salicylic acid, dibenzophenanthrene resorcinol, bis (4-tert-butylbenzylhydrazone) resorcinol, benzophenorylresorcinol, 2, 4 1,2-tert-butylbenzyl 3,5-di-tert-butyl-4-hydroxybenzoate, cetyl 3,5-di-tert-butyl-4-hydroxybenzoate · Octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl -4 monohydroxy monobenzoate 0 2 · 4 ♦ Aromatic esters, such as ethyl α-cyano-1 / 3, / 3-diphenylacrylic acid, isooctyl α-cyano-3, 2 Monophenyl acrylate, methyl oc —carbomethoxycinnamate, Methyl α-cyano-fluorene, / 3-methyl-ρ-methoxy-cinnamate, butyl α-cyano point, > 9-methyl-P-methoxy-cinnamate, methyl α-Carboxymethoxy-ρ-methoxycinnamate and N-(> 9-Carbonmethoxy-1 / 9-cyanovinyl) -2-methylindole_〇2 · 5 ♦ Nickel compounds · For example 2,2'-thio-bis-one [4-((1,1,3,3-tetra-methylbutyl) phenol] nickel complex, such as 1 · 1 or 1: 2 complex With or without additional reactive groups * like η-butylamine, triethanolamine or η-cyclohexyldiethyl 'enzyme amine, nickel dibutyldithiothiocarbamate, 4 monohydroxy-3,5 -Nickel salts of mono-alkyl esters of di-tert-butyl benzylphosphonic acid, such as methyl or ethyl esters, nickel complexes of oxime, such as 2-hydroxy-4, 4-methylphenyl undecyl Ketooxime, 1-57- This paper size is applicable to the Chinese storehouse standard (CNS) Λ4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page) 491871 A7 B7 β) Central Ministry of Economic Affairs Ordnance Consumer Cooperative Prints Phenyl-4, Laurel-I-5 Monohydroxypyrazolyl Nickel Compounds > With or Without Additional Reacting Groups 0 2 6 • St eri C ally hind er ed ami ne S) • For example bis (29 2% 6 »6-tetramethyl monopiperidinyl) sebacate > bis (2 2 1 6 $ 6 tetramethyl-piperidyl) succinate > Bis (1% 2 f 2 1 6 6 pentamethylpyridyl) sebacate > Bis (1 9 2 $ 2 $ 6 $ 6 pentamethylpiperidinyl) η monobutyl-3 $ 5 1,2 tert-butyl- 4 hydroxybenzyl malonate t 1-(2-hydroxyethyl)-2 f 2, 6 »6-tetramethyl-4-hydroxypiperidine butane Acid Concentrates $ N $ N f One bis (2 > 2 f 6 $ 6 Tetramethyl- 4 -piperidinyl) Methylenediamine and 4 -tert-octylamino-2 $ 6 — Di Chloro — 1 > 3 t 5 monotriazine 9 tri — (2 $ 2 > 6 9 6 tetramethyl 4 1-Pyridinyl) > Four (2 f 2 $ 6 $ 6 Tetramethyl- 4-Piperidinyl) 1 1 2 9 3 f 4 Monobutane-tetracarboxylic acid ester $ 1 9 1 t — ( 1 $ 2 monoethanediyl) bis (3 3 9 5 $ 5 tetramethylpiperazinone) 4 monobenzyl — 2 $ 2% 6 > 6 tetramethylpiperidine 5 4 — stearin Methoxy- 2 $ 2 f 6 9 6 tetramethylmethylpyridine 9 bis (1 2 t 2 6 f 6 penta-methylpyridyl)-2-η-butyl-2-(2-hydroxy- 1 3 9 5 — Di-tert-butylbenzyl) malonate 9 3 — η-octyl-7 > 7 $ 9 9 9 one tetra (methyl-1 9 3 dream 8 — diazaspiro C 4 • 5] Sebacin 2 t 4 —dione 9 bis (1 monooctyloxy 2 9 2 V 6 > 6 — tetra-methylpyridyl) sebacate 9 bis (1 monooctyl Alkoxy-2 $ 2 9 6 $ 6 Tetramethylpyridinyl) -58- --------- P, (Please read the notes on the back before filling in this I), ιτ -line This paper size applies to China National Standard Net (rNS) Λ4 regulations (210X 297 mm) 491871 A7 B7 Printed by the Shell Department Consumer Cooperative of the Central Bureau of Standards of Didi Ministry. 5. Description of the invention. Concentrate of 6 —tetramethyl-1, 4-pyridinyl) hexamethylenediamine and 4-monomorpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4, 6-bis (4-a-n-butyl-amino-2,2,6,6-tetramethylpyridinyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ) Concentrate of ethane, 2-chloro-4 * 6-di (4-a-n-butylamino-1,2,2,6,6-pentamethylpyridinyl) -1,3, 5-triazine and 1,2-bis (3-aminopropylamino) ethynyl, 8-ethynyl-3-dodecyl-yl-7,7,9,9-tetramethyl-1, 3,8-triazapyrene [4 * 5] decane-2,4-dione, 3-dodecyl-1 1- (2,2,6,6-tetramethyl-1,4-meridinyl ) Pyrrolidine-2,5-dione, 3-dodecyl-1 1- (1,2,2,6,6-pentamethyl-4 piperidinyl) pyrrole A mixture of alkane-2,5-dione, 4 hexadecyloxy and 4 octadecyloxy-2,2,6,6-tetramethylmethylpyridine, 1 ^, 1 ^ / one double one Condensation products of (2,2,6,6-tetramethyl-4 piperidinyl) hexamethylene diamine and 4 cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-monobutylamino-2,2,6,6 — Condensation product of tetramethylpyridine (CAS Reg.'No. [1 3 6 5 0 4-9 6 -6]); N — (2,2,6,6 —tetramethyl-4pyridinyl ) -N-dodecyl succinimide, N — (1,2,2,6,6-pentamethyl-4 4-pyridinyl) -n-dodecyl succinimide-59 -_________-- (Please read the notes on the back before filling out this page)
V 、11 線 本紙張尺度適川中國國家標卒(rNS ) Λ4規格(210X 297公釐) ^71 ^71 五 經滴部中决標隼局貝工消资合作社印製 Α7 Β7 發明説明(呌) 胺,2 —十一烷基一 7,7,9,9 一四甲基一 1 一氧雑 〜3,8 — 二吖一 4 一 氧一螺〔4 · 5〕癸烷,7,7, 9,9 一四甲基一 2 —環十一烷基一 1 一氧雜一 3,8 — 二吖一 4 -氧螺〔4 · 5〕癸烷和表氯醇的反應產物* 1 ,1 一雙(1 ,2,2,6,6 —五甲基一 4 一锨啶氧基 羰基)一2— (4一甲氧基苯基)乙烯,Ν,Ν' —雙一 甲醯一 Ν,Ν,一雙(2,2,6,6 —四甲基一 4 一顿 啶基)六甲撐二胺,4 一甲氧基一甲撐一丙二酸和1 ,2 ,2,6,6 —五甲基一 4 一羥基哌啶的二酯,聚〔甲基 丙基一 3 —氧一 4 一 (2,2,6,6 —四甲基一 4 一哌 啶基)矽烷*順丁烯二酸一 α—烯烴共聚物和2,2,6 ,6 —四甲基一 4 一胺基呢喷或1 ,2,2,6,6 —五 甲基一4一胺基锨啶的反應產物。 2*7*乙二醯二胺,例如4,4’ 一二辛基氧基氧醯替 苯胺,2,2’ 一二辛基氧基一 5,5’ 一二一叔一丁氧 一醯替苯胺,2,2’ 一二十二烷基氧基一 5,5,一二 一叔一丁氧醢替苯胺,2—乙氧基一2’ 一乙氧醯替苯胺 ,Ν,Ν’ 一雙(3 —二甲基氨基丙基)乙二酿二胺,2 一乙氧基一5—叔一丁基一2’ 一乙氧醯替苯胺及其和2 一乙氧基一2,一乙基一 5,4’ 一二一叔一丁氧基醢替 苯胺的混合物,及鄰一和間-甲氧基二取代之氧醢替苯胺 的混合物,及0 —和Ρ —乙氧基一二取代之氧醯替苯胺。 2-8*2- (2 -羥基苯基)一 1,3·5 —三嗪,例 -60- 本紙張尺度讁州中國國家標蟫(CNS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁) 經滴部中央標枣局Η消費合作.