201139511 六、發明說明： 【發明所屬之技術領域】 本發明係關於內酯改質單末端型聚矽氧多元醇之製造 方法以及胺基甲酸酯樹脂組成物。 【先前技術】 近年來，有機聚矽氧烷化合物，由於低摩擦性、熱安 定性、撥水性、消泡性、脫模性等之界面特性優異，爲改 良塗料、成型品等之合成樹脂的性能而添加使用例如二甲 基聚矽氧烷、聚甲基苯基矽氧烷、含有反應基之二甲基聚 矽氧烷、經聚醚改質之有機聚矽氧烷等之改質劑。 然而’由於此等與樹脂之相溶性不充分或耐熱性不充 分而導致使用範圍受到限制。因此，以改良此等缺點爲目 的而已有提案一種經在聚矽氧烷與甘油單烯丙基醚之加成 反應物加成內酯而成之內酯改質有機聚矽氧烷化合物。（ 發明專利文獻1 ) 然而’其係由於內酯將與甘油單烯丙基醚之複數個經 基進行反應而具有複數個聚內酯鏈使得交聯結構增多，— 級經基與二級羥基同時存在而導致反應性不穩定，因此作 爲聚胺基甲酸酯樹脂用原料來使用則會有困難。因此，希 望開發出一種可更進一步作爲聚胺基甲酸酯樹脂用原料來 使用之含有聚矽氧烷鏈之多元醇（在下文中，則稱爲「衆 矽氧多元醇」）。 〔先前技術文獻〕 (發明專利文獻） 201139511 (發明專利文獻1)日本發明特開平第03_623 0號公報 【發明内容】 〔所欲解決之技術問題〕 本發明之目的是提供一種分子量分布是常態分布（高 斯分布）、分子量乖離率低、未與內酯類反應之未反應一 級羥基少而適合作爲聚胺基甲酸酯樹脂用原料之在側鏈具 有聚矽氧烷鏈的聚矽氧多元醇之製造方法，尤其是提供— 種可用作爲一步成型用聚胺基甲酸酯樹脂原料之聚矽氧多 元醇。 〔解決問題之技術方法〕 本發明之發明人等針對分子量分布是常態分布、未反 應一級羥基少的聚胺基甲酸酯樹脂用之聚矽氧多元醇之製 造方法專心硏討結果，發現藉由將特定聚矽氧烷在特定溫 度且在觸媒的存在下進行製造之方法，即可獲得優異的聚 胺基甲酸酯彈性體原料用之聚矽氧多元醇而終於達成本發 明。 · 亦即’本發明提供一種胺基甲酸酯原料用內酯改質單末 端型聚矽氧多元醇之製造方法，其特徵爲對在單末端具有兩 個一級羥基、在另一端未具有反應性基的分子量爲1 000至 4000之有機聚矽氧烷，以相對於每—個—級羥基爲5至10 莫耳之內酯單體在溫度爲80至140。(：且在觸媒的存在下進 行開環加成聚合；及使用其之胺基甲酸酯樹脂組成物。 〔發明之功效〕 本發明經在特定溫度下將內酯單體之特定量開環加成 201139511 聚合於特定分子量的在單末端具有兩個一級羥基、在另^ 端未具有反應性基之有機聚矽氧烷上，藉此即可製造分+ 量分布是常態分布、分子量乖離率低、未與內醋類反應而 殘留的未反應之一級羥基少的聚矽氧多元醇，因此，可用 作爲一步成型用聚胺基甲酸酯樹脂原料。 【實施方式】 〔本發明之最佳實施方式〕 在本發明所使用的有機聚矽氧烷是在單末端具有兩個 一級羥基、在另一端未具有反應性基之分子量爲1 000至 4000者，較佳爲分子量爲2000至4000。此外，羥基價較 佳爲20至60mgKOH/g、酸價較佳爲0_5 mgKOH/g以下。 若分子量大於4〇〇〇時，則內酯單體與有機聚矽氧烷之反應 無法順利進行而變成兩波峰，使得未反應之一級羥基增多 ，因此爲不佳。此外，若小於1 〇〇〇時，則不能對胺基甲酸 酯樹脂賦予有機聚矽氧烷之功效的低摩擦性等功效。 所謂「在本發明所使用的內酯單體」是包括：例如β-丙內酯、γ -丁內醋、δ -戊內醋、ε -己內酯、γ -巴豆醯內醋 (γ-crotonolactone)等；較佳爲ε -己內醋。在本發明係以相 對於每一個一級羥基爲5至10莫耳之內酯單體進行開環加 成聚合者，但是，較佳爲將每8莫耳之內酯單體加成聚合 於有機聚矽氧烷之單側的兩個一級羥基者。若相對於有機 聚矽氧烷所具有的每一個一級羥基，內酯單體爲少於5莫 耳時，由於未反應一級羥基既增多又無法成爲常態分布而 變成呈帶肩狀者，因此爲不佳。在另一方面，若多於10莫 201139511 耳時，則所獲得樹脂之黏度變高而使得操作使用性劣化。 內酯改質單末端型聚矽氧多元醇之製造條件是在系統 中溫度爲80至140 °C且在觸媒的存在下進行製造，更佳爲 8 0 至 1 2 0 〇C。 若系統中溫度爲低於8 (TC時，則反應速度變慢而需要 長時間之合成。此外，若系統中溫度高於140°C時，則在 單末端具有兩個一級羥基、在另一端未具有反應性基之有 機聚矽氧烷將分解而導致無法獲得所欲內酯改質單末端型 聚矽氧多元醇。 前述所使用的觸媒較佳爲錫系觸媒，特佳爲參-2-乙基 己酸丁基錫。其時，系統中觸媒之濃度較佳爲100至500 p p m ° 欲製造內酯改質單末端型聚矽氧多元醇時，在反應容 器投入在單末端具有兩個一級羥基、在另一端未具有反應 性基的分子量爲1000至4000之有機聚矽氧烷及觸媒，設 定系統中溫度爲80至140 °C、且在氮氣氣體環下，投入以 相對於有機聚矽氧烷之每一個羥基爲5至10莫耳之內酯單 體而進行較佳爲6至24小時，進一步較佳爲8至1 5小時 之反應’當非揮發成分到達9 9.5質量％以上後即結束反應 。然後，取出聚矽氧多元醇即可。 本發明之胺基甲酸酯樹脂組成物是經將前述改質單末 端型聚矽氧多元醇與其他多元醇成分混合作爲多元醇成分 而與聚異氰酸酯進行反應，藉此即可獲得胺基甲酸酯樹脂 成形品。其時’可預先製成胺基甲酸酯預聚物，或將聚異 201139511 氰酸酯、多元醇、鏈段增長劑加以一步成型。 在本發明所使用的聚異氰酸酯是通常使用於聚胺基甲 酸酯樹脂者，其包括：例如2,4_甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯或此等之混合物、間或對伸苯基二異 氰酸酯、對二甲苯二異氰酸酯、伸乙基二異氰酸酯、四亞 甲基- I，4-二異氰酸酯、六亞甲基-1，6-二異氰酸酯、二苯基 甲烷-4,4’-二異氰酸酯、3,3’-二甲基.·二苯基甲烷_4,4_伸聯 苯基二異氰酸酯、3，3 -二氯-4,4 -伸聯苯基二異氰酸酯、4,4-伸聯苯基一異氰酸醋或1,5 -萘二異氰酸醋、二異氰酸聯甲 苯胺、異佛酮二異氰酸酯、環己院二異氰酸醋、甲苯胺二 異氰酸酯、粗製二苯基甲烷二異氰酸酯、及二苯基甲烷二 異氰酸酯、三苯基甲烷三異氰酸酯以及此等之各種衍生物 。此外，也包括將下述多元醇與前述任一聚異氰酸酯進行 反應所獲得末端爲異氛酸醋基之胺基甲酸醋預聚物。 所謂「其他多元醇」是包括習知的聚醚多元醇、聚碳 酸酯多元醇、或一般的聚酯多元醇，亦即，也包括將多元 醇與多元羧酸在觸媒的存在下進行縮合反應而具有酯鍵者 。前述多元醇較佳爲由羥基價所計算得分子量爲500至 5000者，特佳爲1000至3000。 前述「鏈段增長劑」較佳爲使用碳數爲2至10之低分 子量直鏈二醇、二胺化合物。其代表例是包括：乙二醇、 1，2-丙二醇、1，3-丙二醇、2,3-丁 二醇、1,4-丁 二醇、2,2’-二甲基-1,3-丙二醇、二甘醇、1,5-五亞甲基二醇、1，6-六亞 甲基二醇、環己烷- I，4-二醇、環己烷-1，4-二醇、環己烷-1，4- 201139511 二甲醇等之單獨或混合物；伸乙基二胺、1，6 -六亞甲基二 胺、哌阱、2,5 -二甲基哌阱、異佛酮二胺、4,4，-二環己基 甲烷二胺、3,3、二甲基-4,4，-二環己基甲烷二胺、1，4_環己 烷二胺、1，2 -丙二胺、二伸乙基三胺，三伸乙基四胺、3，3，_ 二氯-4,4’-二胺基二苯基甲烷等之胺化合物；以及及肼（聯 胺：hydrazine)、醯肼（acid hydrazide)等之肼類。特佳爲 1，4-丁二醇、三羥甲基丙烷。 本發明之胺基甲酸酯樹脂組成物是可使用先前習知的 聚胺基甲酸酯之製造方法，例如一步法 '預聚物法或準預 聚物法等方法，以及整體聚合、溶液聚合、乳化聚合、乳 化聚合等。生產方式可爲先前習知的方法，亦即，可使用 平板方式、雙輸送帶方式、熱硬化方式、低溫硬化方式、 反應射出成型（RIM: Reaction Injection Molding)方式、 利用開放鑄模之成形、與複合材之一體成形、現場施工方 式、噴霧方式、流延方式、注入、塗布、含浸等方法。在 製造時，較佳爲將聚異氰酸酯與多元醇以0.8至1.1之莫耳 比（NCO/(OH + NH2))進行反應，進一·步較佳爲1.〇至1.05 。