TWI648310B - Process for the preparation of a polyamide - Google Patents
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Abstract
本發明係有關於一用於自二胺及二羧酸製備半芳香族聚醯胺的方法,其包含以下步驟:(i)分配一液體或氣體二胺至含一芳香族二羧酸的經攪拌粉末內以形成一含二胺/二羧酸鹽(DD-鹽)之粉末,及(ii)固態聚合該DD-鹽以獲得該聚醯胺。 The present invention relates to a process for the preparation of a semi-aromatic polyamine from a diamine and a dicarboxylic acid, which comprises the steps of: (i) dispensing a liquid or gaseous diamine to an aromatic dicarboxylic acid-containing process. The powder is stirred to form a powder containing a diamine/dicarboxylate (DD-salt), and (ii) the DD-salt is polymerized in a solid state to obtain the polyamine.
Description
本發明係有關於用於自二胺及二羧酸製備聚醯胺(所謂AA-BB聚醯胺)的方法,且更詳細地,係有關於用於製備半結晶狀半芳香族AA-BB聚醯胺的方法。本發明亦係有關於藉該方法而獲得之產物。 The present invention relates to a process for the preparation of polyamines (so-called AA-BB polyamides) from diamines and dicarboxylic acids, and more particularly to the preparation of semi-crystalline semi-aromatic AA-BBs. The method of polyamine. The invention also relates to products obtained by this method.
有各種製備聚醯胺的方法。已知方法包括熔態聚合反應、溶液聚合反應、懸浮聚合反應、與固態聚合反應、及其等之組合。自二胺及二羧酸製成的聚醯胺通常係藉縮合呈熔態之該二胺及二羧酸而製成。然而,此程序並不適於更具熱敏性及高熔點的聚醯胺,因為其會導致該等聚合物之降解的副反應。因此,對於用於其等之製備的低溫方法(諸如固態聚合反應,其在文中的縮寫為SSP)有興趣。 There are various methods for preparing polyamines. Known methods include melt polymerization, solution polymerization, suspension polymerization, solid state polymerization, and the like. Polyamines made from diamines and dicarboxylic acids are usually prepared by condensing the diamine and dicarboxylic acid in a molten state. However, this procedure is not suitable for polyamines which are more heat sensitive and have a higher melting point because they cause side reactions of degradation of such polymers. Therefore, there is interest in low temperature processes for the preparation thereof, such as solid state polymerization, which is abbreviated as SSP herein.
用於製備聚醯胺之熟知,且廣泛使用的方法為作為另一步驟的含SSP的多步驟方法。其實例包括其中在第一步驟內,一預聚物係在水性溶液中,在一惰性液體內之懸浮液中、或在一熔體中製成的方法。自該溶液或懸浮液離析如此形成的該預聚物,且經固化、或自該熔體直接固化,且在仍呈固態時,進一步聚合以產生一較高分子量聚合物。 此種含使呈該固態之預聚物進一步進行聚合反應的方法亦稱為固態後縮合法或固態潤飾法,且其在文中之縮寫為後SSP。 A well-known and widely used method for preparing polyamines is a multi-step process containing SSP as another step. Examples thereof include a method in which a prepolymer is in an aqueous solution, in a suspension in an inert liquid, or in a melt, in the first step. The prepolymer thus formed is isolated from the solution or suspension and cured or cured directly from the melt and, while still in a solid state, further polymerized to produce a higher molecular weight polymer. Such a method of further subjecting the solid prepolymer to polymerization is also referred to as solid post-condensation or solid-state finishing, and is abbreviated herein as post-SSP.
就AA-BB聚醯胺而言,固態聚合方法亦係已知,其中呈該固態,例如呈粉末形式之二胺及二羧酸的鹽類係直接經聚合而成為一具有所欲分子量的聚醯胺聚合物。此鹽粉末固態聚合反應亦稱為直接固態聚合反應,其在文中之縮寫為直接SSP。 In the case of AA-BB polyamide, a solid state polymerization method is also known in which a salt of a diamine and a dicarboxylic acid, which is in the form of a powder, is directly polymerized to form a polymer having a desired molecular weight. Amidoxime polymer. This salt powder solid state polymerization is also referred to as direct solid state polymerization, which is abbreviated herein as direct SSP.
固態聚合方法(就聚醯胺而言,後SSP及直接SSP)皆亦描述在C.D.Papaspyrides及S.N.Vouyiouka,Wiley,2009之名為“Solid-state Polymerization”的一書內。 Solid state polymerization processes (for polyamines, post-SSP and direct SSP) are also described in the book "Solid-state Polymerization" by C.D. Papaspyrides and S.N. Vouyiouka, Wiley, 2009.
低溫方法之一問題為長反應時間,其典型上係藉使用一催化劑以加速該縮合反應而解決。長反應時間亦為熔態聚合反應之一問題,其中通常使用含磷催化劑。在固態聚合方法內添加催化劑的必要亦在先前經確認。根據R.Pfaender在名為“Solid-state Polymerization”(by.C.D.Papaspyrides and S.N.Vouyiouka,Wiley,2009,第167頁)一書中的描述,該固體方法之反應速率並不夠高且顯著地低於類似的熔體或溶劑方法之反應速率。已知的反應性問題會因為使用芳香族二羧酸(諸如對酞酸及異酞酸)而更突顯,如,例如在該論文“The condensation Kinetics of Polyphthalamides:I.Diamines and Diacids of Dimethylesters”(done by Malluche J.;Hellmann,G.P.;Hewel M.;Liedloff,H.J.;Polym.Eng.Sci.2007,47,1589)中所報告,已知其等的 反應性低於脂肪族二羧酸,諸如己二酸。 One of the problems with low temperature processes is the long reaction time, which is typically solved by the use of a catalyst to accelerate the condensation reaction. Long reaction times are also a problem in the melt polymerization, in which a phosphorus-containing catalyst is usually used. The necessity of adding a catalyst within the solid state polymerization process has also been previously confirmed. According to R. Pfaender's description in the book "Solid-state Polymerization" (by. CDPapaspyrides and SNVouyiouka, Wiley, 2009, p. 167), the reaction rate of the solid process is not high enough and significantly lower than The reaction rate of a similar melt or solvent process. Known reactivity problems are more pronounced due to the use of aromatic dicarboxylic acids such as citric acid and isononanoic acid, such as, for example, in the paper "The condensation Kinetics of Polyphthalamides: I. Diamines and Diacids of Dimethylesters" ( Done by Malluche J.; Hellmann, GP; Hewel M.; Liedloff, HJ; Polym. Eng. Sci. 2007, 47, 1589), known, etc. It is less reactive than an aliphatic dicarboxylic acid such as adipic acid.
有關於用於聚醯胺之後SSP及直接SPP方法之專利的實例如下。 Examples of patents relating to the SSP and direct SPP methods for polyamines are as follows.
JP-62020527-A2描述一自一等莫耳濃度之1,6-己二胺及對酞酸的鹽(文中被縮寫成6T鹽)開始製備聚醯胺-6T的方法。該鹽係自一水性溶液製成,該鹽係呈固體粉末的形式自該水性溶液分離。該聚合法先後包含一懸浮聚合反應步驟及一後SSP步驟。首先係於高溫下,在氮於其中起泡的情況下,於該鹽在甲酚內之懸浮液中製成一預聚物,但是因此該鹽並未經熔融。然後離析該預聚物,且在一氮氣氛下,在作為催化劑的次磷酸鈉存在下進行另一聚合反應。若未使用次磷酸鈉催化劑,則該聚合反應的費時很長且獲得一膠化材料。 JP-62020527-A2 describes a process for preparing polyamido-6T starting from a first-order molar concentration of 1,6-hexanediamine and a salt of citric acid (abbreviated herein as a 6T salt). The salt is prepared from an aqueous solution which is isolated from the aqueous solution in the form of a solid powder. The polymerization process comprises a suspension polymerization step and a post-SSP step. First, at a high temperature, in the case where nitrogen is foamed therein, a prepolymer is formed in the suspension of the salt in cresol, but the salt is thus not melted. The prepolymer was then isolated and subjected to another polymerization in the presence of sodium hypophosphite as a catalyst under a nitrogen atmosphere. If a sodium hypophosphite catalyst is not used, the polymerization takes a long time and a gelled material is obtained.
US-4,925,914描述一懸浮聚合法,其中二胺及二羧酸之鹽係與一含磷催化劑一起分散在一惰性液體內,且在呈懸浮液時經聚合,然後自該反應介質離析該聚合物且經分析。必須藉使用高剪切混合機而進行密集混合以使該鹽及催化劑微細地分散在該反應介質內。該等實例包括各種半芳香族均聚物。所形成聚合物之產率的典型值係在23%至76%的範圍內。 No. 4,925,914 describes a suspension polymerization process in which a salt of a diamine and a dicarboxylic acid is dispersed together with a phosphorus-containing catalyst in an inert liquid and polymerized in the form of a suspension, and then the polymer is isolated from the reaction medium. And analyzed. Intensive mixing must be carried out by using a high shear mixer to finely disperse the salt and catalyst in the reaction medium. These examples include various semi-aromatic homopolymers. Typical values for the yield of the formed polymer are in the range of 23% to 76%.
美國專利US-5,128,442描述一自二胺及二羧酸之一固體鹽進行直接SSP方法。在該US-5,128,442之方法中,該固體鹽係自一含該二羧酸及二胺,與一均勻分佈於其中之催化有效性磷化合物的溶液、懸浮液或分散液製成。該 鹽係於第一反應溫度下呈該固態形式經聚合以形成一預聚物。該預聚物於第二較高反應溫度下進一步經聚合以形成一較高分子量聚合物。在一實例中,係自一6T/66鹽(其係在催化劑存在下自一水性溶液獲得)製成一具有302℃之熔化溫度的半芳香族聚醯胺(PA-6T/66,50/50莫耳/莫耳)。該聚合反應費時33小時,且所形成聚合物具有360至380毫莫耳當量/公斤(meq/kg)之總數量的端基,其相當於僅約3,000克/莫耳之分子量。鑑於該催化劑之存在且甚至可得到一具有較低分子量的聚合物,該反應時間被視為仍相當長。進一步咸信,在本專利之方法內使用較高反應溫度會產生問題且會受固體材料之嚴重黏附現象而顯著受限。 U.S. Patent No. 5,128,442 describes a direct SSP process from a solid salt of one of a diamine and a dicarboxylic acid. In the process of U.S. Patent No. 5,128,442, the solid salt is prepared from a solution, suspension or dispersion containing the dicarboxylic acid and diamine, and a catalytically effective phosphorus compound uniformly distributed therein. The The salt is polymerized in the solid form at a first reaction temperature to form a prepolymer. The prepolymer is further polymerized at a second, higher reaction temperature to form a higher molecular weight polymer. In one example, a semi-aromatic polyamine (PA-6T/66, 50/) having a melting temperature of 302 ° C is formed from a 6T/66 salt obtained from an aqueous solution in the presence of a catalyst. 50 m / m). The polymerization took 33 hours and the resulting polymer had a total number of end groups of 360 to 380 millimoles per kilogram (meq/kg) which corresponded to a molecular weight of only about 3,000 grams per mole. In view of the presence of the catalyst and even a polymer having a lower molecular weight, the reaction time is considered to be still quite long. Further, the use of higher reaction temperatures within the methods of this patent creates problems and is significantly limited by the severe adhesion of solid materials.
該鹽製法典型上係在一溶劑或稀釋劑內進行。首先可以在該溶劑或稀釋劑內藉溶液或懸浮聚合反應而使該鹽經聚合成一預聚物,然後呈一固體預聚物之形式經離析,接著進行後SSP以形成該最終聚合物。或者,該鹽首先呈固體粉末之形式自該溶劑或稀釋劑離析,且藉熔態聚合反應或固態聚合反應而聚合。用於鹽製備的另外方法係描述在美國專利US-5,801,278及US-5,874,520內,其中係使用低溫介質。US-5,874,520描述一其中固體二胺胺基甲酸酯係與固體二羧酸混合的方法。這些化合物尤其係在高剪切條件下經混合,其係顯示具有未經摩擦力摩擦或諸如此類而反應的分子之“新”顆粒表面。低溫介質(例如乾冰或氮)之使用不僅控制該反應之熱,而且使該反應混合物維持固態。US-5,801,278描述在低溫介質(諸如乾冰及液態氮)存在下, 製備二胺/二羧酸鹽的方法。US-5,801,278進一步闡明可形成糊狀物而非自由流動的粉末之未使用一低溫介質所進行的相同方法。使用有機溶劑(如用於懸浮聚合反應)、或低溫介質會使該總製法複雜化且會導致非所欲的額外成本、或甚至妨礙大規模生產。半結晶狀半芳香族聚醯胺為高性能熱塑性塑料,其價格高的部份原因為製造成本。因此有必要使用於裝備該等半結晶狀半芳香族AA-BB聚醯胺的方法最佳化以允許在無膠凝作用下以有效率的方式進行高產率的製備。 The salt process is typically carried out in a solvent or diluent. The salt may first be polymerized into a prepolymer by solution or suspension polymerization in the solvent or diluent, and then isolated as a solid prepolymer, followed by a post-SSP to form the final polymer. Alternatively, the salt is first isolated as a solid powder from the solvent or diluent and polymerized by melt polymerization or solid state polymerization. A further method for the preparation of a salt is described in U.S. Patent Nos. 5,801,278 and 5,874,520, each of which uses a low temperature medium. No. 5,874,520 describes a process in which a solid diamine carbamate is mixed with a solid dicarboxylic acid. These compounds are especially mixed under high shear conditions which exhibit "new" particle surfaces of molecules that have been reacted without frictional friction or the like. The use of a low temperature medium such as dry ice or nitrogen not only controls the heat of the reaction, but also maintains the reaction mixture in a solid state. US-5,801,278 describes in the presence of a cryogenic medium such as dry ice and liquid nitrogen, A process for preparing a diamine/dicarboxylate. US-5,801,278 further clarifies the same process that can be used to form a paste rather than a free flowing powder without the use of a cryogenic medium. The use of organic solvents (such as for suspension polymerization), or low temperature media can complicate the overall process and can result in undesired additional costs, or even hinder mass production. Semi-crystalline semi-aromatic polyamides are high performance thermoplastics, and the high price is partly due to manufacturing costs. It is therefore necessary to optimize the process for equipping such semi-crystalline semi-aromatic AA-BB polyamines to allow for high yield preparations in an efficient manner without gelation.
本發明之一目標為一用於製備半結晶狀半芳香族聚醯胺的最佳化方法。本目標業經根據本發明的方法而達成,該方法包含以下步驟:(i)分配一液體二胺至含一芳香族二羧酸之經攪拌粉末以形成一含二胺/二羧酸鹽的粉末,及(ii)使該二胺/二羧酸鹽進行固態聚合反應以獲得該聚醯胺。 One object of the present invention is an optimized process for the preparation of semi-crystalline semi-aromatic polyamines. The object is achieved according to the process of the invention comprising the steps of: (i) dispensing a liquid diamine to a stirred powder comprising an aromatic dicarboxylic acid to form a diamine/dicarboxylate-containing powder. And (ii) subjecting the diamine/dicarboxylate to solid state polymerization to obtain the polyamine.
根據本發明之該方法的一直接效果在所有步驟係以固態進行,因此不會熔化、溶解或分散在一液體內、或經低溫介質冷卻。可省略溶劑、分散劑、低溫介質之使用、及其等之處理與再生步驟,因此可節省處理及能源成本。使用該根據本發明的方法所製成的半結晶狀半芳香族聚醯胺並未顯示膠凝的跡象且係以高產率獲得。 A direct effect of the process according to the invention is carried out in solid state in all steps and therefore does not melt, dissolve or disperse in a liquid or be cooled by a cryogenic medium. Solvents, dispersants, use of low temperature media, and the like processing and regeneration steps can be omitted, thereby saving processing and energy costs. The semicrystalline semi-aromatic polyamines produced using the process according to the invention did not show signs of gelation and were obtained in high yield.
