201229110 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種生物可分解高分子及其製作方法，尤其 將作為分解促進聚合物的低分子量聚_3 _羥基丁酸' (LMWPHB) ’接入而分子量聚合物中。 【先前技術】 聚-3-羥基丁酸酯（PHB)屬於聚羥基酯類 (P〇lyhydr〇xyalkanoate，PHAS)的一種，最早是在 1926 發現，是 個"T元王被彳政生物降解的咼分子聚g旨類，具生物可相容性， 屬於熱塑性材料’有氣密雜，高舰及高結晶度的性質 於微生物發_的生物可分解高分子，已廣泛地各種生醫 材料、包裝材方面。 …隨著魏S識的細’魏的永續细成為越來越重要的 課通具有較大为子置的聚_3_經基丁酸g旨(pHB)雖然可以被生 物所分解’然而速度贿，且其性質並不能達騎有高分子材 料的需求’喊他錄;5化瓣躲乏_生物可分解性的性 貝有些在南/孤燃燒時不易完全裂解，而產生戴奥辛等毒素， 因此，需要一種能夠具有原來的塑膠性質，且能夠具有生物 解性、生物相容性的高分子材料。 、 【發明内容】 本^明的主要目的是提供一種生物可分解高分子，該生物 ^分=咼分子包含高分子量聚合物以及分解促進聚合物，該高 为子里聚$物可以為各種聚酯類高分子，該分解促進聚合物為 低刀子里t -3-罗里基丁酸醋（i〇w m〇iecuiar polyHiydroxybutymte ’ LMWPHB)，其重量平均分子量在 500曰〜2500 g/mole的範圍，較佳為1767 、而數目平均分 子量在500〜2000g/m〇ie的範圍，較佳為12〇〇g/mde，且佔該 、2〇1229ll〇 生物可分解高分子的總重量百分比5%〜30%’其結構式如下方 化學結構式1所示， 化學結構式1 : CH,201229110 VI. Description of the Invention: [Technical Field] The present invention relates to a biodegradable polymer and a process for producing the same, in particular, a low molecular weight poly- 3 -hydroxybutyric acid (LMWPHB) as a decomposition-promoting polymer Into the molecular weight polymer. [Prior Art] Poly-3-hydroxybutyrate (PHB) belongs to the class of polyhydroxyesters (P〇lyhydr〇xyalkanoate, PHAS), which was first discovered in 1926 and is a biodegradation of T.咼Molecular polyg-type, biocompatible, belongs to the thermoplastic material's biodegradable polymer with air-tight, high-yield and high crystallinity properties, and has been widely used in various biomedical materials. Packaging materials. ... With the fineness of Wei's knowledge, Wei's perpetual fineness becomes an increasingly important lesson. The poly-[3]-butyric acid (pHB) can be decomposed by organisms. Speed bribery, and its nature can not meet the needs of riding polymer materials 'calling his record; 5 petal hiding _ biodegradable sex shells are not easy to completely cleave in the south / solitary burning, and produce dioxin and other toxins Therefore, there is a need for a polymer material which can have the original plastic properties and which is biodegradable and biocompatible. SUMMARY OF THE INVENTION The main object of the present invention is to provide a biodegradable polymer comprising a high molecular weight polymer and a decomposition promoting polymer, which can be various kinds of poly An ester polymer, the decomposition-promoting polymer is a low-knife t -3- ryolithic acid vinegar (i〇wm〇iecuiar polyHiydroxybutymte 'LMWPHB), and its weight average molecular weight is in the range of 500 曰 2500 g/mole. Preferably, it is 1767, and the number average molecular weight is in the range of 500 to 2000 g/m 〇ie, preferably 12 〇〇 g/mde, and accounts for 5% of the total weight of the biodegradable polymer of 2 〇 1229 〇 〜 30%' of its structural formula is shown in the following chemical structural formula 1, chemical structural formula 1: CH,
OH '^C'-0-CH-~€H2-Cv +CH=CH—C—0— !l 2 V I » 0 0 CH, 〇OH '^C'-0-CH-~€H2-Cv +CH=CH—C—0— !l 2 V I » 0 0 CH, 〇
