TWI860716B - Acid nucleating agent for polyhydroxyalkanoate and polyhydroxyalkanoate molded product - Google Patents

本發明屬於生物降解材料領域，且涉及聚羥基烷酸酯的酸類成核劑及聚羥基烷酸酯成型體。本發明提供一種組合物，其包含聚羥基烷酸酯以及成核劑，成核劑為脂肪酸。本發明發現，選用脂肪酸作為製備聚羥基烷酸酯成型體的成核劑，能夠在確保所得成型體具有良好力學性能的同時，顯著地提高聚羥基烷酸酯製備成型體時的結晶速度及結晶度，具有成核效率高、加工方式更加簡便的優點；同時所製得的聚羥基烷酸酯成型體具有透明度高的優點，因而具有更廣泛的應用情境。 The present invention belongs to the field of biodegradable materials and relates to an acid nucleating agent for polyhydroxyalkanoate and a polyhydroxyalkanoate molded body. The present invention provides a composition comprising polyhydroxyalkanoate and a nucleating agent, wherein the nucleating agent is a fatty acid. The present invention finds that the use of a fatty acid as a nucleating agent for preparing a polyhydroxyalkanoate molded body can significantly improve the crystallization rate and crystallinity of the polyhydroxyalkanoate molded body while ensuring that the obtained molded body has good mechanical properties, and has the advantages of high nucleation efficiency and simpler processing methods; at the same time, the obtained polyhydroxyalkanoate molded body has the advantage of high transparency, and thus has a wider range of application scenarios.

聚羥基烷酸酯的酸類成核劑及聚羥基烷酸酯成型體 Acid nucleating agent for polyhydroxyalkanoate and polyhydroxyalkanoate molded body

本發明屬於生物降解材料領域，且涉及聚羥基烷酸酯的酸類成核劑及聚羥基烷酸酯成型體。 The present invention belongs to the field of biodegradable materials and relates to acid nucleating agents for polyhydroxyalkanoate and polyhydroxyalkanoate molded bodies.

聚羥基烷酸酯(PHAs)是由微生物透過各種碳源發酵而合成的不同結構的脂肪族共聚聚酯，屬於天然的高分子生物材料。 Polyhydroxyalkanoates (PHAs) are aliphatic copolyesters of different structures synthesized by microorganisms through fermentation of various carbon sources and are natural polymer biomaterials.

聚羥基烷酸酯具有不同的單體結構，其種類繁多；其中大多數單體是鏈長3至14個碳原子的3-羥基脂肪酸，其側鏈R是高度可變的飽和或不飽和、直鏈或支鏈、脂肪族或芳香族的基團，組成結構的多樣性帶來其性能的多樣化，進而使其在應用中具有明顯的優勢。 Polyhydroxyalkanoates have different monomer structures and are of various types; most of the monomers are 3-hydroxy fatty acids with a chain length of 3 to 14 carbon atoms, and their side chains R are highly variable saturated or unsaturated, straight or branched, aliphatic or aromatic groups. The diversity of the composition structure brings about the diversity of its performance, which in turn gives it a significant advantage in application.

同時，聚羥基烷酸酯是一種生物基來源且在海洋環境中可生物降解的聚合物，能夠解決廢棄塑膠引起的環境問題；而且，聚羥基脂肪酸酯具有優異的生物相容性以及機械性能，因此可以被加工成各類的成型體，例如薄膜、吸管、餐具等。 At the same time, polyhydroxyalkanoate is a bio-based polymer that is biodegradable in the marine environment and can solve the environmental problems caused by discarded plastics. Moreover, polyhydroxy fatty acid esters have excellent biocompatibility and mechanical properties, so they can be processed into various molded bodies, such as films, straws, tableware, etc.

結晶速率的控制是影響聚羥基烷酸酯加工速率的重要因素，但現有聚羥基烷酸酯的熱加工製備各類成型體的過程中，存在有結晶速度慢、結晶度低、加工效率低等缺點。 Control of crystallization rate is an important factor affecting the processing rate of polyhydroxyalkanoates. However, in the process of preparing various types of molded bodies by thermal processing of existing polyhydroxyalkanoates, there are disadvantages such as slow crystallization rate, low crystallinity, and low processing efficiency.

目前，有研究表明，可以透過添加成核劑以提高聚羥基烷酸酯的結晶速度及結晶度，進而提高加工效率。 At present, studies have shown that the crystallization speed and crystallinity of polyhydroxyalkanoates can be increased by adding nucleating agents, thereby improving processing efficiency.

如專利文獻1公開號為CN1503824A的中國發明專利申請中揭露了一種使用成核劑與增塑劑的聚羥基鏈烷酸酯加工的組合物，其成核劑為核化劑，具體選自於由滑石、微米化雲母、碳酸鈣、氮化硼、氯化銨、鈉鹽、以及元素週期表第I族及第II族金屬的羧酸鹽所組成的群組。同時在擠出後在一定溫度下保溫結晶，例如線材是在30至40℃、薄膜是在30至45℃。 For example, the Chinese invention patent application with the publication number CN1503824A of patent document 1 discloses a composition processed by polyhydroxyalkanoate using a nucleating agent and a plasticizer, wherein the nucleating agent is a nucleating agent, specifically selected from the group consisting of talc, micronized mica, calcium carbonate, boron nitride, ammonium chloride, sodium salt, and carboxylates of metals of Group I and Group II of the periodic table. At the same time, after extrusion, the crystallization is kept at a certain temperature, for example, 30 to 40°C for wire and 30 to 45°C for film.

再如專利文獻2公開號為CN102906193A的中國發明專利申請中揭露了含有聚羥基烷酸酯的增韌聚乳酸，具體揭露了包含的成核劑選自於炭黑、氰尿酸、尿嘧啶、胸腺嘧啶、雲母滑石、二氧化矽、氮化硼、氮化鋇、黏土、碳酸鈣、合成矽酸及鹽、有機磷酸的金屬鹽、以及高嶺土、或者其組合。 For example, Patent Document 2, a Chinese invention patent application with publication number CN102906193A, discloses toughened polylactic acid containing polyhydroxyalkanoate, and specifically discloses that the nucleating agent contained is selected from carbon black, cyanuric acid, uracil, thymine, mica talc, silicon dioxide, boron nitride, barium nitride, clay, calcium carbonate, synthetic silica and salts, metal salts of organic phosphoric acid, and kaolin, or a combination thereof.

然而，上述成核劑均以無機物或金屬鹽為主，其雖能夠一定程度提高傳統聚羥基烷酸酯製備成型體的結晶速度及結晶度，但改善程度有限；更為重要的是，這類成核劑會影響聚羥基烷酸酯成型體中生物碳占比，使其難以在海洋中全部降解，同時還會導致成型體帶有顏色，降低其透明度，影響其應用。 However, the above nucleating agents are mainly inorganic substances or metal salts. Although they can improve the crystallization speed and crystallinity of the traditional polyhydroxyalkanoate molded bodies to a certain extent, the improvement is limited; more importantly, this type of nucleating agent will affect the proportion of biocarbon in the polyhydroxyalkanoate molded bodies, making it difficult to completely degrade in the ocean. At the same time, it will also cause the molded body to have color, reduce its transparency, and affect its application.

針對上述技術問題，本發明提供一種聚羥基烷酸酯的酸類成核劑及聚羥基烷酸酯成型體。 In response to the above technical problems, the present invention provides an acid nucleating agent for polyhydroxyalkanoate and a polyhydroxyalkanoate molded body.

第一方面，本發明提供一種組合物，其包含聚羥基烷酸酯以及成核劑；成核劑為脂肪酸。 In the first aspect, the present invention provides a composition comprising a polyhydroxyalkanoate and a nucleating agent; the nucleating agent is a fatty acid.