自二胺及二羧酸所製成的聚醯胺亦稱為AA-BB 聚醯胺。該命名法之使用係遵守Nylon Plastics Handbook,Edited by Melvin I.Kohan,Hanser Publishers,1995;例如PA-6T表示具有建構嵌段,1,6-己二胺及對酞酸之均聚物、PA-66/6T表示一自1,6-己二胺、己二酸及對酞酸製成的共聚物,且PA-66及PA-6T的摻混物被稱為PA-66/PA-6T。 Polyamines made from diamines and dicarboxylic acids are also known as AA-BB Polyamide. This nomenclature is used in accordance with Nylon Plastics Handbook, Edited by Melvin I. Kohan, Hanser Publishers, 1995; for example, PA-6T means a structured block, a homopolymer of 1,6-hexanediamine and p-nonanoic acid, PA -66/6T represents a copolymer made from 1,6-hexanediamine, adipic acid and p-citric acid, and the blend of PA-66 and PA-6T is called PA-66/PA-6T. .
圖1表示藉根據本發明該方法而製成之半結晶狀半芳香族聚醯胺之粉末顆粒的SEM圖。該粉末顆粒具有數百微米大小之大小。該粉末顆粒表示微孔結構,其中於該表面處可看到細孔、裂縫及許多小微晶。在該圖之左側上可看到第二顆粒之一部份。 Figure 1 shows an SEM image of powder particles of semi-crystalline semi-aromatic polyamide produced by the process of the present invention. The powder particles have a size of several hundred microns. The powder particles represent a microporous structure in which pores, cracks, and many small crystallites are visible at the surface. A portion of the second particle can be seen on the left side of the figure.
除非另有明確表示,如文中使用之該名詞“聚醯胺”兼包括均聚醯胺及共聚醯胺。當使用不止一種二胺及/或不止一種二羧酸時,根據本發明之該方法允許製備一共聚醯胺、或聚醯胺共聚物,然而當僅使用一種二胺及一種二羧酸時,則製成一均聚醯胺、或聚醯胺均聚物。文中之均聚醯胺及共聚醯胺一起亦稱為(共)聚醯胺。 The term "polyamine" as used herein, unless otherwise expressly indicated, includes both homopolyamine and copolyamine. When more than one diamine and/or more than one dicarboxylic acid is used, the process according to the invention allows the preparation of a copolyamide or a polyamido copolymer, however when only one diamine and one dicarboxylic acid are used, A homopolyamine or a polyamine homopolymer is then formed. The homopolyamines and copolyamines together are also referred to as (co)polyamines.
除非另有明確或不言明地指定,該措詞“該半芳香族(共)聚醯胺係選自二胺及二羧酸”內之該等名詞“二胺”及“二羧酸”亦有意包括含2或多種不同二胺之二胺、以及含2或多種不同二羧酸之二羧酸。例如就均聚醯胺而言,係僅使用一種二胺及一種二羧酸。 The terms "diamine" and "dicarboxylic acid" are also intended to be used in the phrase "the semi-aromatic (co)polyamine is selected from the group consisting of diamines and dicarboxylic acids" unless otherwise specified or unambiguously specified. These include diamines containing two or more different diamines, and dicarboxylic acids containing two or more different dicarboxylic acids. For example, in the case of homopolyamines, only one diamine and one dicarboxylic acid are used.
使用該方法所獲得之該聚醯胺為半芳香族聚醯 胺。文中之該名詞半芳香族係意指該聚醯胺包含不同於其它重覆單元(特別是脂肪族重覆單元)之含芳香族基團的重覆單元。更特定地,藉該方法而獲得之該半芳香族聚醯胺包含衍生自芳香族二羧酸之重覆單元。芳香族二羧酸為其中該等羧酸基團(-CO2H基團)係直接連接至該等芳香族單元且其間並沒有亞甲基或其它脂肪族單元。 The polyamine obtained by the method is a semi-aromatic polyfluorene amine. The term semi-aromatic as used herein means that the polyamine contains an aromatic group-containing repeating unit different from other repeating units, particularly aliphatic repeating units. More specifically, the semi-aromatic polyamine obtained by this method comprises a repeating unit derived from an aromatic dicarboxylic acid. The aromatic dicarboxylic acid is one in which the carboxylic acid groups (-CO2H groups) are directly attached to the aromatic units and have no methylene or other aliphatic units therebetween.
文中該名詞二胺/二羧酸意指一得自接觸一種二羧酸及一種二胺且自該二羧酸及該二胺之中和反應的二銨二羧酸鹽。文中該名詞“二胺/二羧酸鹽”之縮寫亦為DD鹽。 The term diamine/dicarboxylic acid as used herein means a diammonium dicarboxylate salt obtained by contacting a dicarboxylic acid and a diamine and neutralizing the dicarboxylic acid and the diamine. The abbreviation "diamine/dicarboxylate" is also a DD salt.
在根據本發明之該方法中,二胺/二羧酸鹽係藉分配一種二胺至一含一種芳香族二羧酸的經攪拌粉末而形成。本步驟在文中稱為鹽製備步驟、或步驟(i)。 In the process according to the invention, the diamine/dicarboxylate is formed by dispensing a diamine to a stirred powder comprising an aromatic dicarboxylic acid. This step is referred to herein as the salt preparation step, or step (i).
文中該名詞“經攪拌粉末”意指維持移動的粉末顆粒。其可,例如機械性、或藉氣流、或藉重力、或藉其等之任何組合,如同藉在旋轉容器內進行攪拌、滾轉之攪拌、或藉在一流化床反應器內進行流體化作用而達成。所形成的DD鹽典型上係呈粉末的形式。 The term "stirred powder" as used herein means to maintain moving powder particles. It may, for example, be mechanical, or by air flow, or by gravity, or by any combination thereof, as by stirring in a rotating vessel, stirring by rolling, or by fluidizing in a fluidized bed reactor. Achieved by the role. The DD salt formed is typically in the form of a powder.
文中之粉末係意指由離散且實質上固體的顆粒所組成的顆粒材料。這些顆粒(稱為粉末顆粒)合適地具有一自亞微米至約2毫米或較小的粒度。 By powder herein is meant a particulate material composed of discrete and substantially solid particles. These particles (referred to as powder particles) suitably have a particle size ranging from submicron to about 2 mm or less.
該用於鹽製備步驟(i)內之二羧酸係呈粉末的形式二羧酸粉末在該鹽製備步驟(i)之用途意指該經攪拌粉末具有一在該二羧酸之熔化溫度以下的溫度。該DD鹽在一經攪拌粉末內之製備亦意指該粉末的溫度低於該DD鹽(其在 文中進一步稱為“Tm-鹽”)的熔化溫度。 The use of the dicarboxylic acid powder in the salt preparation step (i) in the form of a powder in the form of the salt preparation step (i) means that the stirred powder has a melting temperature below the dicarboxylic acid temperature. The preparation of the DD salt in a stirred powder also means that the temperature of the powder is lower than the DD salt (which is The melting temperature is further referred to herein as "Tm-salt".
在該二胺之配料期間,該經攪拌粉末的溫度在文中係指該名詞“粉末溫度”。該經攪拌粉末的溫度可藉標準方法(例如使用熱電偶)而測定。 During the formulation of the diamine, the temperature of the agitated powder is referred to herein as the term "powder temperature." The temperature of the agitated powder can be determined by standard methods (e.g., using a thermocouple).
該經攪拌粉末包含至少一芳香族二羧酸。在步驟(i)內之該撹拌粉末可包含2或多種二羧酸(例如2或多種芳香族二羧酸、或一芳香族二羧酸及一脂肪族二羧酸)之混合物。當該二羧酸粉末係由2或多種二羧酸所組成,且其中該二羧酸粉末係由2或多種二羧酸粉末之一物理狀態混合物組成時,該鹽製備步驟(i)同樣可能得到2或多種DD鹽的物理狀態混合物。在該情況下,該粉末溫度應該低於具有最低熔化溫度之該DD鹽之熔化溫度的最低溫度以及具有該最低熔化溫度之該二羧酸之熔化溫度的最低溫度。 The stirred powder comprises at least one aromatic dicarboxylic acid. The chopped powder in step (i) may comprise a mixture of two or more dicarboxylic acids (e.g., two or more aromatic dicarboxylic acids, or one aromatic dicarboxylic acid and one aliphatic dicarboxylic acid). When the dicarboxylic acid powder is composed of two or more dicarboxylic acids, and wherein the dicarboxylic acid powder is composed of a physical state mixture of one or more dicarboxylic acid powders, the salt preparation step (i) is equally likely A mixture of physical states of 2 or more DD salts is obtained. In this case, the powder temperature should be lower than the lowest temperature of the melting temperature of the DD salt having the lowest melting temperature and the lowest temperature of the melting temperature of the dicarboxylic acid having the lowest melting temperature.
在步驟(i)內,該二胺係呈一液體之形式分配至該經攪拌粉末。在其中該二胺於室溫下係為固體之情況下,其可必須首先熔化該二胺以用於製備該液體二胺。 In step (i), the diamine is distributed to the stirred powder in the form of a liquid. In the case where the diamine is a solid at room temperature, it may be necessary to first melt the diamine for the preparation of the liquid diamine.
一旦該二胺分配時,呈經攪拌粉末形式的該二胺及二羧酸可形成一反應混合物,其組成可逐漸改變,原先係包含該二羧酸,經過一段時間後,自混合型二羧酸及二胺/二羧酸鹽改變,且最後可形成二胺/二羧酸鹽粉末。 Once the diamine is dispensed, the diamine and the dicarboxylic acid in the form of a stirred powder form a reaction mixture whose composition can be gradually changed. The dicarboxylic acid is originally contained, and after a period of time, the self-mixing dicarboxylic acid The acid and the diamine/dicarboxylate are altered, and finally the diamine/dicarboxylate powder can be formed.
在根據本發明之方法的步驟(ii)內,該二胺/二羧酸鹽係呈固態經聚合以產生該聚醯胺。該DD鹽較佳呈得自步驟(i)之該粉末形式經聚合。 In step (ii) of the process according to the invention, the diamine/dicarboxylate is polymerized in the solid state to produce the polyamine. Preferably, the DD salt is polymerized in the form of the powder from step (i).
文中該名詞固態聚合反應係意指在可以使該DD 鹽,該聚醯胺及其等之任何中間縮合產物維持該固態的條件下進行該聚合反應。其係藉使用用於該縮合步驟(群)之反應溫度而進行,該反應溫度係低於該DD鹽之熔化溫度,分別低於該聚醯胺、及其等之任何中間產物的熔化溫度。 The term solid state polymerization in the text means that the DD can be made The polymerization is carried out under conditions in which the salt, the polyamine and any intermediate condensation products thereof maintain the solid state. This is carried out by using the reaction temperature for the condensation step (group) which is lower than the melting temperature of the DD salt, respectively lower than the melting temperature of the polyamine, and any intermediate product thereof.
當該方法並未在固態內進行時,其可導致顆粒的熔合以形成團塊及內聚性粉末流動。一旦這些現象發生時,該等反應物開始變得機械性形變的該溫度(亦稱為軟化溫度)係取決於製程及製程條件,且因此最好在真實生活製程條件下,例如以實驗室規模、試驗規模或工廠規模進行測定。其可以於不同溫度(自低於該軟化溫度至接近該軟化溫度)下,藉實驗而完成。在攪拌製程設備內,例如係在加熱期間當自低於該軟化溫度至達到該軟化溫度時,以經測定之扭矩的急遽增加表示該軟化溫度。在靜態聚合反應實驗內,可例如自顯示含熔態及熔融顆粒之團塊的試樣觀察該軟化溫度之獲得。就在根據本發明之該方法中的固態聚合反應而言,係藉施加遠低於該DD鹽、聚醯胺及其等之中間產物的熔化溫度之縮合條件而避免軟化。 When the process is not carried out in the solid state, it can result in fusion of the particles to form agglomerates and cohesive powder flow. Once these phenomena occur, the temperature at which the reactants begin to mechanically deform (also known as the softening temperature) depends on the process and process conditions, and is therefore preferably under real life process conditions, such as laboratory scale. The test scale or factory scale is measured. It can be done experimentally at different temperatures, from below the softening temperature to near the softening temperature. In the agitation process equipment, for example, during heating from below the softening temperature to the softening temperature, the softening temperature is expressed as a sharp increase in the measured torque. In the static polymerization experiment, the softening temperature can be observed, for example, from a sample showing agglomerates containing molten and molten particles. In the case of the solid state polymerization in the process according to the present invention, softening is avoided by applying a condensation condition which is much lower than the melting temperature of the intermediate product of the DD salt, polyamine and the like.
除非另有表示,如文中使用之該名詞熔化溫度(Tm)在文中係意指藉根據ISO 11357-1/3(2009)之方法的DSC(在第一加熱循環內之掃描速率為20℃/分鐘)而測定該吸熱熔化尖峰。 Unless otherwise indicated, the term melting temperature (Tm) as used herein means in the context of a DSC according to the method of ISO 11357-1/3 (2009) (the scanning rate in the first heating cycle is 20 ° C / The endothermic melting peak was measured in minutes.
在一經攪拌粉末內、以及其固態聚合反應之該鹽製法係在該固態內進行。其並未排除在該方法進行期間可添加或形成液體組份。首先可添加呈一液體形式之所有二 胺以進行鹽製備。例如在該固態聚合反應步驟(ii)期間,亦可添加液體二胺。用於步驟(i)內之該二胺可含有少許水。在該聚合反應期間,一旦胺與羧酸基反應時,亦可形成水,該水可蒸發且冷凝。在該鹽製備期間,少許水亦可存在於該等原料內或在該配料步驟期間形成。只要可維持經攪拌粉末,少量水並不成為問題。在該鹽製備期間或其後在該固態聚合反應內進行加熱期間,可藉蒸發而移除該水。 The salt production process in a stirred powder and in its solid state polymerization is carried out in the solid state. It does not exclude the addition or formation of liquid components during the course of the process. First, you can add all two in a liquid form. The amine is used for salt preparation. For example, during the solid state polymerization step (ii), a liquid diamine may also be added. The diamine used in step (i) may contain a little water. During the polymerization, once the amine is reacted with the carboxylic acid group, water may also be formed which may evaporate and condense. During the preparation of the salt, a small amount of water may also be present in the feedstock or formed during the furnishing step. A small amount of water does not become a problem as long as the stirred powder can be maintained. The water may be removed by evaporation during or during the heating of the solid state polymerization during or after the preparation of the salt.
含該如在步驟(i)內所製成之DD鹽的粉末可包含水(例如約7.5重量%、或甚至更高),諸如結晶反應之水,且仍可維持經攪拌粉末的形式。該粉末較佳包含至多5重量%之水、更佳至多2.5重量%或甚至更佳至多1.0重量%或0.5重量%水,其中該重量%(wt%)係相對於該二胺及二羧酸在該DD鹽內的總重量而言。在該鹽製備步驟(i)內,該二胺係呈液體形式分配。在該鹽製備步驟內之呈液體形式的該二胺之分配係必然地意指該二胺係於一分配溫度(亦即於分配時,該二胺的溫度,其係高於該二胺的熔化溫度且低於該二胺的沸騰溫度)下分配。於分配時在使用的壓力條件下測量該沸騰溫度。 The powder containing the DD salt as prepared in step (i) may comprise water (e.g., about 7.5% by weight, or even higher), such as water for crystallization, and still maintain the form of the agitated powder. The powder preferably comprises up to 5% by weight of water, more preferably up to 2.5% by weight or even more preferably up to 1.0% by weight or 0.5% by weight of water, wherein the % by weight (wt%) is relative to the diamine and dicarboxylic acid In terms of the total weight within the DD salt. In the salt preparation step (i), the diamine is distributed in liquid form. The distribution of the diamine in liquid form during the salt preparation step necessarily means that the diamine is at a distribution temperature (i.e., at the time of dispensing, the temperature of the diamine is higher than the diamine The melting temperature is lower than the boiling temperature of the diamine). The boiling temperature is measured under the pressure conditions used during dispensing.
該二胺可以由2或多種二胺的混合物組成。若使用二胺混合物,該二胺的熔化溫度、沸騰溫度及分配溫度係取決於該二胺混合物。 The diamine may consist of a mixture of two or more diamines. If a diamine mixture is used, the melting temperature, boiling temperature and dispensing temperature of the diamine will depend on the diamine mixture.