社印製 491871 A7 B7 五、發明説明(今) 如2,4,6 —三一 (2 —羥基一 4 一辛基氧基一苯基) 一 1 ;,3,5 —三嗪,2- (2 —羥基一 4 一辛基氧基苯 基)一 4,6 — 雙(2,4 一二甲基苯基)一 1,3,5 一三嗪,2 — (2,4 一二羥基苯基)一 4,6 -雙(2 ,4 一二甲基苯基)一 1 ,3,5 —三嚷,2,4 一雙( 2—羥基一4一丙基氧基苯基)一6— (2,4一二甲基 苯基)一 1 ,3,5 —三嗪,2 — (2 —羥基一 4 一辛基 氧基苯基)一 4,6 —雙(4 一甲基苯基)一 1 ,3,5 一三嗪,2— (2—羥基一4一十二烷基一氧基苯基)一 4,6—雙(2,4一二甲基苯基)一1,3,5—三嗪 • 2 - 〔2 —羥基一 4 一 (2羥基一 3 —丁基氧基一丙氧 基)苯基〕一 4,6 —雙(2,4 一二甲基)一 1 ,3, 5-三嗪,2— 〔2—經基一4一 (2—經基一3—辛基 氧基一丙基氧基)苯基〕一 4,6 —雙(2,4 一二甲基 )一 1 ,3,5 -三嗪,2 — 〔4 一 (十二烷氧基/十三 烷氧基一 2 —羥基丙氧基)一 2 —羥基一苯基〕一4,6 一雙(2,4 一二甲基苯基)一 1 ,3 * 5 —三嚷,2 — 〔2—羥基一4一 (2—羥基一3-十二烷氧基一丙氧基 )苯基〕一 4,6 —雙(2,4 一二甲基苯基)一 1 ,3 ,5 -三嗪,2 - (2 -羥基一 4 -己氧基)苯基—4, 6 — 二苯基一 1 ,3,5 — 三嗪,2 - (2 - 羥基一 4 一 甲氧基苯基)一 4,6 —二苯基一 1,3,5 —三嗪,2 ,4,6 —二〔2 — 徑基一 4 一 (3 —丁 氧基一 2 —經基 -61- 本紙張尺度適州中國國家標苹((’奶)八4規格(210'/297公釐) ---------IP— (請先閱讀背面之注意事項再填寫本頁)The paper size of V and 11 papers is suitable for Sichuan National Standards (rNS) Λ4 specification (210X 297 mm) ^ 71 ^ 71 Printed by Wujing Dibei Bid Bureau, Beigong Consumer Cooperative Co., Ltd. Α7 Β7 Description of Invention (呌) Amine, 2-undecyl-7,7,9,9, tetramethyl-1, 1-oxyfluorene ~ 3,8-diazine-4, 4-oxy-spiro [4 · 5] decane, 7, 7, The reaction product of 9,9-tetramethyl-1,2-cycloundecyl-1, 1-oxa-3,8-diazine 4-oxospiro [4 · 5] decane and epichlorohydrin * 1,1 One bis (1,2,2,6,6-pentamethyl-4 4-pyridinyloxycarbonyl) one 2- (4-methoxyphenyl) ethylene, Ν, Ν '-bis-methyl phenyl-N , N, a bis (2,2,6,6-tetramethyl-1,4 pyridyl) hexamethylene diamine, 4 methoxy-methylene-malonic acid and 1,2,2,6, Diester of 6-pentamethyl-4 4-hydroxypiperidine, poly [methylpropyl 3 -oxo-4 1 (2,2,6,6-tetramethyl-4 piperidinyl) silane * cis Butadiene-α-olefin copolymer and 2,2,6,6-tetramethyl-1,4-aminoamine spray or 1,2,2, The reaction product of 6,6-pentamethyl-4aminoamine. 2 * 7 * ethylenediamine diamine, such as 4,4'-dioctyloxyoxopanidine, 2,2'-dioctyloxy-5,5'-di-tert-butoxy-amidine Tefaniline, 2,2'-docosadecyloxy-5,5,1-t-tert-butoxyfluortanilide, 2-ethoxy-2'-ethoxyfluortanilide, Ν, Ν ' A bis (3-dimethylaminopropyl) ethylenediamine diamine, 2 monoethoxy-5-tert-butyl-1 2'-ethoxyfluorethiline and 2 monoethoxy-2, A mixture of monoethyl-5,4'-di-tert-butoxyanilide and a mixture of ortho- and meta-methoxydisubstituted oxotetanil, and 0- and P-ethoxy One or two substituted oxotetanil. 2-8 * 2- (2-hydroxyphenyl) -1,3 · 5-triazine, Example-60- This paper size is the China National Standard (CNS) Λ4 specification (210X 297 mm) (please first Read the notes on the reverse side and fill in this page.) Consumers' cooperation with the Central Bureau of Jujube, Didi Ministry. Printing 491871 A7 B7 V. Description of the invention (today) Such as 2, 4, 6 — Trinity (2 — hydroxy 1 4 1 Octyloxymonophenyl) -1; 3,5-triazine, 2- (2-hydroxy-44-octyloxyphenyl) -4,6-bis (2,4-dimethylbenzene Yl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,2,3,5-triamidine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4dodecyloxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine • 2-[2-Hydroxy-4 1 (2 Hydroxy-3-butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-meryl-4 Mono (2-Cycloyl-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,2,3,5-triazine, 2- [ 4 (dodecyloxy / tridecyloxy 2-hydroxypropoxy) 2- 2-hydroxy-phenyl]-4, 6 bis (2, 4- dimethylphenyl)-1, 3 * 5 -triamidine, 2-[2-hydroxy-4-((2-hydroxy-3-dodecyloxy-propoxy) phenyl]-4,6-bis (2,4-dimethyl Phenyl) -l, 3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-l, 3,5-triazine, 2- (2 -Hydroxy-4 monomethoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-di [2 —Cyclo-4— (3-butoxy 1 2 —Jingji-61- This paper size is suitable for China National Standard Apple (('Milk) 8 4 Specification (210' / 297mm) --------- IP— (Please read the Precautions Complete this page)
、1T 線 經滴部中央標準局匁工消费合作社印製 491871 A7 B7 —__ 五、發明説明(八) 丙氧基)苯基〕一 1 ,3, 5 —三嗪,2 — (2 —羥基 苯基)一 4 一 (4 一甲氧基苯基)一 6 —苯基一 1 ,3, 5 —三嗪,2 — {2 —羥基一 4 一 〔3 — (2 —乙基己基 一 1 一氧基)一 2 —經基丙氧基〕苯基} 一4,6 —雙( 2,4 一二甲基苯基)一 1 ,3,5 —三嚷。 3,金屬去活性瓤,例如N , N,一二苯基乙二醢二胺, N —家楊基一 N,一水楊醢基肼,N,N,一雙(水揚醯 基)肼,N,Ν’ 一雙(3,5 — 二一叔—丁基一 4 一羥 基苯基一丙醯)肼,3 —水楊醯基氨基一 1 ,2,4 一三 唑,雙(苯亞甲基)乙二醢二一醢胼,二醢胼,醯替苯胺 ,異肽醯基,二醯胼,癸二醯雙苯基醢胼,Ν,Ν* —二 一乙醯基己二醯基二醯肼,Ν,Ν’ 一雙(水楊醯基)乙 二醯二醯肼,Ν,Ν’ 一雙(水楊醸基)一硫代丙醯二醯 肼。 4 ♦亞磷酸酯和膦酸藤,例如三苯基亞磷酸酯,二苯基烷 基亞磷酸酯,苯基二烷基亞磷酸酯,三一(壬基苯基)亞 磷酸酯,三月桂基亞磷酸酯,三-十八烷基亞磷酸酯,二 硬脂驢季戊四醇一^亞隣酸醋*二一 (2,4 一二一叔一丁 基苯基)亞磷酸酯,二異癸基季戊四醇二亞磷酸酯,雙( 2,4 一二一叔一丁基苯基)季戊四醇二(亞磷酸酯,雙( 2,6 —二一叔一 丁基一 4 一甲基苯基)一季戊四醇二亞 磷酸酯,二異癸基氧基季戊四醇二亞磷酸醮,雙(2,4 一二一叔一丁基一6-甲基苯基)季戊四酵二亞磷酸酯, -62- 本紙張尺度14川中國國家標冷(CNS ) Λ4規格(210X 297公釐) ~ ---------P, (請先閲讀背面之注意事項再填寫本頁) 訂 線 經满部中央標準局只工消费合作社印製 491871 A7 B7 五、發明説明(5Ί ) 雙(2,4,6 —三一(叔一丁基苯基)季戊四酵二亞磷 酸酯?三硬脂醢山梨糖酵三亞磷酸酯,四個(2,4 一二 一叔一丁基苯基)4,4’ 一聯苯撐二膦酸酯,6—異辛 基氧基一 2,4,8,10 —四一叔一 丁基一 1 2H —二 苯〔d,g〕一 1 ,3,2 —二氧鱗,6 — 氟代一 2,4 ,8,10 —四一叔一 丁基一 12 — 甲基一二苯〔d,g 〕一1 ,3,2 —二氧氧滕辛,雙(2,4 一二一叔一丁 基一 6 —甲基苯基)甲基亞磷酸酯,雙(2,4 一二一叔 一丁基一6—甲基苯基)乙基亞磷酸酯,2,2' ,2々 一氮川〔三乙基二(3,3' ,5,5,一四一叔一丁基 一 1 ,1' 一聯苯基一 2,—二基)亞磷酸酯〕,2 一乙基己基(3,3' ,5,5,一四一叔一 丁基一 1 , 1' 一聯苯基一 2,2' -二基)亞磷酸酯。 5 ·羥基胺,例如,N,N -二苄基羥基胺,N,N —二 乙基羥基胺,N,N —二辛基羥基胺,N,N —二月桂基 羥基胺,N,N -二(十四)烷基羥基胺,N,N —二( 十六烷基)羥基胺,N,N—二(十八烷基)羥基胺,N 一十六烷基一 N -十八烷基羥基胺,N —十七烷基一 N -十八烷基羥基胺,由氫化牛脂胺的N,N —二焼基經基胺 〇 6 ·硝酮,例如,N —苄基一 cx —苯基一硝酮,N 一乙基 一 α —甲基一硝嗣,N —辛基一 cx —庚基一硝嗣’ N —月 桂基一 CX —十一烷基一硝酮,Ν —十四烷基一 α 一十三院 -63- 紙張尺度述用;國國家標卑((”5)八4規格(210:/ 297公釐了 ---------·1, (請先閲讀背面之注意事項再填寫本頁) 訂 經消部中央標準局负工消费合作社印製 491871 A7 __ B7__ 五、發明説明(# ) 基一硝_,N —h六烷基一 α--h五燒基一硝酮,Ν--h 八烷基一 α —十七烷基一硝酮,N -十六烧基一 α —十七 烧基一硝酿I,Ν--h八烧基一 α--h五焼基一硝嗣· Ν — 十七烷基一 ex -·h七烷基一硝酮,N —十八烷基一 a--h 六烷基一硝酮,衍生自氫化牛脂胺之N,N —二烷基羥基 胺的硝嗣。 7 ·硫代協乘劑,例如,二月桂基硫代二丙酸酯或二硬脂 基硫代丙酸酯。 8 ·過氧化物清潔劑,例如/3 —硫代二丙酸的酯,例如月 桂基,硬脂醯,十四烷基或十三烷基酯,氫硫基苯眯唑基 或2 —氫硫基苯咪唑的鋅鹽,二丁基二硫代氨基甲酸鋅, 二十八烷基二硫化物,五一赤丁四醇四個(/3 —十二烷基 氫硫基)丙酸鹽。 9·聚醯胺穩定劑,例如,和碘化物及/或磷化合物结合 之銅鹽,及二價錳的盥類。 