TW201522417A - Aliphatic polycarbonate-polyurethane composition and aliphatic polycarbonate-polyurethane resin - Google Patents
Aliphatic polycarbonate-polyurethane composition and aliphatic polycarbonate-polyurethane resin Download PDFInfo
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Abstract
Description
以下揭露內容係關於一種脂族聚碳酸酯-聚胺甲酸乙酯組合物及使用彼之脂族聚碳酸酯-聚胺甲酸乙酯聚合物。 The following disclosure relates to an aliphatic polycarbonate-polyurethane composition and the use of the same aliphatic polycarbonate-polyurethane polymer.
近來,脂族聚碳酸酯的工業使用係以一種減少產生二氧化碳的方法而進行,作為對抗全球暖化的製備方式。脂族聚碳酸酯為一種具有柔軟質地的橡膠狀塑膠,具有優良加工性,且以其降解性質而言係易於控制的,而因此,已被作為一種可生物降解的聚合物而進行諸多研究。然而,由於脂族聚碳酸酯具有低玻璃轉移溫度(Tg)且於約200℃時易於降解,其被認定為具有弱的抗熱性之性質。此外,其機械物理性質具有低彈性模數,且由其所製備的薄膜產品具有易脆性質,故其於各種領域中的應用受到限制。因此,需要提高玻璃轉移溫度或抗熱性、或藉由與各式樹脂摻合以改進機械強度的技術。舉例而言,美國專利登錄第4,946,884號揭露一種藉由熔融捏合(melt-kneading)聚伸丙烯碳酸酯與聚甲基丙烯酸甲酯(PMMA)或包括一用於陶瓷模製製程 的黏合劑或金屬粉而製造的樹脂組合物,且美國專利登錄第4,912,149號揭露藉由熔融捏合聚氯乙烯乙酯(polyvinyl chloride acetate)而對機械性質的改進。然而,由於該等發明僅限於只藉由與另一種樹脂的摻合而改進機械物理強度,因此需要一種結構上的改進。 Recently, industrial use of aliphatic polycarbonates has been carried out in a manner that reduces the production of carbon dioxide as a means of combating global warming. The aliphatic polycarbonate is a rubbery plastic having a soft texture, has excellent processability, and is easily controlled in terms of its degradation properties, and thus has been studied as a biodegradable polymer. However, since aliphatic polycarbonates have a low glass transition temperature (T g ) and are easily degraded at about 200 ° C, they are considered to have weak heat resistance properties. In addition, its mechanical and physical properties have a low modulus of elasticity, and the film product prepared therefrom has fragile properties, so its application in various fields is limited. Therefore, there is a need for a technique for increasing the glass transition temperature or heat resistance, or by blending with various types of resins to improve mechanical strength. For example, U.S. Patent No. 4,946,884 discloses the use of a melt-kneading propylene carbonate with polymethyl methacrylate (PMMA) or a binder or metal for a ceramic molding process. A resin composition produced by the powder, and an improvement in mechanical properties by melt-kneading polyvinyl chloride acetate is disclosed in U.S. Patent No. 4,912,149. However, since these inventions are limited to improving mechanical physical strength only by blending with another resin, a structural improvement is required.
(專利文獻1)美國專利登錄第4,946,884號 (Patent Document 1) U.S. Patent Registration No. 4,946,884
(專利文獻2)美國專利登錄第4,912,149號 (Patent Document 2) U.S. Patent Registration No. 4,912,149
本發明之一實施態樣係關於提供脂族聚碳酸酯樹脂的各式應用方法。 One embodiment of the present invention is directed to various methods of applying aliphatic polycarbonate resins.
更具體而言,本發明之一實施態樣係關於藉由將脂族聚碳酸酯樹脂與聚胺甲酸乙酯混合,而提供一種可用於各式應用領域的脂族聚碳酸酯-聚胺甲酸乙酯組合物,以及一種由其所製備之脂族聚碳酸酯-聚胺甲酸乙酯聚合物。 More specifically, an embodiment of the present invention relates to an aliphatic polycarbonate-polyuric acid which can be used in various fields of application by mixing an aliphatic polycarbonate resin with polyurethane. Ethyl ester composition, and an aliphatic polycarbonate-polyurethane polymer prepared therefrom.
在一一般態樣中,一種脂族聚碳酸酯-聚胺甲酸乙酯聚合物包括脂族聚碳酸酯(A),其係由將二氧化碳與選自以下群組之一或二或更多種不同的環氧化合物反應而製造:未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C2-C20)環氧烷烴(alkylene oxide);未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C4-C20)環氧環烷烴 (cycloalkylene oxide);及未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、(C6-C20)芳(C1-C20)烷(芳烷)氧基、或(C1-C20)烷基取代的(C8-C20)環氧乙基苯(styrene oxide);以及聚胺甲酸乙酯(B)。 In a general aspect, an aliphatic polycarbonate-polyurethane polymer comprises an aliphatic polycarbonate (A) consisting of carbon dioxide and one or two or more selected from the group consisting of Manufactured by reacting different epoxy compounds: unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl) An oxy-substituted (C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy substituted (C4-C20) epoxycycloalkane (cycloalkylene oxide); and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy, Or (C1-C20)alkyl-substituted (C8-C20) styrene oxide; and polyurethane (B).
在另一一般態樣中,一種脂族聚碳酸酯-聚胺甲酸乙酯組合物包括脂族聚碳酸酯(A),其係由將二氧化碳與選自以下群組之一或二或更多種不同的環氧化合物反應而製造:未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C2-C20)環氧烷烴;未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C4-C20)環氧環烷烴;及未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、(C6-C20)芳(C1-C20)烷(芳烷)氧基、或(C1-C20)烷基取代的(C8-C20)環氧乙基苯;以及聚胺甲酸乙酯(B)。 In another general aspect, an aliphatic polycarbonate-polyurethane composition comprises an aliphatic polycarbonate (A) by combining carbon dioxide with one or two or more selected from the group consisting of Manufactured by reacting different epoxy compounds: unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1- C20) an alkane (aralkyl)oxy-substituted (C4-C20) epoxycycloalkane; and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6- C20) an aryl (C1-C20) alkane (aralkyl)oxy group, or a (C1-C20) alkyl-substituted (C8-C20) epoxyethylbenzene; and a polyurethane (B).
其他特徵與態樣將由以下詳細敘述及申請專利範圍而變得明確。 Other features and aspects will be apparent from the following detailed description and claims.
以下,將詳細描述例示性實施態樣。 Hereinafter, exemplary embodiments will be described in detail.