此外，也可在製造胺基甲酸酯時，以一般使用的添加量 使用習知的胺基甲酸酯化觸媒、界面活性劑、其他助劑等 〇 更進一步本發明之胺基甲酸酯組成物視需要可添加抗 氧化劑、紫外線吸收劑、抗水解劑、塡充劑、著色劑、強 化劑、脫模劑、難燃劑等。並且，可在不致於損及根據本 發明的胺基甲酸酯樹脂組成物之功效範圍內添加其他熱塑 201139511 性聚胺基甲酸酯彈性體、或其以外之泛用熱塑性樹脂 ABS樹脂、AS樹脂、氯乙烯樹脂、聚醯胺等。本發明 成物也可含有選自界面活性劑、觸媒、穩定劑、及顏 之各種添加劑。 本發明之胺基甲酸醋組成物可用作爲熱塑性彈性 T P U )、熱硬化性彈性體（τ S U )、水性聚胺基甲酸酯 、自由基硬化性胺基甲酸酯樹脂而使用於成形材料、 劑、黏著劑、塗料、發泡體、密封劑、光硬化性樹脂 所有領域的聚胺基甲酸酯製品。具體的用途是可使用 、薄膜、薄片、皮帶、軟管、捲筒、輪胎、抗震材、 、鞋底等之三維成形物、以及人工皮革、合成皮革、 •硬質發泡體、纖維材料、工業材料、電機電子材料 學材料、醫療材料、土木建設材料等許多領域。 《實施例》 以下’列舉實施例更具體說明本發明，但是本發 不受限於此等者。此外，文.中之「份」、「％」是以 爲基準。 〔實施例1〕（內酯改質單末端型聚矽氧多元醇之合 在配備氮氣導入管、溫度計、冷卻管、攪拌裝置 公升四頸燒瓶中’置入5 00份之下述結構式之在單末 有兩個一級羥基、在另一端未具有反應性基之有機聚 烷（羥基價：41.1mgKOH/g;酸價：〇,〇5mgKOH/g) 份之ε-己內酯、0·250份之作爲反應觸媒的參-2-乙基 丁基錫，並一邊使氮氣流通一邊在1C1(TC進行反應13 例如 之組 料中 體（ 樹脂 接著 等之 於紗 襯墊 軟質 、光 明並 質量 K ) 之1 端具 矽氧 '335 己酸 小時 -10- 201139511 。（反應終點是適當地測定不揮發分（NV )，在NV到達 9 9.5 %以上時則視爲終點。）經1 3小時反應後，由於NV 到達99.7%，從燒瓶取出樹脂。可獲得反應物之羥基價爲 24.4 mgKOH/g、酸價爲 0.55 mgKOH/g 之在常溫（25°C ) 爲白色固體、在100°C爲透明液體之樹脂。GPC測定之分 子量分布是呈常態分布，C13NMR測定之有機聚矽氧烷之未 反應一級羥基的比例爲5% (亦即，與ε-己內酯進行反應之 一級羥基爲9 5 % )。201139511 VI. Description of the Invention: The present invention relates to a process for producing a lactone-modified single-end polyoxyl polyol and a urethane resin composition. [Prior Art] In recent years, organic polyoxane compounds have excellent interfacial properties such as low friction, thermal stability, water repellency, defoaming property, and mold release property, and are used to improve synthetic resins such as paints and molded articles. For the performance, a modifier such as dimethyl polyoxyalkylene, polymethylphenyl sulfoxane, dimethylpolysiloxane containing a reactive group, polyether modified organic polyoxyalkylene or the like is added. . However, the range of use is limited due to insufficient compatibility with the resin or insufficient heat resistance. Therefore, in order to improve these disadvantages, a lactone-modified organopolyoxyalkylene compound obtained by adding a lactone to an addition reaction of polyoxyalkylene and glycerol monoallyl ether has been proposed. (Patent Document 1) However, it is because the lactone will react with a plurality of radicals of glycerol monoallyl ether to have a plurality of polylactone chains such that the crosslinked structure is increased, and the graded and secondary hydroxyl groups At the same time, since the reactivity is unstable, it is difficult to use it as a raw material for a polyurethane resin. Therefore, it has been desired to develop a polyoxyalkylene chain-containing polyol which can be further used as a raw material for a polyurethane resin (hereinafter, referred to as "polyoxyl polyol"). [Prior Art Document] (Invention Patent Document) 201139511 (Patent Patent Document 1) Japanese Laid-Open Patent Publication No. Hei 03-623 No. 03-623. [Draft of the Invention] [Technical Problem to be Solved] An object of the present invention is to provide a molecular weight distribution which is a normal distribution. (Gaussian distribution), a polyoxyl polyol having a polyoxyalkylene chain in a side chain which is suitable as a raw material for a polyurethane resin, having a low molecular weight drop rate and having less unreacted primary hydroxyl groups which are not reacted with a lactone. The production method, in particular, provides a polyoxyl polyol which can be used as a raw material for a one-step molding polyurethane resin. [Technical method for solving the problem] The inventors of the present invention have focused on the production method of a polyoxyl polyol for a polyurethane resin having a normal