就該DD鹽製備而言,在分配期間之該粉末溫度較佳為在該DD鹽之熔化溫度(Tm鹽)以下至少40℃、更佳在Tm鹽以下至少60℃。經由使用進一步低於Tm鹽之粉末溫度 可減少該二胺及二羧酸之過早反應的潛在發生。該粉末溫度亦較佳維持在220℃以下;更在在180℃以下。由於一脂肪二羧酸係存在於該經攪拌粉末內,所以該粉末溫度較佳在150℃以下,且更佳在130℃以下。該粉末溫度亦最好在水之沸騰溫度以下。文中該沸騰溫度係於該反應進行時所施加的壓力條件下經測定。可經由使用較低的粉末溫度而減少欲凝結在冷點內之經清除的氣態水以及粉末在此等冷卻上之積垢的問題。可如同尤其在脂肪族二羧酸的情況,就更容易進行低溫反應且由於水的軟化作用而導致顆粒的黏附之DD鹽而言,亦可有利地施加此較低粉末溫度。 For the preparation of the DD salt, the temperature of the powder during dispensing is preferably at least 40 ° C below the melting temperature (Tm salt) of the DD salt, more preferably at least 60 ° C below the Tm salt. By using a powder temperature that is further lower than the Tm salt The potential for premature reaction of the diamine and dicarboxylic acid can be reduced. The powder temperature is also preferably maintained below 220 ° C; more preferably below 180 ° C. Since a fatty dicarboxylic acid is present in the stirred powder, the temperature of the powder is preferably 150 ° C or lower, and more preferably 130 ° C or lower. The powder temperature is also preferably below the boiling temperature of the water. The boiling temperature is determined herein under the pressure conditions applied while the reaction is proceeding. The problem of the cleaned gaseous water to be condensed in the cold spot and the fouling of the powder on such cooling can be reduced by using a lower powder temperature. This lower powder temperature can also be advantageously applied, as is especially the case with aliphatic dicarboxylic acids, in which the low temperature reaction is more readily carried out and the DD salt which adheres to the particles due to the softening action of water.
該粉末溫度亦較佳維持高於0℃。就欲存在於該反應混合物內以進行該鹽製備的水而言,其可減少該水凍結的風險。該粉末溫度更佳為至少20℃以允許經由一冷卻壁而移除熱且不會將該壁之組份凍結。 The powder temperature is also preferably maintained above 0 °C. For water intended to be present in the reaction mixture for the preparation of the salt, it reduces the risk of freezing of the water. The powder temperature is more preferably at least 20 ° C to allow heat to be removed via a stave and does not freeze the components of the wall.
該二胺係經分配至該經攪拌粉末以形成一粉末反應混合物且同時可保存經攪拌粉末。因此,該二胺較佳不同時與該二羧酸一起添加並混合在該經攪拌粉末內,否則不適於保有經攪拌粉末,且亦可導致濕化部份的成塊及未濕化部份的不完全中和反應。其會使該等反應組份之合適混合及均質化複雜化並甚至受到抑制。最好限制該分配速率以防止液體二胺局部聚集,因此可防止過份濕化、局部過熱及與水之釋放過早反應而導致過份黏附並使該床之移動複雜化。本分配方式較佳且係以該名詞“逐漸分配”表示。 The diamine is distributed to the stirred powder to form a powder reaction mixture while the stirred powder can be stored. Therefore, the diamine is preferably not added together with the dicarboxylic acid and mixed in the stirred powder, otherwise it is not suitable for retaining the stirred powder, and may also cause agglomerated and unhumided portions of the wetted portion. Incomplete neutralization reaction. It complicates and even inhibits the proper mixing and homogenization of such reaction components. It is preferred to limit the rate of distribution to prevent local accumulation of liquid diamine, thereby preventing excessive wetting, local overheating, and premature reaction with water release resulting in excessive adhesion and complication of movement of the bed. This distribution method is preferred and is expressed by the term "gradually assigned".
作為一指示,該二胺液體最好以在約25分鐘至約36小時之範圍內,例如在約1至20小時之範圍內,最好是在2至10小時之範圍內的時間逐漸分配。只要可保有該經攪拌粉末,可使用少於25分鐘的較短分配時間,例如20分鐘。然而,尤其當以較大規模進行時,其可能更困難。可使用大於36小時的較長分配時間,例如48小時、或更長。然而,就經濟理由而言,此長分配時間較不佳。 As an indication, the diamine liquid is preferably gradually distributed over a period of from about 25 minutes to about 36 hours, such as from about 1 to 20 hours, preferably from 2 to 10 hours. As long as the agitated powder can be retained, a shorter dispensing time of less than 25 minutes can be used, for example 20 minutes. However, it may be more difficult, especially when performed on a larger scale. Longer dispensing times greater than 36 hours can be used, such as 48 hours, or longer. However, for economic reasons, this long allocation time is less good.
亦最好使用以下之一平均分配速率分配該二胺:介於每分鐘0.05莫耳%二胺(mppm)(相當於33.3小時之總分配時間)與每分鐘5莫耳%(20分鐘)二胺(mppm)之間、較佳介於0.1mppm(16.7小時)與4mppm(25分鐘)之間,例如介於0.2mppm(8.35小時)與2mppm(50分鐘)之間、或介於0.25mppm(6.7小時)與1mppm(100分鐘)之間,其中該二胺之莫耳%係相對於該二羧酸之莫耳量計。括弧內之時間表示該對應分配時間。 It is also preferred to use the one of the following average distribution rates to distribute the diamine: 0.05 mole% diamine per minute (mppm) (equivalent to a total distribution time of 33.3 hours) and 5 moles per minute (20 minutes) Between amines (mppm), preferably between 0.1 mppm (16.7 hours) and 4 mppm (25 minutes), such as between 0.2 mppm (8.35 hours) and 2 mppm (50 minutes), or between 0.25 mppm (6.7) Between 1 hour and 1 mppm (100 minutes), wherein the mole % of the diamine is relative to the molar amount of the dicarboxylic acid. The time in parentheses indicates the corresponding allocation time.
可分別在低分配速率下使用長分配時間,且其允許該胺有更多時間與該二羧酸反應,且較佳用以防止該酸或固體DD鹽產生軟化或黏附現象,但是其會使該方法較不合乎經濟。然而,若合適,可分別在較高分配速率下使用短分配時間,為了合適地進行該二羧酸的機械攪拌並使該二胺有效地分散在該反應混合物內,且移除得自該混合步驟之熱(該熱係由二胺與二羧酸的鹽形成反應所產生)以防止該反應混合物黏附及結塊,可需要更有力或特殊的混合機設計。就各情況而言,可藉例行實驗,使用,例如該分 配速率的變量而測定合適的分配速率。 Long dispensing times can be used at low dispensing rates, respectively, and allow the amine to react more time with the dicarboxylic acid, and preferably to prevent softening or sticking of the acid or solid DD salt, but it will This method is less economical. However, if appropriate, short dispensing times can be used at higher dispensing rates, respectively, for proper mechanical agitation of the dicarboxylic acid and efficient dispersion of the diamine in the reaction mixture, and removal from the mixing. The heat of the step (which is produced by the formation of a salt of a diamine with a dicarboxylic acid) to prevent adhesion and agglomeration of the reaction mixture may require a more powerful or special mixer design. In each case, a routine experiment can be used, such as the point The appropriate rate of distribution is determined by assigning a variable to the rate.
在本發明之另一實施例中,該鹽製備步驟(i)包含使用二羧酸接觸二胺以得到一反應混合物,其中該二胺係與該二羧酸反應以形成二胺/二羧酸鹽,其中:(a)該二羧酸包含一芳香族二羧酸;(b)該二羧酸係以粉末形式提供;(c)該二胺係以液體形式提供;(d)藉逐漸將二胺液體分配至二羧酸粉末,且維持該二羧酸粉末呈恆定移動而進行該接觸步驟;(e)直接在該分配完成後,使該反應混合物維持恆定移動,費時一段時間;(f)於一高於0℃且低於以下所有溫度的溫度下進行(d)及(e):該二胺之沸騰溫度及該二羧酸、該二胺/二羧酸鹽及任何中間反應產物之熔化溫度;及(g)在(d)及(e)內,相對於該胺及二羧酸之總重計,該反應混合物包含至多5重量%水。 In another embodiment of the present invention, the salt preparation step (i) comprises contacting the diamine with a dicarboxylic acid to obtain a reaction mixture, wherein the diamine is reacted with the dicarboxylic acid to form a diamine/dicarboxylic acid. a salt, wherein: (a) the dicarboxylic acid comprises an aromatic dicarboxylic acid; (b) the dicarboxylic acid is provided in powder form; (c) the diamine is provided in liquid form; (d) Dissolving the diamine liquid to the dicarboxylic acid powder and maintaining the dicarboxylic acid powder in a constant movement to carry out the contacting step; (e) maintaining the reaction mixture to maintain a constant movement directly after the partitioning is completed, taking a period of time; (d) and (e) at a temperature above 0 ° C and below all temperatures: boiling temperature of the diamine and the dicarboxylic acid, the diamine/dicarboxylate and any intermediate reaction product The melting temperature; and (g) in (d) and (e), the reaction mixture contains up to 5% by weight water relative to the total weight of the amine and dicarboxylic acid.
根據本發明之該方法之本實施例的效用在所獲得之該DD鹽係呈實質上無水之固體微粒形式。“實質上無水”,在文中係意指相對於該總重計,該DD鹽通常含有不超過5重量%水。自該方法所回收的DD鹽為一安定的實質上自由流動之粉末。所獲得之該DD鹽係呈通常為均質產物的形式,其適用於製備聚醯胺聚合物之一般商業方法。可不需要涉及使用有機溶劑之沈澱步驟及不需要在該反應混合物內使用低溫介質,即能獲得本結果。該方法不需要高剪 切混合步驟,且該方法可輕易地調整至工業規模。 The utility of this embodiment of the method according to the invention is such that the DD salt obtained is in the form of substantially anhydrous solid particles. "Substantially anhydrous", as used herein, means that the DD salt typically contains no more than 5% by weight water relative to the total weight. The DD salt recovered from the process is a stable, substantially free flowing powder. The DD salt obtained is in the form of a generally homogeneous product suitable for use in the general commercial process for preparing polyamine polymers. This result can be obtained without the need for a precipitation step involving the use of an organic solvent and without the use of a low temperature medium in the reaction mixture. This method does not require high shear The mixing step is cut and the method can be easily adjusted to an industrial scale.
例如若使用小於一當量之二胺,則該DD鹽仍可含有少量未經反應的二羧酸。例如若使用超過一當量之二胺,該DD鹽亦可含有少量未經反應的二胺。業經發現該DD鹽可含有少過量的二胺且仍可顯示乾固體粉末的特徵。 For example, if less than one equivalent of a diamine is used, the DD salt may still contain a small amount of unreacted dicarboxylic acid. For example, if more than one equivalent of a diamine is used, the DD salt may also contain a small amount of unreacted diamine. It has been found that the DD salt can contain a small excess of diamine and still exhibit the characteristics of a dry solid powder.
在步驟(i)內所形成的該DD鹽可以是一等莫耳濃度之鹽,但未必是一等莫耳濃度鹽。甚至當使用(接近)化學計量之二胺及二羧酸時,如可藉用於該芳香族二羧酸之X射線繞射(XRD)測定而證明,且藉具有用於在該DD鹽內之該二胺的頂部空間取樣器之氣體層析法而分析,未經反應的二羧酸及未經反應的二胺可同時存在於該DD鹽內。非可預期地,其似乎對該固態聚合反應不具有顯著的影響,由於這些反應物主要可在該方法的其餘步驟內找到,且如藉XRD而證明,會形成幾乎不具有任何殘留二羧酸且具有相當高分子量或黏度的產物。 The DD salt formed in step (i) may be a salt of the first molar concentration, but is not necessarily a first molar concentration salt. Even when using (close to) a stoichiometric amount of a diamine and a dicarboxylic acid, as evidenced by X-ray diffraction (XRD) measurements for the aromatic dicarboxylic acid, and for use in the DD salt The gas chromatographic analysis of the headspace sampler of the diamine allows analysis of the unreacted dicarboxylic acid and the unreacted diamine to be present simultaneously in the DD salt. Unexpectedly, it does not appear to have a significant effect on the solid state polymerization, since these reactants can be found mainly in the remaining steps of the process, and as evidenced by XRD, will form almost no residual dicarboxylic acid. And has a relatively high molecular weight or viscosity of the product.
業經進一步發現就二胺過量而言,係在縮合反應的第一部份、或步驟(ii-a)期間,藉二胺之蒸發而至少部份校正該莫耳平衡,然而就二羧酸過量而言,可在該縮合反應的第二部份、或該方法的步驟(ii-a)期間,藉在該步驟期間添加二胺而修正該莫耳平衡。 It has further been found that in the case of a diamine excess, the molar balance is at least partially corrected by evaporation of the diamine during the first part of the condensation reaction or during the step (ii-a), however, the dicarboxylic acid is excessive. In particular, the molar balance can be corrected by adding a diamine during this step during the second part of the condensation reaction or step (ii-a) of the process.
業經發現就二胺很缺乏(例如使用約0.75-0.85之二胺/二羧酸莫耳比)的鹽製備而言,仍可藉在該固相聚合反應期間添加過量二胺而修正該二胺缺乏,並獲得一具有充份高的分子量之聚醯胺。因此,用於根據本發明之該等方法中 的該固體DD鹽最好具有至少0.75之二胺/二羧酸莫耳比。該二胺/二羧酸莫耳比較佳在0.75-1.10之範圍內、更佳0.90-1.10、又更佳0.95-1.05、且最佳0.98-1.02。使用更接近1之二胺/二羧酸莫耳比的優點在該二胺係以更有效的方式使用。 It has been found that in the case of salt preparation in which the diamine is very deficient (for example, using a molar ratio of about 0.75 to 0.85 diamine/dicarboxylic acid molar ratio), the diamine can still be modified by adding an excess of the diamine during the solid phase polymerization. Lack and obtain a polyamine having a sufficiently high molecular weight. Therefore, in the methods according to the invention The solid DD salt preferably has a diamine/dicarboxylic acid molar ratio of at least 0.75. The diamine/dicarboxylic acid moie is preferably in the range of 0.75-1.10, more preferably 0.90-1.10, still more preferably 0.95-1.05, and most preferably 0.98-1.02. The advantage of using a diamine/dicarboxylic acid molar ratio closer to 1 is used in a more efficient manner.
可以以不同方法及不同類型之反應器進行該鹽製備步驟(i)。最好藉將該二胺噴灑或滴在該活動的二羧酸粉末上而使該二胺接觸二羧酸。在分批操作中,最好藉將該二胺噴灑或滴在該活動的二羧酸粉末上,繼而在已添加該二胺後,將該二胺噴灑或滴在該活動的所形成DD鹽與二羧酸粉末之混合物上而使該二胺接觸二羧酸。合適的反應器(其中該二胺及二羧酸可經接觸並混合)為,例如轉筒式混合機、犂頭混合機、錐形混合機、行星式螺桿混合機及流化床反應器。這些混合機為低剪切混合機的實例。雖然原則上亦可使用高剪切混合機,但是基於較高的耗能,該反應混合物之額外冷卻需求、過度濕化之零件的磨耗及可能增加的黏聚現象,所以高剪切混合機較不佳。有關於這些及其它低剪切混合機裝置之進一步資訊可在以下找到:由Paul,Edward L.;Atiemo-Obeng,Victor A.;Kresta,Suzanne M.所編輯的“Handbook of Industrial Mixing-Science and Practice”(Publisher:John Wiley & Sons;2004;;ISBN:978-0-471-26919-9;Electronic ISBN:978-1-60119-414-5),更詳細地,在Chapter 15,Part 15.4及15.11內。 The salt preparation step (i) can be carried out in different ways and in different types of reactors. Preferably, the diamine is contacted with the dicarboxylic acid by spraying or dripping the diamine onto the active dicarboxylic acid powder. In a batch operation, it is preferred to spray or drip the diamine onto the active dicarboxylic acid powder, and then, after the diamine has been added, the diamine is sprayed or dropped into the active formed DD salt. The diamine is contacted with a dicarboxylic acid by a mixture with a dicarboxylic acid powder. Suitable reactors wherein the diamine and dicarboxylic acid can be contacted and mixed are, for example, tumble mixers, plowshare mixers, conical mixers, planetary screw mixers and fluidized bed reactors. These mixers are examples of low shear mixers. Although high shear mixers can also be used in principle, based on higher energy consumption, additional cooling requirements of the reaction mixture, wear of over-humidified parts and possible increased cohesion, so high shear mixers Not good. Further information on these and other low shear mixer installations can be found below: "Handbook of Industrial Mixing-Science and" edited by Paul, Edward L.; Atiemo-Obeng, Victor A.; Kresta, Suzanne M. Practice" (Publisher: John Wiley &Sons;2004;; ISBN: 978-0-471-26919-9; Electronic ISBN: 978-1-60119-414-5), in more detail, in Chapter 15, Part 15.4 and Within 15.11.