本案發明人發現,相較於單獨使用脂族聚碳酸酯樹脂,使用化學或物理混合的脂族聚碳酸酯樹脂與聚胺甲酸乙酯可導致對於抗撓曲性、拉伸強度(tensile strength)、機械強度如延伸率、彈性等之戲劇性的改進,而完成本發明。 The inventors have found that the use of chemically or physically mixed aliphatic polycarbonate resins and polyurethanes results in resistance to flexing, tensile strength, as compared to the use of aliphatic polycarbonate resins alone. The present invention has been completed with dramatic improvements in mechanical strength such as elongation, elasticity, and the like.
尤其,本發明係藉由發現由脂族聚碳酸酯樹脂與聚 胺甲酸乙酯形成互穿聚合物網狀結構(interpenetrating polymer network structure)將可大幅改進機械物理性質的事實而完成。 In particular, the present invention is discovered by the use of aliphatic polycarbonate resins and poly The fact that the urethane forms an interpenetrating polymer network structure will greatly improve the mechanical and physical properties.
本發明一實施態樣係關於一種脂族聚碳酸酯-聚胺甲酸乙酯聚合物,其中該脂族聚碳酸酯(A)樹脂與該聚胺甲酸乙酯(B)樹脂可形成摻合(blending)、複合(compounding)、雜合(hybrid)、或互穿聚合物網狀(IPN)結構。 An embodiment of the invention relates to an aliphatic polycarbonate-polyurethane polymer, wherein the aliphatic polycarbonate (A) resin and the polyurethane (B) resin are capable of forming a blend ( Blending), compounding, hybrid, or interpenetrating polymer network (IPN) structures.
該脂族聚碳酸酯(A)可具有1,000至300,000公克/莫耳(g/mol)之重量平均分子量。 The aliphatic polycarbonate (A) may have a weight average molecular weight of 1,000 to 300,000 g/mole.
本發明中,重量平均分子量係藉由將粉末試樣溶解於THF中,然後使用凝膠滲透層析法(GPC;安捷倫科技(agilent Technologies)1260 infinity型)(以PLgel mixed B(7.5毫米×300毫米)作為管柱,且以聚苯乙烯(Agilent EasyCal)作為標準試樣)而測量。 In the present invention, the weight average molecular weight is obtained by dissolving a powder sample in THF and then using gel permeation chromatography (GPC; agilent Technologies 1260 infinity type) (with PLgel mixed B (7.5 mm × 300) Millimeter) was measured as a column and made of polystyrene (Agilent EasyCal) as a standard sample.
更詳細而言,在本發明摻合、複合、及雜合結構的脂族聚碳酸酯-聚胺甲酸乙酯聚合物的製備中所使用之脂族聚碳酸酯(A)可具有1,000至300,000公克/莫耳之重量平均分子量。此外,在本發明互穿聚合物網狀(IPN)結構的脂族聚碳酸酯-聚胺甲酸乙酯聚合物的製備中所使用之脂族聚碳酸酯(A)可具有1,000至300,000公克/莫耳之重量平均分子量。然而,本發明並不侷限於此。 In more detail, the aliphatic polycarbonate (A) used in the preparation of the blended, composite, and hybrid structure aliphatic polycarbonate-polyurethane polymer of the present invention may have 1,000 to 300,000 Weight average molecular weight of grams per mole. Further, the aliphatic polycarbonate (A) used in the preparation of the interpenetrating polymer network (IPN) structure aliphatic polycarbonate-polyurethane polymer of the present invention may have 1,000 to 300,000 g/ The weight average molecular weight of the mole. However, the invention is not limited thereto.
聚胺甲酸乙酯(B)可具有10,000至1,000,000公克/莫耳之重量平均分子量。 The polyurethane (B) may have a weight average molecular weight of 10,000 to 1,000,000 g/mole.
可藉由在80至200℃下經由擠製機(extruder)將脂族聚碳酸酯(A)樹脂與聚胺甲酸乙酯(B)樹脂熔融捏合,以進行摻 合與複合。在擠製製程中,可使用簡單擠製以經過一簡單熔融捏合步驟,以及可使用反應擠製技術以進行交聯與鏈延長反應。在反應擠製的情況下,表面的界面能被降低以避免相分離並形成一均勻的相,因此提供了對於「脂族聚碳酸酯-聚胺甲酸乙酯組合物」之物理性質與有機/無機添加劑之分散的改進。 The aliphatic polycarbonate (A) resin and the polyurethane (B) resin may be melt-kneaded by an extruder at 80 to 200 ° C for doping. Combination and compounding. In the extrusion process, simple extrusion can be used to pass a simple melt-kneading step, and reactive extrusion techniques can be used to effect crosslinking and chain extension reactions. In the case of reactive extrusion, the surface interface can be lowered to avoid phase separation and form a uniform phase, thus providing physical properties and organic/"organic polycarbonate-polyurethane composition" Improvement in dispersion of inorganic additives.
雜合及互穿聚合物網狀結構係指一藉由包括溶劑而形成的網狀結構。 Heterozygous and interpenetrating polymer network structures refer to a network structure formed by the inclusion of a solvent.
互穿聚合物網狀結構係一種多組分聚合物,其中至少一個組分具有網狀結構,且至少一個組分係於另一個組分存在之下聚合或交聯,由此產生聚合物鏈之間的互穿。由於網狀結構,聚合物的鏈程度(chain degree)高,因此可抑制在聚合物摻合時常發生的相分離,且藉由具有其中兩種組分形成一連續相的二相連續性(dual phase continuity),可預期各種物理性質的改進。 An interpenetrating polymer network is a multicomponent polymer in which at least one component has a network structure and at least one component is polymerized or crosslinked in the presence of another component, thereby producing a polymer chain. Interpenetration between. Due to the network structure, the polymer has a high chain degree, so that phase separation which occurs frequently during polymer blending can be suppressed, and by having two-phase continuity in which two components form a continuous phase (dual Phase continuity), various physical properties can be expected to be improved.
為了形成互穿聚合物網狀結構,脂族聚碳酸酯(A)樹脂、一由多元醇(polyol)與異氰酸酯化合物反應而製造之胺甲酸乙酯預聚物、及一固化劑可反應而製備脂族聚碳酸酯-聚胺甲酸乙酯聚合物。 In order to form an interpenetrating polymer network structure, an aliphatic polycarbonate (A) resin, an urethane prepolymer produced by reacting a polyol with an isocyanate compound, and a curing agent are reacted to prepare Aliphatic polycarbonate-polyurethane polymer.
或是,為了形成互穿聚合物網狀結構,脂族聚碳酸酯、一多元醇化合物、及該多元醇化合物中羥基當量的0.9至1.2倍當量之固化劑被溶解於例如甲基乙基酮的溶劑中,之後使其於80℃反應一段時間,或是使其於120至200℃下經反應擠製。 Alternatively, in order to form an interpenetrating polymer network structure, an aliphatic polycarbonate, a polyhydric alcohol compound, and a hydroxyl group equivalent of 0.9 to 1.2 equivalents of the hydroxyl group in the polyol compound are dissolved in, for example, methyl ethyl group. The solvent of the ketone is then allowed to react at 80 ° C for a period of time or it is subjected to reaction extrusion at 120 to 200 ° C.
