TW574231B - Block copolymer resin - Google Patents
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- TW574231B TW574231B TW91124568A TW91124568A TW574231B TW 574231 B TW574231 B TW 574231B TW 91124568 A TW91124568 A TW 91124568A TW 91124568 A TW91124568 A TW 91124568A TW 574231 B TW574231 B TW 574231B
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574231 A7 B7 五、發明說明C 1 【發明領域】 本發明是關於一種線性共軛二烯系/乙烯基芳香族系欲 段共聚物樹脂，特別是指具有透明性、耐衝擊強度、剛性等 物性平衡，並且具有耐折性佳，以及樹脂成型品時無龜裂現 象之嵌段共聚物樹脂。 【習知技藝說明】 共軛二烯系/乙烯基芳香族系嵌段共聚物樹脂是一種才 廣泛運用的熱可塑性聚合物樹脂，由於其透明性及耐衝擊5 度佳，因此，經常被運用在飲料容器、衣架、玩具等物品^ 型上。此類共聚物樹脂的製法已有很多專利提及，例如： USP4,080,407、4,403,074、4,704,435 等，但在先前專利中 其剛性、耐衝擊強度的平衡上、耐折性及成型應力龜裂等米 性上，仍無法令人完全的滿意。雖然某些專利揭示，可能^ 備良好的剛性及耐衝擊強度，但樹脂的耐折性卻不佳；相肩 而言當樹脂之耐折性佳時，其剛性及耐衝擊強度就無法痛 足’尤其是由某些已知製法製得之嵌段共聚物樹脂在射出成 型時，其成型品容易產生龜裂，特別是厚肉成型品的情況更 為嚴重。因此，使後段共聚物樹腊具備良好的透明度、剛性、 2擊強度等物性平衡，同時在耐折性及射出成型品不會產 腊發進為之共:題二烯系/乙婦基芳香族系嵌段共聚物樹 【發明概要】 本發明之目的是在提供_插4也 而…社.以仏種機械性質良好、透明性佳 耐折性佳，且射出成型品不會產 座生、通微龜裂之嵌段共聚物574231 A7 B7 V. Description of the invention C 1 [Field of the invention] The present invention relates to a linear conjugated diene / vinyl aromatic copolymer, especially refers to its properties such as transparency, impact strength, rigidity, etc. A block copolymer resin that is balanced and has good folding resistance and no cracking when molding resin. [Know-how Description] Conjugated diene / vinyl aromatic block copolymer resin is a widely used thermoplastic polymer resin. Because of its transparency and impact resistance of 5 degrees, it is often used. On beverage containers, hangers, toys, etc. There are many patents mentioned for the preparation of such copolymer resins, such as: USP4,080,407, 4,403,074, 4,704,435, etc., but in the previous patents, the balance of rigidity, impact strength, folding resistance and molding stress cracking, etc. Sexually, it is still not completely satisfactory. Although some patents disclose that it may have good rigidity and impact strength, the folding resistance of the resin is not good. In contrast, when the folding resistance of the resin is good, its rigidity and impact resistance cannot be enough. 'Especially, when the block copolymer resin obtained by some known manufacturing methods is injection molded, the molded product is prone to cracking, especially the thick meat molded product is more serious. Therefore, make the copolymer wax of the later stage have good transparency, rigidity, and two-strength strength, and balance the physical properties. At the same time, the folding resistance and injection molding products will not produce wax. Family block copolymer tree [Summary of the invention] The purpose of the present invention is to provide _insert 4 and so on. The company has a good mechanical properties, good transparency, good folding resistance, and injection molding products will not produce seat. Micro-cracked block copolymer
574231 A7 B7 五、發明說明 脂。 (2 )574231 A7 B7 V. Description of the invention Fat. (2 )
本發明之嵌段共聚物樹脂，係由至少兩個乙烯基芳香族 聚合物嵌段，以及至少一個共軛二烯系聚合物嵌段所組成， 上述嵌段共聚物樹脂並具有下列特徵··The block copolymer resin of the present invention is composed of at least two vinyl aromatic polymer blocks and at least one conjugated diene polymer block. The above block copolymer resin has the following characteristics ...
(1) 為線性排列結構，並選自下列線性結構式： A1-B1-A2-B2-A3 A1-B1-A2-B2-A3-R A1- B 1 ·Α2-Β2-Α3-Β3-Α4 其中，Al、A2、A3、A4係以乙烯基芳香族單體為 主成份的聚合物嵌段；而B1、B2、B3係以共輪二婦系 單體為主成份的聚合物嵌段，R為乙烯基芳香族單體及 共軛二烯系單體所形成的聚合物嵌段，且R中之共輕一 烯系單體的含量大於A3之共軛二烯系單體的含量； (2) 嵌段共聚物樹脂中乙烯基芳香族單體含量與共軛二烯 (3) 嵌段共聚物樹脂之分子量分佈為雙峰分佈，其中，爭俨 共聚物樹脂的雙峰含量比值為55〜85重量％/45〜15重^ %，且其中一波峰之峰值（peak)的分子量介= 120,000〜200,000，另一波峰之峰值的分子量介於 50,000〜90,000 ; ' ⑷散段共聚物_巾之乙稀基芳香族聚合物嵌段之 量分佈至少呈三峰分佈。 77 【較佳實施例之詳細說明】 本發明之嵌段共聚物樹脂為線性排歹"“冓，其結構式是 ί紙張尺度適用中國國家標準（CNS) A4規格（210x ~ ------- 莖4百 574231 五、發明說明（3 ) 選自下列其中一種： A1-B1-A2-B2-A3(1) is a linear arrangement structure and is selected from the following linear structural formulas: A1-B1-A2-B2-A3 A1-B1-A2-B2-A3-R A1- B 1 · Α2-Β2-Α3-Β3-Α4 Among them, Al, A2, A3, and A4 are polymer blocks containing vinyl aromatic monomers as the main component; and B1, B2, and B3 are polymer blocks containing co-rotating dimer monomers as the main component. R is a polymer block formed by a vinyl aromatic monomer and a conjugated diene-based monomer, and the content of the co-light monoene-based monomer in R is greater than the content of the conjugated diene-based monomer of A3; (2) The content of the vinyl aromatic monomer in the block copolymer resin and the conjugated diene (3) The molecular weight distribution of the block copolymer resin is a bimodal distribution, where the ratio of the bimodal content of the copolymer resin is contested 55 to 85% by weight / 45 to 15% by weight, and the molecular weight of the peak of one of the peaks is between 120,000 and 200,000, and the molecular weight of the other peak is between 50,000 and 90,000; The amount distribution of the ethylenic aromatic polymer blocks of the towel is at least a trimodal distribution. 77 [Detailed description of the preferred embodiment] The block copolymer resin of the present invention is a linear arrangement "", its structural formula is ί paper size applicable to Chinese National Standard (CNS) A4 specifications (210x ~ ---- --- Stem 410574231 V. Description of the invention (3) is selected from one of the following: A1-B1-A2-B2-A3