眾所周知的是，脂肪酸是由碳、氫、氧三種元素組成的一種化合物。根據碳鏈長度的不同，脂肪酸分為：短鏈脂肪酸，其碳鏈上的碳原子數小於6，也稱作揮發性脂肪酸；中鏈脂肪酸，指碳鏈上碳原子數為6至12的脂肪酸， 主要成分是辛酸(C8)以及癸酸(C10)；以及長鏈脂肪酸，其碳鏈上碳原子數大於12。而根據碳氫鏈飽和與不飽和的不同可分為3類，即：飽和脂肪酸，碳氫上不具有不飽和鍵；單不飽和脂肪酸，其碳氫鏈鋸有一個不飽和鍵；多不飽和脂肪酸，其碳氫鏈鋸有二個或二個以上不飽和鍵。 As we all know, fatty acids are a type of compound composed of three elements: carbon, hydrogen, and oxygen. According to the length of the carbon chain, fatty acids are divided into: short-chain fatty acids, which have less than 6 carbon atoms on the carbon chain, also known as volatile fatty acids; medium-chain fatty acids, which refer to fatty acids with 6 to 12 carbon atoms on the carbon chain, and the main components are caprylic acid (C8) and capric acid (C10); and long-chain fatty acids, which have more than 12 carbon atoms on the carbon chain. According to the difference between saturated and unsaturated carbon hydrogen chains, they can be divided into three categories, namely: saturated fatty acids, which have no unsaturated bonds on carbon hydrogen; monounsaturated fatty acids, which have one unsaturated bond on their carbon hydrogen chains; polyunsaturated fatty acids, which have two or more unsaturated bonds on their carbon hydrogen chains.

在工業上脂肪酸通常用於丁苯橡膠生產中的乳化劑以及其它表面活性劑、潤滑劑、光澤劑；更可以用於生產高級香皂、透明皂、硬脂酸、以及各種表面活性劑的中間體。 In industry, fatty acids are usually used as emulsifiers in the production of styrene-butadiene rubber, as well as other surfactants, lubricants, and glossing agents; they can also be used to produce high-grade soaps, transparent soaps, stearic acid, and intermediates for various surfactants.

然而，本發明研究發現，脂肪酸可以作為製備聚羥基烷酸酯成型體中的成核劑；並且相較於現有成核劑，脂肪酸或化學式為R-COOH的化合物A在不顯著降低成型體力學性能的前提下，可以顯著地提高聚羥基烷酸酯製備成型體時的結晶速度及結晶度，其具有成核效率高、加工方式更加簡便的優點，同時能夠使得所製得的聚羥基烷酸酯成型體具有透明度高的優點，因而具有更廣泛的應用情境。 However, the present invention has found that fatty acids can be used as nucleating agents in the preparation of polyhydroxyalkanoate molded bodies; and compared with existing nucleating agents, fatty acids or compound A with a chemical formula of R-COOH can significantly improve the crystallization rate and crystallinity of polyhydroxyalkanoate molded bodies without significantly reducing the mechanical properties of the molded bodies. It has the advantages of high nucleation efficiency and simpler processing methods. At the same time, it can make the obtained polyhydroxyalkanoate molded bodies have the advantage of high transparency, so it has a wider range of application scenarios.

實驗表明，在採用本發明所述之成核劑製備聚羥基烷酸酯成型體的過程中，聚羥基烷酸酯系樹脂組合物的結晶度相對更大，說明了成型體的結晶性更高，更利於後續加工成型；並且在具有冷結晶峰的情況下，聚羥基烷酸酯系樹脂組合物的二次升溫冷結晶半峰寬資料相對更小，說明了在加工過程中成型體越易結晶變硬，更利於加工成型。 Experiments show that in the process of preparing polyhydroxyalkanoate molded bodies using the nucleating agent described in the present invention, the crystallinity of the polyhydroxyalkanoate resin composition is relatively higher, indicating that the crystallinity of the molded body is higher and more conducive to subsequent processing and molding; and in the case of a cold crystallization peak, the secondary temperature rise cold crystallization half-peak width data of the polyhydroxyalkanoate resin composition is relatively smaller, indicating that the easier it is to crystallize and harden the molded body during the processing, the more conducive it is to processing and molding.

較佳地，脂肪酸為具有化學式R-COOH(R為C5-C30烷基)結構的化合物或它們的組合物；進一步地，成核劑較佳為月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕櫚酸(十六烷酸)、硬脂酸(十八烷酸)、花生酸(二十烷酸)、山崳酸(二十二烷酸)、木焦油酸(二十四烷酸)、蠟酸(二十六酸)、褐煤酸(二十八酸)、以及蜂花酸(三十烷酸)中的一種或多種。更進一步地，成核劑較佳為山崳酸(二十二烷酸)。 Preferably, the fatty acid is a compound having a chemical formula of R-COOH (R is a C5-C30 alkyl) or a combination thereof; further, the nucleating agent is preferably one or more of lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (lignoceric acid), wax acid (hexacosanoic acid), montanic acid (octacosanoic acid), and melissic acid (triacontanoic acid). Further, the nucleating agent is preferably behenic acid (docosanoic acid).

進一步地，成核劑的添加量為聚羥基烷酸酯質量的0.01%至20%；較佳為0.1%至10%；更佳為0.3%至5%。研究表明，透過控制成核劑的添加比例在此較佳範圍內，可以使得結晶效果更好，且製備的成型體可加工性能也更好。在研究過程中，發現在上述較佳範圍中，典型非限制性地，例如可以為1%、2%、2.5%、3%、4%。 Furthermore, the amount of the nucleating agent added is 0.01% to 20% of the mass of the polyhydroxyalkanoate; preferably 0.1% to 10%; more preferably 0.3% to 5%. Studies have shown that by controlling the addition ratio of the nucleating agent within this preferred range, the crystallization effect can be better and the processability of the prepared molded body is also better. During the research process, it was found that in the above preferred range, typically, but not limited to, for example, it can be 1%, 2%, 2.5%, 3%, 4%.

此外，在熱塑加工領域中，通常將高分子原材料與助劑進行混合後，在高溫熔融(一般高於原材料的熔點溫度)，最後結晶成型，其屬於高分子材料的結晶，其結晶微觀上是高分子鏈部分排列起來的過程，在此過程中，高分子鏈折疊起來，形成有序的區域，這樣的區域成為片晶，片晶可以堆砌成更大的球形結構，稱為球晶，從而構成宏觀上的結晶成形體。其中，溶液結晶(solution crystallization)是從溶液中析出晶體的結晶過程，包含蒸發結晶、冷卻結晶、溶析結晶、反應結晶等。 In addition, in the field of thermoplastic processing, polymer raw materials and additives are usually mixed, melted at high temperature (generally higher than the melting point of the raw materials), and finally crystallized. This belongs to the crystallization of polymer materials. Its crystallization is the process of arranging the polymer chain parts on a microscopic level. In this process, the polymer chain folds up to form an ordered area. Such an area becomes a lamellae, which can be stacked into a larger spherical structure, called a spherulite, thereby forming a macroscopic crystallized body. Among them, solution crystallization is the crystallization process of precipitating crystals from a solution, including evaporation crystallization, cooling crystallization, dissolution crystallization, reaction crystallization, etc.

因為高分子材料的微觀結構的特殊性，其與溶液結晶有著顯著的區別，因此，本研究過程也針對性的探究了一些熱塑加工領域中常用的高分子材料結晶的成核劑。 Due to the particularity of the microstructure of polymer materials, it is significantly different from solution crystallization. Therefore, this research process also specifically explores some commonly used nucleating agents for polymer crystallization in the field of thermoplastic processing.

本發明之聚羥基烷酸酯作為具有優異的全生物降解能力的高分子原料，其玻璃轉變溫度、結晶溫度、熔點、熔程等物理性質與其他聚羥基乙酸(PGA)、聚乳酸(PLA)、聚ε-己內酯(PCL)等材料相比有很大的區別，因此，在常規的加工過程中，聚乳酸等材料很容易快速結晶成型，而聚羥基烷酸酯由於具有較低的玻璃轉變溫度(Tg=0℃，聚乳酸的Tg=60℃)，在加工過程中往往不能快速結晶成型，有鑑於此，本研究進一步探究了聚羥基烷酸酯的結晶性能，並填補了現有技術中缺乏的，適合用於促進聚羥基烷酸酯結晶的技術方案。本發明所述之聚羥基烷酸酯可以為單獨的聚合物，也可以為兩種以上聚合物的組合物。 The polyhydroxyalkanoate of the present invention is a polymer raw material with excellent full biodegradability. Its physical properties such as glass transition temperature, crystallization temperature, melting point, melting range, etc. are very different from those of other materials such as polyhydroxyacetic acid (PGA), polylactic acid (PLA), poly-ε-caprolactone (PCL), etc. Therefore, in the conventional processing process, materials such as polylactic acid are easy to quickly crystallize and form, while polyhydroxyalkanoate has a lower glass transition temperature (Tg=0°C, Tg=60°C of polylactic acid), and often cannot quickly crystallize and form during the processing process. In view of this, this study further explores the crystallization performance of polyhydroxyalkanoate and fills the lack of technical solutions in the existing technology that are suitable for promoting the crystallization of polyhydroxyalkanoate. The polyhydroxyalkanoate described in the present invention can be a single polymer or a combination of two or more polymers.