或是,脂族聚碳酸酯與一環氧化合物可溶解於一溶劑中,之後可等價地加入一固化劑,從而形成一網狀結構;或是一脂族聚碳酸酯、一環氧化合物、及一固化劑可於120至200℃ 下經反應擠製。 Alternatively, the aliphatic polycarbonate and the epoxy compound may be dissolved in a solvent, and then a curing agent may be equivalently added to form a network structure; or an aliphatic polycarbonate or an epoxy compound. And a curing agent can be used at 120 to 200 ° C The reaction is extruded under the reaction.
或是,脂族聚碳酸酯與一丙烯酸化合物(acrylic compound)可溶解於一溶劑中,且一反應性起始劑或一催化劑可等價地加入其中,從而形成一網狀結構;或是一脂族聚碳酸酯、一丙烯酸化合物、及一起始劑或一催化劑可於120至200℃下經反應擠製。 Alternatively, the aliphatic polycarbonate and the acrylic compound may be dissolved in a solvent, and a reactive initiator or a catalyst may be equivalently added thereto to form a network structure; or The aliphatic polycarbonate, the acrylic acid compound, and a starter or a catalyst may be subjected to reaction extrusion at 120 to 200 °C.
該脂族聚碳酸酯-聚胺甲酸乙酯聚合物,基於聚合物的總重,可包括5至95重量%的脂族聚碳酸酯(A),以及5至95重量%的聚胺甲酸乙酯(B)。更詳細而言,該聚合物可包括20至80重量%的脂族聚碳酸酯(A),以及20至80重量%的聚胺甲酸乙酯(B)。可由前述範圍而滿足理想的物理性質。 The aliphatic polycarbonate-polyurethane polymer may comprise from 5 to 95% by weight of the aliphatic polycarbonate (A) and from 5 to 95% by weight of the polyurethane based on the total weight of the polymer. Ester (B). In more detail, the polymer may include 20 to 80% by weight of the aliphatic polycarbonate (A), and 20 to 80% by weight of the polyurethane (B). The desired physical properties can be satisfied by the foregoing ranges.
此外,本發明另一實施態樣係關於一種脂族聚碳酸酯-聚胺甲酸乙酯組合物,包括脂族聚碳酸酯(A)及聚胺甲酸乙酯(B),其係用於製備一脂族聚碳酸酯-聚胺甲酸乙酯聚合物。 Further, another embodiment of the present invention relates to an aliphatic polycarbonate-polyurethane composition comprising an aliphatic polycarbonate (A) and a polyurethane (B) for use in the preparation. An aliphatic polycarbonate-polyurethane polymer.
本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第一實施態樣可為一組合物,其中脂族聚碳酸酯(A)與聚胺甲酸乙酯(B)係經摻合或複合。 The first embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition wherein the aliphatic polycarbonate (A) and the polyurethane (B) are blended or complex.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第二實施態樣可為一組合物,其中脂族聚碳酸酯(A)與聚胺甲酸乙酯(B)係連同用以溶解該等樹脂的溶劑,形成一雜合或互穿聚合物網狀結構。作為該溶劑,可使用選自以下群組之任一者:酮系、乙酸酯系、及醚系溶劑,或其二或更多種之混合物,但並不侷限於此。 Further, the second embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition in which an aliphatic polycarbonate (A) and a polyurethane (B) are used together. The solvent of the resins is dissolved to form a hybrid or interpenetrating polymer network. As the solvent, any one selected from the group consisting of a ketone system, an acetate system, and an ether solvent, or a mixture of two or more thereof may be used, but is not limited thereto.
於此,脂族聚碳酸酯-聚胺甲酸乙酯組合物的固體含 量可為30至50重量%,且隨將製造的模製物(molded article)之用途或其製造方法而改變。 Here, the solid content of the aliphatic polycarbonate-polyurethane composition The amount may be from 30 to 50% by weight, and varies depending on the use of the molded article to be manufactured or the method of producing the same.
在本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第一與第二實施態樣的情況下,脂族聚碳酸酯(A)可具有1,000至300,000公克/莫耳之重量平均分子量,且聚胺甲酸乙酯(B)可具有10,000至1,000,000公克/莫耳之重量平均分子量,但並不侷限於此。由前述範圍,可使該組合物應用於各式領域。 In the case of the first and second embodiments of the aliphatic polycarbonate-polyurethane composition of the present invention, the aliphatic polycarbonate (A) may have a weight average molecular weight of 1,000 to 300,000 g/mole. And the polyurethane (B) may have a weight average molecular weight of 10,000 to 1,000,000 g/mole, but is not limited thereto. From the foregoing range, the composition can be applied to various fields.
此外,該脂族聚碳酸酯-聚胺甲酸乙酯組合物,基於組合物的總重,可包括5至95重量%的脂族聚碳酸酯(A),以及5至95重量%的聚胺甲酸乙酯(B)。由前述含量範圍,可使該組合物具有優良機械物理性質之效果。 Further, the aliphatic polycarbonate-polyurethane composition may include 5 to 95% by weight of the aliphatic polycarbonate (A) and 5 to 95% by weight of the polyamine based on the total weight of the composition. Ethyl formate (B). From the foregoing content range, the composition can have an effect of excellent mechanical physical properties.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第三實施態樣可為一組合物,其中包括了脂族聚碳酸酯(A)樹脂、一由多元醇與異氰酸酯化合物反應而製造之胺甲酸乙酯預聚物、及一固化劑。 Further, a third embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition comprising an aliphatic polycarbonate (A) resin and reacting a polyol with an isocyanate compound. The urethane prepolymer produced, and a curing agent.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第四實施態樣可為一組合物,其中包括了脂族聚碳酸酯(A)樹脂、多元醇、及一固化劑。 Further, the fourth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition comprising an aliphatic polycarbonate (A) resin, a polyol, and a curing agent.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第五實施態樣可為一組合物,其中於第三及第四實施態樣的組合物中,更包括選自以下群組之任一者:環氧化合物、及丙烯酸化合物(acryl compound),或其混合物。 Further, a fifth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition, wherein the composition of the third and fourth embodiments further comprises a group selected from the group consisting of Any of the group: an epoxy compound, and an acryl compound, or a mixture thereof.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第六實施態樣可為一組合物,其中於第三、第四、及第五實施態 樣的組合物中,更包括一溶劑。 Further, the sixth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition in which the third, fourth, and fifth embodiments are The composition also includes a solvent.