A1-B1-A2-B2-A3-R A1-B1.A2-B2-A3.B3.A4 /、中 Al、A2、A3、A4 係以 μ ㈣ f 份的聚合物嵌段……，係以共口：主成 體所形成的聚合物嵌段，且尺中 ：-席系早 ^视一烯系早體的含詈女 ;A3之共軛二烯系單體的含量。上述 Γ、膝耸#妥A 、 4甘入1又共t物樹脂中的 土方香方矢成份係為均-分佈或呈乙婦 增或漸減式的分佈。 货族成伤漸 本發明嵌段共聚物樹脂中乙烯基芳香族單體含量與共 軛二烯系單體含量的比值=65〜95重量％/35〜5重量％，較2 為=5〜90重量％/35〜1〇重量。/〇,更佳為7〇〜8〇重量％/3〇乂〜2〇 重夏❶。當乙烯基芳香族單體含量低於65重量％時，嵌段共 聚物樹脂之剛性差、落錘衝擊強度差、透明度亦不佳。若2 於95重量％，則樹脂之耐衝擊強度與耐折性皆差。 本發明嵌段共聚物樹脂之分子量構造較佳係線性分子 的結構，此對樹脂之流動性、剛性及耐折性之物性平衡上有 良好的效果。本發明嵌段共聚物樹脂之乙烯基芳香族單體具 體例如·苯乙烯、鄰-甲基苯乙稀（〇_methyl styrene)、對-甲 基苯乙烯（p-methyl styrene)、對-第三丁基苯乙烯（p-tert butyl styrene)、ι，3_二丁基苯乙烯（1，3-di-butyl styrene)、甲基 苯乙烯（a -methyl styrene)、乙基苯乙烯、2,4-二曱基苯乙 本紙張尺度適用中國國家標準（CNS) Α4規格（210χ 297公釐） 第5頁 574231 五、發明說明（4 ) 烯、甲基-對-甲基苯乙烯、溪-苯乙烯，上述乙烯基芳 族單體可單獨使用或數種合併使用。 土方 本發明嵌段共聚物樹脂之共軛二烯系單體乃例如· 1 丁二烯、2-甲基-1，3-丁二烯、2,3_雙-甲基十％ 丁二烯、 戊二烯' 1，3-己二烯等，上述化合物可單獨使用一種或兩種 以上混合使用，其中又以丁二烯或2_甲基 較佳。 馬 本發明之嵌段共聚物樹脂的分子量分佈為雙峰分佈，且 其雙峰的含量比值（即高波峰峰值/低波峰峰值）為55〜㈠重量 %/45〜15重置％，在分子量的分佈上，低波峰峰值的分子量 介於50,000〜90,000，而高波峰峰值的分子量介於 120曰，000〜200,000。當本發明雙峰含量比值大於85重量 重量％時，共聚物樹脂之衝擊強度差，耐折性亦差。而當高 低雙峰的含量比值小於55重量％/45重量％時，樹脂之：： 性及f曲彈性率之物性平衡變差。又本發明嵌段共聚物的樹 脂之分子量分佈中，雙峰的峰值之分子量不在前述範圍内 時’則無法達成本發明之目的，即良好之透明性、耐衝 Η性(彎曲彈性率)等物性平衡，並且具有耐折性佳，樹 脂成型時無龜裂現象等優點。 由本發明中銳意研究得去口，就本發明特定構成之嵌段共 聚物樹月曰之物性而言’本發明之嵌段共聚物樹脂以分子量呈 雙峰分佈者為較佳’亦即可得到衝擊強度、剛性之較佳物性 、"：同寺可知到具有較佳耐折性的嵌段共聚物樹脂。當樹 脂之分子量分佈為單峰分佈、三峰分佈或三峰以上的分佈A1-B1-A2-B2-A3-R A1-B1.A2-B2-A3.B3.A4 /, Medium Al, A2, A3, A4 are polymer blocks of μ ㈣ f parts ... Co-portion: the polymer block formed by the main body, and in the ruler:-the content of the conjugated diene-based monomer of the stern-early-prene-early-early body; A3. The above-mentioned components of the earth fragrant herbs in the Γ, knee tower #Tou A, 4 and 1 are co-distributed or have an increasing or decreasing distribution. The ratio of the content of the vinyl aromatic monomer to the content of the conjugated diene monomer in the block copolymer resin of the present invention is 65 to 95% by weight / 35 to 5% by weight. 90% by weight / 35 to 10% by weight. / 〇, more preferably 70-80% by weight / 30-200% by weight. When the vinyl aromatic monomer content is less than 65% by weight, the block copolymer resin has poor rigidity, poor drop impact strength, and poor transparency. If it is 2 to 95% by weight, both the impact strength and folding resistance of the resin are poor. The molecular weight structure of the block copolymer resin of the present invention is preferably a linear molecular structure, which has a good effect on the physical balance of the fluidity, rigidity and folding resistance of the resin. Specific examples of the vinyl aromatic monomer of the block copolymer resin of the present invention include styrene, o-methyl styrene, p-methyl styrene, and p-methyl styrene. Tri-butyl styrene (p-tert butyl styrene), ι, 3-di-butyl styrene (1,3-di-butyl styrene), methyl styrene (a-methyl styrene), ethyl styrene, 2 , 4-Difluorenylbenzene ethyl paper This paper is in accordance with Chinese National Standard (CNS) A4 specification (210 x 297 mm) Page 5 574231 5. Description of the invention (4) olefin, methyl-p-methylstyrene, brook -Styrene, the above-mentioned vinyl aromatic monomers can be used alone or in combination. The conjugated diene monomers of the block copolymer resin of the present invention are, for example, 1 butadiene, 2-methyl-1,3-butadiene, 2,3-bis-methyl ten% butadiene , Pentadiene '1,3-hexadiene, etc., the above-mentioned compounds can be used alone or in combination of two or more, of which butadiene or 2-methyl is preferred. The molecular weight distribution of the block copolymer resin of the present invention is a bimodal distribution, and the content ratio of the bimodal content (that is, the high peak value / low peak value) is 55 ~ ㈠wt% / 45 ~ 15 reset%. In the distribution, the molecular weight of the low peak value is between 50,000 and 90,000, and the molecular weight of the high peak value is between 120 and 200,000. When the bimodal content ratio of the present invention is more than 85 wt%, the impact strength of the copolymer resin is poor, and the folding resistance is also poor. And when the content ratio of the high and low peaks is less than 55% by weight / 45% by weight, the physical properties of the resin: properties and f-curvature elasticity become poor. In the molecular weight distribution of the resin of the block copolymer of the present invention, when the molecular weight of the peak of the doublet is not within the foregoing range, the object of the present invention cannot be achieved, that is, good transparency, impact resistance (bending elasticity), etc. Balanced physical properties, good folding resistance, no cracking during resin molding, etc. From the intensive research in the present invention, as far as the physical properties of the block copolymer tree of the specific composition of the present invention are concerned, 'the block copolymer resin of the present invention preferably has a bimodal distribution of molecular weight' can be obtained. Better physical properties of impact strength and rigidity: "Tongsi knows a block copolymer resin with better folding resistance. When the molecular weight distribution of resin is unimodal, trimodal, or higher
574231 五、發明說明（5 ) 夺，…法達到本發明之目L :分子量採用單峰分佈時， 樹脂之耐衝擊強度差，耐折性亦差，而樹脂之分子量分佈為 二峰時，彎曲強度及彎曲彈性率變差。 上述嵌段共聚物樹脂之分子量分佈的測定方式係由 、c測$而付。檢I線以一般市售標準之苯乙烯聚合物作 成Μ月曰之刀子里分佈中分子量雙峰分佈之含量比值乃以 纟之面積比求知’雙峰相重疊的地方以雙峰相連接的 中間為最低點區分計算而得。 “本發明嵌段共聚物樹脂中最大之乙稀基芳香族聚合物 :欠段佔嵌段共聚物樹脂中之乙烯基芳香族成份的Μ〜”重量 %，較佳為5〇〜7〇重詈。/λ，县从& 更里/〇最佳為50〜65重量％。另外，本發 明樹脂中最小的乙、嫌其^:壬 ^ ^ 烯基方香族聚合物嵌段含量較佳為佔嵌 :、聚物樹脂中全部之乙稀基芳香族成份的3〜2G重量％，更574231 V. Description of the invention (5) To achieve the purpose of the present invention L: When the molecular weight distribution is unimodal, the impact resistance of the resin is poor, and the folding resistance is also poor. When the molecular weight distribution of the resin is two peaks, the bending The strength and the bending elasticity are deteriorated. The measurement method of the molecular weight distribution of the above-mentioned block copolymer resin is paid by measuring c and c. The I line is made of a standard commercially available styrene polymer. The content ratio of the molecular weight bimodal distribution in the distribution of the knife is based on the area ratio of tritium. Where the bimodal overlaps, the middle is connected by the bimodal. Calculated for the lowest point distinction. "The largest ethylenic aromatic polymer in the block copolymer resin of the present invention: the undersegment accounts for M ~ of the vinyl aromatic component in the block copolymer resin" by weight%, preferably 50 ~ 70 weight curse. / λ, xianli from the & more / 0 is preferably 50 to 65% by weight. In addition, the content of the smallest ethylene and arsenic polymer in the resin of the present invention is preferably 3 ~ 2G, which accounts for all of the ethylenic aromatic components in the polymer resin. % By weight and more