10 ♦鹼性共穩劑,例如*密胺,聚乙烯基吡咯烷酮,二 氰二醯胺》三-烯丙基氰尿酸酯,尿素衍生物,肼衍物, 胺,聚醢胺,聚尿烷,較高脂肪酸的鹼金屬或鹼土金靥鹽 類*例如,硬脂酸鈣,硬脂酸鋅,廿二酸鎂,硬脂酸鎂, 蓖麻酸納和十六碳酸鉀,焦兒茶酸銻或焦、兒茶酸鋅。 11·核酸劑,例如,無機物質,像滑石,金屬氧化物, 像二氧化妖或較佳的鹼土金屬之氧化鎂*磷酸鹽,碳酸鹽 或硫酸鹽;有機化合物,像單-或多羧酸及其鹽類,如, -64- 本紙張尺度適州中國國家標卒((、NS ) Λ4規格(210X 297公釐) ---------P! (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中夾標卑局負工消费合作社印製 491871 A7 B7 五、發明説明(β ) 4 一叔一 丁基苯甲基,己二酸,二苯基乙酸,丁二酸納, 或苯甲酸鈉;多聚合化合物,像離子共聚物(離子體( ionomers) ) ° 12 ·填充和補強劑,例如,碳酸鈣,矽酸鹽,玻璃纖維 *石綿,滑石,高敏土,雲母,硫酸鋇,金屬氧化物和氫 氧化物,碳黑,石墨,木材粉末及或其它天然產物的粉末 或纖維,合成纖維。 1 3 ♦其他添加劑,例如,增塑劑,潤滑劑,乳化劑,色 料,流動添加劑,®媒,流動控制劑,光學增亮劑,防火 劑,抗靜電劑和發泡劑(blowing agents ) 〇 14 ·苯並呋喃酮及吲跺酮,例如,描述於 US-A- 4 , 3 2 5 , 8 6 3 ; US + 4, 338,244, US-A-5 , 175,313; US-A- 5,2 1 6 , 0 5 2 , US-A-5 ,252,643, DE + 4 ,316,611; DE-A- 4 , 3 1 6 , 6 2 2 ; DE-A- 4 , 3 1 6 , 8 7 6; EP-A-0,589,839或 EP-A-0,591,102或3 — 〔4一 (2 —乙醯氧基乙氧基)苯 基〕一 5,7 —二一叔一丁基一苯並呋喃一 2 —酮,5, 7—二一叔一丁基一3— 〔4一 (2—硬脂醯氧基乙氧基 )苯基〕苯並呋喃一 2 -酮,3,—雙〔5,7 -二 一叔一 丁基一 3 - (4 一 〔2 —羥基乙氧基〕苯基)苯並 呋喃一 2 —酮〕,5,7 —二叔一 丁基一「3 — (4 一乙氧 基苯基)苯並呋喃一 2 —酮,3 — (4 一乙醯氧基一 3, 5 —二甲基苯基)一 5,7 —二一叔一丁基一苯並呋喃一 2 —酮,3 — (3,5 —二甲基一 4 一三甲基乙醯氧基) -65- 本紙张尺度適外ί中國國家標绛((,NS ) Λ4規格(2丨0 X 297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 線一 經濟部中央標準局兵工消费合作社印製 A7 〜〜_?z__ i、發明説明(&。) 〜5 » 7 —二一叔一丁基一苯並呋喃一 2 —嗣,3 — (3 ,4 了二甲基苯基)一 5,7 —二一叔一丁基苯並呋喃一 2 —酮,3 — (2,3 —二甲基苯基)一 5,7 -二一叔 〜丁基一笨並呋喃一2—嗣。 本發明產物或混合物和傳統添加劑的比例如可是例如 1 : 0 · 5 至 1 : 5 〇 本發明的產物或混合物也可用作穗定劑,尤其是當作 光德定劑,如用作大部份相片重印和其它重印技藝領域內 習知物質的穗定劑,如揭示於Research Disclosure 1990, 31429 (pages 474至 480)。 本發明將Μ下述的實例更詳细的說明*所有的百分比 除非特別指明皆是Κ重量計算。 在下述實例化學式的結構中,η#代表在分子中重覆 單元的數目及所得產物不是均一的。 揭示於實例1Α的中間物之特徵為數量平均分子量 Μη及聚分散度Mw/Mn。 使用GPC (凝膠滲透色譜)當作分離不同尺寸分子 及獲得平均分子量(Mw,Μη)及聚合物莫耳分子量分 佈的分析步驟。 此技藝是習知的,且描述於例如〃 M 0der η Size-Exclusion Liquid Chromatography”,由 W.W. Yan et al.等人編著,J· Wiley & Sons, N.Y· USA, 1 9 7 9 出版 ,pages 4 - 8 , 249-283和 3 1 5-340〇 -66_ >、紙張尺度Hfl中國國家標缚((:NS ) Λ4規格(210X 297公釐) " ---------f (請先閱讀背面之注意事項再填寫本頁), 1T line printed by the Central Bureau of Standards, Machining and Consumer Cooperatives of Didi Ministry 491871 A7 B7 —__ V. Description of the invention (8) Propoxy) phenyl] -1,3,5-triazine, 2 — (2-hydroxy Phenyl) -4 4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-1 4- [2-ethylhexyl-1 (Monooxy)-2 -propylpropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl)-1,3,5-triamidine. 3, metal deactivated fluorene, such as N, N, diphenylethylene dihydrazine diamine, N-Jialyl-N, salicylhydrazine, N, N, bis (salicylidene) hydrazine, N , N′-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propanesulfonyl) hydrazine, 3-salicylamidoamino-1,2,4-triazole, bis (benzylidene) Ethyl hydrazone, hydrazone, acetanilide, isopeptide fluorenyl, hydrazone, sebacium bisphenyl hydrazone, Ν, Ν *-bis acetamidine hexamethylene dihydrazone Hydrazine, N, N 'one pair (salicylidene) ethylenedihydrazine hydrazine, N, N' one pair (salicylidene) thiopropylhydrazine dihydrazine. 4 ♦ Phosphites and phosphonates, such as triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilauric acid Diphosphite, tris-octadecylphosphite, distearyl pentaerythritol-^-o-phosphite * dione (2,4-di-tert-butylphenyl) phosphite, diisodecyl Dipentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di (phosphite, bis (2,6-di-tert-butyl-4-methylphenyl)- Pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphine phosphonium, bis (2,4 t-butyl t-butyl-6-methylphenyl) pentaerythritol diphosphite, -62- The paper size is 14 Sichuan China National Standard Cold (CNS) Λ4 specification (210X 297 mm) ~ --------- P, (Please read the precautions on the back before filling this page) Printed by the Central Bureau of Standards only for the Consumer Cooperative 491871 A7 B7 V. Description of the invention (5Ί) Bis (2,4,6-trione (tert-butylphenyl) pentaerythritol diphosphite? Trihard醢 Sorbus glycosyl triphosphite, four (2,4,12-tert-butylphenyl) 4,4'-biphenylene diphosphonate, 6-isooctyloxy-2,4,8 10, tetra-t-tert-butyl- 1 2H-diphenyl [d, g] -1,3,2-dioxane, 6-fluoro-2,4,8,10-tetra-t-tert-butyl 12-methyl-diphenyl [d, g] -1,3,2-dioxetine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite Esters, bis (2,4,2-tert-butyl-6-methylphenyl) ethylphosphite, 2,2 ', 2'-nitroazine [triethylbis (3,3', 5 , 5,4-tetra-t-butyl-1,1'-biphenyl-2, -diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5,4-tetra-t-tert Monobutyl-1,1'-biphenyl-2,2'-diyl) phosphite. 5-Hydroxylamines, for example, N, N-dibenzylhydroxyamine, N, N-diethylhydroxyl Amine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-di (tetradecyl) hydroxylamine, N, N-di (hexadecane) ) Hydroxylamine, N, N-bis (octadecyl) hydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N, N-dimethylamino via hydrogenated tallowamine. 6 · Nitroketones, for example, N-benzyl-cx-phenyl-nitronone, N-ethyl-α-methyl-nitrofluorene, N —Octyl—cx —Heptyl—Nitrofluorene 'N —Lauryl—CX —Undecyl Mononitrone, N —Tetradecyl —α — Thirteen Houses — 63 — Paper scale description; National Standard Bei (("5) 8 4 specifications (210: / 297 mm --------- · 1, (Please read the precautions on the back before filling in this page)) Printed by the Industrial and Consumer Cooperatives 491871 A7 __ B7__ V. Description of the invention (#) N-hexyl-, N-h hexaalkyl-α-h-pentyl-nitronone, N-h octyl-α-ten Heptadecyl-nitronone, N-hexadecyl-α-heptadecenyl-nitrazine I, Ν--h octadecyl-α-h pentadecyl-nitrazine · Ν-heptadecyl One ex-· h heptyl mononitrone, N-octadecyl-a--h hexaalkyl mononitrone, derived from hydrogenated cattle The amine N, N - dialkyl hydroxylamine nitrate Si. 7. Thio synergists, for example, dilauryl thiodipropionate or distearyl thiopropionate. 