molecular weight distribution and a small amount of unreacted primary hydroxyl groups, and have found that The present invention has finally been attained by a method in which a specific polyoxyalkylene is produced at a specific temperature and in the presence of a catalyst to obtain an excellent polyoxyl polyol for a polyurethane elastomer raw material. · The present invention provides a process for producing a lactam-modified single-end polyoxyl polyol of a urethane raw material, which is characterized in that it has two primary hydroxyl groups at one end and no reaction at the other end. The organic polyoxyalkylene having a molecular weight of from 1 000 to 4,000 is from 5 to 10 moles of lactone monomer per temperature of from 80 to 140. (: and ring-opening addition polymerization in the presence of a catalyst; and a urethane resin composition using the same. [Effect of the invention] The present invention opens a specific amount of a lactone monomer at a specific temperature. Cycloaddition 201139511 is polymerized on a specific molecular weight of an organopolyoxane having two primary hydroxyl groups at one end and no reactive group at the other end, thereby producing a fractional distribution which is a normal distribution and a molecular weight deviation. The polyoxyphthalocl polyol having a low rate and having no unreacted primary hydroxyl group remaining in the reaction with the internal vinegar can be used as a raw material for the one-step molding polyurethane resin. [Embodiment] [The most BEST MODE FOR CARRYING OUT THE INVENTION The organopolyoxane used in the present invention has a molecular weight of from 1,000 to 4,000 having two primary hydroxyl groups at one terminal and no reactive group at the other terminal, and preferably having a molecular weight of from 2,000 to 4,000. Further, the valence of the hydroxyl group is preferably from 20 to 60 mgKOH/g, and the acid value is preferably from 0 to 5 mgKOH/g. If the molecular weight is more than 4 Å, the reaction between the lactone monomer and the organopolyoxane cannot be carried out smoothly. And become two waves It is not preferable because the number of unreacted hydroxyl groups is increased, and if it is less than 1 Å, the effect of imparting low-friction properties to the urethane resin without the effect of the organopolyoxane can not be obtained. The lactone monomer used in the present invention includes, for example, β-propiolactone, γ-butyrolactone, δ-pentane vinegar, ε-caprolactone, γ-crotonolactone. Etc.; preferably ε-hexyl vinegar. In the present invention, the ring-opening addition polymerization is carried out with a lactone monomer of 5 to 10 moles per primary hydroxyl group, but it is preferably every 8 moles. The lactone monomer is added to the two primary hydroxyl groups on one side of the organopolyoxyalkylene. If the primary hydroxyl group is present relative to the organopolyoxyalkylene, the lactone monomer is less than 5 moles. In the case of the ear, since the unreacted primary hydroxyl group increases and cannot become a normal distribution, it becomes a shoulder-like shape, so it is not preferable. On the other hand, if more than 10 mo 201139511 ears, the viscosity of the obtained resin becomes high. The workability is deteriorated. The manufacture of lactone-modified single-end polyoxyl polyol The part is manufactured in the system at a temperature of 80 to 140 ° C and in the presence of a catalyst, more preferably 80 to 1 2 0 〇 C. If the temperature in the