可藉習知方法而控制該反應器內的溫度。可移除一旦該二胺與該二羧酸進行中和反應以形成該二胺/二羧 酸鹽時所產生的熱。就該移除步驟而言,可使用習知方法,例如熱交換器、冷壁、冷攪拌器、或氣流或其等之組合。 The temperature within the reactor can be controlled by conventional methods. Removable once the diamine is neutralized with the dicarboxylic acid to form the diamine/dicarboxyl The heat generated during the acid salt. For the removal step, a conventional method such as a heat exchanger, a cold wall, a cold agitator, or a combination of a gas stream or the like can be used.
該鹽形成反應本身似乎夠快,因此亦允許以合乎經濟的方式在合適設備內進行連續鹽製造。例如可以以連續操作方式,借助於輔助分配設備在一管或槽內之一連續進料混合螺桿周圍進行此方法以製備該鹽,最好,係在一混合區內藉將該二胺噴灑或滴在該經攪拌的二羧酸粉末上而使該二胺接觸二羧酸。 The salt formation reaction itself appears to be fast enough, thus also allowing continuous salt manufacture in a suitable apparatus in a cost effective manner. For example, the process can be carried out in a continuous operation by means of an auxiliary dispensing device around a continuous feed mixing screw in a tube or tank to prepare the salt, preferably by spraying the diamine in a mixing zone or The diamine is contacted with the dicarboxylic acid by dropping it onto the stirred dicarboxylic acid powder.
可不使用高剪切進行根據本發明之該方法中的鹽製備步驟且仍可得到高程度的轉化之事實很令人驚訝。事實上,為了避免該二羧酸粉末之磨耗,可使用低剪切攪拌以產生經攪拌粉末。事實上,該磨耗可以很低、或甚至完全無,因此該粒度分佈幾乎不受影響,其不同於在與該二胺進行反應期間這等二羧酸粉末顆粒的大小通常會增加的事實。在該二羧酸粉末之未磨耗下,此低剪切攪拌的優點在該方法進行期間所產生的微小顆粒之數量低,且積垢、微塵、一旦貯存時的自重下垂、及由於微小顆粒而堵塞的流動性減少之問題減少。 The fact that the salt preparation step in the process according to the invention can be carried out without using high shear and still achieve a high degree of conversion is surprising. In fact, to avoid abrasion of the dicarboxylic acid powder, low shear agitation can be used to produce a stirred powder. In fact, the attrition can be very low, or even completely absent, so that the particle size distribution is hardly affected, unlike the fact that the size of the dicarboxylic acid powder particles generally increases during the reaction with the diamine. The advantage of this low shear agitation under the unavailability of the dicarboxylic acid powder is that the amount of fine particles produced during the process is low, and that fouling, fine dust, sagging self-weight upon storage, and due to minute particles The problem of reduced fluidity of plugging is reduced.
用於根據發明之該方法中的二羧酸粉末較佳包含小部份之具有小粒度的顆粒。該二羧酸粉末亦較佳具有窄粒度分佈。例如該二羧酸粉末具有一具有至少15微米之d10及至多1000微米之d90的粒度分佈。文中,該粒度分佈係藉於20℃下根據ISO 13320之方法經雷射粒度測定法而測定。具有小部份之小顆粒及/或窄粒度分佈之二羧酸粉末 的使用較佳併用低剪切攪拌。其優點在如此製成的DD鹽亦具有較少的小顆粒,分別為相當窄的粒度分佈,且可擇地,甚至更佳的流動性質。 The dicarboxylic acid powder used in the process according to the invention preferably comprises a small fraction of particles having a small particle size. The dicarboxylic acid powder also preferably has a narrow particle size distribution. For example, the dicarboxylic acid powder has a particle size distribution having a d10 of at least 15 microns and a d90 of at most 1000 microns. Herein, the particle size distribution is determined by laser granulometry according to the method of ISO 13320 at 20 °C. a dicarboxylic acid powder having a small fraction of small particles and/or a narrow particle size distribution It is preferably used and stirred with low shear. The advantage is that the DD salt thus produced also has fewer small particles, each having a rather narrow particle size distribution, and optionally, even better flow properties.
該二羧酸粉末之粒度分佈的該d10較佳在15-200微米的範圍內、更佳在16-160微米的範圍內。該d90較佳在100-1000微米的範圍內、更佳在150-800微米的範圍內。該二羧酸粉末最好亦具有在40-500微米的範圍內之中粒度(d50)。該d50較佳在40-400微米的範圍內。該二羧酸粉末亦較佳具有一至多5之Span(跨度)的粒度分佈,其係藉(d84-d16)/d50之比率而定義。該優點在所形成的DD鹽亦具有一較窄的粒度分佈且該流率進一步經改進。 The d10 of the particle size distribution of the dicarboxylic acid powder is preferably in the range of from 15 to 200 μm, more preferably in the range of from 16 to 160 μm. The d90 is preferably in the range of from 100 to 1000 microns, more preferably in the range of from 150 to 800 microns. The dicarboxylic acid powder preferably also has a particle size (d50) in the range of from 40 to 500 μm. The d50 is preferably in the range of 40 to 400 microns. The dicarboxylic acid powder also preferably has a Span (span) particle size distribution of from one to five, which is defined by the ratio of (d84-d16) / d50. This advantage also has a narrower particle size distribution in the formed DD salt and this flow rate is further improved.
經由使用一具有較窄的粒度分佈之二羧酸粉末開始進行反應,且施加低剪切混合步驟可獲得一具有良好可流動性的鹽粉末。 The reaction is started by using a dicarboxylic acid powder having a narrow particle size distribution, and a low shear mixing step is applied to obtain a salt powder having good flowability.
該固體DD鹽較佳具有至少4(更佳至少7)的可流動性(ffc)。該可流動性在文中之定義為固結應力(σ1)對未經限制的降伏強度(σc)之比率(σ1/σc),其係藉根據ASTM D6773之剪切試驗方法而測定。在本發明之一特定實施例內,該固態DD粉末為自由流動粉末,亦即具有一至少10之可流動性(ffc)。使用至少50莫耳%芳香族二羧酸開始進行反應,可更輕易獲得具有此良好可流動性之鹽粉末,其中該莫耳%係相對於該粉末床內之二羧酸的總莫耳數量計。該二羧酸之其餘部份可以是脂肪酸二羧酸。若併用一脂肪酸二胺,所形成鹽粉末包含一芳香族DD鹽及一脂肪族DD鹽。該DD 鹽較佳完全以一芳香族二羧酸為主,亦即得自步驟(i)之該粉末內的DD鹽係由芳香族DD鹽所組成。 The solid DD salt preferably has a flowability (ffc) of at least 4 (more preferably at least 7). This flowability is defined herein as the ratio of the consolidation stress (σ1) to the unrestricted relief strength (σc) (σ1/σc), which is determined by the shear test method according to ASTM D6773. In a particular embodiment of the invention, the solid DD powder is a free flowing powder, i.e., has a flowability (ffc) of at least 10. The salt powder having such good flowability can be more easily obtained by starting the reaction using at least 50 mol% of the aromatic dicarboxylic acid, wherein the molar % is relative to the total number of molars of the dicarboxylic acid in the powder bed. meter. The remainder of the dicarboxylic acid can be a fatty acid dicarboxylic acid. If a fatty acid diamine is used in combination, the salt powder formed contains an aromatic DD salt and an aliphatic DD salt. The DD Preferably, the salt is predominantly an aromatic dicarboxylic acid, i.e., the DD salt from the powder of step (i) consists of an aromatic DD salt.
在另一特定實施例中,該固體DD鹽粉末具有一至少20微米(μm)之d10、及至多1000微米之d90的粒度分佈,其係根據ISO 13320而測定。該等顆粒最好具有一在50-600微米之範圍內的中粒度(d50)。該固體DD鹽較佳具有一粒度分佈,其中該d10係在20-200微米的範圍內,該d50係在50-500微米的範圍內,且該d90係在200-1000微米的範圍內。該DD鹽亦較佳具有一至多5(較佳至多2.5)之Span的粒度分佈,其定義為(d84-d16)/d50之比率。具有此粒度分佈之鹽類可得自具有一相對窄粒度分佈之二羧酸及小量之微小顆粒以及使用上述之低剪切混合機。 In another particular embodiment, the solid DD salt powder has a particle size distribution of at least 20 micrometers (μm) of d10, and at most 1000 micrometers of d90, as determined according to ISO 13320. Preferably, the particles have a medium particle size (d50) in the range of from 50 to 600 microns. The solid DD salt preferably has a particle size distribution wherein the d10 is in the range of 20-200 microns, the d50 is in the range of 50-500 microns, and the d90 is in the range of 200-1000 microns. The DD salt also preferably has a particle size distribution of one to five (preferably up to 2.5) Span, which is defined as the ratio of (d84-d16) / d50. Salts having such a particle size distribution can be obtained from dicarboxylic acids having a relatively narrow particle size distribution and small amounts of fine particles and using the above-described low shear mixer.
該固體DD鹽粉末亦較佳具有至多35%之壓縮率,其係藉(TBD-ABD)/TBD*100%之比率而表示,其中ABD為充氣的總體密度,而TBD為拍填總體密度,其等皆係藉根據ASTM D6393之方法而測定。 The solid DD salt powder also preferably has a compression ratio of up to 35%, expressed as a ratio of (TBD-ABD) / TBD * 100%, wherein ABD is the overall density of the charge, and TBD is the overall density of the fill, These are all determined by the method according to ASTM D6393.
由於在介於如下述之步驟(i)及步驟(ii)間的該固體DD鹽不會進一步成形,所以就如請求項1內所述的方法而言,各該微小顆粒之低含量、窄粒度分佈、高流動性及低壓縮率性質係有利的。 Since the solid DD salt between step (i) and step (ii) as described below is not further shaped, as in the method described in claim 1, the low content and the narrowness of each of the fine particles are Particle size distribution, high flow and low compression properties are advantageous.
藉步驟(i)而獲得之該固體DD鹽為一由含多微晶之粉末顆粒所組成的多晶狀鹽粉末。與該等粉末顆粒之大小相比,該鹽通常具有一相對大的表面積。該DD鹽粉末可有利地具有一至少0.5米2/克、或更特定地,至少0.8米2/克 的高BET值。文中,該BET值係藉根據ISO 9277:2010的方法而測定。 The solid DD salt obtained by the step (i) is a polycrystalline salt powder composed of powder particles containing polycrystallites. The salt typically has a relatively large surface area compared to the size of the powder particles. The DD salt powder may advantageously have a high BET value of at least 0.5 m 2 /g, or more specifically, at least 0.8 m 2 /g. Herein, the BET value is determined by the method according to ISO 9277:2010.
可以在單一反應器或在不同的反應器內進行根據本發明之該方法內的鹽製備步驟(i)及聚合反應步驟(ii)。 The salt preparation step (i) and the polymerization step (ii) in the process according to the invention may be carried out in a single reactor or in separate reactors.
在一較佳實施例中,係在單一反應器內進行以一整體方法進行之在步驟(i)內進行該固體DD鹽的製備以及該聚合反應步驟(ii)。其優點在可減少處理步驟數。另一優點在若該鹽係於高溫下製成,可藉省略步驟(i)後該鹽的冷卻以及用於步驟(ii)的再加熱而節省能源。 In a preferred embodiment, the solid DD salt is prepared in step (i) and the polymerization step (ii) is carried out in a single process in a single reactor. The advantage is that the number of processing steps can be reduced. Another advantage is that if the salt is made at a high temperature, energy can be saved by omitting the cooling of the salt after step (i) and reheating for step (ii).
或者,該鹽製備後,可自第一反應器(稱為配料/混合反應器)將該鹽轉移至另一反應器(該聚合反應器)。 Alternatively, after the salt is prepared, the salt can be transferred from a first reactor (referred to as a furnish/mix reactor) to another reactor (the polymerization reactor).
在一特殊實施例中,係使該DD鹽進行固態成形步驟,然後使該鹽進行聚合反應步驟(ii)。經由使用固態成形步驟,該鹽可保有其含多微晶或實質上多微晶之多晶狀結構。在該固態成形步驟內,該鹽粉末可,例如經粒化以形成顆粒、或壓實成小片。同樣,係獲得分別呈顆粒或小片之得自該縮合步驟的聚醯胺。 In a particular embodiment, the DD salt is subjected to a solid forming step and the salt is then subjected to a polymerization step (ii). By using a solid state forming step, the salt can retain its polycrystalline structure containing multiple crystallites or substantially multiple crystallites. Within the solid forming step, the salt powder can, for example, be granulated to form granules, or compacted into small pieces. Also, polyamines obtained from the condensation step, respectively, in the form of granules or tablets are obtained.
可有利地在靜態床反應器(諸如靜態柱填充)內以批次方法、或使用移動柱填充之連續方法使用固態成形步驟以進一步進行該固態聚合反應的加工,以及進一步在下游使用如此獲得之該聚合物以進行熔態方法。在該方法內之較大顆粒的優點為減少藉該方法內之任何氣體(儘管是用於加熱各該反應物的反應水、清除氣體或氣體)而帶走 粉末。反應後的優點為可改良用於在筒倉及大袋子內進行處理的流動性質,且可更容易並高容量地進行用於後續熱塑性聚合物之加工的熔態擠製機的進料。 It may be advantageous to use a solid state forming step in a batch process, or a continuous process using moving column packing, in a static bed reactor (such as static column packing) to further carry out the processing of the solid state polymerization reaction, and further use in the downstream use. The polymer is subjected to a molten state process. The advantage of larger particles within the process is to reduce the use of any gas within the process (although it is used to heat the reaction water, purge gases or gases of each of the reactants) powder. An advantage after the reaction is that the flow properties for processing in silos and large bags can be improved, and the feeding of the melt extruder for subsequent processing of the thermoplastic polymer can be performed more easily and with high capacity.
可藉將黏合劑噴灑至該粉末上並使該粉末保持活動而進行粒化,其係藉施用,例如流化床粒化法、高剪切粒化法或鼓式粒化法而達成。可藉,例如齒輪製粒法、滾輪壓實法、製片法、或固相萃取法而進行粒化。這些方法的實例可以在以下資料內找到:the Handbook of Powder Technology,vol.11 Granulation,Edited by A.D.Salman,M.J.Hounslow,J.P.K.Seville,Elsevier © 2007,ISBN 978-0-444-51871-2。在各該方法內,水、胺或鹽溶液或其等之混合物可適於作為黏合劑,由於這些物質並不會將外來化學品導入該聚合反應混合物內。並不排除其它合適黏合劑,諸如聚乙烯吡咯啶酮(PVP)、聚乙二醇(PEG)及聚乙烯醇(PVA)。典型上,相對於該粉末的重量,係使用少重量%(例如1-5重量%)的黏合劑。 Granulation can be carried out by spraying a binder onto the powder and keeping the powder active, which is achieved by application, for example, fluidized bed granulation, high shear granulation or drum granulation. Granulation can be carried out, for example, by a gear granulation method, a roller compaction method, a tableting method, or a solid phase extraction method. Examples of such methods can be found in the following materials: the Handbook of Powder Technology, vol. 11 Granulation, Edited by A. D. Salman, M. J. Hounslow, J. P. K. Seville, Elsevier © 2007, ISBN 978-0-444-51871-2. Within each of the methods, a mixture of water, amine or salt solution or the like may be suitable as a binder since these materials do not introduce foreign chemicals into the polymerization mixture. Other suitable binders such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and polyvinyl alcohol (PVA) are not excluded. Typically, less than a weight percent (e.g., 1 to 5% by weight) of binder is used relative to the weight of the powder.