進一步地，聚羥基烷酸酯可以選自於本領域常用的原料，例如含有3羥基烷酸酯結構單元及/或含有4羥基烷酸酯結構單元的聚合物。具體而言，其為含有下述通式(1)表示的結構單元的聚合物：[CHRCH₂COO](1) Furthermore, the polyhydroxyalkanoate can be selected from commonly used raw materials in the art, such as a polymer containing a 3-hydroxyalkanoate structural unit and/or a 4-hydroxyalkanoate structural unit. Specifically, it is a polymer containing a structural unit represented by the following general formula (1): [CHRCH ₂ COO] (1)

在通式(1)中，R表示由C_pH_2p+1所示的烷基，p表示1至15的整數；較佳為1至10的整數，更佳為1至8的整數。 In the general formula (1), R represents an alkyl group represented by C _p H _2p+1 , and p represents an integer of 1 to 15; preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.

R表示C1-C6的直鏈或支鏈狀的烷基。例如，甲基、乙基、丙基、丁基、異丁基、叔丁基、戊基、己基等。 R represents a C1-C6 straight chain or branched chain alkyl group. For example, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc.

在上述組合物中，聚羥基烷酸酯包含至少一種聚(3-羥基鏈烷酸酯)；聚(3-羥基鏈烷酸酯)包含3-羥基丁酸酯結構單元(在下文中可以稱為3HB)以及其他羥基鏈烷酸酯結構單元(例如，4羥基烷酸酯結構單元等)的至少一種。 In the above composition, the polyhydroxyalkanoate comprises at least one poly(3-hydroxyalkanoate); the poly(3-hydroxyalkanoate) comprises at least one of a 3-hydroxybutyrate structural unit (hereinafter referred to as 3HB) and other hydroxyalkanoate structural units (e.g., a 4-hydroxyalkanoate structural unit, etc.).

作為聚羥基烷酸酯的具體示例，可以列舉例出例如：聚(3-羥基丁酸酯)、聚(3-羥基丁酸酯-共-3-羥基丙酸酯)、聚(3-羥基丁酸酯-共-3-羥基戊酸酯)(簡稱：P3HB3HV)、聚(3-羥基丁酸酯共-3-羥基戊酸酯-共-3-羥基己酸酯)、聚(3-羥基丁酸酯-共-3-羥基己酸酯)(簡稱：P3HB3HH)、聚(3-羥基丁酸酯-共-3-羥基庚酸酯)、聚(3-羥基丁酸酯-共-3-羥基辛酸酯)、聚(3-羥基丁酸酯-共-3-羥基壬酸酯)、聚(3-羥基丁酸酯-共-3-羥基癸酸酯)、聚(3-羥基丁酸酯-共-3-羥基十一烷酸酯)、聚(3-羥基丁酸酯-共-4-羥基丁酸酯)(簡稱：P3HB4HB)等。特別是從加工性及機械特性等觀點考量，較佳為聚(3-羥基丁酸酯-共-3-羥基己酸酯)。 Specific examples of polyhydroxyalkanoates include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (abbreviation: P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviation: P3HB 3HH), poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (abbreviation: P3HB4HB), etc. In particular, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferred from the viewpoints of processability and mechanical properties.

研究表明，採用本發明所述的組合物中的成核劑時，通常來說皆可以實現加快結晶，與組合物中的聚羥基烷酸酯中的結構單體的占比沒有關係。本發明所述之聚羥基烷酸酯較佳為特別由微生物產生的聚羥基烷酸酯，在由微生物產生的聚羥基烷酸酯中，3-羥基烷酸酯結構單元全部以(R)3-羥基烷酸酯結構單元的形式含有。其中，在聚(3-羥基鏈烷酸酯)中，包含3-羥基丁酸酯結 構單元與其它結構單元的共聚聚合物，且在聚(3-羥基鏈烷酸酯)中，3-羥基丁酸酯結構單元與其它結構單元的平均含有比率為50/50至99/1(莫耳百分比/莫耳百分比)；較佳為80/20至94/6(莫耳百分比/莫耳百分比)；在聚羥基烷酸酯原料為兩種以上聚羥基烷酸酯的混合物的情況下，平均含有比率表示混合物整體中所含的各單體的莫耳比。 Studies have shown that when the nucleating agent in the composition of the present invention is used, generally, accelerated crystallization can be achieved, regardless of the proportion of the structural monomers in the polyhydroxyalkanoate in the composition. The polyhydroxyalkanoate of the present invention is preferably a polyhydroxyalkanoate produced by a microorganism, in which the 3-hydroxyalkanoate structural unit is all contained in the form of a (R) 3-hydroxyalkanoate structural unit. Among them, in the poly(3-hydroxyalkanoate), a copolymer of 3-hydroxybutyrate structural units and other structural units is included, and in the poly(3-hydroxyalkanoate), the average content ratio of 3-hydroxybutyrate structural units to other structural units is 50/50 to 99/1 (molar percentage/molar percentage); preferably 80/20 to 94/6 (molar percentage/molar percentage); when the polyhydroxyalkanoate raw material is a mixture of two or more polyhydroxyalkanoates, the average content ratio represents the molar ratio of each monomer contained in the mixture as a whole.

進一步地，其它結構單元包含：3-羥基丙酸酯、3-羥基戊酸酯、3-羥基己酸酯、3-羥基庚酸酯、3-羥基辛酸酯、3-羥基壬酸酯、3-羥基癸酸酯、3-羥基十一烷酸酯、以及4-羥基丁酸酯中的一種或多種，較佳為3-羥基己酸酯結構單元；研究表明，其與上述3-羥基丁酸酯結構單元的匹配性更好。 Further, other structural units include: one or more of 3-hydroxypropionate, 3-hydroxypentanoate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, and 4-hydroxybutyrate, preferably 3-hydroxyhexanoate structural unit; studies have shown that it has better matching with the above-mentioned 3-hydroxybutyrate structural unit.

進一步地，聚羥基烷酸酯的重均分子量為10萬至100萬；較佳為20萬至90萬；進一步地，更佳為30萬至80萬。當重均分子量小於10萬時，存在有獲得的聚羥基烷酸酯系樹脂成型體的機械特性變低的傾向。另一方面，當重均分子量超過100萬時，存在有熔融加工時對機械的負荷變高、生產性變低的傾向。 Furthermore, the weight average molecular weight of the polyhydroxyalkanoate is 100,000 to 1,000,000; preferably 200,000 to 900,000; further, 300,000 to 800,000. When the weight average molecular weight is less than 100,000, the mechanical properties of the obtained polyhydroxyalkanoate resin molding tend to be lower. On the other hand, when the weight average molecular weight exceeds 1,000,000, the load on the machine during melt processing tends to be higher and productivity tends to be lower.

第二方面，本發明提供一種聚羥基烷酸酯成型體，其包含由上述組合物的原料製備而成。本發明所得聚羥基烷酸酯成型體具有透明度高、力學性能較好的優點，因而具有更廣泛的應用情境。 In the second aspect, the present invention provides a polyhydroxyalkanoate molded body, which is prepared from the raw materials of the above-mentioned composition. The polyhydroxyalkanoate molded body obtained by the present invention has the advantages of high transparency and good mechanical properties, and thus has a wider range of application scenarios.

此外，在不抑制本發明的效果的前提下，可以進一步根據成型體的生產需要，添加添加劑等助劑與組合物複配。添加劑可以包含增塑劑、交聯劑、擴鏈劑、潤滑劑等有機或無機材料。有機或無機材料可以單獨使用，也可以兩種以上組合使用。 In addition, under the premise of not inhibiting the effect of the present invention, additives and other auxiliary agents can be further added to the composition according to the production needs of the molded body. The additives can include organic or inorganic materials such as plasticizers, crosslinking agents, chain expanders, lubricants, etc. Organic or inorganic materials can be used alone or in combination of two or more.