system is lower than 8 (TC, the reaction speed becomes It takes a long time to synthesize slowly. In addition, if the temperature in the system is higher than 140 ° C, the organopolyoxane having two primary hydroxyl groups at one end and no reactive group at the other end will be decomposed and will be unable to be synthesized. The desired lactone-modified single-end polyoxyl polyol is used. The catalyst used above is preferably a tin-based catalyst, particularly preferably butyl-2-ethylhexanoate. In the system, the catalyst is used in the system. The concentration is preferably from 100 to 500 ppm °. When the lactone-modified single-end polyoxyl polyol is to be produced, the molecular weight of the first-stage hydroxyl group at the single end and the non-reactive group at the other end is 1000 to 4000 organic polyoxane and catalyst, set the temperature in the system to 80 to 140 ° C, and under a nitrogen gas ring, put 5 to 10 moles per hydroxyl group relative to the organic polyoxane The lactone monomer is preferably carried out for 6 to 24 hours, further preferably 8 to 15 The reaction of the hour is completed when the nonvolatile component reaches 99.5 mass% or more. Then, the polyoxyl polyol can be taken out. The urethane resin composition of the present invention is obtained by reacting the modified single-end polyoxyl polyol with other polyol components as a polyol component and reacting with a polyisocyanate, whereby an amine group can be obtained. An ester resin molded article. At this time, the urethane prepolymer may be preliminarily prepared, or the polyisocyanate 201139511 cyanate, polyol, and chain extender may be molded in one step. The polyisocyanate used in the present invention is generally used in polyurethane resins, and includes, for example, 2,4-methylphenyl diisocyanate, 2,6-methylphenylene diisocyanate or the like. Mixture, meta- or para-phenylene diisocyanate, p-xylene diisocyanate, ethyl diisocyanate, tetramethylene-I,4-diisocyanate, hexamethylene-1,6-diisocyanate, diphenyl Methane-4,4'-diisocyanate, 3,3'-dimethyl.diphenylmethane_4,4_exbiphenyl diisocyanate, 3,3-dichloro-4,4-diphenyl Diisocyanate, 4,4-extended biphenyl-isocyanate or 1,5-naphthalene diisocyanate, toluidine diisocyanate, isophorone diisocyanate, cycloheximide diisocyanate Vinegar, toluidine diisocyanate, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate, triphenylmethane triisocyanate, and various derivatives thereof. Further, a urethane prepolymer having an oleic acid group at the end obtained by reacting the following polyol with any of the above polyisocyanates is also included. The term "other polyols" includes conventional polyether polyols, polycarbonate polyols, or general polyester polyols, that is, also includes the condensation of a polyol with a polycarboxylic acid in the presence of a catalyst. The reaction has an ester bond. The above polyol is preferably a molecular weight of from 500 to 5,000, particularly preferably from 1,000 to 3,000, calculated from the hydroxyl value. The above "segment growth agent" is preferably a low molecular weight linear diol or diamine compound having a carbon number of 2 to 10. Representative examples include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 2,2'-dimethyl-1,3 -propylene glycol, diethylene glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol, cyclohexane-I,4-diol, cyclohexane-1,4-diol , cyclohexane-1,4-201139511 diethanol or the like alone or in a mixture; ethylene diamine, 1,6-hexamethylenediamine, pipe