Sr18 ’最佳為5〜Μ重量I上述樹脂中最大或 敢小的乙烯基芳香族平人&+ λ 、Λ 。匆甘入丰又$量在前述範圍内時，耐衝 剛性、耐折性及成型品耐龜裂性等物性平衡上更佳。 ，所謂乙稀基芳香族嵌段係指4段共聚物樹脂構造 ，以乙稀基芳香族單體為主成分之嵌 A3、A4,前述 A1、A2 A2 芳香族單體所構成。 A4㈣係⑽重量％的乙烯基 烯基：香為二達：本發明之目的’嵌段共聚物樹脂中最大的乙 =! Γ 段之數平均分子量以6〇，_.，_為 =’而最小之乙烯基芳香族聚合物嵌段之數平均分子量較 為3，_〜1()，_。^在前述範圍内時，可得到更佳之透明Sr18 'is preferably 5 to M weight I. The largest or dare small vinyl aromatic flat man & + λ, Λ among the above resins. When the amount is in a hurry and the amount is within the above range, the physical properties such as impact resistance, folding resistance, and crack resistance of the molded product are better. The so-called ethylene aromatic block refers to a 4-stage copolymer resin structure, which is composed of A3, A4 and A1, A2 and A2 aromatic monomers, which are mainly composed of ethylene aromatic monomers. A4 ㈣ series ⑽% by weight of vinyl alkenyl: fragrant is two: the purpose of the present invention 'the largest ethylene in block copolymer resin =! Γ number of segments average molecular weight is 60, _., _ Is =' and The number average molecular weight of the smallest vinyl aromatic polymer block is relatively 3, _ ~ 1 (), _. ^ Within the aforementioned range, better transparency can be obtained
574231 五、發明說明（6 性、耐衝擊強度、剛性等物性平 成型品之耐龜裂性。 、並且具有更佳耐折性及 本發明之嵌段共聚物樹脂中乙 之分子量分佈至少呈三峰分佈為較佳，若=合物嵌段 分佈時，樹脂之流動性、厚肉 峰或雙峰以下 物性平衡不佳。 出成L 口耐龜裂性及剛性之 T共聚物樹脂中最大的乙稀基芳香族聚合物 入又為A1 ’而最小的C烯基芳香族聚合物嵌 仏上述誠中乙稀基芳香族聚合㈣段之分子量分佈j 及最大及最小之乙烯基芳香族聚合物的數平均分子量的測 定方法’可以由聚合時單體之添加比例計 …及第三丁…化氣(ter二者二 _ορ⑽xide)分解丁二稀喪段後，得乙稀基芳香族聚合物嵌 段之混合物，再以 GPC 分析 [L.M.KOLTHOFF.etal，J.p〇lym.Sci.429(1946)]而得。 本發明之嵌段共聚物樹脂在聚合時，乃將乙烯基芳香族 系單體、共軛二烯系單體、起始劑以及溶劑等原料，依序加 入反應槽中反應。在每一階段單體反應完全之後，再進行下 一階段之反應單體入料。反應完全與否，可依反應溫度來判 斷’當反應溫度停止上升時即代表反應完全。本發明單體係 在起始劑存在的狀況下聚合，可使用於本發明之起始劑為有 機鹼金屬化合物，其通式可以RM來表示，其中R可為··燒 基、環烷基、含4〜8個碳原子之芳基，較佳為烷基，而M代 表驗金屬，較佳為鐘。上述起始劑之用量依其嵌段分子量決 本紙張尺度適用中國國家標準（CNS) A4規格（210X 297公釐） 第8頁 574231 A7 B7 五、發明說明（7 ) "— 疋，一般是相對於100重量份單體的O Mq 〇重量份。 可使用☆本發明之有機鋰化合物為含有一個以上鋰原 子之化合物，其具體例選自：乙基鋰、正_戊基鋰、異丙基鋰、 正-丁基鋰、次級丁基鋰、己基鋰、環己基鋰、苯基鋰、苯甲 基鋰、萘基鋰、第三丁基鋰、三亞甲基二鋰、四亞甲基二鋰、 丁二烯雙鋰及異戊二烯雙鋰等一種或兩種以上混合使用。 本發明所使用溶劑之具體例如：戊烷、己烷、辛烷、環 己烷等。 又本發明欲段共聚物樹脂在聚合時之聚合速率、1，2_乙 婦基含量’以及二烯系單體與乙烯基芳香族單體的反應性比 及亂排化狀態，可由極性化合物或亂排（rand〇m)化劑來調 整。上述極性化合物或亂排化劑乃選自··醚類、胺類（amine)、 硫醚類、烷基苯、磺（sulfon)酸類、烷基氧化物之鉀或鈉鹽。 適合於本發明之具體例如： (a) 醚類：二甲基醚、二乙基醚、二丁基醚、二苯基醚、四 氫呋喃（tetrahydrofuran)、四氫吡喃、二乙二醇二甲基 醚（diethylglycol dimethyl ester)、乙二醇二丁基醚、二 乙二醇二乙醚、二乙二醇二丁醚、二苯醚等。 (b) 胺類：三級胺、三甲基胺、三乙基胺、三丙基胺、三丁 基胺、四-甲基-次乙基雙胺、二乙苯胺、吡啶、環三級 胺等。 (c) 膦（phosphine)或膦醢胺類：三-苯基膦、六甲基膦酿胺 等。 (d) 烷基氧化物之鉀或鈉鹽：丁氧鉀（potasstium butoxide) ° 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公釐） 第9頁 574231 A7 B7 五、發明說明 本發明共聚物樹脂的製造方法中，聚合溫度一般在_4〇 °C〜15(TC，最佳為40〜12(rc ,聚合時間及聚合慶力乃隨聚合 條件不同而異，其中聚合時間通常是在2〇小時内，特別2 在。·5〜1〇小時間，最佳是。.5〜5小時，聚合時需防止例如疋 水、酸類、二氧化碳等不純物之混入。 本發明在聚合時之起始劑、單體之入料順序可用於製造 具有直線排列結構式之化合物，該聚合反應的步驟可如 所舉具體例： 舉例1 步驟1:起始劑及乙婦基芳香族單體同時入料，或者起始劑 先加，再加入乙烯基芳香族單體，或者乙烯基芳香 族單體先加入，再加入起始劑。 步驟2 起始劑及乙烯基芳香族單體同時 ^ ^ 丁八料，或者起始劑 先加，再加入乙烯基芳香族單體，或者乙烯基芳香 族單體先加入，再加入起始劑。 步驟3 步驟4 步驟5 步驟6 步驟1 加入共輛二烯系單體。 加入乙烯基芳香族單體。 加入共軛二烯系單體。 加入乙稀基芳香族單體。 舉例2 起始劑及乙烯基芳香族單體同時入 Α. , ^ , 或者起始劑 先加，再加入乙烯基芳香族單體， ^ χ ^ ^者己埽基芳香 族早體先加入，再加入起始劑。 步驟2··起始劑及乙烯基芳香族單體同時入 或者起始劑 本紙張尺度適用家標準（CNS) Α4規彳公釐） 篦10百 574231 五、發明說明（9 ) 步驟3 步騍4 步驟5 步驟6 步驟7 步驟8 步驟1 先加再加入乙烯基芳香族單體，或 族單體先加入，再加入起始劑。 烯基芳香 加入共軛二烯系單體。 加入乙烯基芳香族單體。 加入共軛二烯系單體。 加入乙烯基芳香族單體。 加入共軛二烯系單體。 加入乙烯基芳香族單體。 鲞例3 力乙：基芳香族單體同時入料，或者起始劑 步驟2 步驟3 步驟4 步驟5 步驟6 步驟7 二LT浠基芳香族單體，或者乙烯基芳香 族早體先加入，再加入起始劑。 起始劑及乙烯基芳香族I，间 Α^ 錢早體叫人料，或者起始劑 先加，再加入乙烯基芳香族單體。 加入共軛二烯系單體。 加入乙稀基芳香族單體。 加入共輛二烯系單體。 加入乙烯基芳香族單體。 乙烯基芳香族單體及共軛二烯系單體一起加入。 本發明共聚物樹脂在聚合反應全部結束後，可加入故止 ，合$鏈之活性的終止劑，終止劑之用量通常依據起始劑用 S而定，一般是相對於起始劑用量的5〇〜2〇()重量％皆可。前 述終止劑如··水、醇類、酚類化合物、有機酸、無機酸等化 合物’其中有機酸係指廣義具有酸性的有機化合物，其選 本紙張尺度適財國國家標準（CNS) Α4規格（210Χ 297公爱 第11頁 574231 A7 __B7 _ 五、發明說明（10) 自··叛酸（carboxylic acid)、績酸（sulfonic acid)、亞橫酸 (sulfinic acid)、盼（phenol)等化合物，最好是含有敌基 (carboxyl)的有機化合物，其具體例子有：甲酸、醋酸、戊酸、 辛酸（octylic acid)、癸酸（capric acid)、月桂酸（lauroylic acid)、肉豆寇酸（myristinic acid)、棕櫊酸（palmitinic acid)、 硬脂酸（stearylic acid)、油酸（oleic acid)、次亞麻仁油酸 (linoleic acid)、亞麻酸（linolenic acid)、篦麻酸（ricinoleic acid)、松香酸（rosin acid)、二十二烧酸（behenic acid)、新癸 酸（neodecenoic acid或versatic acid)等，其中以新癸酸為較 佳。 而無機酸乃例如：鹽酸、硫酸、硝酸、硼酸、填酸等。 醇類化合物例如：曱醇、乙醇、丙醇等之低級醇、C6〜C18之 兩級醇，以及乙二醇、丙二醇、丙三醇等之多價醇。盼類化 合物乃例如：酚、2,6-二-第三丁基-4-甲基酚、雙酚A等。 如上所述，本發明嵌段共聚物樹脂之反應係由單體溶於 /谷劑中進行反應而得’反應後共聚物即溶於溶劑中形成聚人 物膠漿，上述膠漿通常含有10〜35重量％的固形物，前述膠 漿可以直接或以減壓或加熱等方式預先再濃縮至〜99重量 %的固形物，再以真空烘箱、去揮發押出機，或導入熱水中 以移除剩餘溶劑。 前述喪段共聚物樹脂回收後可藉由研磨、押出等方式製 成所需的形狀。在反應後至回收過程中，可加入適當的添加 劑，例如：抗氧化劑、螯劑、滑劑、抗靜電劑、耐候劑等。° 其中，抗氧化劑宜使用如酚系抗氧化劑、硫醚系抗氧化574231 V. Description of the invention (6) Crack resistance of flat molded products such as physical properties, impact strength, rigidity, etc., and has better folding resistance and the molecular weight distribution of ethylene in the block copolymer resin of the present invention has at least three peaks The distribution is better. If the composition is distributed, the resin's fluidity, thick meat peaks, or bimodal peaks are not well balanced. The largest ethylene copolymer in the T copolymer resin with crack resistance and rigidity at the mouth. The dilute aromatic polymer is A1 'and the smallest C alkenyl aromatic polymer is embedded with the molecular weight distribution j of the above-mentioned ethylene aromatic polymer segment and the largest and smallest vinyl aromatic polymer. The method for measuring the number average molecular weight can be calculated from the addition ratio of monomers during polymerization ... and the third dibutylene ... This