並且，可以進一步根據生產需要，調整添加劑的添加量，本發明對此沒有特別限制。 Furthermore, the amount of additives added can be further adjusted according to production needs, and the present invention has no special restrictions on this.

本發明所述的聚羥基烷酸酯成型體可以包含多種形式，如聚合體、薄膜、吸管、瓶、等。 The polyhydroxyalkanoate molded body described in the present invention can include various forms, such as polymers, films, straws, bottles, etc.

第三方面，本發明進一步提供一種製備聚羥基烷酸酯成型體的方法，包含：將包含上述組合物在高於成型體的熔融溫度下(第一溫度)加熱後熔融；在玻璃轉變溫度與熔點溫度之間的溫度(第二溫度)下冷卻成型。 In a third aspect, the present invention further provides a method for preparing a polyhydroxyalkanoate molded body, comprising: heating the above-mentioned composition at a temperature higher than the melting temperature of the molded body (first temperature) and then melting it; and cooling and molding it at a temperature between the glass transition temperature and the melting point temperature (second temperature).

本發明研究發現，第一階段溫度越低，成型體在第二階段下不發生黏連的所需時間越短；但第一階段溫度越高，羥基烷酸酯的流動性會增加，更有利於成型。綜合考量，在第一階段中，控制體系溫度高於聚羥基烷酸酯熔點10℃至60℃。 The present invention has found that the lower the temperature in the first stage, the shorter the time required for the molded body to not stick in the second stage; however, the higher the temperature in the first stage, the greater the fluidity of the hydroxyalkanoate, which is more conducive to molding. Taking all factors into consideration, in the first stage, the system temperature is controlled to be 10°C to 60°C higher than the melting point of the polyhydroxyalkanoate.

同時本發明更發現，第二階段溫度影響聚羥基烷酸酯成型體達到不發生黏連狀態的所需時間的長短；透過大量實驗驗證，第二階段體系溫度在所獲得的成型體的玻璃轉變溫度與熔點溫度之間，較佳為在高於所得成型體的玻璃化轉變溫度30℃以上、且低於所獲得的成型體的熔點溫度20℃以下之間。 At the same time, the present invention further discovered that the temperature of the second stage affects the length of time required for the polyhydroxyalkanoate molded body to reach a non-adhesive state; through a large number of experimental verifications, the second stage system temperature is between the glass transition temperature and the melting point temperature of the obtained molded body, preferably between 30°C higher than the glass transition temperature of the obtained molded body and 20°C lower than the melting point temperature of the obtained molded body.

同時，本發明所述的成型方式分為熱加工成型方式以及非熱加工成型方式；熱加工成型方式包含擠出成型、注塑成型、壓延成型、流延成型、吹塑成型、雙向拉伸成型等；非熱加工成型方式包含溶液澆注等。較佳為使用熱加工成型方式。 At the same time, the molding methods described in the present invention are divided into thermal processing molding methods and non-thermal processing molding methods; thermal processing molding methods include extrusion molding, injection molding, calendering molding, cast molding, blow molding, biaxial stretching molding, etc.; non-thermal processing molding methods include solution pouring, etc. It is preferred to use thermal processing molding methods.

與現有技術相比，本發明的主要優點包含： Compared with the prior art, the main advantages of the present invention include:

第一，本發明提供的用於聚羥基烷酸酯成型體的成核劑，具有成核效率高、加工方式更加簡便的優點，可以改善聚羥基烷酸酯在熱塑加工製備各類成型體的過程中存在的結晶速度慢、加工效率低等缺點。 First, the nucleating agent for polyhydroxyalkanoate molded bodies provided by the present invention has the advantages of high nucleating efficiency and simpler processing methods, and can improve the shortcomings of slow crystallization speed and low processing efficiency in the process of preparing various types of molded bodies by thermoplastic processing of polyhydroxyalkanoate.

第二，本發明提供的成核劑來源廣泛且產品價格較低，可以降低各類聚羥基烷酸酯成型體的原料成本；同時，本發明提供的成核劑為生物來源，不影響聚羥基烷酸酯成型體的生物碳占比，其仍可達到100%生物來源。 Second, the nucleating agent provided by the present invention has a wide range of sources and a relatively low product price, which can reduce the raw material cost of various types of polyhydroxyalkanoate molded bodies; at the same time, the nucleating agent provided by the present invention is of biological origin, which does not affect the biocarbon ratio of the polyhydroxyalkanoate molded body, and it can still reach 100% of biological origin.

第三，相較於現有無機成核劑或金屬鹽成核劑，本發明提供的用於聚羥基烷酸酯成型體的成核劑所製備的各類聚羥基烷酸酯成型體具有較高的透明度，不會影響各類成型體的顏色。 Third, compared with existing inorganic nucleating agents or metal salt nucleating agents, the various types of polyhydroxyalkanoate molded bodies prepared by the nucleating agent for polyhydroxyalkanoate molded bodies provided by the present invention have higher transparency and will not affect the color of various types of molded bodies.

第四，本發明提供的成核劑所製備的各類聚羥基烷酸酯成型體更具有較好的力學性能，具有更廣泛的應用情境。 Fourth, the various types of polyhydroxyalkanoate molded bodies prepared by the nucleating agent provided by the present invention have better mechanical properties and a wider range of application scenarios.

以下對本發明的具體實施方式進行詳細說明。應當理解的是，此處所說明的具體實施方式僅用於說明以及解釋本發明，並不用於限制本發明。在下文中將透過實施例對本發明進行詳細說明。以下實施例中，如無特別說明，所用的各材料均可透過商購獲得，如無特別說明，所用的方法為本領域的常規方法。 The specific implementation of the present invention is described in detail below. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention. The present invention will be described in detail through examples below. In the following examples, unless otherwise specified, all materials used can be obtained through commercial purchase, and unless otherwise specified, the methods used are conventional methods in this field.

在本文中所披露的範圍的端值以及任何數值都不限於所述的精確的範圍或數值，這些範圍或數值應當理解為包含接近這些範圍或數值的值。對於數值範圍來說，各個範圍的端值之間、各個範圍的端值以及單獨的點值之間，以及單獨的點值之間可以彼此組合而獲得一個或多個新的數值範圍，這些數值範圍應被視為在本文中具體揭露。 The end values of the ranges and any numerical values disclosed in this article are not limited to the exact ranges or numerical values described, and these ranges or numerical values should be understood to include values close to these ranges or numerical values. For numerical ranges, the end values of each range, the end values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

透過以下實施例對本發明做更詳細的說明，但所述的實施例均不構成對本發明的限制。在以下各實施例中，除了具有特殊說明之外，對於實施例中所使用到的所有原料均為市購。 The present invention is described in more detail through the following examples, but the examples do not constitute a limitation of the present invention. In the following examples, except for special instructions, all raw materials used in the examples are commercially available.

採用原材料： Raw materials used:

PHBH-330：聚(3-羥基丁酸酯-共-3-羥基己酸酯)，北京藍晶微生物科技有限公司。 PHBH-330: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), Beijing Lanjing Microbiology Technology Co., Ltd.

PHBH-350：聚(3-羥基丁酸酯-共-3-羥基己酸酯)，北京藍晶微生物科技有限公司。 PHBH-350: Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), Beijing Lanjing Microbiology Technology Co., Ltd.

聚(3-羥基丁酸酯-共-3-羥基戊酸酯)(PHBV)，自製。 Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), homemade.

聚(3-羥基丁酸酯-共-3-羥基辛酸酯)(PHBO)，自製。 Poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (PHBO), homemade.

聚(3-羥基丁酸酯共-3-羥基戊酸酯-共-3-羥基己酸酯(P3HB3HV3HH)，自製。 Poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate (P3HB3HV3HH), homemade.

聚(3-羥基丁酸酯-共-4-羥基丁酸酯)(P34HB)，自製。 Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB), homemade.

採用設備： Equipment used:

混料設備，採用高速混料機中在室溫下共混。 Mixing equipment: blending at room temperature in a high-speed mixer.