本發明的另一目的在提供一種生物可分解高分子之製作方 法’該方法包含一分解促進聚合物製備步驟以及一掺合步驟， 分解促進聚合物製備步驟係從聚-3-羥基丁酸酯(PHB)分離出 作為分解促進聚合物的低分子量聚-3-羥基丁酸酯，而該掺合 步驟係將分離出的低分子量聚-3-羥基丁酸酯掺入高分子量聚 合物中’其掺入的方法可以為擠壓、攪拌混練、混溶等，且分 解促進聚合物製備步驟又包含混合步驟、通入氣氛步驟、加熱 反應步驟以及清洗過濾步驟，混合步驟係將聚_3_羥基丁酸酯 (PHB)與聚乙二醇(PEG)以一特定比例在一容器中混合唯一混 合溶液；通入氣氛步驟係將氮氣通入該容器中；加熱反應步驟 係將該容器加熱，使該混合溶液在高溫下反應一段時間，而形 ，反應溶液，清洗過濾步驟係將反應溶液以去離子水清洗多 次，再經過過濾而分離為產物及未反應溶液，再將該產物除 水，而獲得低分子量聚_3_羥基丁酸酯(LMWPHB)，以作為 分解促進聚合物.。 不毛月所挺供的生物可分解高分子及其製作方法，藉由將 PHB材料在劣解過程產出巴豆酸寡聚物之不飽和化合物即 作，分解促進聚合物的低分子量聚_3_經基丁酸自旨，掺入高分 子里，合物中，利用低分子量聚_3_羥基丁酸酯(LMWpHB)易 於被菌類分解的特性，而能夠改善一般高分子量聚合物的生物 相容性’而使得—般塑膠材料能夠在使用一段時 間後此被生物所分解，而達到環保的效益。 、201229110 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做更詳細 的說明，俾使熟習該項技藝者在研讀本說明書後能據以實施。 一種生物可分解高分子，主要包含高分子量聚合物以及分 解促進聚合物’該高分子量聚合物可以為熱塑性的聚氯乙烯 (PVC)、丙烯酸酯(Acrylate)、聚對苯二曱酸二乙酉旨(PET)、聚 曱基丙烯酸曱酯(PMMA)、聚羥基丁酸酯(PHB)，熱固性的環 氧樹脂、不飽和聚酯樹脂(Unsaturated polyester)以及聚胺基曱 酸醋(PU)的至少其中之一，該分解促進聚合物為低分子量聚_3_ 沒基丁 酸酉旨（low molecular weight poly-3-hydroxybutyrate， 鲁 LMWPHB) ’其重量平均分子量在500〜2500 g/mole的範圍， 較佳為1767 g/mole、而數目平均分子量為500〜2000 g/mole的 範圍，較佳為1200 g/mole，且佔該生物可分解高分子的總重 量百分比5%〜30%，其結構式如下方化學結構式1所示， 化學結構式1 :Another object of the present invention is to provide a method for producing a biodegradable polymer, which comprises a decomposition promoting polymer preparation step and a blending step, and the decomposition promoting polymer preparation step is from poly-3-hydroxybutyrate (PHB) separates low molecular weight poly-3-hydroxybutyrate as a decomposition promoting polymer, and the blending step incorporates the separated low molecular weight poly-3-hydroxybutyrate into the high molecular weight polymer' The method of incorporation may be extrusion, stirring and kneading, miscible, etc., and the decomposition-promoting polymer preparation step further comprises a mixing step, an atmosphere-passing step, a heating reaction step, and a washing and filtering step, and the mixing step is to be collected. Hydroxybutyrate (PHB) and polyethylene glycol (PEG) are mixed in a specific ratio in a specific mixing solution; the atmosphere is introduced into the vessel; the heating step is to heat the vessel. The mixed solution is allowed to react at a high temperature for a period of time, and the reaction solution is washed and filtered. The reaction solution is washed several times with deionized water, and then separated into products by filtration and not inverted. Solution was added and the product water removal, to obtain a low molecular weight polyethylene _3_ hydroxybutyrate (LMWPHB), as a decomposition accelerating polymer .. The biodegradable polymer which is supplied by the hairless moon and the preparation method thereof, by using the unsaturated compound of the crotonic acid oligomer in the process of inferior decomposition of the PHB material, the decomposition promotes the low molecular weight poly-polymer of the polymer_3_ By the addition of butylbutyric acid to the polymer, the low molecular weight poly- 3 -hydroxybutyrate (LMWpHB) is easily decomposed by fungi, and the biocompatibility of the general high molecular weight polymer can be improved. The nature of the plastic material can be decomposed by the organism after a period of use, and achieve environmental benefits. [2012] [Embodiment] The embodiments of the present invention will be described in more detail below with reference to the drawings and the reference numerals, and can be implemented by those skilled in the art after studying this specification. A biodegradable polymer mainly comprising a high molecular weight polymer and a decomposition promoting polymer. The high molecular weight polymer may be a thermoplastic