顆粒及小片之大小典型上大於該等粉末顆粒,因此各該顆粒及小片可包含多個粉末顆粒。該等顆粒可具有一以下的粒度:自亞毫米至厘米規模,通常自約0.5毫米至4厘米,例如自約2毫米至約2厘米。該等小片最好可具有一以下的最大直徑:數毫米,例如自約1至8毫米,諸如約2-5毫米。該等小片最好可具有一自毫米至厘米規模的粒度,一般而言係自約1毫米至1厘米,例如自約2至5毫米。 The size of the granules and tablets is typically greater than the powder particles, and thus each of the granules and tablets may comprise a plurality of powder granules. The particles may have a particle size of from about submillimeter to centimeter scale, typically from about 0.5 mm to 4 cm, such as from about 2 mm to about 2 cm. Preferably, the dice may have a maximum diameter of one or less: a few millimeters, such as from about 1 to 8 millimeters, such as from about 2 to about 5 millimeters. Preferably, the tablets may have a particle size ranging from millimeters to centimeters, typically from about 1 mm to 1 cm, such as from about 2 to 5 mm.
在本發明該方法內,係使該固體DD-鹽進行固態 聚合反應以獲得該聚醯胺。可使用適於用於製備聚醯胺之直接固態聚合反應之已知條件進行本固態聚合反應。 In the method of the present invention, the solid DD-salt is solidified Polymerization is carried out to obtain the polyamine. The solid state polymerization can be carried out using known conditions suitable for the direct solid state polymerization of polyamine.
在本縮合步驟從頭至尾,步驟(ii)內之該縮合溫度於最初及最後至少係維持在該DD-鹽的熔化溫度(Tm-鹽)以下。文中該縮合溫度最好在Tm-鹽以下至少10℃、較佳至少15℃、更佳在Tm-鹽以下至少20℃。 From the beginning to the end of the condensation step, the condensation temperature in step (ii) is maintained at least initially and at least below the melting temperature (Tm-salt) of the DD-salt. The condensation temperature herein is preferably at least 10 ° C below the Tm-salt, preferably at least 15 ° C, more preferably at least 20 ° C below the Tm-salt.
根據本發明之第一較佳方面,步驟(ii)包含兩亞步驟:(ii-a)於在該DD-鹽之熔點以下至少10℃的第一縮合溫度(Tc1)下,縮合步驟(i)內所獲得之該DD-鹽以產生一固體預聚物;及(ii-b)進一步於在該預聚物之熔化溫度以及欲獲得該聚醯胺之熔化溫度以下至少15℃的第二縮合溫度(Tc2)下,縮合得自步驟(ii-a)之該固體預聚物,藉此獲得呈固態的該聚醯胺。 According to a first preferred aspect of the invention, step (ii) comprises a two-step process: (ii-a) at a first condensation temperature (Tc1) of at least 10 ° C below the melting point of the DD-salt, the condensation step (i The DD-salt obtained therein to produce a solid prepolymer; and (ii-b) further to a second temperature of at least 15 ° C below the melting temperature of the prepolymer and the melting temperature at which the polyamine is to be obtained. The solid prepolymer obtained in the step (ii-a) is condensed at a condensation temperature (Tc2), whereby the polyamine is obtained in a solid state.
本發明該第一較佳方面之優點在可以於高反應溫度下進行本方法,同時可獲得高反應速率,且非可預期地以高產率製備半芳香族聚醯胺並在相當短的反應時間內產生高度聚合反應,且不會發生膠化現象。本發明該方面之效用為一總體上很有效率的製法,其允許製造能力的高利用。即便不需添加催化劑,且儘管該等羧酸主要包含芳香族二羧酸的事實,仍可獲得以上的結果。 The advantage of this first preferred aspect of the invention is that the process can be carried out at high reaction temperatures while achieving high reaction rates, and unpredictably producing semi-aromatic polyamines in high yields with relatively short reaction times A high degree of polymerization occurs inside and no gelation occurs. The utility of this aspect of the invention is a generally efficient process that allows for the high utilization of manufacturing capabilities. The above results are obtained even without the need to add a catalyst, and despite the fact that the carboxylic acids mainly contain an aromatic dicarboxylic acid.
因此,在該第一亞步驟內,係維持該縮合溫度在該DD鹽之熔化溫度(Tm-鹽)以下之至少10℃以下,且在第二 或另一亞步驟內,可提高該縮合溫度,使其最後甚至高於該DD鹽之熔化溫度,且可維持在該預聚物之熔化溫度,該欲獲得之聚醯胺的熔化溫度及其等之任何中間縮合產物的熔化溫度以下。在此第二或另一亞步驟內之該縮合溫度最好在該聚醯胺及其任何中間縮合產物的熔化溫度以下至少15℃、較佳至少20℃、更佳至少25℃。 Therefore, in the first sub-step, the condensation temperature is maintained below at least 10 ° C below the melting temperature (Tm-salt) of the DD salt, and in the second Or in another substep, the condensation temperature may be increased to be even higher than the melting temperature of the DD salt, and may be maintained at the melting temperature of the prepolymer, the melting temperature of the desired polyamine and The melting temperature of any intermediate condensation product is equal to or lower. The condensation temperature in this second or further substep is preferably at least 15 ° C, preferably at least 20 ° C, more preferably at least 25 ° C below the melting temperature of the polyamine and any intermediate condensation products thereof.
除了使用各別的亞步驟外,亦可藉以下步驟而進行該方法:施加一自在Tm鹽以下至少10℃的縮合溫度逐漸上升至一較高溫度的溫度梯度並維持在該聚醯胺及其任何中間縮合產物之熔化溫度以下至少15℃下。 In addition to the use of separate sub-steps, the method can be carried out by applying a temperature gradient from a condensation temperature of at least 10 ° C below the Tm salt to a higher temperature and maintaining the polyamine and its Any intermediate condensation product has a melting temperature below at least 15 °C.
就得自步驟(i)之含不同DD鹽之混合物的鹽粉末而言,這些鹽也許可具有不同熔化溫度及於一特定溫度下之不同縮合速率。其情況為,例如其中該鹽粉末包含一脂肪族DD鹽及一芳香族DD鹽的混合物。就具有最低熔化溫度之該DD鹽可具有最高縮合速率而言,步驟(ii)可以以兩亞步驟進行,其中在第一亞步驟內,係於一在該等鹽熔化溫度之最低溫度以下至少10℃的溫度下,使該具有最低熔化溫度之鹽經縮合成一聚醯胺預聚物,然後可以提高該溫度,且維持在該預聚物之熔化溫度以下至少15℃及在其它鹽之熔化溫度以下至少10℃,與任何其它聚醯胺預聚物及其等之任何中間產物以下之至少15℃。就該具有最低熔化溫度之DD鹽可具有相同或較低縮合速率而言,在步驟(ii-a)內之Tc1可維持在該鹽熔化溫度之最低溫度以下。 In the case of salt powders from the mixture of step (i) containing different DD salts, these salts may have different melting temperatures and different condensation rates at a particular temperature. The case is, for example, wherein the salt powder comprises a mixture of an aliphatic DD salt and an aromatic DD salt. Insofar as the DD salt having the lowest melting temperature can have the highest condensation rate, step (ii) can be carried out in two sub-steps, wherein in the first sub-step, at least below the minimum temperature of the salt melting temperature The salt having the lowest melting temperature is condensed into a polyamidamide prepolymer at a temperature of 10 ° C, and then the temperature can be raised and maintained at least 15 ° C below the melting temperature of the prepolymer and in other salts. At least 10 ° C below the melting temperature, at least 15 ° C below any other polyamine precursors and any intermediates thereof. Insofar as the DD salt having the lowest melting temperature can have the same or lower condensation rate, Tc1 in step (ii-a) can be maintained below the lowest temperature of the salt melting temperature.
值得注意的是Tc1及Tc2未必不同,其等可相同。 若不同,Tc2較佳高於Tc1,且更佳亦高於Tm鹽,因此其可得到較高縮合速率。 It is worth noting that Tc1 and Tc2 are not necessarily different, and the like may be the same. If different, Tc2 is preferably higher than Tc1, and more preferably higher than Tm salt, so that a higher condensation rate can be obtained.
文中之預聚物係意指具有至少8毫升/克之黏度值的聚醯胺縮合產物。在使Tc2上升高於Tm鹽,該預聚物較佳具有至少10毫升/克、更佳至少15毫升/克,且甚至更佳至少20毫升/克之黏度值。 By prepolymer herein is meant a polyamine condensation product having a viscosity value of at least 8 ml/g. In order to raise Tc2 above the Tm salt, the prepolymer preferably has a viscosity value of at least 10 ml/g, more preferably at least 15 ml/g, and even more preferably at least 20 ml/g.
Tc1較佳為至少210℃,更佳地,Tc1係高於220℃、更佳至少230℃、又更佳至少240℃。就Tc1而言,較高的反應溫度可以使反應更快速且反應時間更短。 Tc1 is preferably at least 210 ° C, and more preferably, Tc1 is higher than 220 ° C, more preferably at least 230 ° C, still more preferably at least 240 ° C. In the case of Tc1, a higher reaction temperature can make the reaction faster and the reaction time shorter.
Tc2較佳為至少240℃。而且在一較佳實施例中、Tc2為在該預聚物、聚醯胺及其等之任何中間縮合產物之熔化溫度以下至少25℃。 Tc2 is preferably at least 240 °C. Also in a preferred embodiment, Tc2 is at least 25 ° C below the melting temperature of the intermediate, condensation product and any intermediate condensation products thereof.
文中該黏度值係藉根據ISO 307(第4版)之方法,於25℃下,在96%硫酸(0.005克/毫升)內測定。 The viscosity values herein are determined in accordance with ISO 307 (4th edition) at 25 ° C in 96% sulfuric acid (0.005 g / ml).
在步驟(ii-b)內,係進一步縮合該聚醯胺預聚物而獲得具有所欲分子量之該聚醯胺。該步驟(ii-b)之持續時間可取決於加工條件及所欲聚合程度。該陳述“所欲聚合程度”並不限於一方法或次數。該所欲聚合度通常可取決於該聚醯胺的目的用途。其可藉任何合適方法而測定該聚合度。例如可以以聚合物性質(諸如黏度、機械性質、或分子量)測定該聚合度。該聚合度亦可衍生自該等羧酸基團及胺基團之轉化率且係藉,例如比率1/(1-ρ)而表示。文中該轉化率ρ為相對於最先存在於該DD鹽內之這些官能基之初總莫耳量的經反應之該等羧酸基團及胺基團的莫耳。 In step (ii-b), the polyamido prepolymer is further condensed to obtain the polyamine having a desired molecular weight. The duration of this step (ii-b) may depend on the processing conditions and the degree of polymerization desired. The statement "degree of polymerization desired" is not limited to one method or number of times. The desired degree of polymerization can generally depend on the intended use of the polyamine. It can be determined by any suitable method. The degree of polymerization can be determined, for example, by polymer properties such as viscosity, mechanical properties, or molecular weight. The degree of polymerization can also be derived from the conversion of the carboxylic acid groups and the amine groups and is expressed, for example, by the ratio 1/(1-ρ). The conversion ρ herein is the mole of the reacted carboxylic acid groups and amine groups relative to the initial total moles of these functional groups present in the DD salt.
可以以適於習知SSP方法的任何方式在,例如固定床反應器、移動床反應器、或攪拌反應器內進行該縮合步驟(ii)、以及各該亞步驟(ii-a)及(ii-b)。就較低熔化DD鹽、及就一旦釋放水時容易黏附的DD鹽(諸如就脂肪族DD鹽而言)而言,步驟(ii-a)較佳使用攪拌床反應器,諸如旋轉容器或機械攪拌的反應器,其中係攪拌該固體DD鹽及固體預聚物,因此可維持活動並循環。攪拌床反應器之使用有助於得到以下結果:藉該方法而獲得之該聚合物為一非黏性粉末或顆粒材料。該聚醯胺粉末最後具均勻自由流動性。就該第二縮合步驟(ii-b)而言,固定床反應器(諸如分批操作的直立柱反應器)、或移動床反應器(諸如連續操作的直立柱反應器)可以是一合乎經濟的更好選擇。 The condensation step (ii), and each of the substeps (ii-a) and (ii) may be carried out in any manner suitable for the conventional SSP process, such as in a fixed bed reactor, a moving bed reactor, or a stirred reactor. -b). In the case of a lower melting DD salt and a DD salt which is readily adhered upon release of water (such as in the case of an aliphatic DD salt), step (ii-a) preferably uses a stirred bed reactor such as a rotating vessel or machine. The stirred reactor in which the solid DD salt and the solid prepolymer are stirred, thereby maintaining activity and recycling. The use of a stirred bed reactor helps to obtain the result that the polymer obtained by this method is a non-sticky powder or particulate material. The polyamide powder finally has a uniform free flow. In the case of the second condensation step (ii-b), a fixed bed reactor (such as a batch operated upright column reactor) or a moving bed reactor (such as a continuously operated upright column reactor) may be an economical one. Better choice.
在該根據本發明之方法內之鹽製備步驟(i)、以及固態聚合反應(ii)適合在惰性氣體氣氛內進行。就該惰性氣體氣氛而言,可使用一般已知用於聚醯胺之聚合反應之技藝的合適氣體。此惰性氣體典型為無氧或本質上無氧的惰性氣體、及無其它氧化反應性氣體,諸如O3、HNO3、HClO4等。最好使用氮氣作為該惰性氣體。最好於常壓或於微過壓(例如在介於1與5巴間的範圍內,例如於約1.5、或2或3巴下)下進行該鹽製備以及該等聚合反應步驟。使用一過壓之優點為可減少在鹽製備期間的二胺損失,即便有損失,也很少。 The salt preparation step (i) and the solid state polymerization (ii) in the process according to the invention are suitably carried out in an inert gas atmosphere. As the inert gas atmosphere, a suitable gas generally known for the polymerization of polyamine can be used. The inert gas is typically an oxygen-free or essentially oxygen-free inert gas, and no other oxidation-reactive gases such as O3, HNO3, HClO4, and the like. It is preferred to use nitrogen as the inert gas. The salt preparation and the polymerization steps are preferably carried out at atmospheric pressure or under slight overpressure (e.g., in the range between 1 and 5 bar, for example, at about 1.5, or 2 or 3 bar). The advantage of using an overpressure is that the loss of diamine during salt preparation can be reduced, even if there is a loss.
在鹽製備步驟(i)期間且更有利的是,在該固態聚合反應步驟(ii)期間,係使用一惰性氣體沖洗以進行該方法。 在該固態聚合反應前之加熱步驟期間,可使用一惰性氣體沖洗移除原先存在於該DD鹽內的任何水。一惰性氣體沖洗亦有助於有效移除得自該縮合反應的水,因此可減少該反應混合物黏附(結塊)的風險,並有助於,例如防止減壓閥、計量管線及在該方法內的其它(沖洗)管線並保護機械封接。最好根據經濟性及效率以選擇該氣體滌洗劑的合適含量,且可藉例行實驗而測定。 During the salt preparation step (i) and more advantageously, during the solid state polymerization step (ii), an inert gas purge is used to carry out the process. During the heating step prior to the solid state polymerization, an inert gas purge can be used to remove any water originally present in the DD salt. An inert gas flush also helps to effectively remove water from the condensation reaction, thereby reducing the risk of adhesion (agglomeration) of the reaction mixture and contributing to, for example, the pressure relief valve, the metering line, and the method Other (flush) lines inside and protect the mechanical seal. Preferably, the appropriate level of the gas scrubbing agent is selected based on economy and efficiency and can be determined by routine experimentation.