trap, 2,5-dimethylpiper well, different Buddha Ketodiamine, 4,4,-dicyclohexylmethanediamine, 3,3, dimethyl-4,4,-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2- An amine compound such as propylenediamine, di-ethyltriamine, tri-ethyltetramine, 3,3,-dichloro-4,4'-diaminodiphenylmethane; and hydrazine (hydrazine: Hydroquinone, acid hydrazide, etc. Particularly preferred are 1,4-butanediol and trimethylolpropane. The urethane resin composition of the present invention can be produced by a conventional method for producing a polyurethane, such as a one-step method such as a prepolymer method or a quasi-prepolymer method, and a whole polymerization solution. Polymerization, emulsion polymerization, emulsion polymerization, and the like. The production method can be a conventional method, that is, a flat plate method, a double conveyor belt method, a heat curing method, a low temperature curing method, a reaction injection molding (RIM: Reaction Injection Molding) method, a molding using an open mold, and the like. One-piece composite forming, on-site construction, spray, casting, injection, coating, impregnation, etc. In the production, it is preferred to react the polyisocyanate with the polyol at a molar ratio of 0.8 to 1.1 (NCO / (OH + NH2)), preferably from 1. to 1.05. Further, in the case of producing a urethane, a conventional urethane catalyst, a surfactant, another auxiliary agent or the like may be used in an amount generally used, and the urethane of the present invention may be further further added. The ester composition may optionally contain an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a chelating agent, a coloring agent, a strengthening agent, a releasing agent, a flame retardant, and the like. Further, other thermoplastic 201139511-type polyurethane elastomer, or a general-purpose thermoplastic resin ABS resin thereof, may be added within a range that does not impair the efficacy of the urethane resin composition according to the present invention. AS resin, vinyl chloride resin, polyamine, and the like. The composition of the present invention may also contain various additives selected from the group consisting of surfactants, catalysts, stabilizers, and pigments. The urethane composition of the present invention can be used as a thermoplastic elastomer (TPU), a thermosetting elastomer (τ SU ), an aqueous polyurethane, a radical curable urethane resin, and a molding material. Polyurethane articles in all fields of agents, adhesives, coatings, foams, sealants, and photocurable resins. Specific uses are three-dimensional shapes for use, films, sheets, belts, hoses, rolls, tires, seismic materials, soles, etc., as well as artificial leather, synthetic leather, rigid foam, fiber materials, industrial materials. , electrical and electronic materials materials, medical materials, civil construction materials and many other fields. <<Embodiment>> Hereinafter, the present invention will be more specifically described by the following examples, but the present invention is not limited thereto. In addition, the "parts" and "%" in the text are based on the benchmark. [Example 1] (The combination of a lactone-modified single-end polyoxyl polyol was placed in a nitrogen-introducing tube, a thermometer, a cooling tube, and a stirring device in a four-necked flask, and 500 parts of the following structural formula were placed. An organopolyalkane having two primary hydroxyl groups at the end and having no reactive group