8. Peroxide cleaners, such as / 3-thiodipropionic acid esters, such as lauryl, stearyl, tetradecyl or tridecyl esters, hydrothiobenzoxazolyl, or 2-hydrogen Zinc salt of thiobenzimidazole, zinc dibutyl dithiocarbamate, octadecyl disulfide, pentaerythritol tetraol, four (/ 3-dodecyl hydrogenthio) propionate . 9. Polyamide stabilizers, such as copper salts combined with iodide and / or phosphorus compounds, and toilet articles of divalent manganese. 10 ♦ Basic co-stabilizers, such as * melamine, polyvinylpyrrolidone, dicyandiamide, tri-allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurea Alkane, higher fatty acid alkali metal or alkaline earth metal phosphonium salts * For example, calcium stearate, zinc stearate, magnesium succinate, magnesium stearate, sodium ricinole and potassium hexadecanoate, pyrocatechin Antimony acid or coke, zinc catechin. 11. Nucleic acid agents, for example, inorganic substances, like talc, metal oxides, like magnesium oxide * or magnesium oxide * phosphates, carbonates or sulfates of preferred alkaline earth metals; organic compounds, like mono- or polycarboxylic acids And its salts, such as, -64- This paper size is suitable for Chinese national standard ((, NS) Λ4 size (210X 297mm) --------- P! (Please read the note on the back first) Please fill in this page again) Order printed by the Ministry of Economic Affairs and the Ministry of Economic Affairs, printed by the Bureau of Work and Consumer Cooperatives 491871 A7 B7 V. Description of the invention (β) 4 Mono-tert-butylbenzyl, adipic acid, diphenylacetic acid, butyl Sodium diacid, or sodium benzoate; polymer compounds, like ionic copolymers (ionomers) ° 12 · Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fiber * asbestos, talc, high-sensitivity clay, Mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and other powders or fibers of natural products, synthetic fibers. 1 3 ♦ Other additives, such as plasticizers, lubricants, emulsifiers , Colorants, flow additives, ® media, flow control agents , Optical brighteners, fire retardants, antistatic agents and blowing agents 〇14 · benzofuranone and indone, for example, described in US-A-4, 3 2 5, 8 6 3; US + 4, 338,244, US-A-5, 175,313; US-A- 5,2 1 6, 0 5 2, US-A-5, 252,643, DE + 4, 316,611; DE-A- 4, 3 1 6, 6 2 2; DE-A- 4, 3 1 6, 8 7 6; EP-A-0,589,839 or EP-A-0,591,102 or 3 — [4-one (2-ethoxyethoxyethoxy) Phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- 3- [4-stearyl-2-ethoxyethoxy ) Phenyl] benzofuran-2-one, 3, -bis [5,7-di-tert-butylbutyl 3-(4-[[2-hydroxyethoxy] phenyl) benzofuran 2- Ketone], 5,7-di-tert-butyl- "3- (4-ethoxyphenyl) benzofuran 2-ketone, 3- (4-ethylacetoxy-3,5-dimethyl Phenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4,4-trimethylacetoxy) -65- paper size China National standard ((, NS) Λ4 specifications (2 丨 0 X 297 mm) (Please read the precautions on the back before filling out this page) Order line 1 Printed by the Military Industry Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ~~ _ ? z__ i, & Description of Invention (&. ) ~ 5 »7-Di-tert-butyl-benzofuran-2-pyrene, 3- (3,4 dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 Ketone, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzylfuran- 2-fluorene. The ratio of the product or the mixture of the present invention to the traditional additives may be, for example, 1: 1. 5 to 1: 5. The product or the mixture of the present invention may also be used as a spike fixative, especially as a light-determining agent, such as for example Some photoreprints and other conventional materials in the field of reprinting techniques are described in Research Disclosure 1990, 31429 (pages 474 to 480). The present invention will be illustrated in more detail by the following examples * All percentages are calculated by K weight unless otherwise specified. In the structure of the following example chemical formula, η # represents the number of repeating units in the molecule and the resulting product is not uniform. The intermediate disclosed in Example 1A is characterized by a number average molecular weight Mη and a polydispersity Mw / Mn. GPC (Gel Permeation Chromatography) was used as the analytical step to separate molecules of different sizes and obtain the average molecular weight (Mw, Mη) and the molecular weight distribution of the polymer. This technique is well known and is described in, for example, "M 0der η Size-Exclusion Liquid Chromatography", edited by WW Yan et al. Et al., J. Wiley & Sons, NY · USA, 1 9 7 9 published, pages 4-8, 249-283 and 3 1 5-340〇-66_ > Paper size Hfl China National Standard ((: NS) Λ4 specification (210X 297 mm) " --------- f (Please read the notes on the back before filling in this page)