此外,本發明脂族聚碳酸酯-聚胺甲酸乙酯組合物的第七實施態樣可為一組合物,其中於第三、第四、及第五實施態樣的組合物中,更包括一起始劑或一催化劑。 Further, the seventh embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition, wherein the composition of the third, fourth, and fifth embodiments further includes An initiator or a catalyst.
以下,將詳細描述使用於脂族聚碳酸酯-聚胺甲酸乙酯聚合物與脂族聚碳酸酯-聚胺甲酸乙酯組合物中的各個組分。 Hereinafter, the respective components used in the aliphatic polycarbonate-polyurethane polymer and the aliphatic polycarbonate-polyurethane composition will be described in detail.
本發明的脂族聚碳酸酯(A)可藉由二氧化碳與選自以下群組之一或二或更多種不同的環氧化合物之共聚反應而製造:未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C2-C20)環氧烷烴;未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、或(C6-C20)芳(C1-C20)烷(芳烷)氧基取代的(C4-C20)環氧環烷烴;及未經取代或經鹵素、(C1-C20)烷氧基、(C6-C20)芳氧基、(C6-C20)芳(C1-C20)烷(芳烷)氧基、或(C1-C20)烷基取代的(C8-C20)環氧乙基苯。 The aliphatic polycarbonate (A) of the present invention can be produced by copolymerization of carbon dioxide with an epoxy compound different from one or two or more of the following groups: unsubstituted or halogenated, (C1- C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl(C1-C20)alk(aralkyl)oxy substituted (C2-C20) alkylene oxide; unsubstituted or via Halogen, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl(C1-C20)alkane(aralkyl)oxy substituted (C4-C20) epoxycycloalkane And unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy, or (C1- C20) alkyl-substituted (C8-C20) epoxyethylbenzene.
於此,該環氧化合物可為選自以下群組之一或二或更多者:環氧乙烷、環氧丙烷、環氧丁烷、環氧戊烷、環氧己烷、環氧辛烷、環氧癸烷、環氧十二烷、環氧十四烷、環氧十六烷、環氧十八烷、環氧丁烯(butadiene monoxide)、1,2-環氧-7-辛烯(1,2-epoxide-7-octene)、環氧氟丙烷(epifluorohydrin)、環氧氯丙烷、環氧溴丙烷、環氧丙基甲基醚(glycidyl methyl ether)、環氧丙基乙基醚、環氧丙基正丙基醚、環氧丙基二級丁基醚、環氧丙基正戊基或異戊基醚(glycidyl n- or isopentyl ether)、環氧丙基正己基醚、環氧丙基正庚基醚、環氧丙基正辛基或2-乙基己基醚 (glycidyl n-octyl or 2-ethyl-hexyl ether)、環氧丙基正壬基或異壬基醚(glycidyl n- or isononyl ether)、環氧丙基正癸基醚、環氧丙基正十二基醚、環氧丙基正十四基醚、環氧丙基正十六基醚、環氧丙基正十八基醚、環氧丙基正二十基醚、異丙基環氧丙基醚、丁基環氧丙基醚、三級丁基環氧丙基醚、2-乙基己基環氧丙基醚、烯丙基環氧丙基醚、環氧環戊烷、環氧環己烷、環氧環辛烷、環氧環十二烷、環氧α-蒎烯(α-pinene oxide)、2,3-環氧降莰烯(2,3-epoxide norbornene)、環氧檸檬烷(limonene oxide)、狄氏劑(dieldrin)、2,3-環氧丙基苯(2,3-epoxide propyl benzene)、環氧乙基苯、苯基環氧丙烷、環氧二苯乙烷(stilbene oxide)、環氧氯二苯乙烷(chlorostilbene oxide)、環氧二氯二苯乙烷、1,2-環氧-3-苯氧丙烷(1,2-epoxy-3-phenoxypropane)、芐氧甲基環氧乙烷(benzyloxymethyl oxirane)、環氧丙基-甲基苯基醚、氯苯基-2,3-環氧丙基醚(chlorophenyl-2,3-epoxide propyl ether)、環氧丙基甲氧苯基醚(epoxypropyl methoxyphenyl ether)、聯苯基環氧丙基醚、環氧丙基萘基醚、環氧丙基乙酸酯(glycidyl acetic acid ester)、丙酸環氧丙酯(glycidyl propionate)、丁酸環氧丙酯、正戊酸環氧丙酯、正己酸環氧丙酯、庚酸環氧丙酯、正辛酸環氧丙酯、2-乙基己酸環氧丙酯、正壬酸環氧丙酯、正癸酸環氧丙酯、正十二酸環氧丙酯、正十四酸環氧丙酯、正十六酸環氧丙酯、正十八酸環氧丙酯、及二十酸環氧丙酯。 Here, the epoxy compound may be selected from one or two or more of the following groups: ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, epoxy octane Alkane, epoxy decane, epoxy dodecane, epoxytetradecane, epoxy hexadecane, epoxy octadecane, butadiene monoxide, 1,2-epoxy-7-octane 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromopropane, glycidyl methyl ether, epoxypropylethyl Ether, glycidyl n-propyl ether, epoxypropyl secondary butyl ether, glycidyl n- or isopentyl ether, epoxypropyl n-hexyl ether, Epoxypropyl n-heptyl ether, epoxypropyl n-octyl or 2-ethylhexyl ether (glycidyl n-octyl or 2-ethyl-hexyl ether), glycidyl n- or isononyl ether, glycidyl n-decyl ether, epoxy propyl Di-ether ether, glycidyl n-tetradecyl ether, glycidyl n-hexadecyl ether, glycidyl n-octadecyl ether, epoxypropyl n-hexyl ether, isopropyl epoxide Ether, butyl epoxypropyl ether, tert-butyl butyl epoxide, 2-ethylhexyl epoxypropyl ether, allyl epoxypropyl ether, epoxy cyclopentane, epoxy ring Hexane, epoxy cyclooctane, epoxycyclododecane, alpha-pinene oxide, 2,3-epoxide norbornene, epoxy lemon Limonene oxide, dieldrin, 2,3-epoxide propyl benzene, epoxy ethylbenzene, phenyl propylene oxide, epoxy diphenylethane (stilbene oxide), chlorostilbene oxide, epoxy dichlorodiphenylethane, 1,2-epoxy-3-phenoxypropane, Benzyloxymethyl oxirane, epoxypropyl-methylphenyl ether, chlorophenyl-2,3-ring Chlorophenyl-2,3-epoxide propyl ether, epoxypropyl methoxyphenyl ether, biphenyl epoxypropyl ether, epoxypropyl naphthyl ether, propylene oxide Glycidyl acetic acid ester, glycidyl propionate, glycidyl butyrate, glycidyl n-pentanoate, glycidyl n-hexanoate, glycidyl heptanoate , n-octyl epoxidate, 2-ethylhexanoate propyl acrylate, n-decyl epoxidate, n-decyl epoxidate, n-dodecyl epoxidate, n-tetradecanoate epoxide Propyl ester, n-hexadecanoate, propyl propyl hexadecanate, and glycidyl octadecanoate.