at the other end (hydroxyl price: 41.1 mgKOH/g; acid value: 〇, 〇5 mgKOH/g) of ε-caprolactone, 0· 250 parts of cis-2-ethylbutyltin as a reaction catalyst, while circulating nitrogen gas at 1C1 (TC is reacted, for example, in a composition of the material (resin is then waited for the softness, brightness and mass K of the yarn liner) One end has helium oxygen '335 hexanoic acid hour -10- 201139511. (The end point of the reaction is to determine the non-volatile content (NV) appropriately, and the NV is considered to be the end point when the NV reaches above 9.5%.) After 13 hours of reaction Thereafter, since the NV reached 99.7%, the resin was taken out from the flask, and the hydroxyl value of the reactant was 24.4 mgKOH/g, and the acid value was 0.55 mgKOH/g at room temperature (25 ° C) as a white solid at 100 ° C. Transparent liquid resin. The molecular weight distribution measured by GPC is a normal distribution, determined by C13 NMR. A proportion of unreacted hydroxyl machine poly silicon of 5% siloxane (i.e., ε- caprolactone with a hydroxyl group of the reaction is 95%).
〔實施例2至4〕 除了以表1所示混合份數、合成條件以外，其餘則以 與實施例1相同的方式進行合成。 〔比較例1至7〕 除了以表2所示混合份數、合成條件以外，其餘則以 與實施例1相同的方式進行合成。 以下述所示方法測定經以上述實施例及比較例所獲得 樹脂之非揮發成分' 羥基價、酸價、分子量乖離率、未反 應一級羥基的比例、使用GPC測定之分子量分布。 <非揮發成分> 在金屬培養皿取1克之試料並加入5毫升之甲苯，測 定經在1 0 7 · 5 °C乾燥1小時後之殘量。[Examples 2 to 4] The synthesis was carried out in the same manner as in Example 1 except that the mixing ratio and the synthesis conditions are shown in Table 1. [Comparative Examples 1 to 7] The synthesis was carried out in the same manner as in Example 1 except that the mixing ratio and the synthesis conditions are shown in Table 2. The nonvolatile content of the resin obtained in the above Examples and Comparative Examples was determined by the method described below as the hydroxyl group value, the acid value, the molecular weight separation ratio, the ratio of the unreacted primary hydroxyl group, and the molecular weight distribution measured by GPC. <Non-volatile component> A sample of 1 g of the sample was placed in a metal petri dish and 5 ml of toluene was added thereto, and the residual amount after drying at 1 0 5 ° C for 1 hour was measured.
非揮發成分（％) = (B - C) / (A-C) xlOO -11- 201139511 但是， A: 金屬培養皿+乾燥前之試料的質量（克）、 B: 金屬培養皿+乾燥後之試料的質量（克）、 C: 金屬培養皿之質量（克）。 <羥基價〉 對試料加入由醋酸酐及吡啶所構成之乙醯化劑後，加 以1 1 5 °c X 1小時乙醯化。接著，加水使得過量的醋酸酐分 解成醋酸，並加入丙酮、甲苯後，使用N/2氫氧化鉀乙醇 溶液將醋酸中和滴定。 羥基價（mgKOH/g) = ( B - T ) xFx 28.05/S + AN 但是， B : 在空白試驗的N/2氫氧化鉀乙醇之滴下量（毫升）、 T: 在正式試驗的N/2氫氧化鉀乙醇之滴下量（毫升）、 F: N/2氫氧化鉀乙醇之滴定率、 S : 試料採取量（克）、 A N :試料之酸價。 <酸價> 在試料加入中性溶劑（甲苯/甲醇）加以溶解後，以〇 . 1 N氫氧化鉀乙醇進行中和滴定。Non-volatile content (%) = (B - C) / (AC) xlOO -11- 201139511 However, A: metal culture dish + mass of sample before drying (g), B: metal culture dish + sample after drying Mass (g), C: mass of metal petri dish (g). <Hydroxylevalency> After adding an acetalizing agent composed of acetic anhydride and pyridine to the sample, it was added with 1 1 5 ° C for 1 hour. Next, water was added to dissolve the excess acetic anhydride into acetic acid, and after adding acetone and toluene, the acetic acid was neutralized and titrated using a N/2 potassium hydroxide ethanol solution. Hydroxyl valence (mgKOH/g) = (B - T) xFx 28.05/S + AN However, B: amount of N/2 potassium hydroxide in the blank test (ml), T: N/2 in the formal test The amount of potassium hydroxide ethanol (ml), F: N/2 potassium hydroxide ethanol titration, S: sample amount (g), AN: acid value of the sample. <Acid value> After the sample was dissolved in a neutral solvent (toluene/methanol), it was neutralized and titrated with N1N potassium hydroxide ethanol.