、1T 線一 經滴部中央榡牟局另.X消费合作社印^ ^1871 A7 _B7^_ 五、發明説明U| ) 下述實例中的GPC分析是在HPLC儀器中進行, 型號 ®TSP AS-1000,裝置有 ®UV 1 0 0 0UV/VIS 偵測器,波長250nm,所使用的管柱為〃 GPC — S S — 250x7*7mmx3/8〃,® Valco-Microgel-3混合膠。 洗提劑為四氫呋喃(流速:1毫升/分鐘)一光譜分 析用的 ® Uvaso 1 ( ® Mer ck-1 · 0 0 0 1 6 ) + 0 · 02 萁耳 /升的二 乙醇胺(®Fluka 31590)。Ο · 5克的樣品溶解於1 00 毫升的洗提劑中。 注射體積為20α/ 1 ,進行層析時間為15分鐘。 實例1 : Α)下式化合物的製備Once the 1T line is passed by the Central Ministry of Economic Affairs, the Ministry of Education, and printed by X Consumer Cooperatives ^ ^ 1871 A7 _B7 ^ _ V. Description of the Invention U |) The GPC analysis in the following example is performed in an HPLC instrument, Model ® TSP AS-1000 The device has a UV UV 100 UV / VIS detector with a wavelength of 250nm. The column used is 〃 GPC — SS — 250x7 * 7mmx3 / 8〃, Valco-Microgel-3 mixed glue. The eluent was tetrahydrofuran (flow rate: 1 ml / min)-Uvaso 1 (® Mer ck-1 · 0 0 0 1 6) + 0 · 02 dethanol / liter diethanolamine (® Fluka 31590) for spectral analysis . 0 · 5 g of sample was dissolved in 100 ml of eluent. The injection volume was 20α / 1 and the chromatographic time was 15 minutes. Example 1: A) Preparation of a compound of formula
於一含221♦2克(1·2莫耳)氰尿醯氯溶於 1 286克二甲苯的溶液中,在搅拌和氮氣氣氛之下•於 -6 7 - 本紙張尺度適用中國國家標率((、NS ) Λ4規格(210X 297公釐) (請先閲讀背面之注意事項再填寫本頁) -5-¾ 線一 491871 經漓部中次標準局萸工消費合竹社印製 A7 B7五、發明説明(t>) 2小時的時間內加入254 · 8克(1 · 2莫耳)的N — (2,2 · 6,6 —四甲基一 4 一派咱基)一正一 丁基胺 ,在加入時保持溫度約為3 0*0 *可得一濃稠但仍可攬拌 的懸浮液•且再於所示的溫度下維持1 5分鐘。 接著,在2小時內加入一含176 · 3克NaOH 30% (%w/v)水溶液及200克水的混合物,維持 溫度在約3 ο υ,可得一薄懸浮液*且再於該溫度維持 2 ♦ 5小時。 然後*分離出鹼性溶液,且將反應混合物在5 3C至 5 ,於2小時內和攪拌下加入至一含300克水, 355·2 克(0·9 莫耳)Ν,Ν' — 雙(2,2,6 ,6 —四甲基一 4 一锨啶基)一 1 ,6 —己烷二胺和 268 · 3克的Na0H30% (%w/v)水溶液的混 合物中,加入30克的二甲苯,且維持反應混合物在上述 溫度1小時。接著,在1小時内加熱反應混合物至80Ό ,且維持在該溫度再1小時。 在真空下蒸餾出380克的二甲苯(68 — 82口/ 200~120mbar),然後加入170克的二甲苯 及2 0 0克的水,在密封反應器後,Μ氮惰性化,反應溫 度在2小時加熱至1 60Ρ。維持混合物4 1 6 0 下6 小時(5*4bar壓力)。 在冷却至60C後,加入89 · 0克(0 · 69冥耳 )的二一正一丁基胺和86 ·4克的Na0H30% (% -6 8 _ ^紙張尺度適州中國國家標缚((、NS ) Λ4規格(2丨0X 297公釐) (請先閱讀背面之注意事項再填寫本頁) #1 訂 -線 經滴部中央標涞局負工消费合竹私印製 491871 A7 B7 五、發明説明(4 ) w / v )水溶液。 再度密閉反應器,混合物在1小時內加熱至1 6 ο υ ,且維持在此溫度下4小時(5b a r壓力)。 在冷却至6〇υ後,加入1 30克的二甲苯及1 50 克的水,在攪拌下加熱混合物至9 2¾,然後分離出水溶 液0 有機相M400克的水洗濯兩次,過濾(8〇υ)及 在真空下濃縮(125 — 230Ό/350 — lmbar )。冷却時,熔融產物可得到一具有ιη·ρ·(熔點)= 133—137¾的固體產物。 Μη (由GPC=凝膠滲透層析色譜)= 2060克/冥 耳。In a solution containing 221 ♦ 2 grams (1.2 moles) of cyanuric chloride dissolved in 1 286 grams of xylene, under stirring and nitrogen atmosphere. • At -6 7-This paper applies Chinese national standard. ((, NS) Λ4 specifications (210X 297 mm) (Please read the precautions on the back before filling out this page) -5-¾ Line 491871 Printed by Hezhu Co., Ltd. V. Description of the invention (t >) 254 · 8 g (1 · 2 moles) of N-(2, 2 · 6, 6-tetramethyl-4-1-Phenyl)-1-1 D are added within 2 hours. The base amine is kept at a temperature of about 30 * 0 * when added. A thick but still suspension can be obtained. And it is maintained at the indicated temperature for 15 minutes. Then, add one within 2 hours. A mixture containing 176 · 3 grams of NaOH 30% (% w / v) aqueous solution and 200 grams of water, maintaining a temperature of about 3 ο υ, yields a thin suspension * and maintains at that temperature for 2 ♦ 5 hours. Then * The alkaline solution was separated, and the reaction mixture was added to a solution containing 300 g of water, 355.2 g (0.9 mol) N, N '-double (2 , 2, 6 To a mixture of 6-tetramethyl-1, 4-pyridinyl) -1,6-hexanediamine and 268.3 grams of NaOH 30% (% w / v) aqueous solution, 30 grams of xylene was added and the reaction was maintained The mixture was at the above temperature for 1 hour. Next, the reaction mixture was heated to 80 ° C within 1 hour and maintained at this temperature for another 1 hour. 380 g of xylene (68-82 mouths / 200 ~ 120mbar) was distilled off under vacuum, and then Add 170 g of xylene and 200 g of water. After sealing the reactor, the M nitrogen is inert, and the reaction temperature is heated to 1 60 P in 2 hours. Maintain the mixture at 4 1 6 0 for 6 hours (5 * 4 bar pressure) After cooling to 60C, add 89 · 0 g (0.69 gram) of di-n-butylamine and 86.4 g of Na0H30% (%-6 8 _ ^ paper size Shizhou China national standard ((, NS) Λ4 specification (2 丨 0X 297 mm) (Please read the precautions on the back before filling in this page) # 1 Ordering-Consumer Consumption and Printing by Zhuzhu Private Label 491871 A7 B7 V. Description of the invention (4) w / v) aqueous solution. The reactor was closed again, and the mixture was heated to 1 6 ο υ within 1 hour and maintained at this temperature. After 4 hours (5 bar pressure). After cooling to 60o, add 1 30 g of xylene and 150 g of water, heat the mixture to 9 2¾ with stirring, and then separate the aqueous solution 0 organic phase M400 g of Washed with water twice, filtered (80 °) and concentrated under vacuum (125-230 ° F / 350-lmbar). When cooled, the molten product gives a solid product with η · ρ · (melting point) = 133-137¾. Mη (by GPC = gel permeation chromatography) = 2060 g / mol.
Mw/Mn=l · 55 GPC分析顯示如圖1的圖譜。 在所得產物中主要單一成份的比例為: π 7 =1的化合物:η' = 2的化合物=1 ♦ 07 : 1 η 7 =1的化合物:η,= 3的化合物=0 · 81 : 1 n ==1的化合物:η' = 4的化合物=0 · 99 : 1 此四種主要單一成份(n' =1) , (η' =2), (η / = 3 ) ,(11/=4)在此聚分散<產物中的遒共量 為6 0 · Φ凳耳%。 B)下式化合物的製備 -6 9 - 本紙張尺度適用中國國家標洋(〇^)八4規格(210、/ 297公釐) ---------Φ-I (請先閱讀背面之注意事項再填寫本!)Mw / Mn = l · 55 GPC analysis shows the spectrum shown in Figure 1. The proportion of the main single component in the obtained product is: π 7 = 1 compound: η '= 2 compound = 1 ♦ 07: 1 η 7 = 1 compound: η, = 3 compound = 0 · 81: 1 n == 1 compound: η '= 4 compound = 0 · 99: 1 These four main single components (n' = 1), (η '= 2), (η / = 3), (11 / = 4 ) The total amount of fluorene in this polydisperse < product is 60% Φ stool ear%. B) Preparation of the compound of the following formula 6 9-This paper size is applicable to China National Standard Ocean (〇 ^) 8 4 specifications (210, / 297 mm) --------- Φ-I Note on the back then fill out this!)