在本發明一實施態樣中,脂族聚碳酸酯(A)可為聚伸烷基碳酸酯,其中之伸烷基(alkylene)包括伸乙基(ethylene)、伸丙基(propylene)、1-伸丁基(1-butylene)、環氧環己烷、烷基 環氧丙基醚、正丁基、及正辛基,但並不侷限於此。 In one embodiment of the present invention, the aliphatic polycarbonate (A) may be a polyalkylene carbonate, wherein the alkylene includes an ethylene group, a propylene group, and 1 - 1-butylene, epoxycyclohexane, alkyl Epoxypropyl ether, n-butyl, and n-octyl, but are not limited thereto.
本發明的脂族聚碳酸酯可為聚伸丙基碳酸酯(polypropylene carbonate)或聚伸乙基碳酸酯(polyethylene carbonate)。 The aliphatic polycarbonate of the present invention may be polypropylene carbonate or polyethylene carbonate.
根據本發明一例示性實施態樣的脂族聚碳酸酯,其特點在於具有1,000至300,000公克/莫耳之重量平均分子量(Mw),且重量平均分子量之範圍可隨製備方法與欲製備的材料而改變。較佳為30,000至250,000公克/莫耳之重量平均分子量。此外,聚伸烷基碳酸酯樹脂之玻璃轉移溫度(Tg)可為20至105℃,且熔融指數(150℃/5公斤)可為0.01至350。於前述範圍的聚伸烷基碳酸酯樹脂可有利地應用於造粒製程(pelletization process)。 An aliphatic polycarbonate according to an exemplary embodiment of the present invention is characterized by having a weight average molecular weight (Mw) of 1,000 to 300,000 g/mole, and the weight average molecular weight may range depending on the preparation method and the material to be prepared. And change. It is preferably a weight average molecular weight of 30,000 to 250,000 g/mole. Further, the polyalkylene carbonate resin may have a glass transition temperature (Tg) of 20 to 105 ° C and a melt index (150 ° C / 5 kg) of 0.01 to 350. The polyalkylene carbonate resin in the foregoing range can be advantageously applied to a pelletization process.
根據本發明一例示性實施態樣的用於製備具有互穿聚合物網狀結構的脂族聚碳酸酯-聚胺甲酸乙酯聚合物之組合物,基於100重量份的脂族聚碳酸酯,可含有5至950重量份的多元醇化合物,及該多元醇中羥基當量的0.9至1.2倍當量之固化劑。超出前述範圍,組合物可能有剩餘的未反應聚異氰酸酯,或是由固化產生的交聯程度不足。 A composition for preparing an aliphatic polycarbonate-polyurethane polymer having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention, based on 100 parts by weight of an aliphatic polycarbonate, The polyol compound may be contained in an amount of from 5 to 950 parts by weight, and from 0.9 to 1.2 equivalents of the hydroxyl group equivalent of the polyol. Beyond the foregoing range, the composition may have remaining unreacted polyisocyanate or insufficient degree of crosslinking due to curing.
根據本發明一例示性實施態樣的具有互穿聚合物網狀結構之組合物中,作為固化劑,可使用以下群組之任一或二或更多種化合物:異氰酸酯系、三聚氰胺系、胺系、酸酐系、咪唑系、以及硫醇系化合物。 In the composition having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention, as the curing agent, any one or two or more of the following groups may be used: isocyanate type, melamine type, amine A system, an acid anhydride system, an imidazole system, and a thiol compound.
於此,更佳將異氰酸酯系化合物及隨後將三聚氰胺系化合物作為固化劑反應。若二或更多種固化劑於交聯反應中同 時引入,IPN的結構可能依照該等二或更多種固化劑的反應速率而改變,且因此,難以控制反應以獲得理想的結構。因此,可藉由使用一種固化劑進行反應,再隨後引入另一種固化劑,以得到具均一結構的IPN。 Here, it is more preferable to react an isocyanate-based compound and subsequently a melamine-based compound as a curing agent. If two or more curing agents are in the same crosslinking reaction When introduced, the structure of the IPN may vary depending on the reaction rates of the two or more curing agents, and thus, it is difficult to control the reaction to obtain a desired structure. Therefore, the reaction can be carried out by using a curing agent, followed by introduction of another curing agent to obtain an IPN having a uniform structure.
本發明的異氰酸酯系固化劑可為選自以下群組之任一或更多者:2,4-三氯乙烯二異氰酸酯(2,4-trilene diisocyanate)、2,6-三氯乙烯二異氰酸酯(2,6-trilene diisocyanate)、氫化三氯乙烯二異氰酸酯(hydrogenated trilene diisocyanate)、1,3-二甲苯二異氰酸酯、1,4-二甲苯二異氰酸酯、二苯甲烷-4,4-二異氰酸酯、1,3-雙異氰酸甲基環己烷(1,3-bisisocyanate methyl cyclohexane)、四甲基二甲苯二異氰酸酯、1,5-萘二異氰酸酯、2,2,4-三甲基伸己基二異氰酸酯(2,2,4-trimethyl hexamethylene diisocyanate)、2,4,4-三甲基伸己基二異氰酸酯、及三苯基甲烷三異氰酸酯。 The isocyanate curing agent of the present invention may be selected from any one or more of the following groups: 2,4-trilene diisocyanate, 2,6-trichloroethylene diisocyanate ( 2,6-trilene diisocyanate), hydrogenated trilene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4-diisocyanate, 1 ,3-bisisocyanate methyl cyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylexylene Isocyanate (2,2,4-trimethyl hexamethylene diisocyanate), 2,4,4-trimethylhexyldiisocyanate, and triphenylmethane triisocyanate.
本發明的三聚氰胺系化合物可為選自以下群組之任一或更多者:六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、六戊氧基甲基三聚氰胺、及六己氧基甲基三聚氰胺。 The melamine-based compound of the present invention may be selected from any one or more of the following groups: hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl Melamine, hexaethoxyoxymethyl melamine, and hexahexyloxymethyl melamine.
本發明的多元醇化合物可為選自以下群組之任一或更多者:聚酯多元醇、聚醚多元醇、及聚碳酸酯多元醇。 The polyol compound of the present invention may be selected from any one or more of the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols.