造粒設備，可使用不同長徑比的平行同向雙螺桿擠出機、平行異向雙螺桿擠出機、錐形雙螺桿擠出機、以及單螺桿機等本領域常用的擠出造粒設備；將組合物置於雙螺桿擠出機的下料斗或失重秤中；擠出造粒設備的溫度設定在50至180℃(第一溫度)的範圍內，主機轉速為50至500r/min，投料量或產能根據實際生產狀態進行調整；後續可以使風冷拉條切粒、水浴拉條切粒、磨面熱切、水環切、以及水下切粒等切粒方式進行製粒，並在生產加工的過程中保 持40至65℃(第二溫度)的水浴條件；製備的粒子使用鼓風乾燥箱，烘乾，排除水分對粒子性能的影響，同時使粒子結晶完全。 The granulation equipment may be a parallel co-rotating twin-screw extruder, a parallel counter-rotating twin-screw extruder, a conical twin-screw extruder, a single-screw extruder, or other commonly used extrusion granulation equipment in the field; the composition is placed in a lower hopper or a loss-in-weight scale of the twin-screw extruder; the temperature of the extrusion granulation equipment is set within a range of 50 to 180° C. (first temperature), the main machine speed is 50 to 500 r/min, The feed amount or production capacity is adjusted according to the actual production status; the pelletizing can be carried out by air-cooled strand pelletizing, water-bath strand pelletizing, grinding hot cutting, water ring cutting, and underwater pelletizing, and the water bath condition of 40 to 65°C (second temperature) is maintained during the production process; the prepared particles are dried in a blast drying oven to eliminate the influence of moisture on the particle performance and make the particles completely crystallized.

薄膜製作設備，採用單層或多層吹膜機等本領域常用製膜或製管設備，螺桿與模頭溫度設定溫度50至180℃(第一溫度)；製備的薄膜在收卷前使用烘道在40至65℃(第二溫度)的條件下進行產線上結晶。 Film making equipment uses single-layer or multi-layer film blowing machines and other commonly used film or tube making equipment in this field. The screw and die temperature are set at 50 to 180°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 40 to 65°C (second temperature) before winding.

實施例一 Implementation Example 1

本實施例提供一種組合物，包含聚羥基烷酸酯以及成核劑，其中聚羥基烷酸酯包含：聚(3-羥基丁酸酯-共-3-羥基己酸酯)(在下文中簡稱為PHBH-330)、聚(3-羥基丁酸酯-共-3-羥基己酸酯)(在下文中簡稱為PHBH-350)、聚(3-羥基丁酸酯-共-3-羥基戊酸酯)(在下文中簡稱為PHBV)、聚(3-羥基丁酸酯-共-3-羥基辛酸酯)(在下文中簡稱為PHBO)、聚(3-羥基丁酸酯共-3-羥基戊酸酯-共-3-羥基己酸酯(在下文中簡稱為P3HB3HV3HH)、聚(3-羥基丁酸酯-共-4-羥基丁酸酯)(在下文中簡稱為P34HB)、以及其組合；其中，成核劑為脂肪酸，具體包含：二十二酸、硬脂酸、木焦油酸、蜂花酸、月桂酸、蠟酸、褐煤酸、棕櫚酸、花生酸、肉豆蔻酸、以及其組合；本實施例中所選擇的組合物，具體參照下列表1。 The present embodiment provides a composition comprising a polyhydroxyalkanoate and a nucleating agent, wherein the polyhydroxyalkanoate comprises: poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter referred to as PHBH-330), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter referred to as PHBH-350), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter referred to as PHBV), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (hereinafter referred to as PHB O), poly (3-hydroxybutyrate co-3-hydroxyvalerate-co-3-hydroxyhexanoate (hereinafter referred to as P3HB3HV3HH), poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (hereinafter referred to as P34HB), and combinations thereof; wherein the nucleating agent is a fatty acid, specifically including: behenic acid, stearic acid, linalool acid, melissic acid, lauric acid, wax acid, montanic acid, palmitic acid, arachidic acid, myristic acid, and combinations thereof; the composition selected in this embodiment is specifically referred to in Table 1 below.

實施例二(造粒) Example 2 (granulation)

實驗例1：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中的組合物1。 Experimental Example 1: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 1 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末與成核劑二十二酸(山崳酸)置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powder of PHBH-BP350 and the nucleating agent behenic acid (behenic acid) in a high-speed mixer, and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of the twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為350(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 160°C and a main machine speed of 350 (r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，並將造粒水浴溫度設定為45℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water bath stranding and granulation method, and set the granulation water bath temperature to 45℃; use a blast drying oven to dry the prepared particles at 60℃ for more than 4 hours to eliminate the effect of moisture on particle performance and make the particles crystallize completely.

實驗例2：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中的組合物2。 Experimental Example 2: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 2 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末以及粒子的混合品與成核劑二十二酸(山崳酸)置於高速混料機中，在室溫下使用混料轉速100(r/min)以及混料時間10(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the mixture of PHBH-BP350 powder and particles and the nucleating agent behenic acid (behenic acid) in a high-speed mixer, and mix at room temperature with a mixing speed of 100 (r/min) and a mixing time of 10 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在60至170℃的範圍內，主機轉速為400(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 60 to 170°C and a main machine speed of 400 (r/min).

步驟三，造粒冷卻：採用風冷拉條切粒的方式；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: adopt air-cooled strand cutting method; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles crystallize completely.

實驗例3：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物3。 Experimental Example 3: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 3 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的其他成型體(注塑產生的廢料)、成核劑硬脂酸、以及木焦油酸置於高速混料機中，在室溫下使用混料轉速 400(r/min)以及混料時間10(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the other molded bodies of PHBH-BP350 (waste produced by injection molding), nucleating agent stearic acid, and wood tar acid in a high-speed mixer, and mix at room temperature with a mixing speed of 400 (r/min) and a mixing time of 10 (min); after mixing, place the mixture in the lower hopper of the twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至150℃的範圍內，主機轉速為50(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 150°C and a main machine speed of 50 (r/min).

步驟三，造粒冷卻：採用水下切粒的方式，水溫60℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: underwater granulation is used, the water temperature is 60℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles crystallize completely.

實驗例4：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物4。 Experimental Example 4: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 4 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粒子、成核劑硬脂酸、以及蜂花酸置於高速混料機中，在室溫下使用混料轉速600(r/min)以及混料時間7(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the PHBH-BP350 particles, nucleating agent stearic acid, and melic acid in a high-speed mixer, and mix at room temperature at a mixing speed of 600 (r/min) and a mixing time of 7 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在100至180℃的範圍內，主機轉速為450(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 100 to 180°C and a main machine speed of 450 (r/min).

步驟三，造粒冷卻：採用風冷拉條切粒的方式進行切粒；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use air-cooled strand pelletizing to pelletize; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on particle performance and make the particles completely crystallized.

實驗例5：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物5。 Experimental Example 5: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 5 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末、粒子或其他成型體(注塑產生的廢料)的混合品與成核劑月桂酸以及蠟酸置於高速混料機中，在室溫下使用混料轉速250(r/min)以及混料時間6(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the mixture of PHBH-BP350 powder, granules or other molded bodies (waste produced by injection molding) with nucleating agent lauric acid and wax acid in a high-speed mixer, and mix at room temperature with a mixing speed of 250 (r/min) and a mixing time of 6 (min); after mixing, place the mixture in the lower hopper of the twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至180℃的範圍內，主機轉速為500(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 50 to 180°C and at a main machine speed of 500 (r/min).

步驟三，造粒冷卻：採用水環切粒的方式，水溫65℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water ring granulation method, water temperature 65℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on particle performance and make the particles crystallize completely.

實驗例6：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物6。 Experimental Example 6: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 6 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末及粒子的組合品與成核劑褐煤酸置於高速混料機中，在室溫下使用混料轉速350(r/min)以及混料時間3(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the combination of PHBH-BP350 powder and particles and the nucleating agent montanic acid in a high-speed mixer, and mix at room temperature with a mixing speed of 350 (r/min) and a mixing time of 3 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在70-140℃的範圍內，主機轉速為150r/min的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 70-140℃ and at a main machine speed of 150r/min.

步驟三，造粒冷卻：採用水下切粒的方式，水溫60℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: underwater granulation is used, the water temperature is 60℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles crystallize completely.

實驗例7：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物7。 Experimental Example 7: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 7 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末與成核劑棕櫚酸、花生酸、以及蜂花酸置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間10(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: PHBH-BP350 powder and nucleating agents palmitic acid, arachidic acid, and melissic acid are placed in a high-speed mixer, and mixed at room temperature with a mixing speed of 200 (r/min) and a mixing time of 10 (min); after mixing, the mixture is placed in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在80至180℃的範圍內，主機轉速為100(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 80 to 180°C and a main machine speed of 100 (r/min).