mixture was obtained by GPC analysis [LMKOLTHOFF. Etal, Jpolym. Sci. 429 (1946)]. When the block copolymer resin of the present invention is polymerized, a vinyl aromatic monomer, Conjugated diene monomer, initiator and solvent Wait for the raw materials to be added to the reaction tank in order. After each stage of the monomer reaction is complete, proceed to the next stage of the reaction monomer feed. The reaction is complete or not, you can judge according to the reaction temperature 'When the reaction temperature stops rising This means that the reaction is complete. The single system of the present invention is polymerized in the presence of a starter, and the starter used in the present invention can be an organic alkali metal compound, and its general formula can be represented by RM, where R can be ... An alkyl group, a cycloalkyl group, an aryl group containing 4 to 8 carbon atoms, preferably an alkyl group, and M represents a metal test, preferably a bell. The amount of the above-mentioned initiator depends on the block molecular weight of the paper. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) Page 8 574231 A7 B7 V. Description of the invention (7) " 疋, generally it is O Mq 〇 parts by weight relative to 100 parts by weight of monomer. Use ☆ The organic lithium compound of the present invention is a compound containing one or more lithium atoms, and specific examples thereof are selected from the group consisting of ethyl lithium, n-pentyl lithium, isopropyl lithium, n-butyl lithium, secondary butyl lithium, Hexyl lithium, cyclohexyl lithium, phenyl lithium, benzyl Lithium, naphthyl lithium, third butyl lithium, trimethylene dilithium, tetramethylene dilithium, butadiene dilithium, and isoprene dilithium, or two or more of them may be used in combination. Specific examples of the solvent include: pentane, hexane, octane, cyclohexane, etc. Also, the polymerization rate of the copolymer resin of the present invention during polymerization, the content of 1,2-ethynyl 'and the diene monomer and The reactivity ratio and disordered state of the vinyl aromatic monomer can be adjusted by polar compounds or randomizers. The polar compounds or randomizers are selected from the group of ethers and amines (Amine), thioethers, alkylbenzenes, sulfon acids, potassium or sodium salts of alkyl oxides. Specific examples suitable for the present invention: (a) Ethers: dimethyl ether, diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, tetrahydrofuran, diethylene glycol dimethyl Diethylglycol dimethyl ester, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diphenyl ether, and the like. (b) Amines: tertiary amines, trimethylamines, triethylamines, tripropylamines, tributylamines, tetra-methyl-ethylidenebisamines, diethylaniline, pyridine, and cyclotertiary Amine, etc. (c) Phosphine or phosphonium amines: tri-phenylphosphine, hexamethylphosphine, and the like. (d) Potassium or sodium salt of alkyl oxide: potassium butoxide (potasstium butoxide) ° This paper size applies Chinese National Standard (CNS) A4 (210x 297 mm) Page 9 574231 A7 B7 V. Description of the invention In the production method of the copolymer resin of the present invention, the polymerization temperature is generally _40 ° C ~ 15 (TC, and the best is 40 ~ 12 (rc). The polymerization time and polymerization power are different depending on the polymerization conditions. The polymerization time is usually It is within 20 hours, especially 2 hours. 5 to 10 hours, and most preferably 5 to 5 hours. During the polymerization, it is necessary to prevent impurities such as water, acids, carbon dioxide and other impurities from being mixed in. During the polymerization of the present invention, The starting sequence of the starting materials and monomers can be used to produce compounds with a linear structural formula. The steps of the polymerization reaction can be as specific examples: Example 1 Step 1: Starter and ethyl ethyl aromatic monomer Feed at the same time, or add the starter first, and then add the vinyl aromatic monomer, or add the vinyl aromatic monomer first, and then add the starter. Step 2 Simultaneous starter and vinyl aromatic monomer ^ ^ Dingba ingredients, or starter added first, then Add vinyl aromatic monomer, or vinyl aromatic monomer first, and then add the initiator. Step 3 Step 4 Step 5 Step 6 Step 1 Add a total of diene monomers. Add vinyl aromatic monomer Add conjugated diene monomers. Add vinyl aromatic monomers. Example 2 Simultaneously start A and vinyl aromatic monomer into A., ^, or add the initiator first, and then add vinyl aromatic. Group monomer, ^ χ ^ ^ Hexyl aromatic early body is added first, and then add the starter. Step 2 · Starter and vinyl aromatic monomer are added at the same time or the starter is suitable for this paper. Standard (CNS) A4 Regulation (mm) 篦 100 574231 V. Description of the Invention (9) Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 Step 1 Add the vinyl aromatic monomer or family monomer first. Add the body first, and then add the initiator. Alkenyl aroma is added to the conjugated diene monomer. Vinyl aromatic monomer is added. Conjugated diene monomer is added. Vinyl aromatic monomer is added. Conjugation is added Diene monomer. Vinyl aromatic monomer is added. Example 3 ： Base aromatic monomers are fed at the same time, or starter Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Two LT fluorenyl aromatic monomers or vinyl aromatic precursors are added first, and then the starter is added. . Starter and vinyl aromatic I, meta-A ^ early body is called anthropogenic, or starter is added first, and then add vinyl aromatic monomer. Add conjugated diene monomer. Add ethylene Aromatic monomers. Co-diene monomers are added. Vinyl aromatic monomers are added. Vinyl aromatic monomers and conjugated diene monomers are