可藉加熱該用於滌洗之惰性氣體、或藉加熱文中該等反應器器壁或內部或其等之任何組合而進行該加熱及冷卻。較佳使用用於該加熱之溫度急升法而進行該加熱。其會使該反應器內容物之溫度逐漸增加,並得到一用於該等縮合反應溫度的梯度。其優點在經過一較長時間後,可釋放自該縮合反應所產生的水,且更容易移除,因此使生銹的機會減至最小。 The heating and cooling can be carried out by heating the inert gas used for scrubbing, or by heating any combination of the reactor walls or the interior or the like. This heating is preferably carried out using a temperature rise method for the heating. It gradually increases the temperature of the contents of the reactor and gives a gradient for the temperature of the condensation reaction. The advantage is that after a long period of time, the water produced by the condensation reaction can be released and removed more easily, thus minimizing the chance of rusting.
可,例如如下述進行該固態聚合反應步驟(ii)。係在一聚合反應器內製備該DD鹽,或者可將該DD鹽裝入一聚合反應器內。最好使該DD鹽首先經第一溫度急升加熱至在100-160℃之範圍內的指定溫度(最好約130℃)以允許該DD鹽內之任何水藉蒸發而釋放且經由該滌洗氣體而帶走,同時使其中之該反應器器壁及內部的溫度維持於相同溫度或較高的溫度下而避免在該等表面上發生縮合反應。若有必要移除該DD鹽內的水,最好於該指定溫度下製成該固體DD鹽。其可,例如藉一水收集器而確認。一旦完成或幾乎完成該水移除步驟時,該固體DD鹽係經第二溫度急升 法加熱至一等於Tc1的指定點。可藉該水凝液形成速率(其係緩慢地開始,然後才增加)而追蹤該第一縮合反應步驟。該預聚合反應典型上會進行直到該凝液收集速率顯著下降為止。該DD鹽之轉換的完成亦可在用於該DD鹽之熔化尖峰的殘留熔化焓之不存在下經DSC而確認。就該第二縮合反應步驟而言,所形成該固體預聚物可維持於相同溫度(亦即Tc2等於Tc1)下、或進一步於一較低溫度下經縮合、或可藉第三溫度急升法而加熱至一等於Tc2且高於Tc1的指定點。使該聚醯胺維持於該溫度,直到獲得所欲聚合度為止。一旦該聚合反應完成時,冷卻該聚合物且自該反應器排出。 The solid state polymerization step (ii) can be carried out, for example, as follows. The DD salt is prepared in a polymerization reactor, or the DD salt can be charged into a polymerization reactor. Preferably, the DD salt is first heated to a specified temperature (preferably about 130 ° C) in the range of from 100 to 160 ° C by a first temperature ramp to allow any water in the DD salt to be released by evaporation and via the polyester The gas is purged and carried away while maintaining the temperature of the reactor wall and interior therein at the same temperature or at a higher temperature to avoid condensation reactions on the surfaces. If it is necessary to remove water from the DD salt, it is preferred to prepare the solid DD salt at the specified temperature. It can be confirmed, for example, by a water collector. Once the water removal step is completed or almost completed, the solid DD salt is subjected to a second temperature rise The method is heated to a specified point equal to Tc1. The first condensation reaction step can be followed by the rate of formation of the condensate, which begins slowly and then increases. This prepolymerization will typically proceed until the condensate collection rate drops significantly. The completion of the conversion of the DD salt can also be confirmed by DSC in the absence of residual melting enthalpy for the melting peak of the DD salt. In the second condensation reaction step, the solid prepolymer formed can be maintained at the same temperature (ie, Tc2 is equal to Tc1), or further condensed at a lower temperature, or can be swelled by a third temperature. The method is heated to a specified point equal to Tc2 and higher than Tc1. The polyamine is maintained at this temperature until the desired degree of polymerization is obtained. Once the polymerization is complete, the polymer is cooled and discharged from the reactor.
業經發現在該第一縮合反應步驟(ii-a)期間,該二胺的損失受到相當地限制。就一具有大於一之二胺/二羧酸莫耳比的DD鹽而言,該損失通常不比相當該二胺之過量的數量大很多。就一具有約一或小於一之二胺/二羧酸莫耳比的DD鹽而言,該損失通常約僅數百分率,即便不是,也很少。尚未發現可能造成的二胺缺乏會減少該反應速率。根據本發明之該方法的優點在相對於聚合反應速率之二胺的少量損失而言,該方法並非如此苛求。可輕易獲得一中至高分子量的聚合物。如此獲得之該聚醯胺具有以下的黏度值:至少20毫升/克、較佳至少35毫升/克、更佳至少50毫升/克、或甚至至少65毫升/克。 It has been found that during the first condensation reaction step (ii-a), the loss of the diamine is considerably limited. In the case of a DD salt having a diamine/dicarboxylic acid molar ratio greater than one, the loss is generally not much greater than the amount corresponding to the excess of the diamine. For a DD salt having about one or less than one diamine/dicarboxylic acid molar ratio, the loss is typically on the order of only a few hundred, if not, rarely. It has not been found that a possible diamine deficiency will reduce the rate of the reaction. The advantages of this method according to the invention are not so demanding in terms of a small loss of diamine relative to the rate of polymerization. A medium to high molecular weight polymer can be readily obtained. The polyamine thus obtained has a viscosity value of at least 20 ml/g, preferably at least 35 ml/g, more preferably at least 50 ml/g, or even at least 65 ml/g.
可藉限制該第一縮合反應步驟內之該氣體物料流而增加該聚合度。為了獲得較高聚合度,最好在該固態聚合反應期間添加二胺。最好藉將液體二胺噴灑至各該反 應組份上或藉該惰性氣體滌洗劑而導入呈氣體形式的二胺以添加增補的二胺。其可在,例如步驟(ii-a)或步驟(ii-b)、或其等之任何組合期間進行。 The degree of polymerization can be increased by limiting the flow of the gas within the first condensation reaction step. In order to obtain a higher degree of polymerization, it is preferred to add a diamine during the solid state polymerization. It is best to spray liquid diamine to each of the opposite The diamine in gaseous form is introduced on the component or by the inert gas scrubbing agent to add the supplemental diamine. It can be carried out, for example, during step (ii-a) or step (ii-b), or any combination thereof.
就典型上可形成較低熔化鹽(甚至在使用芳香族二羧酸(例如對酞酸)的情況下)之分支性二胺而言,最好在步驟(ii-b)期間添加二胺。分支性二胺為沿著伸烷二胺單體主鏈含有一或多個烷基的二胺。分支性脂肪族二胺之實例為2,2-二甲基-1,3-丙二胺、2-甲基-1,5-五亞甲二胺、2-甲基-1,9-壬二胺、三甲基-1,6-六亞甲二胺及異佛酮二胺。 In the case of branched diamines which typically form lower molten salts, even in the case of aromatic dicarboxylic acids (e.g., for citric acid), it is preferred to add the diamine during step (ii-b). The branched diamine is a diamine containing one or more alkyl groups along the main chain of the alkylene diamine monomer. Examples of branched aliphatic diamines are 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentamethylenediamine, 2-methyl-1,9-anthracene. Diamine, trimethyl-1,6-hexamethylenediamine and isophorone diamine.
在根據本發明該方法之一較佳實施例中,係在該第二縮合反應步驟(ii-b)期間添加增補的二胺。 In a preferred embodiment of the process according to the invention, a supplemental diamine is added during the second condensation reaction step (ii-b).
在該方法的另一較佳實施例中,係在該第二縮合反應步驟期間,添加一單官能性單體。該單官能性單體最好是單官能性胺,例如十二胺;或單官能性羧酸,例如苯甲酸。添加該鏈中止劑之優點在該方法允許以合理的短時間獲得一高分子量聚醯胺,且同時就在熔態加工期間之黏度保持而言,可以使該聚醯胺具有很好的熔態安定性。相對於該二羧酸之總數量,該單官能性單體之數量最好至多2.0莫耳%、較佳至多1.0莫耳%。 In another preferred embodiment of the method, a monofunctional monomer is added during the second condensation reaction step. The monofunctional monomer is preferably a monofunctional amine such as dodecylamine; or a monofunctional carboxylic acid such as benzoic acid. The advantage of adding the chain terminator allows the high molecular weight polyamine to be obtained in a reasonably short time, and at the same time, the polyamine can be well melted in terms of viscosity retention during the melt processing. Stability. The amount of the monofunctional monomer is preferably at most 2.0 mol%, preferably at most 1.0 mol%, relative to the total amount of the dicarboxylic acid.
亦可添加三官能性或更高官能性單體,其等較佳於該第二縮合反應步驟期間添加。此等單體可作為支化劑。為了防止過度支化及膠化,相對於該二羧酸之總莫耳量,此等單體之數量最好至多1.0莫耳%、較佳至多0.5莫耳%。 Trifunctional or higher functional monomers may also be added, which are preferably added during the second condensation reaction step. These monomers can act as branching agents. To prevent excessive branching and gelation, the amount of such monomers is preferably at most 1.0 mole%, preferably at most 0.5 mole%, relative to the total moles of the dicarboxylic acid.
若合適,添加增補二胺及/或鏈中止劑及/或三/ 更高官能性單體的組合。 If appropriate, add supplemental diamines and / or chain stoppers and / or three / A combination of higher functional monomers.
在根據本發明之該方法內,該固體DD鹽可包含小量不會使該鹽之熔點降低太多,且仍可獲得本發明之效果的催化劑。然而,該數量應該受限,藉以使Tm鹽不低於265℃。較佳在無含磷的聚縮合反應鹽的情況下製備該固體DD鹽。 In the process according to the present invention, the solid DD salt may contain a small amount of a catalyst which does not lower the melting point of the salt too much and which still obtains the effects of the present invention. However, the amount should be limited so that the Tm salt is not lower than 265 °C. Preferably, the solid DD salt is prepared in the absence of a phosphorus-containing polycondensation reaction salt.
在本發明該方法中,係藉使自二胺及含一芳香族二羧酸的二羧酸所製成的二胺/二羧酸鹽(DD鹽)進行固態聚合反應而製成一AA-BB聚醯胺。 In the method of the present invention, a solid-state polymerization reaction is carried out by diamine/dicarboxylate (DD salt) prepared from a diamine and a dicarboxylic acid containing an aromatic dicarboxylic acid to prepare an AA- BB polyamine.
係藉將二胺分配至一含芳香族二羧酸之經攪拌粉末而獲得根據本發明該方法之步驟(ii)內所提供的該DD鹽。該二胺最好由一種二胺、或至少兩種二胺之混合物所組成。該二羧酸亦可由一種二羧酸所組成,或包含至少兩種二羧酸的混合物。該DD鹽最好為至少一芳香族二羧酸以及一至少兩二胺的混合物之鹽。 The DD salt provided in step (ii) of the process according to the invention is obtained by partitioning the diamine to a stirred powder comprising an aromatic dicarboxylic acid. Preferably, the diamine consists of a diamine or a mixture of at least two diamines. The dicarboxylic acid may also consist of a dicarboxylic acid or a mixture of at least two dicarboxylic acids. Preferably, the DD salt is a salt of at least one aromatic dicarboxylic acid and a mixture of at least two diamines.
該DD鹽亦可以是一含兩不同鹽的物理混合物。可藉使用一含至少兩種二羧酸之物理混合物的經攪拌粉末而製備此種物理混合物。或者,可藉首先根據步驟(i)分別製備該鹽類(因此如步驟(i),其各包括將二胺分配至一含芳香族二羧酸的經攪拌粉末),並在進行步驟(ii)前混合該等鹽而製成該物理混合物。 The DD salt can also be a physical mixture containing two different salts. This physical mixture can be prepared by using a stirred powder comprising a physical mixture of at least two dicarboxylic acids. Alternatively, the salts may be prepared separately according to step (i) (thus as in step (i), each comprising partitioning the diamine to a stirred powder containing an aromatic dicarboxylic acid) and performing step (ii) The physical mixture is prepared by premixing the salts.
該芳香族二羧酸最好包含對酞酸、2,6-萘二羧酸及聯苯-4,4’-二羧酸、或其等之組合。該芳香族二羧酸較佳選自對酞酸、2,6-萘二羧酸及聯苯-4,4’-二羧酸。這些較佳 的芳香族二羧酸有助於形成該呈固體粉末的DD鹽並形成允許較高加工溫度之具有較高熔化溫度的DD鹽。該二羧酸又更佳包含對酞酸或甚至由對酞酸所組成。 The aromatic dicarboxylic acid preferably comprises a combination of p-nonanoic acid, 2,6-naphthalene dicarboxylic acid and biphenyl-4,4'-dicarboxylic acid, or the like. The aromatic dicarboxylic acid is preferably selected from the group consisting of p-citric acid, 2,6-naphthalenedicarboxylic acid and biphenyl-4,4'-dicarboxylic acid. These are better The aromatic dicarboxylic acid contributes to the formation of the DD salt as a solid powder and forms a DD salt having a higher melting temperature which allows higher processing temperatures. More preferably, the dicarboxylic acid comprises p-citric acid or even p-citric acid.
製備該DD鹽之二羧酸亦可進一步包含一脂肪族二羧酸。該脂肪族二羧酸最好為非環狀二羧酸(直鏈或分支鏈)、或環狀二羧酸、或其等之組合。該脂肪族二羧酸最好為一具有4-8個碳原子的脂肪族二羧酸。該脂肪族二羧酸亦最好選自以下之群組:1,4-丁二酸(亦稱為琥珀酸)、1,6-己二酸(亦稱為己二酸)、1,8-辛二酸(亦稱為栓酸)及1,4-環己二羧酸。 The dicarboxylic acid from which the DD salt is prepared may further comprise an aliphatic dicarboxylic acid. The aliphatic dicarboxylic acid is preferably an acyclic dicarboxylic acid (straight or branched chain), a cyclic dicarboxylic acid, or a combination thereof. The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 4 to 8 carbon atoms. The aliphatic dicarboxylic acid is also preferably selected from the group consisting of 1,4-succinic acid (also known as succinic acid), 1,6-hexanedioic acid (also known as adipic acid), 1,8 - Suberic acid (also known as succinic acid) and 1,4-cyclohexanedicarboxylic acid.
該脂肪族二羧酸較佳包含己二酸、或反式-1,4-環己二羧酸、或其等之組合、或更佳由其等所組成。己二酸為最廣泛用於半結晶狀聚醯胺之脂肪族二羧酸,且反式-1,4-環己二酸可用於製備具有較高熔點的半結晶狀聚醯胺。 The aliphatic dicarboxylic acid preferably comprises, or preferably consists of, adipic acid, or trans-1,4-cyclohexanedicarboxylic acid, or a combination thereof. Adipic acid is the most widely used aliphatic dicarboxylic acid for semi-crystalline polyamines, and trans-1,4-cyclohexanedioic acid can be used to prepare semi-crystalline polyamines having a higher melting point.
該脂肪族二羧酸及芳香族二羧酸最好呈各該二羧酸之粉末的物理混合物存在。在該情況下,如在DSC測定法中通常可藉各該鹽之不同熔化溫度的觀察而確認,該鹽製備步驟可得到鹽類之物理混合物。 The aliphatic dicarboxylic acid and the aromatic dicarboxylic acid are preferably present in a physical mixture of the powders of the respective dicarboxylic acids. In this case, as is generally observed in the DSC assay by observation of the different melting temperatures of the respective salts, the salt preparation step provides a physical mixture of salts.
在本發明之一較佳實施例中,該二羧酸係由以下所組成:(a)一選自對酞酸-2,6-萘二羧酸及聯苯-4,4’-二羧酸、或其等之組合的芳香族二羧酸;(b)可擇地,一選自己二酸及環己二羧酸、或其等之組合的脂肪族二羧酸;及(c)相對於該二羧酸之總莫耳量,至多10莫耳%另一種二羧酸。 In a preferred embodiment of the present invention, the dicarboxylic acid is composed of (a) one selected from the group consisting of p-phthalic acid-2,6-naphthalenedicarboxylic acid and biphenyl-4,4'-dicarboxylate. An aromatic dicarboxylic acid of an acid, or a combination thereof; (b) alternatively, an aliphatic dicarboxylic acid selected from the group consisting of adipic acid and cyclohexanedicarboxylic acid, or a combination thereof; and (c) relative The total molar amount of the dicarboxylic acid is up to 10 mol% of the other dicarboxylic acid.