、1T 線 491871 A7 B7 五、發明説明(叫)1T line 491871 A7 B7 V. Description of invention (called)
(請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)
、1T 經濟部中央標洋局员工消费合作社印粼 一機械攪拌的100毫升4頸燒瓶,將置有4克( 〇·〇16莫耳)的A)產物,0·04克的Mo〇3 , 及32毫升的環己烷。加熱混合物至迴流溫度,且在30 分鐘内加入8·24克(0·064莫耳)的70%叔一 丁基過氧化氫。共沸蒸餾收集水,且持續迴流1小時。反 應混合物轉移至一機械搜拌的玻璃製壓力瓶中,且維持在 1 3 0 C 5小時。冷却反應混合物至7 0卞,過濾出 Μ 〇 0 3 ,漶液M2克的Na2S〇3溶於10毫升水中 之溶液洗濯1小時(60Ό),分離不同相層,有機相以 M g S 0 4乾燥,總共的體積減少至約1 0毫升。溶液溶 -70- 本紙張尺度適用中國國家標净((〕NS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明(β ) 於50毫升的甲酵中(5C),過濾出沈澱物和將其乾燥 ° ! 產量:5 · 5 7克 熔點範圍:129-152^ 1 H NMR:0*85 - 2·4ρργπ (複合混合物) ;3·2 - 3*45ppm(s,寬,NCH2); 3·55 - 3*70ppm(s,寬,N0CH); 4.9 一 5*4ppm(s,寬,NCH)。在 3·2 ppm,3 · 55ppm及4 · 9ppm的質子比例為2 :1 : 1 〇 1 3 c NMR:82ppm (NOC) ; 1 6 5 p p m (三嗪C )。 (請先閱讀背面之注意事項再填寫本頁) 備 製 的 物 合 化 式 下 2 例 實 C V Η 經濟部中夾標準局賀工消費合作社印製1T mechanically stirred 100 ml 4-necked flasks of Yin Tiaoyi, a consumer cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs, will be filled with 4 g (0.016 mol) of A) product and 0.04 g of MoO3, And 32 ml of cyclohexane. The mixture was heated to reflux temperature, and 8.24 g (0.064 mol) of 70% tert-butyl hydrogen peroxide was added over 30 minutes. Water was collected by azeotropic distillation and refluxed for 1 hour. The reaction mixture was transferred to a mechanically searched glass pressure bottle and maintained at 130 C for 5 hours. The reaction mixture was cooled to 70 ° F, and M03 was filtered. The solution of M2g of Na2S03 in 10 ml of water was washed for 1 hour (60 ° C), the different phases were separated, and the organic phase was separated by MgS 0 4 Dry and reduce the total volume to approximately 10 ml. Solution-70- This paper size applies to Chinese National Standard (() NS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention (β) in 50 ml of formazan (5C), filter out the precipitate And drying it °! Yield: 5 · 5 7 g Melting point range: 129-152 ^ 1 H NMR: 0 * 85-2 · 4ρργπ (composite mixture); 3 · 2-3 * 45ppm (s, broad, NCH2 ); 3.55-3 * 70ppm (s, width, NOCH); 4.9-5 * 4ppm (s, width, NCH). The ratio of protons at 3 · 2 ppm, 3 · 55ppm and 4 · 9ppm is 2: 1 : 1 〇 1 3 c NMR: 82 ppm (NOC); 16 5 ppm (triazine C). (Please read the precautions on the back before filling this page) Prepared CV 2 2 examples of CV Η Economy Printed by the Ministry of Standards and Industry Bureau He Gong Consumer Cooperative
Hn cHn c
n H 8 〇——c 本紙張尺度適用中國國家標率(CNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明(味) 經濟部中央標準局貞工消费合作社印絜 一機械攪拌的1 00毫升4頸燒瓶,將置有4克( 〇·〇16莫耳)的A)產物,0,04克的Mo〇3 , 及3 2毫升的正一辛烷。加熱混合物至迴流溫度,且在 30分鐘内加入10 · 3克(0 · 08莫耳)的70%叔 一 丁基過氧化氫。共沸蒸餾收集水*且持鑛迴流6小時。 過漶出Mo〇3 *滅液K2克的Na2S〇3溶於10毫 升水中之溶液洗灌30分鐘(60^) *分離不同相層, 有機相Ml 0毫升飽和NaC 1溶液洗濯,及Κ Mg S〇4乾燥,然後蒸發總共的體積減少至約1 0毫升 。溶液溶於50毫升的甲醇中(5¾) *在真空下(55 υ)乾燥沈澱物(軟玻璃體),接著Κ研磨機粉碎,然後 再於真空下乾燥。 產量:5 · 5 3克 熔點範圍:96 — 118¾ 1 H NMR:0.85 - 2·4ρργπ' (複合混合物) ;3·15 - 3*55ppm(s,寬,NCHz); 3·65 - 3.9ppm(s,寬,NOCH); 4·9 一 5.4ppm(s,寬,NCH)。在 3· 15 -72- >、紙張尺度適用中國國家標_ ( (、NS ) Λ4規格(21〇X297公釐) ---------? (請先閲讀背面之注意事項再填寫本頁)n H 8 〇——c This paper size is applicable to China National Standards (CNS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention (taste) Printed by a mechanical stirrer of Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs In a 100 ml 4-necked flask, 4 g (0.016 mol) of the A) product, 0,04 g of MoO 3, and 32 ml of n-octane were placed. The mixture was heated to reflux temperature and 10 · 3 g (0.08 mol) of 70% tert-butyl hydrogen peroxide was added over 30 minutes. Water was collected azeotropically and held under reflux for 6 hours. Wash out Mo〇3 * Solution of K2 g of Na2SO3 dissolved in 10 ml of water and rinse for 30 minutes (60 ^) * Separate the different phases, wash the organic phase with 10 ml of saturated NaC 1 solution, and K Mg S04 was dried and then evaporated to reduce the total volume to about 10 ml. The solution was dissolved in 50 ml of methanol (5¾) * The precipitate (soft glass body) was dried under vacuum (55 υ), then pulverized by a K-mill, and then dried under vacuum. Yield: 5 · 5 3 g Melting point range: 96 — 118¾ 1 H NMR: 0.85-2 · 4ρργπ '(composite mixture); 3.15-3 * 55ppm (s, broad, NCHz); 3.65-3.9ppm ( s, width, NOCH); 4.9 to 5.4 ppm (s, width, NCH). At 3 · 15 -72- >, the paper size applies the Chinese national standard _ ((, NS) Λ4 specification (21 × 297 mm) ---------? (Please read the precautions on the back before (Fill in this page)
、1T -線一 491871 五 _I___ 經滴部中央標準局Μ工消费合作社印製 A7 B7 發明説明(叫) ppm,3 · 65ppm及4 · 9ppm的質子比例為 2:1:1。 13 C NMR:78 - 84ppm (NOC, C8 Hi 7異構物混合物);165ppm (三嗪C)。 實例I :對聚丙烯纖維的光穗定作用 2 · 5克表1的穩定劑,1克三(2,4 一二一叔一 丁基苯基)亞磷酸酯,1克的單乙基3 * 5 —二一叔一丁 基一 4 一羥基苄基一膦酸鈣,1克的硬脂酸鈣及2 · 5克 的二氧化鈦在一慢混合器中和1 000克的聚丙烯粉末( 具有熔融指數=1 2克/1 0分鐘,在2 30 °C和 2 · 1 6公斤下測量)混合。 在200 — 23〇υ下擠出混合物•可得聚合物顆料 ,然後使用導引型式裝置(Pilot-type)將其轉化為纖維 (® 1 eonard-Sumirago (VA), Italy),且在下列條件下 操作: 擠出溫度: 230 — 245*0, 1T-line one 491871 five _I___ Printed by the Central Standards Bureau of the Ministry of Industry and Technology Co., Ltd. A7 B7 Invention description (called) ppm, the proton ratio of 3 · 65ppm and 4 · 9ppm is 2: 1: 1. 13 C NMR: 78-84 ppm (NOC, C8 Hi 7 isomer mixture); 165 ppm (triazine C). Example I: Light spike effect on polypropylene fibers 2.5 g of stabilizer of Table 1, 1 g of tris (2,4 t-butyl-butylphenyl) phosphite, 1 g of monoethyl 3 * 5-Di-tert-butyl-1, 4-hydroxybenzyl monophosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide in a slow mixer and 1 000 g of polypropylene powder (with Melt index = 12 g / 10 minutes, measured at 2 30 ° C and 2 · 16 kg) mixing. Extrude the mixture at 200 — 23 〇 • Polymer pellets can be obtained, which are then converted into fibers using a pilot-type device (® 1 eonard-Sumirago (VA), Italy), and the following Operating under conditions: Extrusion temperature: 230 — 245 * 0