步驟三，造粒冷卻：採用磨面熱切的方式；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: adopt the method of hot grinding; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on the performance of the particles and make the particles crystallize completely.

實驗例8：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物8。 Experimental Example 8: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 8 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350以及PHBH-BP330的粉末與成核劑肉豆蔻酸以及褐煤酸置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powders of PHBH-BP350 and PHBH-BP330 and the nucleating agents myristic acid and montanic acid in a high-speed mixer, and mix them at room temperature at a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為350(r/min(的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 160°C and a main machine speed of 350 (r/min().

步驟三，造粒冷卻：採用水浴拉條切粒的方式，水溫45℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water bath strand cutting method, water temperature 45℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on particle performance and make the particles crystallize completely.

實驗例9：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物9。 Experimental Example 9: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 9 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350以及PHBH-BP330的粉末與粒子的混合物與成核劑月桂酸以及蠟酸置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the mixture of powder and particles of PHBH-BP350 and PHBH-BP330, the nucleating agents lauric acid and wax acid in a high-speed mixer, and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在60至145℃的範圍內，主機轉速為300(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 60 to 145°C and at a main machine speed of 300 (r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，水溫55℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water bath strand cutting method, water temperature 55℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on particle performance and make the particles completely crystallized.

實驗例10：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物10。 Experimental Example 10: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 10 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP330的粉末與成核劑月桂酸以及蠟酸置於高速混料機中，在室溫下使用混料轉速450(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powder of PHBH-BP330, the nucleating agent lauric acid and wax acid in a high-speed mixer, and mix at room temperature with a mixing speed of 450 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of the twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在80至160℃的範圍內，主機轉速為250(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 80 to 160°C and at a main machine speed of 250 (r/min).

步驟三，造粒冷卻：採用水下切粒的方式，水溫50℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: underwater granulation is used, the water temperature is 50℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles completely crystallized.

實驗例11：製作粒子成型體，採用雙螺桿擠出造粒；原料)採用表1中組合物11。 Experimental Example 11: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material was composition 11 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBV的粒子與成核劑二十二酸(山崳酸)置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the PHBV particles and the nucleating agent behenic acid (behenic acid) in a high-speed mixer, and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為350(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 160°C and a main machine speed of 350 (r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，並將造粒水浴溫度設定為45℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water bath stranding and granulation method, and set the granulation water bath temperature to 45℃; use a blast drying oven to dry the prepared particles at 60℃ for more than 4 hours to eliminate the effect of moisture on particle performance and make the particles crystallize completely.

實驗例12：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物12。 Experimental Example 12: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 12 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBV以及P34HB的粒子與成核劑二十二酸(山崳酸)置於高速混料機中，在室溫下使用混料轉速100(r/min)以及混料時間10(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the particles of PHBV and P34HB and the nucleating agent behenic acid (behenic acid) in a high-speed mixer, and mix at room temperature with a mixing speed of 100 (r/min) and a mixing time of 10 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在60至170℃的範圍內，主機轉速為400(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 60 to 170°C and a main machine speed of 400 (r/min).

步驟三，造粒冷卻：採用風冷拉條切粒的方式；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: adopt air-cooled strand cutting method; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles crystallize completely.

實驗例13：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物13。 Experimental Example 13: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 13 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350以及PHBV的組合物粉末與成核劑硬脂酸以及木焦油酸置於高速混料機中，在室溫下使用混料轉速400(r/min)以及混料時間10(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the composite powder of PHBH-BP350 and PHBV, the nucleating agent stearic acid and wood tar acid in a high-speed mixer, and mix at room temperature with a mixing speed of 400 (r/min) and a mixing time of 10 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至150℃的範圍內，主機轉速為50(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 150°C and a main machine speed of 50 (r/min).

步驟三，造粒冷卻：採用水下切粒的方式，水溫60℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: underwater granulation is used, the water temperature is 60℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on the particle performance and make the particles crystallize completely.

實驗例14：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物14。 Experimental Example 14: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 14 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將P3HB3HV3HH以及PHBO的粉末與成核劑硬脂酸以及蜂花酸置於高速混料機中，在室溫下使用混料轉速600(r/min)以及混料時間7(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powders of P3HB3HV3HH and PHBO and the nucleating agents stearic acid and melissic acid in a high-speed mixer, and mix them at room temperature at a mixing speed of 600 (r/min) and a mixing time of 7 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在100至180℃的範圍內，主機轉速為450(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 100 to 180°C and a main machine speed of 450 (r/min).

步驟三，造粒冷卻：採用風冷拉條切粒的方式進行切粒；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use air-cooled strand pelletizing to pelletize; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on particle performance and make the particles completely crystallized.

實驗例15：製作粒子成型體，採用雙螺桿擠出造粒；原料採用表1中組合物15。 Experimental Example 15: To prepare a particle molding, twin-screw extrusion granulation was used; the raw material used was composition 15 in Table 1.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350、PHBV、以及P34HB組合物的粉末與成核劑月桂酸以及蠟酸置於高速混料機中，在室溫下使用混料轉速250(r/min)以及混料時間6(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powders of PHBH-BP350, PHBV, and P34HB composition, the nucleating agents lauric acid and wax acid in a high-speed mixer, and mix at room temperature with a mixing speed of 250 (r/min) and a mixing time of 6 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至180℃的範圍內，主機轉速為500(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 50 to 180°C and at a main machine speed of 500 (r/min).

步驟三，造粒冷卻：採用水環切粒的方式，水溫65℃；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Step 3, granulation cooling: Use water ring granulation method, water temperature 65℃; the prepared particles are dried in a blast drying oven at 60℃ for more than 4 hours to eliminate the influence of moisture on particle performance and make the particles crystallize completely.

比較實驗例1：相較於實驗例1中的組合物1，比較實驗例1不添加成核劑二十二酸，同樣製作粒子成型體，且採用雙螺桿擠出造粒；原料採用100重量份的PHBH-BP350。 Comparative Experimental Example 1: Compared with Composition 1 in Experimental Example 1, the nucleating agent docosanoic acid is not added in Comparative Experimental Example 1, and the particle molding is made in the same way, and twin-screw extrusion granulation is adopted; the raw material adopts 100 parts by weight of PHBH-BP350.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powder of PHBH-BP350 in a high-speed mixer and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為350(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 160°C and a main machine speed of 350 (r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，並將造粒水浴溫度設定為45℃；但是在實際操作過程中，擠出機擠出時不穩定，成型體黏連且無法分離。 Step 3, granulation cooling: adopt water bath stranding and granulation method, and set the granulation water bath temperature to 45℃; however, in the actual operation process, the extruder is unstable during extrusion, and the molded bodies are adhered and cannot be separated.

比較實驗例2：相較於實驗例1中的組合物1，比較實驗例2將所添加的成核劑山崳酸替換為山崳酸醯胺，同樣製作粒子成型體，且採用雙螺桿擠出造粒；原料採用100重量份的PHBH-BP350以及1重量份的山崳酸醯胺。 Comparative Experimental Example 2: Compared with Composition 1 in Experimental Example 1, the added nucleating agent behenic acid in Comparative Experimental Example 2 is replaced with behenic acid amide, and the particle molding is made in the same way, and twin-screw extrusion granulation is adopted; the raw materials are 100 parts by weight of PHBH-BP350 and 1 part by weight of behenic acid amide.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末與山崳酸醯胺置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powder of PHBH-BP350 and behenyl amide in a high-speed mixer, and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為350(r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation at a temperature range of 50 to 160°C and a main machine speed of 350 (r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，並將造粒水浴溫度設定為45℃；但是在實際操作時，擠出機擠出時不穩定，成型體會黏連，但一段時間後可以透過震動大致分離。 Step 3, granulation cooling: Use water bath stranding and granulation method, and set the granulation water bath temperature to 45℃; however, in actual operation, the extruder is not stable during extrusion, and the molded body will stick together, but after a period of time, it can be roughly separated by vibration.