added together. The copolymer resin of the present invention after all polymerization reactions are completed A terminating agent that can stop the activity of the chain can be added. The amount of the terminating agent usually depends on the use of the initiator S, and it is generally 50% to 20% by weight relative to the amount of the initiator. The aforementioned terminating agents include compounds such as water, alcohols, phenolic compounds, organic acids, inorganic acids, etc., where organic acids refer to organic compounds with acidity in a broad sense, and the paper size is suitable for National Standards (CNS) A4 specifications (210χ 297 public love page 11 574231 A7 __B7 _ V. Description of the invention (10) Since · compounds such as carboxylic acid, sulfonic acid, sulfinic acid, phenol and other compounds Organic compounds containing carboxyl are preferred. Specific examples include: formic acid, acetic acid, valeric acid, octylic acid, capric acid, lauroylic acid, and myristic acid. (Myristinic acid), palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid), rosin acid, behenic acid, neodecenoic acid or versatic acid, etc. Among them, neodecanoic acid is preferred. The inorganic acids are, for example, hydrochloric acid, sulfuric acid , Nitric acid, boric acid Fill acid, etc. Alcohol compounds such as lower alcohols such as methanol, ethanol, propanol, two-stage alcohols C6 to C18, and polyvalent alcohols such as ethylene glycol, propylene glycol, glycerol, etc. Hope compounds are for example : Phenol, 2,6-di-third-butyl-4-methylphenol, bisphenol A, etc. As described above, the reaction of the block copolymer resin of the present invention is a reaction in which the monomer is dissolved / cereal After the reaction, the copolymer is dissolved in a solvent to form a polymer figure glue. The glue usually contains 10 to 35% by weight of solids. The glue can be re-concentrated to ~ 99% by weight of solids, then vacuum oven, devolatization extruder, or introduction into hot water to remove the remaining solvent. After recovering the aforementioned copolymer copolymer resin, it can be made into the desired shape by grinding, extrusion, etc. . After the reaction to the recovery process, appropriate additives can be added, such as: antioxidants, chelants, slip agents, antistatic agents, weathering agents, etc. ° Among them, antioxidants such as phenolic antioxidants and thioethers are suitable. anti-oxidation
第12百 574231 A7 B7 五、發明說明（u ) 劑、碟系抗氧化劑，而酚系抗氧化劑的添加量以〇.〇〇5〜2 〇 重’置份（相對於嵌段共聚物樹脂丨〇〇重量份）為佳，具代表性 者有·十八燒基（3,5-雙第三丁基-4 -經苯基）-丙酸酯、三乙 一醇雙[3 -（3-第三丁基-5-甲基-4-羥苯基）丙酸酯]、四[甲 撐基-3-(3,5-雙第三丁基-4-羥苯基）丙酸酯]甲烷、2_第三丁 基-6-(3-第三丁基_2-羥基_6-甲基苯甲基）甲基苯基丙烯酸 酯、2,2、甲撐基-雙（4-甲基-6_第三丁基酚）、2,2，-硫雙（4-甲基 -6-第三丁基酚）、2,6_二-第三丁基·仁甲基酚、2,2，_硫代二乙 撐基-雙[3-(3,5-雙第三丁基-4-羥苯基）丙酸酯]、2,2，-乙二醯 胺-雙[乙基-3-(3，5_雙-第三丁基-4-羥苯基）丙酸酯]等。 硫_系抗氧化劑的添加量以〇·〇〇5〜2.0重量份（相對於 肷段共聚物樹脂1 〇 〇重量份）為佳，具代表性者有：二硬脂 醯硫二丙酸酯、二棕櫚醯硫二丙酸酯、五赤蘚醇-四-(冷一十 二甲基-硫丙酸酯）、雙十八烷基硫醚、2,4-雙（正-辛基硫甲 基）-6-甲基紛[2,4-bis(n-octyl thio methy l)-6-methyl phenol]、2,4-雙（2’，3，-二-羥丙基硫甲基）_3,6_二甲基酚 [2,4-bis(2’，3、di-hydroxy propyl thio methyl)-3,6-di-methyl phenol]、2，4-雙（2、乙醯氧基乙基硫甲基）-3,6-二-甲基酚 [2,4 bis(2 -acetyloxy ethyl thio methyl)-3,6-di-methyl phenol]、4,6_ 雙（辛基硫甲基）-鄰-甲酚[4,6-bis(octyl thio methyl)-0-cresol]等，其中以4,6-雙（辛基硫曱基）·鄰·曱酚為 較佳。 填系抗氧化劑為亞磷酸酯系抗氧化劑或磷酸酯抗氧化 劑，其添加量以〇·015〜2〇重量份（相對於嵌段共聚物樹脂 本紙張尺度適用中國國家標準（CNS) Α4規格（210χ 297公釐） 574231 A7No. 12th 574231 A7 B7 V. Description of the invention (u) agent, dish-based antioxidant, and phenol-based antioxidant is added in an amount of 0.0005 to 2 weight percent (relative to the block copolymer resin 丨〇〇parts by weight) is preferred, and representative examples include octadecyl (3,5-bis-tertiarybutyl-4-phenyl) -propionate, triethylene glycol bis [3-(3- Third butyl-5-methyl-4-hydroxyphenyl) propionate], tetrakis [methylidene-3- (3,5-bis-third butyl-4-hydroxyphenyl) propionate] Methane, 2-tert-butyl-6- (3-tert-butyl_2-hydroxy-6-methylbenzyl) methphenylacrylate, 2,2, methylene-bis (4- Methyl-6-tert-butylphenol), 2,2, -thiobis (4-methyl-6-tert-butylphenol), 2,6_di-tert-butyl · renmethylphenol, 2,2, -thiodiethylene-bis [3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate], 2,2, -ethylenediamine-bis [ Ethyl-3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate] and the like. The addition amount of the sulfur-based antioxidant is preferably from 0.05 to 2.0 parts by weight (1,000 parts by weight with respect to the fluorene copolymer resin). Representative examples include distearylthiodipropionate. , Dipalmitamidinethiodipropionate, pentaerythritol-tetra- (cold dodecamethyl-thiopropionate), dioctadecylsulfide, 2,4-bis (n-octylsulfide Methyl) -6-methyl phenol [2,4-bis (n-octyl thio methy l) -6-methyl phenol], 2,4-bis (2 ', 3, -di-hydroxypropylthiomethyl) ) _3,6_Dimethylphenol [2,4-bis (2 ', 3, di-hydroxy propyl thio methyl) -3,6-di-methyl phenol], 2,4-bis (2, acetoxyl Ethyl ethylthiomethyl) -3,6-bis-methylphenol [2,4 bis (2 -acetyloxy ethyl thio methyl) -3,6-di-methyl phenol], 4,6_ bis (octylthiomethyl) Group) -o-cresol [4,6-bis (octyl thio methyl) -0-cresol], etc. Among them, 4,6-bis (octylthiomethyl) · o-phenol is preferred. Filler antioxidants are phosphite-based antioxidants or phosphate-based antioxidants, and the added amount is from 0.015 to 20 parts by weight (relative to block copolymer resins. This paper applies Chinese National Standard (CNS) A4 specifications ( 210 × 297 mm) 574231 A7