擠出頭溫度: 255—260C 拉伸比例: 1 : 3 · 5 線性密度: 1 1丹/絲 、 Κ此方法製得的纖維在固定在一白板上後,於一 6 5 WR Weather-O-Meter (ASTM D 2 5 6 5 - 8 5 )中曝曬,黑板溫度 為 6 3 υ。 -73- 本紙張尺度適用中國國家標肀(CNS〉Λ4規格(210X297公釐) ---------I (請先閱讀背面之注意事項再填寫本頁) 訂 線 491871 經滴部中夾標準局貞工消费合作社印來 A7 B7 五、發明説明(0 ) 樣品經過各種時間的曝光後,使用定速張力計測量殘 留韌度,然後計算曝瞩至起先韌度一半(τ5 0 )所需時 間。 表 1 : 毽定劑 Τ 5 〇 (小時) 實例1Α化合物 2 7 4 0 表1的化合物顯示在聚丙烯纖維中良好的光穩定性。 實例I I :對於聚丙烯膠帶的光穗定作用 1克表2的每一個化合物,1克三(2,4 一二一叔 一丁基苯基)亞磷酸酯,0 · 5克的季戊四醇四〔3 — ( 3,5 —二一叔一 丁基一 4 一羥基苯基)丙酸酯〕及1克 的硬脂酸鈣和1 000克的聚丙烯粉末(具有熔融指數 2 · 1 (在23 0°C和2 · 16公斤下測量)在一加速混 合器中混合。 混合物在200 - 220它擠出成聚合物顆粒,接著 使用半工業級型式的裝置將其延伸製成5 0 厚及 2 . 5 m m 寬的膠帶(® L e ο n a r d - S u ία i r a g 〇 ( V A) - 11 a 1 y) ,且在下述條件下操作: vExtrusion head temperature: 255-260C Stretching ratio: 1: 3 · 5 Linear density: 1 1 denier / filament, K The fiber prepared by this method was fixed on a white board, and then the temperature was 6-5 WR Weather-O- Meter (ASTM D 2 5 6 5-8 5), blackboard temperature is 6 3 υ. -73- This paper size applies to Chinese national standard (CNS> Λ4 size (210X297 mm) --------- I (Please read the precautions on the back before filling this page). Thread 491871 Printed by A7 B7, Zhengong Consumer Cooperative of Zhongjia Standard Bureau. 5. Description of the invention (0) After the sample has been exposed for various times, use a constant speed tensiometer to measure the residual toughness, and then calculate the exposure to half of the initial toughness (τ50) The time required. Table 1: T5 O (hour) stabilizer Example 1A compound 2 7 4 0 The compound of Table 1 shows good light stability in polypropylene fibers. Example II: Photo spike determination for polypropylene tape 1 g of each of the compounds in Table 2, 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 0.5 g of pentaerythritol tetra [3-(3,5 -di-tert-one Butyl-1, 4-hydroxyphenyl) propionate] and 1 g of calcium stearate and 1 000 g of polypropylene powder (with a melt index of 2 · 1 (measured at 23 0 ° C and 2 · 16 kg) Mix in an accelerated mixer. The mixture is extruded into polymer granules at 200-220 and then used in semi-industrial Type device which extends made 50 thick and 2 5 m m wide tape (® L e ο n a r d - S u ία i r a g billion (V A) - 11 a 1 y), and is operated under the following conditions:. V
擠出溫度: 210 — 230D 擠出頭溫度: 240-260^ 拉伸比例: 1:6 -74- 本紙張尺度適用中國國家標枣((、NS ) Λ4規格(210X 297公釐) --------- (請先閲讀背面之注意事項再填寫本頁)Extrusion temperature: 210 — 230D Extrusion head temperature: 240-260 ^ Stretching ratio: 1: 6 -74- This paper size applies to Chinese national standard date ((, NS) Λ4 specification (210X 297 mm) --- ------ (Please read the notes on the back before filling this page)
,1T 線 M71 A7 B7 五、 發明説明(Μ ) Μ此方法製得的膠帶在固定在一白板上後,於一65 WR Weather-O-Meter (ASTM D 2 5 6 5 -85)中曝曬,黑板溫度 為 6 3 t 0 樣品經過各種時間的曝光後,使用定速張力計測量殘 留韌度,然後計算曝曬至起先韌度一半(Τ5 〇 )所需時 間。 表 锩定劑 實例1 A化合物 2 T 5 〇 (小時) >19 9 0 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貞工消费合作社印繁 表2中所列的化合物對於聚丙烯膠帶顯示有良好的光 穗定性。 實例I I I ··顔料在聚丙烯測試板中的交互作用 5 · 625克表3之穩定劑,1 3 · 500克Pigment Blue 15 ”Flush" ( 5 0 %混合於聚乙烯中)和 25 · 875克的聚丙烯粉末(具有熔融指數約14,在 2301和2 · 16公斤測量)加入至一® Haake內混合器 中(室溫)(Haake Buchler Rheochord System 40,使用 600〇3塊具有歪輪刀的111^〇1^\61〇^歪輪刀的旋轉速 度為5 RPM (轉/分鐘),使用一5公斤的唧子封住 碗口處,溫度上升至1 8〇υ,及維持在1 80Ό。總共 時間為3 0分鐘。 -75- 本紙浪尺度適用中國國家標冷(rNS ) Λ4規格(210X 297公釐) 491871 A7 B7 五、發明説明() 混合物在1 8 Ο Ό下3 0分鐘後移出,冷却至室溫, 所得混合物"稱作濃縮物'需再使用。 Ο·900克的此濃縮物》3·600克的二氧化鈦 "Flush" (50%混合物/聚乙烯),及40· 500克 的聚丙烯粉末(具有熔融指數約1 4,在2 3 0 C和 2· 16公斤下測量)加至一® Η AAKE混合碗狀容器中,溫 度為1 60¾,歪輪刀再K20RPM旋轉,使用一 5公 斤的唧子封住碗口處,溫度上升至1 7〇υ,RPM上升 至125。總共時間為30分鐘。 熔融混合物在1 70C移出*轉移至一手操作工具中 (室溫)及形成一1毫米x25毫米直徑的圓測試板,如 此所得混合物稱成〃降低物(letdown) 〃,而此測試板稱 作〃降低物測試板〃。 經濟部中央標率局負工消费合作社印製 (請先閱讀背面之注意事項再填寫本頁) 色澤差異,測量包含表3穩定劑樣品降低(letdown )測試板和不含毽定劑控制降低(letdown)測試板之 delta E (CIE 色澤差異等式),此測量是使用App 1 i ed Color Systems Spectrophotometer Model CS-5 (USA)進 行,測量參數是400 - 700nm —掃描,小區域檢視 ,反應,螢光D65,10度觀察。 上述方法條件是模擬顔料和穩定劑政縮物(母體)的 製造和接下來的降低(let-down)(稀釋)至最終塑膠物品 中的過程。 愈高的delta E值代表顔料聚集及不良的分散。delta -76- 本紙張尺度適用中國國家標卒(CNS ) Λ4規格(210X 297公釐) 經消部中夾標準局爲工消费合作社印製 491871 A7 ________B7___ 五、發明説明(7丨) E值0 · 5或更少不能由眼睛看出差異。 ; 表 3 : 穩定劑 Delta £ 實例1A的化合物 0·8 實例I V : 染色的熱塑性烯烴(ΤΡΟ)顆粒由混合聚烯烴混合 物(含乙烯一丙烯共聚物之聚丙烯;® p〇1ytr〇pe τρρ1T line M71 A7 B7 V. Description of the invention (Μ) Μ The tape prepared by this method is fixed on a white board and exposed to a 65 WR Weather-O-Meter (ASTM D 2 5 6 5 -85). The blackboard temperature is 6 3 t 0 After the sample has been exposed for various times, the residual toughness is measured using a constant speed tensiometer, and then the time required for exposure to half the initial toughness (T50) is calculated. Example of Scheduler 1 A Compound 2 T 5 0 (hours) > 19 9 0 (Please read the notes on the back before filling out this page) Printed in Table 2 by Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs The compound showed good light spike characterization for polypropylene tapes. Example III. Interaction of pigments in polypropylene test boards 5. 625 grams of stabilizers from Table 3, 1 500 grams Pigment Blue 15 "Flush " (50% mixed in polyethylene) and 25.875 grams Polypropylene powder (having a melt index of approximately 14, measured at 2301 and 2.16 kg) was added to a Haake internal mixer (room temperature) (Haake Buchler Rheochord System 40, using 6000 pieces of The rotation speed of 111 ^ 〇1 ^ \ 61〇 ^ is 5 RPM (revolutions per minute). A 5 kg ladle is used to seal the bowl mouth. The temperature rises to 180 and maintains it at 180 °. The total time is 30 minutes. -75- This paper wave scale is applicable to the Chinese National Standard Cold (rNS) Λ4 specification (210X 297 mm) 491871 A7 B7 V. Description of the invention () The mixture is 30 minutes under 1 8 〇 Remove and cool to room temperature. The resulting mixture "referred to as a concentrate" needs to be reused. 