於此,多元醇可為低分子量多元醇,其重量平均分子量為200至30,000。在前述範圍之外,藉由固化反應的交聯並不容易。若多元醇具有過低的分子量,由固化反應製造的聚合物幾乎無法具有50,000以上的分子量;而若多元醇具有30,000以上的分子量,將難以產生對於聚伸烷基碳酸酯分子的有效穿透,且 因此,在固化反應後可能難以具有有效的IPN結構。 Here, the polyol may be a low molecular weight polyol having a weight average molecular weight of 200 to 30,000. Outside of the foregoing range, crosslinking by the curing reaction is not easy. If the polyol has an excessively low molecular weight, the polymer produced by the curing reaction hardly has a molecular weight of 50,000 or more; and if the polyol has a molecular weight of 30,000 or more, it is difficult to produce effective penetration of the polyalkylene carbonate molecule. And Therefore, it may be difficult to have an effective IPN structure after the curing reaction.
在本發明一實施態樣中,異氰酸酯化合物可為選自以下群組之任一或二或更多種化合物:2,4-三氯乙烯二異氰酸酯、2,6-三氯乙烯二異氰酸酯、氫化三氯乙烯二異氰酸酯、1,3-二甲苯二異氰酸酯、1,4-二甲苯二異氰酸酯、二苯甲烷-4,4-二異氰酸酯、1,3-雙異氰酸甲基環己烷、四甲基二甲苯二異氰酸酯、1,5-萘二異氰酸酯、2,2,4-三甲基伸己基二異氰酸酯、2,4,4-三甲基伸己基二異氰酸酯、及三苯基甲烷三異氰酸酯。 In an embodiment of the present invention, the isocyanate compound may be any one or two or more compounds selected from the group consisting of 2,4-trichloroethylene diisocyanate, 2,6-trichloroethylene diisocyanate, hydrogenation Trichloroethylene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,3-bisisocyanate methylcyclohexane, four Methyl xylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexyl diisocyanate, 2,4,4-trimethylhexyl diisocyanate, and triphenylmethane triisocyanate .
在本發明一實施態樣中,固化劑可為選自以下群組之任一或二或更多種化合物:異氰酸酯系、三聚氰胺系、胺系、酸酐系、咪唑系、以及硫醇系化合物。 In an embodiment of the present invention, the curing agent may be any one or two or more compounds selected from the group consisting of isocyanate, melamine, amine, acid anhydride, imidazole, and thiol compounds.
在本發明一實施態樣中,環氧化合物可為選自以下群組之任一或二或更多種化合物:環氧丙基醚(glycidyl ether)系、環氧丙基酯系、環氧丙基胺系、直鏈脂族、及環脂族化合物。 In an embodiment of the present invention, the epoxy compound may be any one or two or more compounds selected from the group consisting of glycidyl ether, glycidyl ester, epoxy. A propylamine, a linear aliphatic, and a cycloaliphatic compound.
在本發明一實施態樣中,丙烯酸化合物可為選自以下群組之任一或二或更多種化合物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸庚酯、丙烯酸-2-乙基己酯、丙烯酸辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸癸酯、及甲基丙烯酸-2-乙基丁酯。 In an embodiment of the present invention, the acrylic compound may be any one or two or more compounds selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, acrylic acid. 2-Ethylhexyl ester, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate, and 2-ethylbutyl methacrylate.
在本發明一實施態樣中,作為起始劑或催化劑,可不受限制地使用任何只要是本領域常用的起始劑或催化劑。具體而言,例如,可使用選自以下群組之任一或更多者:有機錫化合物,如:辛酸錫(tin octylate)、三乙酸單丁基錫(monobutyltin triacetate)、三辛酸單丁基錫、單辛酸單丁基錫、馬來酸單丁基錫 (monobutyltin maleate)、二乙酸二丁基錫、二辛酸二丁基錫、二硬脂酸二丁基錫、二月桂酸二丁基錫、及馬來酸二丁基錫;有機鈦化合物,如:鈦酸四異丙酯(tetraisopropyl titanate)、及鈦酸四正丁基酯;以及三級胺(tert-amine),如:三乙胺、N,N-二乙基環己胺、N,N,N',N'-四甲基伸乙基二胺、及三伸乙基二胺。 In one embodiment of the present invention, as the initiator or catalyst, any initiator or catalyst which is conventionally used in the art can be used without limitation. Specifically, for example, any one or more selected from the group consisting of organotin compounds such as tin octylate, monobutyltin triacetate, monobutyltin trioctoate, monooctanoic acid may be used. Monobutyltin, monobutyltin maleate (monobutyltin maleate), dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate, and dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate And tetra-n-butyl titanate; and tert-amine, such as: triethylamine, N,N-diethylcyclohexylamine, N,N,N',N'-four Base ethyl diamine, and tri-ethyl diamine.
根據本發明一例示性實施態樣的脂族聚碳酸酯-聚胺甲酸乙酯聚合物可具有一互穿聚合物網狀結構,其係藉由包括一脂族聚碳酸酯;一環氧化合物,選自環氧丙基醚系、環氧丙基酯系、環氧丙基胺系、直鏈脂族、及環脂族化合物;以及一可被聚合、交聯、或與該等化合物反應之固化劑而得,其中環氧化合物可為具有重量平均分子量為100至10,000之低分子量化合物,使得可以產生脂族聚碳酸酯分子中的有效穿透,而在固化反應後形成優良IPN結構。 An aliphatic polycarbonate-polyurethane polymer according to an exemplary embodiment of the present invention may have an interpenetrating polymer network structure comprising an aliphatic polycarbonate; an epoxy compound , selected from the group consisting of a glycidyl ether system, a glycidyl ester system, a glycidylamine system, a linear aliphatic group, and a cycloaliphatic compound; and a polymerizable, crosslinked, or reacted with the compound The curing agent is obtained, wherein the epoxy compound may be a low molecular weight compound having a weight average molecular weight of 100 to 10,000, so that effective penetration in the aliphatic polycarbonate molecule can be produced, and a good IPN structure is formed after the curing reaction.
根據本發明一例示性實施態樣的脂族聚碳酸酯-聚胺甲酸乙酯聚合物可具有一互穿聚合物網狀結構,其係藉由包括一脂族聚碳酸酯;任一或更多種選自以下群組之丙烯酸化合物:丙烯酸烷酯(alkyl acrylate)或甲基丙烯酸烷酯(alkyl methacrylate),如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸庚酯、丙烯酸-2-乙基己酯、丙烯酸辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸癸酯、及甲基丙烯酸-2-乙基丁酯;以及一可被聚合、交聯、或與該等化合物反應之固化劑而得,其中丙烯酸化合物可為具有重量平均分子量為100至10,000之低分子量化合物,使得可以產生脂族聚碳酸酯分子中的有效穿透,而在固化反應後形成優良IPN結構。 An aliphatic polycarbonate-polyurethane polymer according to an exemplary embodiment of the present invention may have an interpenetrating polymer network structure by including an aliphatic polycarbonate; a plurality of acrylic compounds selected from the group consisting of alkyl acrylates or alkyl methacrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate, and 2-ethylbutyl methacrylate; and one can be polymerized, cross-linked And a curing agent which reacts with the compounds, wherein the acrylic compound can be a low molecular weight compound having a weight average molecular weight of from 100 to 10,000, so that effective penetration in the aliphatic polycarbonate molecule can be produced, while curing A good IPN structure is formed after the reaction.