比較實驗例3：相較於實驗例1中的組合物1，比較實驗例3將所添加的成核劑山崳酸替換為山崳酸鈣，同樣製作粒子成型體，且採用雙螺桿擠出造粒；原料採用100重量份的PHBH-BP350以及1重量份的山崳酸鈣。 Comparative Experimental Example 3: Compared with Composition 1 in Experimental Example 1, in Comparative Experimental Example 3, the added nucleating agent behenic acid is replaced with calcium behenate, and the particle molding is made in the same way, and twin-screw extrusion granulation is adopted; the raw materials are 100 parts by weight of PHBH-BP350 and 1 part by weight of calcium behenate.

製作步驟為： The production steps are:

步驟一，混料：將PHBH-BP350的粉末與山崳酸鈣置於高速混料機中，在室溫下使用混料轉速200(r/min)以及混料時間5(min)進行混料；混料後，將混料置於雙螺桿擠出機的下料斗或失重秤中。 Step 1, mixing: Place the powder of PHBH-BP350 and calcium behenate in a high-speed mixer, and mix at room temperature with a mixing speed of 200 (r/min) and a mixing time of 5 (min); after mixing, place the mixture in the lower hopper of a twin-screw extruder or a loss-in-weight scale.

步驟二，擠出：設定擠出造粒設備的條件，在50至160℃的範圍內，主機轉速為35(0r/min)的條件下，進行擠出造粒。 Step 2, extrusion: Set the conditions of the extrusion granulation equipment to perform extrusion granulation within the range of 50 to 160°C and at a main machine speed of 35 (0r/min).

步驟三，造粒冷卻：採用水浴拉條切粒的方式，並將造粒水浴溫度設定為45℃；但是在實際操作時，擠出機擠出時不穩定，成型體黏連且無法分離。 Step 3, granulation cooling: adopt the method of water bath stranding and granulation, and set the granulation water bath temperature to 45℃; however, in actual operation, the extruder is unstable during extrusion, and the molded bodies are adhered and cannot be separated.

將上述實驗例1至實驗例15以及比較實驗例1至比較實驗例3得到的成型體，透過在下文中說明的聚羥基烷酸酯成型體的性能評價方式，將聚羥基烷酸酯成型體透過注塑機製得符合相應標準要求的測試件，且測定後進行評價。 The molded bodies obtained from the above Experimental Examples 1 to 15 and Comparative Experimental Examples 1 to 3 are subjected to the performance evaluation method of the polyhydroxyalkanoate molded body described below. The polyhydroxyalkanoate molded body is made into test pieces that meet the requirements of the corresponding standards through an injection molding machine, and the test pieces are evaluated after measurement.

在此需要注意的是，上述實驗例1至實驗例15以及比較實驗例1至比較實驗例3的原材料也可以直接製備其他成型體，如製管、製膜、注塑等；此外在不抑制本發明的效果的前提下，可以進一步根據成型體的生產需要，來添加添加劑等助劑與組合物複配。添加劑可以包含增塑劑、交聯劑、擴鏈劑、潤滑劑等有機或無機材料。有機或無機材料可以單獨使用，也可以兩種以上組合 使用。並且，可以進一步根據生產需要來調整添加劑的添加量，本發明對此沒有特別限制。 It should be noted that the raw materials of the above-mentioned Experimental Examples 1 to 15 and Comparative Experimental Examples 1 to 3 can also be directly used to prepare other molded bodies, such as pipe making, film making, injection molding, etc.; in addition, under the premise of not inhibiting the effect of the present invention, additives and other auxiliary agents can be further added to the composition according to the production needs of the molded body. The additives can include organic or inorganic materials such as plasticizers, crosslinking agents, chain expanders, lubricants, etc. Organic or inorganic materials can be used alone or in combination of two or more. Moreover, the amount of additives added can be further adjusted according to production needs, and the present invention has no special restrictions on this.

聚羥基烷酸酯成型體的性能評價方式如下所述：玻璃化轉變溫度Tg、熔融溫度Tm、結晶度：使用差示掃描量熱計(TA Instrument公司製，DSC25型)，計量聚羥基烷酸酯成型體2製10mg，以10℃/分的升溫速度從-50℃一次升溫至180℃時獲取的差示掃描量熱(Differential scanning calorimetry，DSC)曲線。 The performance evaluation method of the polyhydroxyalkanoate molded body is as follows: glass transition temperature Tg, melting temperature Tm, crystallinity: using a differential scanning calorimeter (manufactured by TA Instrument, DSC25 model), 10 mg of the polyhydroxyalkanoate molded body 2 was measured and the temperature was raised from -50°C to 180°C at a rate of 10°C/min to obtain the differential scanning calorimetry (DSC) curve.

結晶度(%)=100%×(熔融焓-冷結晶焓)/100%結晶熔融焓，其中100%結晶熔融焓為147.4J/g。 Crystallinity (%) = 100% × (melting enthalpy - cold crystallization enthalpy) / 100% crystallization melting enthalpy, where 100% crystallization melting enthalpy is 147.4 J/g.

二次升溫冷結晶半峰寬：使用差示掃描量熱計(TA Instrument公司製，DSC25型)，計量聚羥基烷酸酯成型體2製10mg，以10℃/分的升溫速度從-50℃一次升溫至180℃，在180℃保溫3分鐘，以10℃/分的降溫速度從180℃降溫至-50℃，以10℃/分的升溫速度從-50℃二次升溫至180℃，獲取二次升溫的DSC曲線。 Secondary heating cold crystallization half peak width: Using a differential scanning calorimeter (manufactured by TA Instrument, DSC25 model), 10 mg of the polyhydroxyalkanoate molded product 2 was weighed, and the temperature was raised from -50°C to 180°C at a heating rate of 10°C/min, kept at 180°C for 3 minutes, and then lowered from 180°C to -50°C at a cooling rate of 10°C/min, and then raised from -50°C to 180°C at a heating rate of 10°C/min to obtain the DSC curve of the secondary heating.

重均分子量：使用了氯仿溶液的凝膠滲透色譜儀(島津製作所株式會社製，HPLCGPCsystem)並透過聚苯乙烯換算來進行測定。作為此凝膠滲透色譜儀中的色譜柱，使用適用於測定重均分子量的色譜柱即可。 Weight average molecular weight: measured using a gel permeation chromatograph (HPLCGPC system manufactured by Shimadzu Corporation) using a chloroform solution and converted to polystyrene. As the column in this gel permeation chromatograph, a column suitable for measuring weight average molecular weight can be used.

將聚羥基烷酸酯成型體透過注塑機製得相應標準要求的測試件：依照ISO1133-1：2011，在190℃及2.16kg的條件下測定熔體流動速率；熔體流動速率的單位為g/10min；依照ISO527-2-2012，在測試速度為5mm/min的條件下測定拉伸強度以及斷裂伸長率；拉伸強度單位為MPa，斷裂伸長率單位為%；依照ISO179-1：2019，測定缺口衝擊強度；缺口衝擊強度單位為J/m²。 The polyhydroxyalkanoate molded body is made into test pieces according to the corresponding standard requirements through an injection molding machine: According to ISO1133-1:2011, the melt flow rate is measured at 190°C and 2.16kg; the unit of melt flow rate is g/10min; according to ISO527-2-2012, the tensile strength and elongation at break are measured at a test speed of 5mm/min; the unit of tensile strength is MPa, and the unit of elongation at break is %; according to ISO179-1:2019, the notched impact strength is measured; the unit of notched impact strength is J/ ^m2 .

說明：Tg為玻璃化轉變溫度；Tm為熔點。 Note: Tg is the glass transition temperature; Tm is the melting point.

表2中的熱塑加工難度的符號表示說明如下： The symbols for thermoplastic processing difficulty in Table 2 are explained as follows:

○：可連續穩定加工，切粒穩定。 ○: Can process continuously and stably, and pelletizing is stable.

△：熱塑加工時基本穩定，切粒狀態一般。 △: Basically stable during thermoplastic processing, and the pelletizing state is average.

×：擠出機擠出時不穩定，無法連續切粒。 ×: The extruder is not stable during extrusion and cannot perform continuous pelletizing.

由表2可以得知，採用本發明所述成核劑製得的成型體粒子的熱塑加工難度相對更低，可以連續且穩定地加工，且聚合體成型體品質較好。 It can be seen from Table 2 that the thermoplastic processing difficulty of the molded particles prepared by using the nucleating agent of the present invention is relatively lower, and they can be processed continuously and stably, and the quality of the polymer molded body is better.