100重量份）為佳’具代表性者有：三（壬基苯基）亞填酸醋、 十二院基亞磷酸醋、環狀新戊炫四氫萘基雙（十八烧基亞磷酸 ㈤基雙（3-甲基_6_第三丁基苯基_雙十三烧基亞麟 酸醋）、三（2,4-第三丁基苯基）亞磷酸醋、四（2,4_第三丁基笨 基）-4,4’-伸聯苯基磷酸醋、9，1〇_二氫_9_氧-1〇_磷酸菲_ι〇-氧 撐等。 聲劑的添加量以〇·〇〇1〜2.0重量份（相對於嵌段共聚物 樹脂1 00重量份）為佳，具代表性者有：二苯曱醯基甲烷、 二乙胺四醋酸的納鹽等。 滑劑具代表性者有：硬脂酸鈣、硬脂酸鎂、硬脂酸鋰等 之金屬肥皂、乙撐二硬脂醯胺、曱撐二硬脂醯胺、棕櫊酸醯 胺、硬脂酸丁酯、硬脂酸棕櫚酯、聚丙酸醇三硬脂酸酯、正 二十二烷酸、硬脂酸等之化合物、聚乙烯蠟、二十八烷酸蠟、 巴西棕櫚蠟（Carnuba wax )、石油蠟等；滑劑的添加量相 對於肷段共聚物樹脂1〇〇重量份的〜5〇重量份。 此外，在不顯著損及本發明嵌段共聚物樹脂之透明性的 情況下，可進一步調配其他的樹脂，例如：苯乙烯系均聚物、 苯乙烯系一丙烯腈系共聚物、苯乙烯系一丙烯酸酯系一丙烯 腈系共聚物、笨乙烯系一甲基丙烯酸酯系一丙烯腈系共聚 物、苯乙烯系-丙烯酸酯系共聚物、笨乙烯系一甲基丙烯酸酯 系共聚物、苯乙烯系_丙烯酸酯系-丙烯腈系_馬來醯亞胺系共 聚物、苯乙烯系-甲基丙烯酸酯系·丙烯腈系_馬來醢亞胺系共 聚物、苯乙烯系-丙烯酸酯系·馬來醯亞胺系共聚物、苯乙烯 系-甲基丙烯酸酯系·馬來醯亞胺系共聚物、丙烯酸酯系-馬來 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公釐) ' -- 篦 U 百 574231 A7100 parts by weight) are the best. Representative examples are: tris (nonylphenyl) vinegar, dodecanyl phosphite, cyclic neopentyl tetrahydronaphthyl bis (octadecyl phosphite) Fluorenyl bis (3-methyl-6-third butylphenyl_bistridecyl linyl vinegar), tris (2,4-third butylphenyl) phosphite, tetrakis (2, 4-tert-butylbenzyl) -4,4'-biphenylphenyl phosphate, 9,1__dihydro_9_oxy-1__phenanthrene phosphate_ι〇-oxo, etc. The added amount is preferably from 0.001 to 2.0 parts by weight (100 parts by weight relative to the block copolymer resin). Representative examples include diphenylfluorenylmethane, sodium salt of diethylamine tetraacetic acid, etc. Representatives of lubricants include: metal soaps such as calcium stearate, magnesium stearate, lithium stearate, ethylene distearylamine, ethylene distearylamine, ammonium palmitate, Butyl stearate, palmityl stearate, polyalcohol tristearate, n-docosaic acid, stearic acid and other compounds, polyethylene wax, octacosanoic acid wax, carnauba wax ( Carnuba wax), petroleum wax, etc .; the added amount of the lubricant is relative to the fluorene copolymer 100 parts by weight to 50 parts by weight. In addition, without significantly impairing the transparency of the block copolymer resin of the present invention, other resins such as a styrene-based homopolymer, Styrene-acrylonitrile-based copolymer, styrene-acrylonitrile-acrylonitrile-based copolymer, styrene-methacrylate-methacrylate-acrylonitrile-based copolymer, styrene-acrylic-based copolymer, Stupid vinyl-methacrylate copolymer, styrene-acrylic-acrylonitrile-maleimide-imine copolymer, styrene-methacrylate-acrylonitrile-malea Imine-based copolymer, styrene-acrylic-based · maleimide-based copolymer, styrene-methacrylate-based · maleimide-based copolymer, acrylate-Malay paper Dimensions are applicable to China National Standard (CNS) A4 specifications (210x 297 mm) '-篦 U 百 574231 A7
醯亞胺系共聚物、甲基丙烯酸酯系_馬來醯亞胺系共聚物，或 經二烯系橡膠改質（或接枝改質之前述共聚物），其中以添加 本乙婦系均聚物為最佳。 前述其他成份或樹脂之添加混合，可藉由布拉本德塑性 儀、班伯立混練機、捏合_混合機、滾壓機、一軸或二軸押出 機等之一般混合混練機混合製得。通常藉這些押出機等混合 混練後，再將押製出的押出物冷卻、粒化，上述混練一般係 在140 280 C下進行，而以16〇〜250°C為佳，又前述各調配 成伤之混合混練並無順序上的特別限制。 【物性測試】 1、 落鐘衝擊強度（FDI):以TOYOSEIKI社製作之落錘衝擊 強度試驗機測定，在2公斤荷重下試片沒有破裂的最大 高度（mm)。 «式片規格·厚度1/8忖、直徑55mm之射出成型圓盤。 單位：mm 2、 彎曲彈性率（FM)及彎曲強度（FS):依ASTM d-790法測 試而得。試片規格：厚度1M吋，單位為kg/cm2。 3 加工性（流動性’間稱ΜI):依據A S T M D -12 3 8標準測 定樹脂在200°C X 5kg下之流動係數。 4、 透明性（霧度，Haze):將樹脂射出成型3mm厚之試片， 並依ASTM D-1003標準測定透明性，當Haze值越高表 不透明性越差。 5、 嵌段共聚物樹脂之分子量分佈、雙峰的含量比值，以及 最兩及最低波峰之峰值分子量測定方法：以Gpc測量 本紙張尺度適用中國國家標準（CNS) A4規格（210χ 297公釐） 第15頁 立、赞切說明（14 :$線以-般市t標準之苯乙烯單體聚合物做 Hi分子4分㈣中’卩咖曲線之面積比 =!分佈的含量比值。其中，雙峰相重疊的地方， 峰相連接的中間最低點區分所計算而得。 ’=乙烯基芳香族聚合物嵌段之分子量分佈、最大的 =基芳香族聚合物嵌段數平均分子量，以及最小的乙 :基芳香族聚合物欲段數平均分子量的測定：分子量分 係以四礼化餓(os〇4)及第三丁基過氧化氫分解丁二 稀队段後’得乙烯基芳香族聚合物谈段之混合物，再以 ^pc刀析，則何_ ’而最大及最小之乙婦基芳香族聚合物喪 平句刀子量’係以聚合時單體之添加比例計算而 得。 7、 樹脂中最大及最小的乙稀基芳香族共聚物嵌段佔全部 之乙烯基芳香族共聚物嵌段的比率，以及樹脂中最大及 最小的乙烯基芳香族聚合物嵌段之數平均分子量的測 疋方法·由聚合時單體的添加比例計算而得。 8、 耐折性（Hinge)測定方法：以引張試驗之試片，以約5〇 次/分之頻率手動往返360度對折1〇〇次，再目視判斷 折痕處破裂程度。 〇·表示折痕處無破裂 X :表示折痕處破裂嚴重 9、 樹脂之厚肉射出成型品之龜裂性測定方法：射出1 /4吋 後的衝擊強度試片，放置3天後，觀察試片是否有裂痕 發生。 本紙張尺度適用中國國豕標準（CNS) A4規格（210χ 297公爱） 第16百 574231 A7 __B7 五、發明說明（15 ) Ο ·表不無破裂 X :表示裂痕嚴重 【實施例及比較例說明】 下列實施例及比較例嵌段共聚物樹脂之製備及其機械 性質’所舉例中，乙烯基芳香族單體為苯乙烯，共軛二烯為 1，3-丁二烯，起始劑使用濃度為8重量％的正丁基鋰作代表， 並使用少量的四氫呋喃（tetrahydrofuran，簡稱THF)，而溶劑 使用環己烷。反應完成後加入2,6-二-第三丁基-4甲基齡 (2,6-di-tert-butyl-4_methyl phenol，簡稱 BHT)。苯乙烯/丁二 烯嵌段共聚物係在氮氣存下，於批次反應器聚合而成，反應 壓力約1〜3 Kg/cm2、反應溫度在5〇〜12〇t：、反應時間約 60 150刀鐘。反應器谷積為16〇公升，進料順序如表一所示。 反應完成後膠漿約含1 5重量％的固形份，每丨〇〇重量份之嵌 段共聚物中加入約〇·2 5重量份的十八烷基（3,5 —雙第三丁基 - 4-羥苯基）-丙酸酯（簡稱Ιχ1〇76)，以及〇·6重量份之三亞 磷酸壬苯基酯（簡稱ΤΝΡΡ)。嵌段共聚物樹脂係將膠漿通入熱 水中脫除溶劑，回收得濕膠粒再以押出機押出乾燥脫水，造 粒後射出試片評價其機械性質，機械性質評價結果如表三。 由本發明之貫施例及比較例得知，在比較例1中，乙烯 基芳香族嵌段之分子量分佈為雙峰分佈，且樹脂之分子量構 le為A1-Β 1-Α2時，嵌段共聚物樹脂之流動性差，厚肉射出 成型品龜裂嚴重。比較例2中共聚物樹脂之分子量分佈為單 峰刀佈乙基芳香方矣嵌段之分子量分佈A雙峰，且樹脂之 分子構造為A1-B1-A2時，樹脂之落錘衝擊強度差、耐折性醯 imine-based copolymer, methacrylic acid ester_maleimide-based imine-based copolymer, or modified by diene rubber (or the aforementioned copolymer modified by grafting). Polymers are optimal. The aforementioned other ingredients or resins can be added and mixed by a general mixing kneader such as a Brabender plastic meter, a Banbury mixer, a kneading mixer, a roller press, a one-axis or two-axis extruder, and the like. Usually, these extruder machines are used to mix and knead, and then the extruded material is cooled and granulated. The above-mentioned kneading is generally performed at 140 280 C, and preferably at 160-250 ° C. There is no particular restriction on the order of injury and mixing. [Physical property test] 1. Falling bell impact strength (FDI): The maximum height (mm) of the test piece without cracking under the load of 2 kg was measured by a falling hammer impact strength tester manufactured by TOYOSEIKI. «Type sheet specifications · Injection molding disc with thickness 1/8 忖 and diameter 55mm. Unit: mm 2. Flexural modulus (FM) and flexural strength (FS): Measured in accordance with ASTM d-790. Specimen of test piece: thickness 1M inches, unit is kg / cm2. 3 Processability (flowability 'is called MI): The flow coefficient of the resin at 200 ° C X 5kg was measured in accordance with A S T M D -12 38. 4. Transparency (haze, Haze): Inject the resin into a 3mm thick test piece and measure the transparency according to ASTM D-1003. The higher the Haze value, the worse the opacity. 