0 · 900 g of this concentrate "3.600 g of titanium dioxide" Flush "(50% mixture / polyethylene), and 40 500 grams of polypropylene powder (having a melt index of about 14 at 2 3 0 C and 2.16 kg Amount) was added to a Η AKE AAKE mixing bowl-shaped container, the temperature was 1 60 ¾, the twisted-knife was rotated by K20RPM, and a 5 kg ladle was used to seal the bowl mouth. The temperature rose to 170 and the RPM rose to 125. The total time is 30 minutes. The molten mixture is removed at 1 70C * and transferred to a hand-operated tool (room temperature) and a circular test plate of 1 mm x 25 mm diameter is formed. The resulting mixture is called 〃letdown〃 This test board is called 〃Lowering Material Test Board 印. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). (Letdown) test panel and delta E (CIE color difference equation) without halting agent control test panel. This measurement was performed using App 1 i ed Color Systems Spectrophotometer Model CS-5 (USA). The parameters are 400-700nm-scanning, small area inspection, reaction, fluorescent D65, 10-degree observation. The above method conditions are to simulate the manufacture of pigments and stabilizers (precursors) and subsequent reduction (let-down) ) (Dilution) to the final plastic article. Higher delta E values represent pigment aggregation and poor dispersion. delta -76- This paper size applies to the Chinese National Standards (CNS) Λ4 specification (210X 297 mm) The Bureau of Standards and Standards of the Ministry of Economic Affairs printed 491871 A7 ________B7___ 5. Description of the invention (7 丨) E value 0 5 or less can not see the difference by the eyes. Table 3: Stabilizer Delta £ Compound of Example 1A 0 · 8 Example IV: Dyeing thermoplastic olefin (TPO) particles from a mixed polyolefin mixture (polypropylene containing ethylene-propylene copolymer; ® p〇1ytr〇pe τρρ
518-01,由® A. SchuliBan,I nc · ; Akron,Ohio,US A生產 )和下表所列的添加劑在裝置有全一目的輥的® Superior/MPM 1"單輥擠出器(24 : 1 L/D)中,K 溫度2 ο ου混合,然後在水浴中冷却。在擠出和成型前 ,添加劑是在一滾動乾燥器中乾燥混合。 添加劑: 0.25 % *)的@110(1 3Β (紅色色素Π7,色澤指數65300), 〇·〇5 X *)的季戊四醇四[3-(3,5-二-叔-丁基-4-羥基苯基) 丙酸酯] 〇.〇5%*)的三[2,4-二-叔-丁基苯基]亞磷酸酯, 〇.235*)的2-(2,-羥基-3,,5’-二-叔-戊基苯基)苯並三唑 0·23ί *)的雙(卜辛氧基-2,2,6,6-四甲基」4-哌啶基)癸二酸 酯 〇 · 1 % * )的硬脂酸鈣, 約10Χ *)的滑石,及 -77- 本紙張尺度適用中國國家標率(CNS ) Λ4規格(210Χ 297公釐) ~ ---------0-1 (請先閲讀背面之注意事項再填寫本頁} 訂 線一 491871 A7 _B7_ 五、發明説明(>) 〇 ·2Χ *)的實例V-1或V-2化合物 *)依據聚烯烴混合物的重量百分比 结果粒狀物在約1 9 OC下於®BOY 30 Μ射出成型機中 楔製成1 · 524mm厚,2〃 χ2〃的測試板。 測試板固定在一金屬框上且在一 ® Atlas Ci65 Xenon Arc Weather-O-meter 中 M黑板溫度 7 0*0,Ο · 55 瓦/ 公尺2 ,340nm,50%相對溼度,間欺性的Μ光亮 /黑暗週期及漉水曝曬(® Society of Automotive Engineers -SAE J 1960 Test Procedure-Exterior Automotive conditions) 〇 測試板在大約6 2 5仟耳間隔,在Applied Color Systems光譜計上依據A S TM D2 244 — 7 9反射模 式測量色澤變化。光澤度是依據ASTM D 523在 ® BYK-GARDNER Haze/Gloss Meter計中0° 測量。 經穩定的樣品在U V光曝曬下顯示良好的光澤持久性 ,及良好的色澤變化阻抗性。 (請先閲讀背面之注意事項再填寫本頁) ^wi.518-01, manufactured by ® A. SchuliBan, I nc ;; Akron, Ohio, US A) and the additives listed in the table below are equipped with a one-size roll of Superior® / MPM 1 " single-roll extruder (24 : 1 L / D), K temperature 2 ο ου mixed, and then cooled in a water bath. Before extrusion and molding, the additives are dry-mixed in a tumble dryer. Additive: 0.25% *) @ 110 (1 3Β (red pigment Π7, color index 65300), 0.005 X *) of pentaerythritol tetra [3- (3,5-di-tert-butyl-4-hydroxyl Phenyl) propionate] 0.05% *) tris [2,4-di-tert-butylphenyl] phosphite, 0.235 *) 2- (2, -hydroxy-3, , 5'-di-tert-pentylphenyl) benzotriazole 0.23ί *) bis (buthyloxy-2,2,6,6-tetramethyl "4-piperidinyl) decane Acid ester 0.1% *) calcium stearate, about 10 × *) talc, and -77- This paper size applies to China National Standard (CNS) Λ4 specification (210 × 297 mm) ~ ----- ---- 0-1 (Please read the precautions on the back before filling this page} Order 1491871 A7 _B7_ V. Description of the invention (>) 〇 2 × *) Examples of V-1 or V-2 compounds * ) According to the weight percentage of the polyolefin mixture, the pellets were wedged in a BOY 30 M injection molding machine at about 19 OC to make a 1. 524 mm thick, 2〃 × 2〃 test plate. The test board is fixed on a metal frame and in a ® Atlas Ci65 Xenon Arc Weather-O-meter M blackboard temperature 7 0 * 0, 0 · 55 W / m 2, 340nm, 50% relative humidity, insidious Μ Light / Dark Cycle and Water Exposure (® Society of Automotive Engineers-SAE J 1960 Test Procedure-Exterior Automotive conditions) 〇 The test board is at approximately 6 2 5 仟 intervals on an Applied Color Systems spectrometer according to AS TM D2 244 — 7 9 Reflection mode measures color change. Gloss is measured at 0 ° in ® BYK-GARDNER Haze / Gloss Meter according to ASTM D 523. The stabilized samples showed good gloss durability under UV light exposure, and good resistance to color change. (Please read the notes on the back before filling this page) ^ wi.
、1T 線 經滴部中失標準局負工消费合作社印製 -78- 本紙張尺度用中國國家標冷((、NS ) Λ4規格(210 X 297公釐) 491871Line 1T Printed by the Consumers' Cooperative of the Ministry of Standards and Loss Standards Bureau -78- This paper size is in accordance with China National Standard Cold ((, NS) Λ4 specifications (210 X 297 mm) 491871
補充說明 圖1爲實例Ι-a產物的GPC分析圖譜Supplementary explanation Figure 1 is the GPC analysis spectrum of the product of Example Ⅰ-a
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