相對於在根據本發明之步驟(i)之該經攪拌粉末內的二羧酸之總莫耳量,該芳香族二羧酸較佳佔至少50莫耳%的數量。因此,相對於該DD鹽內之二羧酸的總莫耳量,在自其所形成的該DD鹽內,該DD鹽內之二羧酸可包含至少50莫耳%之芳香族二羧酸。該優點在鹽製備步驟(i)允許更容易製備一輕易可流動的粉末。另一優點在可進一步減少在可提高該溫度之前的第一縮合步驟(i)所需的時間且不會產生黏附問題,因此允許芳香族DD鹽更快進行聚縮合反應,且就一其中該芳香族二羧酸的數量小於50莫耳%的混合物而言,可縮短總聚合反應的時間。 The aromatic dicarboxylic acid preferably accounts for at least 50 mole % relative to the total moles of dicarboxylic acid in the stirred powder in step (i) of the present invention. Thus, the dicarboxylic acid in the DD salt may comprise at least 50 mole % of the aromatic dicarboxylic acid in the DD salt formed therefrom relative to the total molar amount of the dicarboxylic acid in the DD salt. . This advantage allows for easier preparation of a readily flowable powder in the salt preparation step (i). Another advantage is that the time required for the first condensation step (i) before the temperature can be raised can be further reduced without causing adhesion problems, thus allowing the aromatic DD salt to undergo a polycondensation reaction faster, and In the case where the amount of the aromatic dicarboxylic acid is less than 50 mol%, the total polymerization reaction time can be shortened.
相對於該二羧酸的總莫耳量,分別在步驟(i)內之該經攪拌粉末中,及在步驟(ii)內之該DD鹽內的該二羧酸包含至少75莫耳%芳香族二羧酸。由於具有較高含量的芳香族二羧酸,所以允許更高的縮合反應溫度及更快轉化成聚醯胺的速率且不會使該反應器積垢及/或形成塊狀物。 The dicarboxylic acid in the stirred powder in step (i) and the dicarboxylic acid in the DD salt in step (ii), respectively, comprises at least 75 mole percent, relative to the total moles of the dicarboxylic acid Group dicarboxylic acid. Due to the higher content of aromatic dicarboxylic acid, a higher condensation reaction temperature and a faster rate of conversion to polyamine are allowed without fouling and/or formation of agglomerates.
該二羧酸最佳基本上由芳香族二羧酸(亦即至少99莫耳%)所組成,或由芳香族二羧酸所組成,其中該芳香族二羧酸係選自對酞酸、2,6-萘二羧酸及聯苯-4,4’-二羧酸、或其等之組合。其甚至允許更高的加熱速率及縮合反應溫度以及甚至更短的反應時間。 Preferably, the dicarboxylic acid consists essentially of an aromatic dicarboxylic acid (i.e., at least 99 mole %) or an aromatic dicarboxylic acid selected from the group consisting of citric acid, A combination of 2,6-naphthalenedicarboxylic acid and biphenyl-4,4'-dicarboxylic acid, or the like. It even allows for higher heating rates and condensation reaction temperatures and even shorter reaction times.
該用於根據本發明之方法的二胺最好選自脂肪族二胺及脂肪族-芳香族二胺或其等之組合。脂肪族-芳香族二胺為其中各該胺基係直接連接至一脂肪族分子團,且該等脂肪族分子團接著連接至一芳香族分子團的二胺。 The diamine used in the process according to the invention is preferably selected from the group consisting of aliphatic diamines and aliphatic-aromatic diamines or combinations thereof. The aliphatic-aromatic diamine is a diamine in which each of the amine groups is directly bonded to an aliphatic molecular group, and the aliphatic molecular groups are then linked to an aromatic molecular group.
該脂肪族二胺可包含一直鏈脂肪族二胺、一分支鏈脂肪族二胺或一環脂肪族二胺、或其等之組合。 The aliphatic diamine may comprise a linear aliphatic diamine, a branched aliphatic diamine or a monoaliphatic diamine, or a combination thereof.
該脂肪族二胺最好包含一C2-C10二胺,亦即一具有自2至10個碳原子的二胺。該C2-C10脂肪族二胺最好選自1,2-乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、及1,4-環己二胺,其等係為C2-C6二胺的實例;及1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、及1,10-癸二胺,其等係為C7-C10二胺之實例。 The aliphatic diamine preferably comprises a C2-C10 diamine, i.e., a diamine having from 2 to 10 carbon atoms. The C2-C10 aliphatic diamine is preferably selected from the group consisting of 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexane. An amine, and 1,4-cyclohexanediamine, which are examples of a C2-C6 diamine; and 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine, which is an example of a C7-C10 diamine.
該脂肪族二胺較佳包含一C4-C6二胺,諸如1,4-丁二胺、1,5-戊二胺、1,6-己二胺、反式-1,4-環己二胺。 The aliphatic diamine preferably comprises a C4-C6 diamine such as 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, trans-1,4-cyclohexane amine.
該二胺更佳包含一直鏈C4-C10二胺,更特定地,1,4-丁二胺、1,5-戊二胺、及1,6-己二胺、或反式-1,4-環己二胺或其等之組合。其可得到一具有更高熔點的DD鹽,其可允許較高的縮合反應溫度且可限制顆粒黏附的風險。 More preferably, the diamine comprises a straight chain C4-C10 diamine, more specifically, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine, or trans-1,4 a combination of cyclohexanediamine or the like. It provides a DD salt with a higher melting point which allows for higher condensation reaction temperatures and limits the risk of particle sticking.
相對於該DD鹽內之二胺的總莫耳量,該二胺亦更佳包含至少50莫耳%C2-C6二胺、且甚至更佳至少75莫耳%。其亦可得到具有較高熔化溫度之鹽及共聚醯胺,因此在縮合反應步驟(ii-a)及(ii-b)期間允許較高的加工溫度且不會增加黏附的風險。 The diamine also more preferably comprises at least 50 mole % C2-C6 diamine, and even more preferably at least 75 mole %, relative to the total moles of diamine in the DD salt. It also gives salts with higher melting temperatures and copolyamines, thus allowing higher processing temperatures during the condensation reaction steps (ii-a) and (ii-b) without increasing the risk of adhesion.
自該芳香族二羧酸製成之該DD鹽合適地具有一至少240℃(其中℃為攝氏度數)之熔化溫度、更佳至少250℃,例如在260-330℃的範圍內。 The DD salt prepared from the aromatic dicarboxylic acid suitably has a melting temperature of at least 240 ° C (where ° C is Celsius), more preferably at least 250 ° C, for example in the range of 260-330 ° C.
此等鹽類之實例包括XY鹽類,其中X為C2-C10二胺、或其等之組合,且Y係選自對酞酸、2,6-萘二羧酸及 聯苯-4,4’-二羧酸、或其等之組合。 Examples of such salts include XY salts wherein X is a C2-C10 diamine, or combinations thereof, and Y is selected from the group consisting of p-nonanoic acid, 2,6-naphthalenedicarboxylic acid, and Biphenyl-4,4'-dicarboxylic acid, or a combination thereof.
因此,得自該等芳香族DD鹽之該半結晶狀半芳香族聚醯胺較佳具有一至少260℃、最好至少280℃之熔化溫度。該半結晶狀聚醯胺最好具有在260-370℃之範圍內的熔化溫度、或甚至更佳在自280-350℃的範圍內。其允許該聚醯胺經熔態加工。而且,得自該芳香族DD鹽與一脂肪酸DD鹽之組合的該聚醯胺亦可經熔態加工且形成一均質共聚醯胺。事實上,令人驚訝地,儘管就該聚合反應而言,係使用鹽類的物理混合物且該聚合反應係在該固態內進行的事實,該方法可得到該脂肪族DD鹽之脂肪族聚醯胺、與該芳香族DD鹽之半芳香族聚醯胺的嵌段共聚物,如自該聚合物之熔化溫度可發現,經由發生在該熔體內之醯胺轉化反應,該嵌段共聚物輕易地轉化成一無規共聚醯胺。得自該等芳香族DD鹽之該半結晶狀半芳香族聚醯胺亦可具有一370℃或更高的熔化溫度。其情況可以是在XY鹽類之均聚物中,X為,例如1,2-乙二胺、1,4-丁二胺、1,6-己二胺或反式-1,4-環己二胺,且Y為對酞酸、2,6-萘二羧酸或聯苯-4,4’-二羧酸。 Accordingly, the semicrystalline semi-aromatic polyamine obtained from the aromatic DD salts preferably has a melting temperature of at least 260 ° C, preferably at least 280 ° C. The semicrystalline polyamine preferably has a melting temperature in the range of from 260 to 370 ° C, or even more preferably in the range of from 280 to 350 ° C. It allows the polyamine to be processed in a molten state. Moreover, the polyamine which is derived from the combination of the aromatic DD salt and a fatty acid DD salt can also be processed in a molten state to form a homogeneous copolyamide. In fact, surprisingly, in spite of the fact that in the case of the polymerization, a physical mixture of salts is used and the polymerization is carried out in the solid state, the process can obtain an aliphatic polyfluorene of the aliphatic DD salt. a block copolymer of an amine, a semi-aromatic polyamine with the aromatic DD salt, such as from the melting temperature of the polymer, is found to be easily via a guanamine conversion reaction occurring in the melt The ground is converted into a random copolyamide. The semi-crystalline semi-aromatic polyamine obtained from the aromatic DD salts may also have a melting temperature of 370 ° C or higher. The case may be that in the homopolymer of the XY salt, X is, for example, 1,2-ethanediamine, 1,4-butanediamine, 1,6-hexanediamine or trans-1,4-cyclod. Hexamethylenediamine, and Y is p-citric acid, 2,6-naphthalenedicarboxylic acid or biphenyl-4,4'-dicarboxylic acid.
在本發明之一特定實施例中,得自步驟(i)之該DD鹽包含一芳香族二羧酸(Y)及一脂肪族二胺(X),且藉該方法而獲得之聚醯胺為半芳香族聚醯胺均聚物(其係以PA-XY代表)。用於此等均聚物之合適鹽的實例包括XT鹽,其中T為對酞酸,且X為選自1,2-乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、及1,6-己二胺的直鏈C2-C8二胺。合 適的聚醯胺均聚物之實例包括PA-2T、PA-3T、PA-4T、PA-5T、PA-6T、PA-7T、及PA-8T。即便此等均聚物可具有很高的熔化溫度、或甚至在熔化前會降解,經由使用本發明的方法,可以於一仍遠低於該聚合物之熔化/降解溫度下進行這些鹽類的聚合反應,且可得到很高轉化率並得到高分子量,且不會發生會導致膠化的副反應。 In a particular embodiment of the invention, the DD salt from step (i) comprises an aromatic dicarboxylic acid (Y) and an aliphatic diamine (X), and the polyamine obtained by the method It is a semi-aromatic polyamine homopolymer (which is represented by PA-XY). Examples of suitable salts for such homopolymers include XT salts wherein T is p-nonanoic acid and X is selected from the group consisting of 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butane A linear C2-C8 diamine of an amine, 1,5-pentanediamine, and 1,6-hexanediamine. Combined Examples of suitable polyamine homopolymers include PA-2T, PA-3T, PA-4T, PA-5T, PA-6T, PA-7T, and PA-8T. Even if such homopolymers can have very high melting temperatures, or even degrade before melting, by using the process of the invention, these salts can be carried out at a temperature that is still well below the melting/degradation temperature of the polymer. The polymerization is carried out, and a high conversion rate is obtained and a high molecular weight is obtained, and a side reaction which causes gelation does not occur.
根據本發明第二較佳方面,該二羧酸包含一選自對酞酸、2,6-萘二羧酸及聯苯-4,4’-二羧酸的芳香族二羧酸,且該液體二胺包含一種含至少兩選自C2-C10二胺的脂肪族二胺之混合物。 According to a second preferred aspect of the present invention, the dicarboxylic acid comprises an aromatic dicarboxylic acid selected from the group consisting of p-citric acid, 2,6-naphthalenedicarboxylic acid and biphenyl-4,4'-dicarboxylic acid, and The liquid diamine comprises a mixture of at least two aliphatic diamines selected from the group consisting of C2-C10 diamines.
業經發現在本發明該DD鹽內包含一第二脂肪族二胺非可預期地可加速本發明該方法之步驟(ii)內之固態聚合反應的速率。 The inclusion of a second aliphatic diamine in the DD salt of the present invention has been found to undesirably accelerate the rate of solid state polymerization within step (ii) of the process of the present invention.
該DD鹽更佳主要含一芳香族二羧酸(Y)及至少兩二胺(X1及X2)以及可擇地,一或多種另外的二胺(一起稱為Xn)。該等鹽類可分別以X1Y/X2Y鹽及X1Y/X2Y/XnY鹽表示。該等相應的共聚醯胺同樣地分別以PA-X1Y/X2Y及PA-X1Y/X2Y/XnY表示。 More preferably, the DD salt comprises predominantly an aromatic dicarboxylic acid (Y) and at least two diamines (X 1 and X 2 ) and, optionally, one or more additional diamines (collectively referred to as X n ). These salts can be represented by X 1 Y/X 2 Y salts and X 1 Y/X 2 Y/X n Y salts, respectively. The corresponding copolyamines are likewise represented by PA-X 1 Y/X 2 Y and PA-X 1 Y/X 2 Y/X n Y, respectively.
該等相應的鹽類可藉鹽製備步驟(i)而製成,其係藉首先製造含至少兩二胺的液體混合物,然後分配該液體混合物至含該二羧酸粉末的經攪拌粉末。 The corresponding salts can be prepared by the salt preparation step (i) by first producing a liquid mixture containing at least two diamines and then dispensing the liquid mixture to the stirred powder containing the dicarboxylic acid powder.
該半芳香族共聚醯胺較佳包含至少一脂肪族C2-C6二胺,亦即X1為C2-C6二胺。X2及/或Xn可擇地包含一非脂肪族二胺的二胺。X1更佳係與至少另一脂肪族 C2-C10二胺合併,亦即X2為脂肪族C2-C10二胺。 The semi-aromatic copolyamine preferably comprises at least one aliphatic C2-C6 diamine, that is, X1 is a C2-C6 diamine. X2 and/or Xn may optionally comprise a diamine of a non-aliphatic diamine. X1 is better with at least another aliphatic The C2-C10 diamines are combined, that is, X2 is an aliphatic C2-C10 diamine.
該等二胺之比率可大不同。例如該莫耳比X1/(X2+Xn)係在99/1-1/99之範圍內。若高於99/1之比率,該(共)聚醯胺最好被視為是均聚醯胺,且經常有可能存在微量之其它二胺。該莫耳比X1/(X2+Xn)最好在95/5-5/95之範圍內、或更佳90/10-10/90及75/25-25/75。相對於該等二胺之總莫耳量,該C2-C6二胺之莫耳量最好是至少50莫耳%。 The ratio of these diamines can vary widely. For example, the molar ratio X 1 /(X 2 +X n ) is in the range of 99/1-1/99. If it is higher than the ratio of 99/1, the (co)polyamine is preferably regarded as a homopolyamine, and it is often possible to have a trace amount of other diamine. The molar ratio X 1 /(X 2 +X n ) is preferably in the range of 95/5-5/95, or more preferably 90/10-10/90 and 75/25-25/75. Preferably, the C2-C6 diamine has a molar amount of at least 50 mole percent relative to the total moles of the diamines.
該DD鹽及相應的半結晶狀半芳香族(共)聚醯胺具有此種使該熔化溫度在280-350℃(更佳300-340℃)範圍內的單體組合。這些(共)聚醯胺具有良好加工性質以及良好的高溫性質。 The DD salt and the corresponding semi-crystalline semi-aromatic (co)polydecylamine have such a monomer combination which allows the melting temperature to be in the range of from 280 to 350 ° C (more preferably from 300 to 340 ° C). These (co)polyamines have good processing properties as well as good high temperature properties.