5. The molecular weight distribution of block copolymer resin, the content ratio of double peaks, and the peak molecular weight of the two and the lowest peaks. Measurement method: GPC measurement. The paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm). Explanation on page 15 (14: $ line is based on the standard of styrene monomer polymer-standard city t 4 minutes of Hi molecule in the molecular ratio of the 'coffee curve =! Distribution content ratio. Among them, double Where the peaks overlap, the lowest point at the middle of the peak connection is calculated. '= Molecular weight distribution of the vinyl aromatic polymer block, the largest = the average molecular weight of the number of base aromatic polymer blocks, and the smallest B: Determination of the average molecular weight of the desired number of segments of the aromatic polymer: The molecular weight system is obtained by decomposing the butadiene segment with serotonin (os04) and the third butyl hydrogen peroxide to obtain a vinyl aromatic polymer. The mixture of the paragraphs is analyzed with a ^ pc knife. Then, “the largest and smallest amount of the ethyl ethyl aromatic polymer is equal to the amount of the knife” is calculated based on the addition ratio of the monomers during polymerization. 7. Resin Largest and smallest B Method for measuring the ratio of the base aromatic copolymer block to the total vinyl aromatic copolymer block and the number and average molecular weight of the largest and smallest vinyl aromatic polymer block in the resin. Calculated by adding the ratio. 8. Hinge resistance measurement method: Take the test piece of the tensile test, and manually fold it back and forth 360 times in 360 degrees at a frequency of about 50 times per minute, and then visually judge the crease. Degree of cracking: 〇 · indicates no cracking at the crease X: indicates severe cracking at the crease 9: Measurement of the cracking property of the thick resin injection molded product: Impact strength test piece after injection of 1/4 inch, left for 3 days After that, observe whether the test piece has cracks. This paper size applies the Chinese National Standard (CNS) A4 specification (210χ 297 public love) No. 160 574231 A7 __B7 V. Description of the invention (15) 〇 · No cracks in the table: Indicates severe cracks [Explanation of Examples and Comparative Examples] In the following examples and comparative examples, the preparation and mechanical properties of the block copolymer resins are as follows. In the example, the vinyl aromatic monomer is styrene and the conjugated diene is 1. 3-butadiene As the starter, n-butyllithium with a concentration of 8% by weight was used as a representative, and a small amount of tetrahydrofuran (THF) was used, and the solvent was cyclohexane. After the reaction was completed, 2,6-di-third-butyl was added. -4 methyl age (2,6-di-tert-butyl-4_methyl phenol, BHT for short). The styrene / butadiene block copolymer is polymerized in a batch reactor under nitrogen and the reaction pressure About 1 ~ 3 Kg / cm2, the reaction temperature is 50 ~ 120t :, the reaction time is about 60 to 150 knife minutes. The reactor valley volume is 160 liters, and the feeding sequence is shown in Table 1. After the reaction is completed, the cement slurry contains about 15% by weight of solids, and about 0.25 parts by weight of octadecyl (3,5-bis-tertiarybutyl) is added to each of the block copolymers. -4-Hydroxyphenyl) -propionate (abbreviated as Ix1076), and 0.6 parts by weight of nonphenyl triphosphite (abbreviated as TNP). The block copolymer resin is made by passing the dope into hot water to remove the solvent, and the wet rubber pellets are recovered, and then the pellets are extruded to dry and dehydrate. The pellets are ejected to evaluate the mechanical properties. Table 3 shows the results of the mechanical property evaluation. It is known from the conventional examples and comparative examples of the present invention that in Comparative Example 1, when the molecular weight distribution of the vinyl aromatic block is a bimodal distribution and the molecular weight structure of the resin is A1-B 1-A2, block copolymerization is performed. The resin has poor fluidity, and the thick meat injection molded product is severely cracked. When the molecular weight distribution of the copolymer resin in Comparative Example 2 is a singlet molecular weight distribution A bimodal molecular weight distribution of the ethyl aromatic square fluorene block, and the molecular structure of the resin is A1-B1-A2, the resin's drop weight impact strength is poor, Folding resistance
笛17 百 574231Flute 17 hundred 574231
差。由比較例3得知，樹脂之分子量為三峰分佈時，樹浐之 f曲強度、-曲彈性率變差。由比較例4得知，樹脂心子 結構為分歧構造(Α1-Β1-Α2-Β2·Α3)ηΥ時，樹脂之耐折性差， 流動性及-曲彈性率亦稍差。由比較例5得知，樹脂中之高 低雙峰含量比值太低，樹脂之大波峰（即高峰）峰值的分子量 太大，且樹脂之分子構造為Α1-Β1_Α2日夺，樹脂之耐折性； 差，流動性稍差。由比較例6中得知，樹脂中之高波峰的峰 值分子量太小，且低波峰之峰值的分子量太小時，樹脂之落 錘衝擊強度、彎曲強度及彎曲彈性率極差。由比較例7得知' 當樹脂中t高波峰之峰值的分子量太小’ I樹脂中高低雙峰 含量比值太小時，樹脂之落錘衝擊強度差、耐折性差。由比 較例8得知，當樹脂中乙烯基芳香族單體含量與共軛二烯系 單體含量之比值太小，且樹脂為分歧狀結構（Α1_Βι)ηγ，另 外乙烯基芳香族嵌段分子量分佈為單峰分佈時，樹脂之落錘 衝擊強度差、彎曲強度及透明度差。 惟以上所述者’僅為本發明之較佳實施例而已，當不能 以此限定本發明實施之範圍，即大凡依本發明申請專利範圍 及發明說明書内容所作之簡單的等效變化與修飾，皆應仍屬 本發明專利涵蓋之範圍内。 表一··本發明各實施例的組成。 二：本發明各比較例的組成。 三：本發明各實施例及比較例之物性比較。 本紙張尺度適用中國國家標準（CNS) Α4規格（210χ 297公爱） 第18頁 574231 A7 B7 五、發明說明（17 ) : 1 > THF 謹 2 ' SM :谢Z# 3 iD : 1VTH藥 t niBULi : IET槪蜃鑒 5 ^ BD/SM，lvThfz#llllf^^M4sbif ? BHT : 2,6-Z：丨nlllTS-4.,馨 Όλ OJ fo H—^ oo crs )~^ 撕1醇 翻旨結構1 BKT(g) |BD/SM*(g/g) | |SM(g) 1 |BD(g) 1 |SM(g) 1 |BD(g) | |SM(g) 1 |BD(g) 1 |SM(g) 1 n-BuLi(g) |SM(g) 1 |n-BuLi(g) | |SM(g) 1 n-BuLi(g) THF(g) ΛΙ /ZZjS, 1 1 Α1·Β1·Α2ΒΜ3 1 1 1 1 1,500 1 I 1,500 | § s 1 1 (1,500 1 β 5,100 § I Η—^ Α1·Β1^2ΒΜ^Μ 1 1^500 1—^ s o § 〇 § 1,020 t 1 i On y\ s 44.4 s i to Α1ΰ1-Α2-Β2·Α3 K—^ 1 1 1 1,560 €： 8 § I 1,500 I 1 1 2,160 白 La I 4,320 | Ln | 〇3 Α1·Β1^2Β2·Α3 Ln 1 1 1 1 1500 § ι,5ω 1 1 1,620 Vy 5,160 馨 A1-B1-A2B2-A3 K—^ 1 1 着 2,520 1,500 § i 1 1 b—^ i H—^ 4,080 6 1—^ I A1«1^2-B2-A3R ··〇 144/% 1 1 1,476 i 1,476 1 1 1~k 5,040 t o § w 1 〇\ 22.7 120/480 1 1 i h—^ i § i 1 1 )~^ 1 4,800 衾 o § | f - i^wll 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公釐） 第19頁 574231 A7 B7 五、發明說明（18 9 会雲·1-Β1}ηγ _ snw fffl建#ο 7:si i蠢3)¾震2)囊養2)=70/30mMiM♦麗。 