酸價（mgKOH/g) = VxF><5.61 1/S 201139511 <分子量乖離率> 由單末端二醇型有機聚矽氧烷之羥基價、酸價、及ε-己內酯/單末端二醇型有機聚矽氧烷之莫耳比所計算得之 目標分子量、與所獲得樹脂之羥基價、酸價所計算得之實 驗分子量計算出乖離率。 分子量乖離率（％)=(目標分子量一實驗分子量）/ 目標分子量χίοο 但是，分子量= 5610〇χ2/(羥基價+酸價）。 <未反應一級經基的比例> 將試料溶解於氘化氯仿，以慣用方法測定13c-nmr。 由顯示於65.5 ppm (相當於鄰接於未反應一級羥基之碳原 子）之波峰與顯示於6 2.0 ppm (鄰接於與內酯進行反應的 一級羥基之碳原子）之波峰進行計算。 未反應一級羥基的比例（％ )= 65.5 ppm波峰面積/ ( 65.5ppm波峰面積+62.0ppm波峰面積）xlOO <利用GPC測定之分子量分布> 將試料溶解於四氫呋喃（THF ) ( 0.4%溶液），進行 凝膠透層析法分析。加以評估所獲得圖之形狀。 〔測定條件〕溶離液：THF ;管柱：TSKgel流量：1.0 毫升/分鐘 管柱：T S K g e 1 G 5 · 4 . 3 . 2 ;偵測器：RI。 〔實施例〕（胺基甲酸酯彈性體薄片之製造） (胺基甲酸酯預聚物之合成） 在2公升燒瓶中，置入484.1份之4,4_二苯基甲烷二 -13- 201139511 異氰酸酯，混合1000份之P〇LYLITEOD-X-640M(DIC公 司製造之聚酯多元醇分子量爲2000)與50.1份之實施例1 的內酯改質單末端型聚矽氧多元醇，在氮氣氣體環境下， 在70°C進行反應約5小時，以獲得NCO當量爲5 2 5之含有 聚矽氧之胺基甲酸酯預聚物。 (胺基甲酸酯彈性體之製造） 混合400份之經溫控成80°C之含有聚矽氧之胺基甲酸 酯預聚物與32.6份之1，4-丁二醇/三羥甲基丙烷的7 0/3 0 ( 重量比）混合物，以離心成形機鑄塑，在140 °C X 1小時之 條件進行硬化後，在1 1 〇°C X 1 6小時之條件進行二次硬化， 以獲得2 mm厚之胺基甲酸酯彈性體薄片。所獲得之薄片 是稍呈白濁，但是獲得具有透明感之強韌薄片。 表1 實施例1 實施例2 實施例3 實施例4 置入 份數 (克） 單末端二醇型有機聚矽氧烷（克） 羥基價：41.1 mgKOH/g、酸價：0.05 mgKOH/g 、分子量：2727 500 500 550 450 ε-己內酯（克） 335 335 276 377 參-2-乙基己酸丁基錫 0.250 0.250 0.248 0.248 鈦酸四異丙酯 ε -己內酯/單末端二醇型有機聚矽氧烷之莫耳比 16 16 12 20 計算 合成酿ΓΟ 100 120 100 100 合成 條件 合成時間（小時） 13 15 15 14 非揮發成分（％) 99.7 99.7 99.8 99.7 所獲得 樹脂之 特性 羥基價（mgKOH/g) 24.4 23.2 26.2 21.7 酸價（mgKOH/g) 0.55 0.65 0.6 0.45 分子量乖離率（％) *1 -1 3 2 1 未反應一級經基的比例（％) *2 5 8 7 3 GPC測定之分子量分布 常態分布. 常態分布 常態分布 常態分布 -14- 201139511 表2 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 置入 份數 (克） 單末端二醇型有機聚矽氧院 (克） 羥基價：41.1mgKOH/g、酸 價：0.05mgKOH/g'分子量 ：2727 500 500 600 700 700 500 單末端二醇型有機聚矽氧垸 (克） 羥基價：22.0mgKOH/g，酸 價：0.05 mgKOH/g、分子量 ：4998 600 ε-己內酯（克） 335 335 201 117 117 219 335 參-2-乙基己酸丁基錫 0.245 鈦酸四異丙酯 0.013 0.013 0.012 0.012 0.012 0,250 計算 ε-己內酯/單末端二醇型有 機聚矽氧烷之莫耳比 16 16 8 4 4 16 16 合成 條件 合成溫度rc) 180 150 150 150 100 100 100 合成時間（小時） 9 10 11 11 32 20 反應 未結束 所獲得 樹脂 之特性 非揮發成分（％) 99.5 99.5 99.6 99,7 99.6 99.8 - 羥基價（mgKOH/g) 19.9 22.9 28.9 33.6 32.9 15.4 — 酸價（mgKOH/g) 0.28 0.5 0.25 0.3 0.31 0.65 - 分子量乖離率（％) *1 22 5 6 4 6 54 — 未反應一級羥基 的比例（％ ”2 19 16 30 44 29 20 — GPC測定之分子量分布 常態 分布 常態 分布 常態 分布 有肩 分布 有肩 分布 雙峰 — 【圖式簡單說明】 魅〇Acid value (mgKOH/g) = VxF><5.61 1/S 201139511 <Molecular weight separation rate> Hydroxyl valence, acid value, and ε-caprolactone/single from a single-end diol type organopolyoxane The molar ratio of the molecular weight calculated by the molar ratio of the terminal diol type organopolyoxane to the calculated molecular weight of the obtained resin and the acid value of the obtained resin was calculated. Molecular weight separation rate (%) = (target molecular weight - experimental molecular weight) / target molecular weight χίοο However, molecular weight = 5610 〇χ 2 / (hydroxyl price + acid value). <Ratio of unreacted primary warp group> The sample was dissolved in deuterated chloroform, and 13c-nmr was measured by a conventional method. The peak shown at 65.5 ppm (corresponding to a carbon atom adjacent to the unreacted primary hydroxyl group) was calculated from the peak shown at 6 2.0 ppm (a carbon atom adjacent to the primary hydroxyl group reacting with the lactone). Ratio (%) of unreacted primary hydroxyl group = 65.5 ppm peak area / (65.5 ppm peak area + 62.0 ppm peak area) xlOO <Molecular weight distribution measured by GPC> The sample was dissolved in tetrahydrofuran (THF) (0.4% solution) , performing gel permeation chromatography analysis. The shape of the obtained graph is evaluated. [Measurement conditions] Dissolved solution: THF; Column: TSKgel flow rate: 1.0 ml/min Tube column: T S K g e 1 G 5 · 4 . 