藉由包括脂族聚碳酸酯;任一或更多種選自以下群組之化合物:多元醇化合物、環氧系化合物、及丙烯酸系化合物;以及一可被聚合、交聯、或與該等化合物反應之固化劑而得之具有一互穿聚合物網狀結構的聚伸烷基碳酸酯樹脂組合物係較佳藉由反應擠製而具有互穿聚合物網狀結構,且該互穿聚合物網狀結構可藉由溶液反應形成,但並不侷限於此。 By including an aliphatic polycarbonate; any one or more compounds selected from the group consisting of polyol compounds, epoxy compounds, and acrylic compounds; and one that can be polymerized, crosslinked, or otherwise The polyalkylene carbonate resin composition having an interpenetrating polymer network structure obtained by curing the compound reaction agent preferably has an interpenetrating polymer network structure by reaction extrusion, and the interpenetrating polymerization The mesh structure can be formed by solution reaction, but is not limited thereto.
根據本發明一例示性實施態樣的具有互穿聚合物網狀結構的脂族聚碳酸酯-聚胺甲酸乙酯聚合物可更包括任一或二或更多種選自以下群組之添加劑:顏料、染料、填料、抗氧化劑、防曬劑、抗靜電劑、抗結塊劑、滑動劑(slip agent)、無機填料、捏合劑(kneading agent)、穩定劑、增黏樹脂(tackifying resin)、改質樹脂、調平劑(leveling agent)、光學增亮劑、分散劑、熱穩定劑、光穩定劑、UV吸收劑、及潤滑劑。 The aliphatic polycarbonate-polyurethane polymer having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention may further comprise any one or two or more additives selected from the group below : pigments, dyes, fillers, antioxidants, sunscreens, antistatic agents, anti-caking agents, slip agents, inorganic fillers, kneading agents, stabilizers, tackifying resins, A modified resin, a leveling agent, an optical brightener, a dispersant, a heat stabilizer, a light stabilizer, a UV absorber, and a lubricant.
根據本發明的脂族聚碳酸酯-聚胺甲酸乙酯組合物,及使用該組合物製備的脂族聚碳酸酯-聚胺甲酸乙酯聚合物,可應用於各種產業領域。 The aliphatic polycarbonate-polyurethane composition according to the present invention, and the aliphatic polycarbonate-polyurethane polymer prepared using the composition, can be applied to various industrial fields.
更具體而言,根據本發明一例示性實施態樣的脂族聚碳酸酯-聚胺甲酸乙酯組合物可藉由例如擠製、射出、鑄造等的方法而用於製造一模製物,且可依照要製造的模製物種類而選擇該方法。 More specifically, the aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment of the present invention can be used to manufacture a molded article by a method such as extrusion, injection, casting, or the like. The method can be selected according to the type of molding to be manufactured.
使用根據本發明一例示性實施態樣的脂族聚碳酸酯-聚胺甲酸乙酯組合物而製造之模製物可包括人造皮革、膜、可延展發泡體(expandable foam)、及片板(sheet)等,但並不侷限於此。 Molds made using an aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment of the present invention may include artificial leather, film, expandable foam, and sheet. (sheet), etc., but is not limited to this.
此外,根據一例示性實施態樣的脂族聚碳酸酯-聚胺甲酸乙酯組合物可用於各種領域,例如墨水組合物、漆料組合物、黏合劑組合物等。 Further, the aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment can be used in various fields such as an ink composition, a paint composition, a binder composition and the like.
以下,將由後附實施例更完整地理解本發明,該等實施例係用於例示本發明,並非用於限制本發明保護範圍。 In the following, the invention will be more completely understood from the following examples, which are intended to illustrate the invention and not to limit the scope of the invention.
[實施例1] [Example 1]
基於100重量份之重量平均分子量為2,000公克/莫耳的聚碳酸酯二醇(G3452,旭化成(Asahi Kasei))、23重量份的4,4-二苯基甲烷二異氰酸酯(MDI)及0.1重量份的二月桂酸二丁基錫(DBTDL)被加入反應器中,且於使用一布拉班德混合器(Brabender mixer)在60rpm及120℃攪拌下進行反應1小時,而獲得胺甲酸乙酯預聚物。對該胺甲酸乙酯預聚物加入1,4-丁二醇(BD),且於60rpm及190℃攪拌下進行反應5分鐘,而獲得聚胺甲酸乙酯樹脂。於此,異氰酸酯指數(NCO指數,即異氰酸酯與二醇之間的當量比例)為1.2,且多元醇、伸甲基二苯基異氰酸酯(MDI)、與1,4-丁二醇(BD)的莫耳比例為1.3:4.8:2.7。該聚胺甲酸乙酯與重量平均分子量為30,000公克/莫耳的聚伸丙基碳酸酯(SK新技術)係以70:30之重量比例摻合以製備聚伸丙基碳酸酯-聚胺甲酸乙酯組合物。 100 parts by weight of polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) and 0.1 weight A portion of dibutyltin dilaurate (DBTDL) was added to the reactor, and the reaction was carried out for 1 hour while stirring at 60 rpm and 120 ° C using a Brabender mixer to obtain a urethane prepolymer. Things. To the urethane prepolymer, 1,4-butanediol (BD) was added, and the reaction was carried out for 5 minutes while stirring at 60 rpm and 190 ° C to obtain a polyurethane resin. Here, the isocyanate index (NCO index, ie, the equivalent ratio between isocyanate and diol) is 1.2, and polyol, methyl diphenyl isocyanate (MDI), and 1,4-butanediol (BD) The molar ratio is 1.3:4.8:2.7. The polyurethane and a poly(propyl propylene carbonate) having a weight average molecular weight of 30,000 g/mole were blended in a weight ratio of 70:30 to prepare a poly(propyl carbonate)-polyuric acid. Ethyl ester composition.