〇〇 n3 H—^ OO -0 ON OO H—^ 綱丨辭 謹 m(s 謙 m BHIXg) BD/SM*(g/g) SM(g) BD(g) SM(g) BD(g) |SM(g) 1 |BD(g) 1 |SM(g) 1 n-BuLi(g) |SM(g) 1 n-BuLi(g) |SM(g) 1 n-BuLi(g) THF(g) 1 i r-wT Al-Bl·^- 8 1 1 1 1 1 1,120 CT\ 1 1 1,120 LO vo Ln 1 6,396 Π LO Lm s Vr Q7 1 Al-B1^2 ν〇 1 1 1 1 1 U) o U) o 1 1 1 1 6?3〇〇 88.0 § t\mn A1-B1-A2-B2-A3 to bo 1 1 1 1,560 1 1500 | s § 1 l，5〇〇 | LO 2,580 | 21.2 | 2,580 v〇 § 腳丨J3 ，1^2Β2Α3)ιΥ 1 1 1 1—^ i H—^ i H—» i 1~^ i 1 1 H—^ i 48.0 4,800 ?〇 o § vr Q7 1 Α1ΰ1^2 Ltx 1 1 1 1 1 1,800 OO § 1 1 tSJ § 4,800 Ϊ^ 〇\ § YT UrflV 獲 Α1ΰ1^2Β2·Α3 1 1 1 H—4 S 8 1，500 1 1 § ON CTs 5,400 OO § nr cx 疆 Os Α1ΰ1^2-Β2·Α3 •各 1 1 1 〇\ H—^ s to s 1 1 1 1 8,136 OO ON o s 1—^ 腳!J7 Lo 1 1 1 2M 2^80 2, 1 1 1 2.592 8 § (ΑΗΒ1)ιΥ 1 11.2(SiCl4) 1 1 1 1 1 1 1 7200 1 1 1 1 4,800 228.0 Vr Q7 遲 OO 0U - 本紙張尺度適用中國國家標準（CNS) A4規格（210x 297公釐） 第20頁difference. From Comparative Example 3, when the molecular weight of the resin is a three-peak distribution, the f-curve strength and -curvature elasticity of the tree shrews are deteriorated. From Comparative Example 4, it was found that when the resin core structure was a bifurcated structure (A1-B1-A2-B2 · A3) ηΥ, the resin had poor folding resistance, and the fluidity and -flexural elasticity were also slightly inferior. It is known from Comparative Example 5 that the ratio of the content of the high and low peaks in the resin is too low, the molecular weight of the large peak (ie, the peak) of the resin is too large, and the molecular structure of the resin is A1-B1_Α2, and the folding resistance of the resin; Poor, slightly poor fluidity. From Comparative Example 6, it is known that the molecular weight of the peaks of the high peaks in the resin is too small and the molecular weight of the peaks of the low peaks is too small, and the drop impact strength, flexural strength, and flexural modulus of the resin are extremely poor. From Comparative Example 7, it is known that 'when the molecular weight of the peak of the high t peak in the resin is too small', the ratio of the content of the high and low double peaks in the resin is too small, and the resin has poor drop impact strength and poor folding resistance. It is known from Comparative Example 8 that when the ratio of the content of the vinyl aromatic monomer to the content of the conjugated diene monomer in the resin is too small, and the resin has a branched structure (Α1_Βι) ηγ, the molecular weight of the vinyl aromatic block When the distribution is a unimodal distribution, the resin has poor drop weight impact strength, poor bending strength, and poor transparency. However, the above-mentioned ones are only the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited by this, that is, the simple equivalent changes and modifications made according to the scope of the patent application and the content of the invention specification, All should still fall within the scope of the invention patent. Table 1. Composition of each embodiment of the present invention. 2: Composition of each comparative example of the present invention. 3: Comparison of the physical properties of the examples and comparative examples of the present invention. This paper size applies the Chinese National Standard (CNS) A4 specification (210x 297 public love) Page 18 574231 A7 B7 V. Description of the invention (17): 1 > THF 2 'SM: Thank Z # 3 iD: 1VTH medicine t niBULi: IET 槪 蜃 槪 蜃 5 ^ BD / SM, lvThfz # llllf ^^ M4sbif? BHT: 2,6-Z: 丨 nlllTS-4., XinΌλ OJ fo H— ^ oo crs) ~ ^ Structure 1 BKT (g) | BD / SM * (g / g) | | SM (g) 1 | BD (g) 1 | SM (g) 1 | BD (g) | | SM (g) 1 | BD ( g) 1 | SM (g) 1 n-BuLi (g) | SM (g) 1 | n-BuLi (g) | | SM (g) 1 n-BuLi (g) THF (g) ΛΙ / ZZjS, 1 1 Α1 · Β1 · Α2ΒΜ3 1 1 1 1 1,500 1 I 1,500 | § s 1 1 (1,500 1 β 5,100 § I Η— ^ Α1 · Β1 ^ 2ΒΜ ^ Μ 1 1 ^ 500 1— ^ so § 〇§ 1,020 t 1 i On y \ s 44.4 si to Α1ΰ1-Α2-Β2 · Α3 K— ^ 1 1 1 1,560 €: 8 § I 1,500 I 1 1 2,160 white La I 4,320 | Ln | 〇3 Α1 · Β1 ^ 2Β2 · Α3 Ln 1 1 1 1 1500 § ι, 5ω 1 1 1,620 Vy 5,160 Xin A1-B1-A2B2-A3 K— ^ 1 1 2,520 1,500 § i 1 1 b— ^ i H— ^ 4,080 6 1— ^ I A1 «1 ^ 2-B2-A3R ・ 〇144 /% 1 1 1,476 i 1,476 1 1 1 ~ k 5,040 to § w 1 〇 \ 22.7 120/480 1 1 ih ^ i § i 1 1) ~ ^ 1 4,800 衾 o § | f-i ^ wll This paper size applies to Chinese National Standard (CNS) A4 (210x 297 mm) Page 19 574231 A7 B7 V. Description of the invention (18 9 Huiyun · 1-Β1} ηγ _snw fffljian # ο 7: si i stupid 3) ¾ shock 2) captive 2) = 70 / 30mMiM ♦ Li. 〇〇n3 H— ^ OO -0 ON OO H— ^ Outline 丨 Speech m (s mm BHIXg) BD / SM * (g / g) SM (g) BD (g) SM (g) BD (g) | SM (g) 1 | BD (g) 1 | SM (g) 1 n-BuLi (g) | SM (g) 1 n-BuLi (g) | SM (g) 1 n-BuLi (g) THF ( g) 1 i r-wT Al-Bl · ^-8 1 1 1 1 1 1,120 CT \ 1 1 1,120 LO vo Ln 1 6,396 Π LO Lm s Vr Q7 1 Al-B1 ^ 2 ν〇1 1 1 1 1 U ) o U) o 1 1 1 1 6? 3〇〇8.08.0 § t \ mn A1-B1-A2-B2-A3 to bo 1 1 1 1,560 1 1500 | s § 1 l, 5〇〇 | LO 2,580 | 21.2 | 2,580 v〇§ Feet 丨 J3, 1 ^ 2Β2Α3) ιΥ 1 1 1 1— ^ i H— ^ i H— »i 1 ~ ^ i 1 1 H— ^ i 48.0 4,800? 〇o § vr Q7 1 Α1ΰ1 ^ 2 Ltx 1 1 1 1 1 1,800 OO § 1 1 tSJ § 4,800 Ϊ ^ 〇 \ § YT UrflV Α1ΰ1 ^ 2B2 · Α3 1 1 1 H-4 S 8 1,500 1 1 § ON CTs 5,400 OO § nr cx Xinjiang Os Α1ΰ1 ^ 2-Β2 · Α3 • Each 1 1 1 〇 \ H— ^ s to s 1 1 1 1 8,136 OO ON os 1— ^ feet! J7 Lo 1 1 1 2M 2 ^ 80 2, 1 1 1 2.592 8 § (ΑΗΒ1) ιΥ 1 11.2 (SiCl4) 1 1 1 1 1 1 1 7200 1 1 1 1 4,800 228.0 Vr Q7 Late OO 0U-This paper size applies to China National Standard (CNS) A4 (210x 297 mm) Page 20
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI568786B (en) * | 2014-06-06 | 2017-02-01 | Denki Kagaku Kogyo Kk | A resin composition containing a block copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI568786B (en) * | 2014-06-06 | 2017-02-01 | Denki Kagaku Kogyo Kk | A resin composition containing a block copolymer |
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