polyvinyl chloride (PVC), an acrylate (Acrylate) or a polyethylene terephthalate. (PET), poly(mercapto methacrylate) (PMMA), polyhydroxybutyrate (PHB), thermosetting epoxy resin, unsaturated polyester resin (Unsaturated polyester), and polyamino phthalic acid vinegar (PU) One of the decomposition promoting polymers is a low molecular weight poly-3-hydroxybutyrate (LMWWB) having a weight average molecular weight of 500 to 2500 g/mole. Preferably, it is 1767 g/mole, and the number average molecular weight is in the range of 500 to 2000 g/mole, preferably 1200 g/mole, and accounts for 5% to 30% of the total weight of the biodegradable polymer, and its structural formula As shown in the chemical formula 1 below, the chemical structural formula 1:
严 y0H 4一 0-€H—CH2—C、 +CH=CH-C-(>-~ l \ I ii 0 υ ch3 ο ο φ 參閱第一圖，本發明生物可分解高分子之製作方法的流程 圖。如第一圖所示，生物可分解高分子之製作方法S1包含分 解促進聚合物製備步驟S10以及一掺合步驟S20分解促進聚合 物製備步驟S10係從聚-3-羥基丁酸酯(ΡΗΒ)分離出作為分解促 進聚合物的低分子量聚-3-羥基丁酸酯，而該掺合步驟S20係 將分離出的低分子量聚_3_羥基丁酸酯掺入高分子量聚合物 中，其掺入的方法可以為擠壓、攪拌混練、混溶等。 參閱第二圖’分解促進聚合物製備步驟的細項步驟流程 圖。如第二圖所示，分解促進聚合物製備步驟S10包含混合步 驟S11、通入氣氛步驟S13、加熱反應步驟S15以及清洗過濾 步驟S17 ’混合步驟S11係將聚-3-羥基丁酸酯(ΡΗΒ)與聚乙二 5 、201229110 醇(PEG)以一特定比例在一容器中混合唯一混合溶液，該特定 比例較佳為重量比例1:2 ;通入氣氛步驟S13係將氮氣通入該 容器中，加熱反應步驟S15係將該容器加熱，使該混合溶液在 一尚溫下反應一特定時間’如165〇C下反應4小時，而形成反 應溶液，清洗過濾步驟S17係將反應溶液以去離子水清洗多 次，再經過過濾而分離為產物及未反應溶液，再將該產物除 水，而獲得作為分解促進聚合物的低分子量聚_3_羥基丁酸酯 (LMWPHB)。 日Yan y0H 4 -0-H-CH2-C, +CH=CH-C-(>-~ l \ I ii 0 υ ch3 ο ο φ Referring to the first figure, the method for producing the biodegradable polymer of the present invention As shown in the first figure, the biodegradable polymer production method S1 comprises a decomposition promoting polymer preparation step S10 and a blending step S20 decomposition promoting polymer preparation step S10 is from poly-3-hydroxybutyric acid. The ester (ΡΗΒ) separates the low molecular weight poly-3-hydroxybutyrate as a decomposition promoting polymer, and the blending step S20 incorporates the separated low molecular weight poly-3-hydroxybutyrate into the high molecular weight polymer The method of incorporation may be extrusion, stirring and kneading, miscible, etc. Refer to the second figure, a flow chart of the detailed steps of the decomposition-promoting polymer preparation step. As shown in the second figure, the decomposition-promoting polymer preparation step S10 includes a mixing step S11, an inlet atmosphere step S13, a heating reaction step S15, and a washing and filtering step S17. The mixing step S11 is performed by using poly-3-hydroxybutyrate (ΡΗΒ) with polyethylene glycol 5, 201229110 alcohol (PEG). Mixing a unique mixed solution in a container at a specific ratio, the specific The ratio is preferably 1:2 by weight; the atmosphere is introduced into step S13 to pass nitrogen into the vessel, and the heating step S15 is to heat the vessel to react the mixture to a specific temperature for a specific time. The reaction is carried out for 4 hours under 〇C, and a reaction solution is formed. The washing and filtering step S17 is carried out by washing the reaction solution several times with deionized water, separating it into a product and an unreacted solution by filtration, and then removing the product to obtain water. Decomposition-promoting polymer low molecular weight poly-3-hydroxybutyrate (LMWPHB).