[實施例2] [Embodiment 2]
基於100重量份之重量平均分子量為2,000公克/莫耳的聚碳酸酯二醇(G3452,旭化成)、23重量份的4,4-二苯基甲烷二異氰酸酯(MDI)及0.1重量份的二月桂酸二丁基錫(DBTDL)被加入反應器中,且於使用一布拉班德混合器在60rpm及120℃ 攪拌下進行反應1小時,而獲得胺甲酸乙酯預聚物。70重量份的該胺甲酸乙酯預聚物、30重量份的重量平均分子量為30,000公克/莫耳的聚伸丙基碳酸酯(SK新技術)、以及50重量份的1,4-丁二醇(BD)被加入反應器中。於此,異氰酸酯指數(NCO指數,即異氰酸酯與二醇之間的當量比例)為1.2,且多元醇、伸甲基二苯基異氰酸酯(MDI)、與1,4-丁二醇(BD)的莫耳比例為1.3:4.8:2.7。反應混合物於60rpm及190℃攪拌下進行反應5分鐘,以製備雜合聚合的聚伸丙基碳酸酯-聚胺甲酸乙酯組合物。 100 parts by weight of polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) and 0.1 part by weight of dilaurin Dibutyltin acid (DBTDL) was added to the reactor and used at a temperature of 60 rpm and 120 °C using a Brabender mixer The reaction was carried out for 1 hour with stirring to obtain an ethyl carbamate prepolymer. 70 parts by weight of the urethane prepolymer, 30 parts by weight of poly(propylcellulose) having a weight average molecular weight of 30,000 g/mole (SK New Technology), and 50 parts by weight of 1,4-butane Alcohol (BD) was added to the reactor. Here, the isocyanate index (NCO index, ie, the equivalent ratio between isocyanate and diol) is 1.2, and polyol, methyl diphenyl isocyanate (MDI), and 1,4-butanediol (BD) The molar ratio is 1.3:4.8:2.7. The reaction mixture was subjected to a reaction under stirring at 60 rpm and 190 ° C for 5 minutes to prepare a hybrid polymerized poly-propyl carbonate-polyurethane composition.
[比較實施例1] [Comparative Example 1]
基於100重量份之重量平均分子量為2,000公克/莫耳的聚碳酸酯二醇(G3452,旭化成),23重量份的4,4-二苯基甲烷二異氰酸酯(MDI)、及0.1重量份的二月桂酸二丁基錫(DBTDL)被加入反應器中,且於使用一布拉班德混合器在60rpm及120℃攪拌下進行反應1小時,而獲得胺甲酸乙酯預聚物。對該胺甲酸乙酯預聚物加入1,4-丁二醇(BD),且於60rpm及190℃攪拌下使進行反應5分鐘,而獲得聚胺甲酸乙酯樹脂。 100 parts by weight of a polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI), and 0.1 part by weight of two Dibutyltin laurate (DBTDL) was charged into the reactor, and the reaction was carried out for 1 hour while stirring at 60 rpm and 120 ° C using a Brabender mixer to obtain an ethyl urethane prepolymer. To the urethane prepolymer, 1,4-butanediol (BD) was added, and the reaction was carried out for 5 minutes while stirring at 60 rpm and 190 ° C to obtain a polyurethane resin.
(評估) (assessment)
於前述實施例與比較實施例中所製備的產物塗覆於一PET膜上,然後將該膜乾燥,以製備具下列表1所示厚度的試樣。試樣的各種物理性質係藉由依照ASTM標準之方法而測量。於此,測量係分別於縱向(machine direction,MD)與橫向(transverse direction,TD)方向上進行。此外,黏合力與抗水解性係以下列方法評估: The products prepared in the foregoing examples and comparative examples were coated on a PET film, and then the film was dried to prepare a sample having the thickness shown in Table 1 below. The various physical properties of the samples were measured by methods in accordance with ASTM standards. Here, the measurement is performed in the machine direction (MD) and the transverse direction (TD) directions, respectively. In addition, adhesion and hydrolysis resistance are evaluated in the following ways:
(1)黏合力 (1) Adhesion
在所製備的試樣於50巴(bar)之壓力及下列表1所示的溫度條件之下加壓30秒,然後於室溫冷卻5秒之後,於180℃及200毫米/分鐘之條件下,使用剝離測試儀(peel tester)測量該試樣的最高黏合力。 The prepared sample was pressurized at a pressure of 50 bar and under the temperature conditions shown in Table 1 for 30 seconds, and then cooled at room temperature for 5 seconds, at 180 ° C and 200 mm / min. The highest adhesion of the sample was measured using a peel tester.
(2)抗水解性 (2) Resistance to hydrolysis
在該試樣被掛在水浴上且置於60℃爐中5天之後,藉由比較測試前後的拉伸強度,測量其改變率。 After the sample was hung on a water bath and placed in a furnace at 60 ° C for 5 days, the rate of change was measured by comparing the tensile strength before and after the test.
如以上表1及表2,可見根據本發明的實施例1及實施例2表現出優良的機械物理性質如拉伸強度、延伸率、撕裂強度、以及硬度;於實現這些優良機械物理性質的同時,其拉伸強度與延伸率的改變率低,而因此改進了抗水解性;並且,顯現了最高87.75(牛頓/公分)的優良黏合力。相反地,可確認單獨使用聚胺甲酸乙酯(而非根據本發明與聚伸烷基碳酸酯摻合或雜合聚合)的比較實施例1,相較於該等實施例,其具有明顯較差的機械物理性質、抗水解性、以及黏合力。 As shown in Tables 1 and 2 above, it can be seen that Example 1 and Example 2 according to the present invention exhibit excellent mechanical physical properties such as tensile strength, elongation, tear strength, and hardness; in achieving these excellent mechanical physical properties. At the same time, the rate of change in tensile strength and elongation is low, and thus the hydrolysis resistance is improved; and, the excellent adhesion of up to 87.75 (Newton/cm) is exhibited. Conversely, it can be confirmed that Comparative Example 1 using polyurethane alone (instead of blending or hybrid polymerization with polyalkylene carbonate according to the present invention) is significantly inferior to the examples. Mechanical and physical properties, hydrolysis resistance, and adhesion.
根據本發明的脂族聚碳酸酯-聚胺甲酸乙酯聚合物相較於單獨的脂族聚碳酸酯,具有之效果為優良的耐性,例如抗撓曲性、抗水解性、可印刷性等。 The aliphatic polycarbonate-polyurethane polymer according to the present invention has an effect of excellent resistance such as flex resistance, hydrolysis resistance, printability, etc. compared to the aliphatic polycarbonate alone. .
此外,根據本發明的脂族聚碳酸酯-聚胺甲酸乙酯組合物,藉由含有脂族聚碳酸酯,可當作環保的聚胺甲酸乙酯使用。 Further, the aliphatic polycarbonate-polyurethane composition according to the present invention can be used as an environmentally friendly polyurethane by containing an aliphatic polycarbonate.
雖以上已詳細揭露本發明之較佳實施例,然任何所屬領域技術人士將可在不悖離本發明如後附申請專利範圍所定義之精神與範圍之下,做出發明之多種更改。因此,本發明並不侷限於前述實施例。 While the invention has been described in detail, the preferred embodiments of the present invention may be Therefore, the present invention is not limited to the foregoing embodiments.
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