3 . 2 ; Detector: RI. [Examples] (Production of urethane elastomer sheet) (Synthesis of urethane prepolymer) In a 2 liter flask, 484.1 parts of 4,4-diphenylmethane II-13 was placed. - 201139511 Isocyanate, mixed with 1000 parts of P〇LYLITEOD-X-640M (polyester polyol manufactured by DIC Corporation has a molecular weight of 2000) and 50.1 parts of the lactone modified single-end type polyoxyl polyol of Example 1 The reaction was carried out at 70 ° C for about 5 hours under a nitrogen atmosphere to obtain a polyoxyl urethane prepolymer having an NCO equivalent of 5 2 5 . (Manufacture of urethane elastomer) 400 parts of a polyoxymethane-containing urethane prepolymer which was temperature-controlled to 80 ° C and 32.6 parts of 1,4-butanediol / trihydroxyl A mixture of 70/30 (by weight) of methyl propane was cast by a centrifugal molding machine, hardened at 140 ° C for 1 hour, and then subjected to secondary hardening at 1 1 ° C for 16 hours. A 2 mm thick urethane elastomer sheet was obtained. The obtained sheet was slightly cloudy, but a tough sheet having a transparent feeling was obtained. Table 1 Example 1 Example 2 Example 3 Example 4 Number of parts (g) Single-end diol type organopolyoxane (g) Hydroxyl valence: 41.1 mgKOH/g, acid value: 0.05 mgKOH/g, Molecular weight: 2727 500 500 550 450 ε-caprolactone (g) 335 335 276 377 butyl-2-ethylhexanoate butyltin 0.250 0.250 0.248 0.248 tetraisopropyl titanate ε-caprolactone / single-end diol type organic Polyoxane molar ratio 16 16 12 20 Calculated synthetic ΓΟ 100 120 100 100 Synthesis conditions Synthesis time (hours) 13 15 15 14 Non-volatile content (%) 99.7 99.7 99.8 99.7 Properties of the obtained resin hydroxyvalence (mgKOH /g) 24.4 23.2 26.2 21.7 Acid value (mgKOH/g) 0.55 0.65 0.6 0.45 Molecular weight separation rate (%) *1 -1 3 2 1 Ratio of unreacted primary meridian (%) *2 5 8 7 3 GPC measurement Molecular weight distribution normal distribution. Normal distribution Normal distribution Normal distribution-14-201139511 Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Number of parts (g) Single-end diol type Organic Polyoxane (g) Hydroxyl Price: 41.1mgKOH /g, acid value: 0.05 mg KOH / g 'molecular weight: 2727 500 500 600 700 700 500 single-end diol type organopolyfluorene oxime (g) Hydroxyl valence: 22.0 mg KOH / g, acid value: 0.05 mg KOH / g, molecular weight :4998 600 ε-caprolactone (g) 335 335 201 117 117 219 335 butyl-2-ethylhexanoate butyltin 0.245 tetraisopropyl titanate 0.013 0.013 0.012 0.012 0.012 0,250 Calculate ε-caprolactone / single-end two Mohr ratio of alcohol type organic polyoxyalkylene 16 16 8 4 4 16 16 Synthesis conditions Synthesis temperature rc) 180 150 150 150 100 100 100 Synthesis time (hours) 9 10 11 11 32 20 Characteristics of the obtained resin after the reaction is not completed Non-volatile content (%) 99.5 99.5 99.6 99,7 99.6 99.8 - Hydroxy value (mgKOH/g) 19.9 22.9 28.9 33.6 32.9 15.4 - Acid value (mgKOH/g) 0.28 0.5 0.25 0.3 0.31 0.65 - Molecular weight separation rate (%) * 1 22 5 6 4 6 54 — ratio of unreacted primary hydroxyl group (% ” 2 19 16 30 44 29 20 — molecular weight distribution measured by GPC normal distribution normal distribution normal distribution shoulder distribution shoulder distribution double peak— 【Simple description Charm
/> \N 【主要元件符號說明】 並。 J\ \\ -15-/> \N [Key component symbol description] and. J\ \\ -15-