本發明的特點在於’本發明的生物可分解高分子及其製作 方法，藉由將PHB材料在劣解過程產出巴豆酸寡聚物^不飽 和化合物，即作為分解促進聚合物的低分子量聚經基丁^ 醋(LMWPHB) ’捧入高分子量聚合物中’利用低分子量聚3 羥基丁酸酯(LMWPHB)易於被菌類分解的特性，而能约改A盖一 般高分子量聚合物的生物降解性和生物相容性，而使得—般 膠材料能夠在使用一段時間後能被生物所分解，而達到環^ 效益。 i… [實驗實施例] 以下所提供的實驗實施例係比較未添加低分子量聚_3__ 基丁酸酯（LMWPHB)的聚-3-羥基丁酸酯（PHB)、添= 16%LMWPHB 的 PHB、25%LMWPHB 的 PHB，其實驗二‘ [附圖一】The invention is characterized in that the biodegradable polymer of the present invention and the preparation method thereof produce low-molecular weight polycondensation as a decomposition-promoting polymer by producing a crotonic acid oligomer/unsaturated compound by a PHB material in a decomposing process. The use of low molecular weight poly(3 hydroxybutyrate) (LMWPHB) is easily decomposed by fungi, and the biodegradation of general high molecular weight polymers can be modified by the use of butyl ketone (LMWPHB). Sexual and biocompatible, so that the gel material can be decomposed by the organism after a period of use, and the benefits are achieved. i... [Experimental Example] The experimental examples provided below compare the poly-3-hydroxybutyrate (PHB) without adding a low molecular weight poly- 3_-butyrate (LMWPHB), and the PHB of the addition = 16% LMWPHB. 25% of LMWPHB's PHB, experiment 2' [Fig. 1]
6 .2012291106.201229110
據用以解釋本發明之較佳實施例，並非企圖 ^ 乂對本創作做任何形式上之關，是以，凡有在相同之精 51有，創作之任何修傳或變更’皆仍應包括在本創作意 圃保遷之範臂。 【圖式簡單說明】 ，一圖係本發明生物可分解高分子之製作方法的流程圖。 第二圖係分解促進聚合物製備步驟的細項步驟流程圖。 【主要元件符號說明】 S1 生物可分解高分子之製作方法 S10 分解促進聚合物製備步驟 S11 混合步驟 S13 通入氣氛步驟 S15 加熱反應步驟 S17 清洗過濾步驟 S20 掺合步驟 7In order to explain the preferred embodiment of the present invention, it is not an attempt to make any form of the creation of the present invention, so that any modifications or changes in the creation of the same essence should still be included in This creation is intended to be the arm of the move. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for producing a biodegradable polymer of the present invention. The second figure is a flow chart of the detailed steps of the decomposition-promoting polymer preparation step. [Main component symbol description] S1 Biodegradable polymer manufacturing method S10 Decomposition promoting polymer preparation step S11 Mixing step S13 Passing into the atmosphere step S15 Heating reaction step S17 Cleaning and filtering step S20 Blending step 7