在採用本發明所述成核劑來製備聚羥基烷酸酯成型體的過程中，聚羥基烷酸酯系樹脂組合物的結晶度相對更大，表示成型體的結晶性更高，更利於後續加工成型。並且在具有冷結晶峰的情況下，聚羥基烷酸酯系樹脂組合物的二次升溫冷結晶半峰寬資料相對更小，表示在加工過程中成型體越易結晶變硬，更利於加工成型。 In the process of using the nucleating agent of the present invention to prepare a polyhydroxyalkanoate molded body, the crystallinity of the polyhydroxyalkanoate resin composition is relatively larger, indicating that the crystallinity of the molded body is higher and more conducive to subsequent processing and molding. In addition, in the case of a cold crystallization peak, the secondary temperature rise cold crystallization half-peak width data of the polyhydroxyalkanoate resin composition is relatively smaller, indicating that the molded body is easier to crystallize and harden during the processing process, which is more conducive to processing and molding.

實施例三(製備薄膜) Example 3 (Preparation of thin film)

進一步地，選擇上述實驗例1、實驗例3、實驗例9、實驗例11、以及實驗例13中製備的粒子置於單層或多層吹膜機中製備薄膜，螺桿與模頭溫度設定溫度50至180℃(第一溫度)；所製備的薄膜在收卷前使用烘道在40至65℃(第二溫度)的條件下進行產線上結晶。其中，在製備薄膜前，先將製備的粒 子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。具體實施過程如下所述。 Furthermore, the particles prepared in the above Experimental Examples 1, 3, 9, 11, and 13 are placed in a single-layer or multi-layer film blowing machine to prepare a film, and the screw and die temperature are set at 50 to 180°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 40 to 65°C (second temperature) before winding. Before preparing the film, the prepared particles are first dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the performance of the particles and to make the particles completely crystallized. The specific implementation process is described as follows.

實驗例16：將實驗例1中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度50至160℃(第一溫度)；製備的薄膜在收卷前使用烘道在45℃(第二溫度)的條件下進行產線上結晶；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Experimental Example 16: The particles prepared in Experimental Example 1 are placed in a single-layer or multi-layer film blowing machine, and the screw and die temperature are set at 50 to 160°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 45°C (second temperature) before winding; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the particle performance and to make the particles completely crystallized.

實驗例17：將實驗例3中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度70至140℃(第一溫度)；製備的薄膜在收卷前使用烘道在50℃(第二溫度)的條件下進行產線上結晶；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Experimental Example 17: The particles prepared in Experimental Example 3 are placed in a single-layer or multi-layer film blowing machine, and the screw and die temperature are set at 70 to 140°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 50°C (second temperature) before winding; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the particle performance and to make the particles completely crystallized.

實驗例18：將實驗例9中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度80至180℃(第一溫度)；製備的薄膜在收卷前使用烘道在55℃(第二溫度)的條件下進行產線上結晶；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Experimental Example 18: The particles prepared in Experimental Example 9 are placed in a single-layer or multi-layer film blowing machine, and the screw and die temperature are set to 80 to 180°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 55°C (second temperature) before winding; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the particle performance and to make the particles completely crystallized.

實驗例19：將實驗例11中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度80至180℃(第一溫度)；製備的薄膜在收卷前使用烘道在55℃(第二溫度)的條件下進行產線上結晶；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Experimental Example 19: The particles prepared in Experimental Example 11 are placed in a single-layer or multi-layer film blowing machine, and the screw and die temperature are set to 80 to 180°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 55°C (second temperature) before winding; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the particle performance and to make the particles completely crystallized.

實驗例20：將實驗例13中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度80至180℃(第一溫度)；製備的薄膜在收卷前使用烘道在55℃(第二溫度)的條件下進行產線上結晶；製備的粒子使用鼓風乾燥箱，在60℃的溫度下烘乾4小時以上，排除水分對粒子性能的影響，同時使粒子結晶完全。 Experimental Example 20: The particles prepared in Experimental Example 13 are placed in a single-layer or multi-layer film blowing machine, and the screw and die temperature are set to 80 to 180°C (first temperature); the prepared film is crystallized on the production line using a drying oven at 55°C (second temperature) before winding; the prepared particles are dried in a blast drying oven at 60°C for more than 4 hours to eliminate the effect of moisture on the particle performance and to make the particles completely crystallized.

比較實驗例4：相較於實驗例16，不添加成核劑二十二酸，便將比較實驗例3中製備的粒子置於單層或多層吹膜機中，螺桿與模頭溫度設定溫度50至160℃(第一溫度)；製備的薄膜在收卷前使用烘道在45℃(第二溫度)的條件下進行產線上結晶，由於沒有添加成核劑，擠出機擠出時不穩定，成型體黏連且無法分離，無法成膜。 Comparative Experiment 4: Compared with Experiment 16, the particles prepared in Comparative Experiment 3 were placed in a single-layer or multi-layer film blowing machine without adding the nucleating agent behenic acid, and the screw and die temperature were set at 50 to 160°C (first temperature); the prepared film was crystallized on the production line using a drying tunnel at 45°C (second temperature) before winding. Since no nucleating agent was added, the extruder was unstable during extrusion, the molded body adhered and could not be separated, and film formation could not be achieved.

在此需要注意的是，薄膜成形體也可以直接由本發明所述的組合物的混合原粉料直接製備，不限定於上述實施例中造粒獲取的聚合體為原料製備薄膜。在實際應用中，也可以採用與上述實施例中的原材料相同或相近組成的成型體，例如加工的廢棄邊角料，或者廢棄邊角料與原粉料的混合物作為原料用於製備薄膜成型體。 It should be noted that the film forming body can also be directly prepared from the mixed raw powder of the composition described in the present invention, and is not limited to the polymer obtained by granulation in the above embodiment as the raw material for preparing the film. In practical applications, a forming body with the same or similar composition as the raw materials in the above embodiment, such as processed waste scraps, or a mixture of waste scraps and raw powders, can also be used as a raw material for preparing a film forming body.

薄膜成型體的測試：薄膜成型體的測試依照ISO527-2-2012，在測試速度為500mm/min條件下測定其縱向拉伸強度以及縱向斷裂伸長率；薄膜的縱向拉伸強度單位為MPa，且薄膜的縱向斷裂伸長率單位為%。 Film forming body test: Film forming body test is carried out in accordance with ISO527-2-2012, and its longitudinal tensile strength and longitudinal elongation at break are measured at a test speed of 500 mm/min; the longitudinal tensile strength of the film is measured in MPa, and the longitudinal elongation at break of the film is measured in %.

表3中的熱塑加工難度的符號表示說明如下： The symbols for thermoplastic processing difficulty in Table 3 are explained as follows:

○：可連續穩定加工。 ○: Continuous and stable processing is possible.

△：熱塑加工時基本穩定，但會有膜泡晃動等問題。 △: It is basically stable during thermoplastic processing, but there may be problems such as film bubble shaking.

×：擠出機擠出時不穩定，無法連續成膜。 ×: The extruder is not stable during extrusion and cannot form a film continuously.

由表3可以得知，上述覆蓋採用的純料PHA/混料以及不同的成核劑的組合物來製備薄膜成型體，可以得知採用本發明所述的成核劑與聚羥基烷酸酯的組合物製得的成型體薄膜的熱塑加工難度相對更低，可以連續且穩定地加工成膜，且成型體品質更好。而且薄膜的縱向拉伸強度以及縱向斷裂伸長率較好，符合後續產品加工要求。 From Table 3, it can be seen that the above-mentioned coating uses a pure PHA/mixture and a composition of different nucleating agents to prepare a film molded body. It can be seen that the thermoplastic processing difficulty of the molded body film prepared by using the composition of the nucleating agent and polyhydroxyalkanoate described in the present invention is relatively lower, and it can be processed into a film continuously and stably, and the quality of the molded body is better. In addition, the longitudinal tensile strength and longitudinal elongation at break of the film are good, which meets the requirements of subsequent product processing.

雖然在上文中已經使用一般性說明及具體實施方案對本發明作了詳盡的說明，但在本發明基礎上，可以對其進行一些修改或改進，這對本領域具有通常知識者而言是顯而易見的。因此，在不偏離本發明精神的基礎上所做的這些修改或改進，均屬於本發明要求保護的範圍。 Although the present invention has been described in detail above using general descriptions and specific implementation schemes, it is obvious to those with ordinary knowledge in this field that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.