可使用本發明該方法製成的合適共聚醯胺之實例包括以下之共聚物:PA-2T、PA-3T、PA-4T、PA-5T、PA-6T,諸如PA-4T/XT、PA-6T/XT,例如PA-4T/6T、PA-6T/5T、PA-4T/10T,PA-6T/10T,PA-6T/4T/10T,PA-6T/9T,PA-6T/7T、PA-4T/8T、PA-4T/6T/10T及PA-4T/10T、PA-6T/8T、PA4T/DACHT(其中DACH係指反式-1,4-二胺基環己烷)、及相應的共聚醯胺,其中對酞酸(T)係藉2,6-萘二羧酸或聯苯-4-4’二羧酸而取代。文中,4代表衍生自1,4-丁二胺之重複單元,5代表衍生自1,5-戊二胺之重複單元,6代表衍生自1,6-己二胺之重複單元,7代表衍生自1,7-庚二胺之重複單元,8代表衍生自1,8-辛二胺之重複單元,10代表衍生自1,10-癸二胺之重複單元。D代表衍生自2-甲基五亞甲二胺之重複單元,而2-Me8代表衍生自2-甲基-1,8-辛二胺之重複單元。 Examples of suitable copolyamines which can be made using the process of the invention include the following copolymers: PA-2T, PA-3T, PA-4T, PA-5T, PA-6T, such as PA-4T/XT, PA- 6T/XT, such as PA-4T/6T, PA-6T/5T, PA-4T/10T, PA-6T/10T, PA-6T/4T/10T, PA-6T/9T, PA-6T/7T, PA -4T/8T, PA-4T/6T/10T and PA-4T/10T, PA-6T/8T, PA4T/DACHT (where DACH refers to trans-1,4-diaminocyclohexane), and corresponding Copolyamines, wherein the tannic acid (T) is substituted with 2,6-naphthalene dicarboxylic acid or biphenyl-4-4' dicarboxylic acid. Herein, 4 represents a repeating unit derived from 1,4-butanediamine, 5 represents a repeating unit derived from 1,5-pentanediamine, 6 represents a repeating unit derived from 1,6-hexanediamine, and 7 represents a derivative. From the repeating unit of 1,7-heptanediamine, 8 represents a repeating unit derived from 1,8-octanediamine, and 10 represents a repeating unit derived from 1,10-nonanediamine. D represents a repeating unit derived from 2-methylpentamethylenediamine, and 2-Me8 represents a repeating unit derived from 2-methyl-1,8-octanediamine.
若即便有也極少,該鹽製法內之光鏈脂肪族二胺的含量較佳限於該等二胺之10莫耳%。 If it is rare, the content of the optical chain aliphatic diamine in the salt process is preferably limited to 10 mol% of the diamine.
最佳為主要含以下組份之DD鹽:一選自對酞酸、2,6-萘二羧酸或聯苯-4-4’二羧酸之芳香族二羧酸、以及至少兩選自C4、C6及C10二胺之脂肪族二胺。 Preferably, it is a DD salt mainly comprising the following components: an aromatic dicarboxylic acid selected from the group consisting of citric acid, 2,6-naphthalenedicarboxylic acid or biphenyl-4-4' dicarboxylic acid, and at least two selected from the group consisting of Aliphatic diamines of C4, C6 and C10 diamines.
一般而言,芳香族二羧酸之鹽類的熔化溫度高於其等之脂肪族二羧酸鹽相似物。 In general, salts of aromatic dicarboxylic acids have melting temperatures higher than their aliphatic dicarboxylate analogs.
自該脂肪族二羧酸所製成的DD鹽(文中稱為脂肪族DD鹽,其可以與根據本發明該方法之步驟(i)內之自該芳香族二羧酸所製成的DD鹽(稱為芳香族DD鹽)一起製成)最好具有一至少170℃、較佳至少180℃或至少190℃的熔化溫度。此等鹽類之實例包括XY鹽,其中X為1,4-丁二胺、1,5-戊二胺、或1,6-己二胺,且Y為己二酸或反式-1,4-環己二羧酸。 a DD salt prepared from the aliphatic dicarboxylic acid (referred to herein as an aliphatic DD salt which may be derived from the DD salt of the aromatic dicarboxylic acid in step (i) of the process according to the invention The (referred to as an aromatic DD salt) preferably has a melting temperature of at least 170 ° C, preferably at least 180 ° C or at least 190 ° C. Examples of such salts include XY salts wherein X is 1,4-butanediamine, 1,5-pentanediamine, or 1,6-hexanediamine, and Y is adipic acid or trans-1, 4-cyclohexanedicarboxylic acid.
若共聚醯胺係自含一芳香族DD鹽及一脂肪族DD鹽的混合物製成,則該二胺及脂肪族二羧酸較佳經選擇可致使一僅得自該脂肪族DD鹽的脂肪族聚醯胺成為半結晶狀聚醯胺。此脂肪族半結晶狀聚醯胺最好可具有一以下之熔化溫度:至少230℃、較佳至少240℃、更佳至少250℃、且最好在260-300℃的範圍內。使用此脂肪族DD鹽與該芳香族DD鹽(至少是至少50莫耳%該等芳香族DD鹽)的組合之優點在該第一縮合步驟(ii-a)內使該脂肪族DD鹽轉化成一預聚物後,經過一較短時間後,可增加該第二縮合步驟(ii-b)之溫度Tc2,且該等顆粒不會黏附,同時獲得高反應速率及 短轉化時間,且獲得所欲聚合反應程度之聚醯胺的該聚合反應所需之總時間可縮短。 If the copolyamine is prepared from a mixture comprising an aromatic DD salt and an aliphatic DD salt, the diamine and the aliphatic dicarboxylic acid are preferably selected to result in a fat derived only from the aliphatic DD salt. The polyamidoamine becomes a semi-crystalline polyamine. The aliphatic semi-crystalline polyamine may preferably have a melting temperature of at least 230 ° C, preferably at least 240 ° C, more preferably at least 250 ° C, and most preferably in the range of 260-300 ° C. The advantage of using a combination of this aliphatic DD salt with the aromatic DD salt (at least at least 50 mole % of the aromatic DD salts) converts the aliphatic DD salt in the first condensation step (ii-a) After forming a prepolymer, after a short period of time, the temperature Tc2 of the second condensation step (ii-b) can be increased, and the particles do not adhere, and a high reaction rate is obtained. The total time required for the polymerization of the short conversion time and the polyamine to obtain the desired degree of polymerization can be shortened.
合適的共聚醯胺之實例包括PA-XT與PA-X6或PA-XCHDA的共聚物(其中X包含C4-C6二胺)、或其等之組合。例如PA-4T/46、PA-4T/4CHDA、PA-6T/66、PA-6T/6CHDA及PA4T/DACH6。文中CHDA代表經重複單元衍生的反式-1,4-環己二羧酸。 Examples of suitable copolyamines include copolymers of PA-XT with PA-X6 or PA-XCHDA (wherein X comprises a C4-C6 diamine), or combinations thereof. For example, PA-4T/46, PA-4T/4CHDA, PA-6T/66, PA-6T/6CHDA, and PA4T/DACH6. CHDA herein represents trans-1,4-cyclohexanedicarboxylic acid derivatized by a repeating unit.
本發明亦有關於藉根據本發明該方法而製成的聚醯胺、及其等之任何特定或較佳實施例。本發明特別係有關於一藉該根據本發明之方法而獲得的聚醯胺,其中該聚醯胺為半結晶狀半芳香族均聚醯胺、或半結晶狀半芳香族共聚醯胺。 The invention also relates to polyamines made by the process according to the invention, and any particular or preferred embodiments thereof. The invention relates in particular to a polyamine obtained by the process according to the invention, wherein the polyamine is a semi-crystalline semi-aromatic homopolyamine or a semi-crystalline semi-aromatic copolyamine.
該聚醯胺最好具有一至少20毫升/克、較佳至少35毫升/克、更佳至少50毫升/克、或甚至至少65毫升/克的黏度值。 Preferably, the polyamine has a viscosity value of at least 20 ml/g, preferably at least 35 ml/g, more preferably at least 50 ml/g, or even at least 65 ml/g.
業經發現該藉根據本發明之方法而獲得的聚醯胺具有一獨特的外表,其特徵為一特殊形貌。步驟(i)內所製成的該DD鹽為一通常由含多微晶之多晶狀顆粒所組成。在該等鹽之固態聚合反應期間,係直接以該粉末開始反應、或首先在固態條件下粒化或小片化該粉末,該等DD鹽粉末之一般物理性質,諸如基本形貌,係主要藉如此獲得之該等聚醯胺粉末而保持。使用根據本發明該方法所獲得之聚醯胺粉末顆粒之一實例係示於圖1內。 Polyamines obtained by the process of the present invention have been found to have a unique appearance characterized by a particular morphology. The DD salt produced in step (i) is generally composed of polycrystalline particles containing polycrystallites. During the solid state polymerization of the salts, the powder is directly reacted with the powder, or the powder is first granulated or sized in a solid state, and the general physical properties of the DD salt powder, such as the basic morphology, are mainly borrowed. The polyamide powder thus obtained is maintained. An example of a polyamide pigment particle obtained using the method according to the present invention is shown in Figure 1.
圖1表示藉根據本發明該方法而製成之半結晶狀 半芳香族聚醯胺之粉末顆粒的SEM圖。該粉末顆粒具有數百微米大小之大小。該粉末顆粒表示微孔結構,其中於該表面處可看到細孔、裂縫及許多小微晶。在該圖之左側上可看到第二顆粒之一部份。 Figure 1 shows a semi-crystalline form made by the method according to the invention SEM image of powder particles of semi-aromatic polyamine. The powder particles have a size of several hundred microns. The powder particles represent a microporous structure in which pores, cracks, and many small crystallites are visible at the surface. A portion of the second particle can be seen on the left side of the figure.
就該聚醯胺粉末而言,該微晶狀微孔結構係以相當高的BET表面值表示,且含相當大的顆粒。藉根據ISO 9277:2010之方法而測定,該聚醯胺粉末最好具有一至少0.4m2/g之BET值,且藉根據ISO 13320之方法而測定,同時具有一至少50微米(μm)之d 50粒度分佈。該BET值甚至可在0.6-1.5m2/g之範圍內,且d50至少100微米。 In the case of the polyamide powder, the microcrystalline microporous structure is represented by a relatively high BET surface value and contains relatively large particles. Preferably, the polyamide powder has a BET value of at least 0.4 m2/g as determined by the method of ISO 9277:2010, and is determined by the method according to ISO 13320, and has a d of at least 50 micrometers (μm). 50 particle size distribution. The BET value may even be in the range of 0.6-1.5 m2/g and the d50 is at least 100 microns.
進一步以下述非限制性實例及比較實驗闡明本發明。 The invention is further illustrated by the following non-limiting examples and comparative experiments.
對酞酸:粉末,工業級(粒度分佈:d10=35.8微米;d50=127微米;d90=264微米;跨距2.36);熔化溫度高於400℃。 For tannic acid: powder, technical grade (particle size distribution: d10 = 35.8 microns; d50 = 127 microns; d90 = 264 microns; span 2.36); melting temperature above 400 °C.
己二酸:粉末,工業級(粒度分佈:d10=102微米;d50=349微米;d90=758微米;跨距1.49);熔化溫度152℃。 Adipic acid: powder, technical grade (particle size distribution: d10 = 102 microns; d50 = 349 microns; d90 = 758 microns; span 1.49); melting temperature 152 °C.
1,4-丁二胺:(1,4-二胺丁烷,DAB)工業級;最大1重量%水,在ppm範圍內的雜質;熔化溫度27.5℃。 1,4-butanediamine: (1,4-diaminebutane, DAB) technical grade; up to 1% by weight of water, impurities in the ppm range; melting temperature 27.5 °C.
1,6-己二胺:(六亞甲二胺,HMDA)工業級;最大1重量%水,在ppm範圍內之雜質;熔化溫度41℃。 1,6-hexanediamine: (hexamethylenediamine, HMDA) technical grade; maximum 1% by weight water, impurities in the ppm range; melting temperature 41 °C.
1,10癸二胺;最大1重量%水,在ppm範圍內之雜質;熔化溫度62℃。 1,10 癸 diamine; up to 1% by weight of water, impurities in the ppm range; melting temperature 62 ° C.
次磷酸鈉單水合物,得自Sigma Aldrich,最大1重量%水,在ppm範圍內的雜質。 Sodium hypophosphite monohydrate, available from Sigma Aldrich, up to 1% by weight water, impurities in the ppm range.
藉使用具有一Metrohm combi電極之Metrohm類型Titrando 808處理器,使用如已取得之3M KCl填充溶液,以電位滴定法測定該等DD鹽內之NH2及CO2H含量。稱出0.1克鹽試樣並裝入一配備經PTFE(Teflon)塗覆的磁性攪拌棒之100毫升玻璃圓柱滴定容器內並使其溶解在12.5毫升水中,然後添加37.5毫升乙醇。使用0.1N HCl在水中之溶液滴定該溶液以獲得NH2含量。就該CO2H端基滴定法而言,係如上述裝備一試樣溶液且經0.1N NaOH在水中之溶液滴定。使用50毫升之75體積%/25體積%乙醇/水溶劑對這兩種滴定法進行空白試驗。根據以下方程式計算該NH2及CO2H端基含量。 The NH2 and CO2H contents in the DD salts were determined by potentiometric titration using a Metrohm type Titrando 808 processor having a Metrohm combi electrode using a 3M KCl fill solution as obtained. 0.1 g of the salt sample was weighed out and placed in a 100 ml glass cylindrical titration vessel equipped with a PTFE (Teflon) coated magnetic stir bar and dissolved in 12.5 ml of water, followed by the addition of 37.5 ml of ethanol. The solution was titrated with a solution of 0.1 N HCl in water to obtain a NH2 content. For the CO2H end-group titration, a solution of a sample solution as described above and titrated with 0.1 N NaOH in water was used. The two titrations were subjected to a blank test using 50 ml of a 75 vol%/25 vol% ethanol/water solvent. The NH2 and CO2H end group content was calculated according to the following equation.
其中:VHCl1=用於試樣滴定之HCl滴定液毫升數 Where: VHCl 1 = HCl titration solution for sample titration
VHCl0=用於空白滴定之HCl滴定液毫升數 VHCl 0=ml of HCl titration solution for blank titration
VNaOH1=用於試樣滴定之NaOH滴定液毫升數 VNaOH 1 = milliliters of NaOH titrant for sample titration
VNaOH0=用於空白滴定之NaOH滴定液毫升數 VNaOH 0 = number of milliliters of NaOH titrant for blank titration
tHCl=該HCl滴定液之莫耳濃度(莫耳/升) tHCl = molar concentration of the HCl titrant (mole / liter)
tNaOH=該NaOH滴定液之莫耳濃度(莫耳/升) tNaOH = molar concentration of the NaOH titrant (mole / liter)
a=試樣數量(克) a = number of samples (g)
根據ISO 307(第4版)測定該黏度值(VN)。使用一預先乾燥的聚合物試樣進行該測定,於80℃在高真空(亦即小於50毫巴)下,在24小時內進行其乾燥步驟。係於25.00±0.05℃下,在0.5克聚合物之100毫升硫酸96.00±0.15% m/m的濃度下進行該黏度值之測定。於25℃下,使用一得自Schott(參考資料號第53020號)之DIN-Ubbelohde測定該溶液之流動時間(t)及該溶劑之流動時間(to)。該VN之定義為
其中:VN=以毫升/克表示之黏度值 Where: VN = viscosity value expressed in milliliters per gram
t=以秒數表示之該試樣溶液的平均流動時間 t = average flow time of the sample solution expressed in seconds
t0=以秒數表示之該溶劑的平均流動時間 t 0 = average flow time of the solvent in seconds
c=以克/毫升表示之濃度(=0.005) c = concentration expressed in grams per milliliter (=0.005)
該鹽以及該聚合物之熔化溫度(Tm)的測定、及藉DSC方法而測定之熔化焓(△Hm) The salt and the melting temperature (Tm) of the polymer and the melting enthalpy (ΔHm) determined by the DSC method
藉習知差示掃描量熱法(DSC),使用根據ISO 11357-3(2009)之方法而研究該等鹽之熱性質及特徵(諸如熔化溫度及熔化焓)、中間產物之殘留熔化焓、及該等聚合物之熔化溫度。使用殘留的熔化焓之測定法作為一用於該等鹽之反應的轉化率之內對照值並使其轉化成聚醯胺(預)聚物。 Using the differential scanning calorimetry (DSC), the thermal properties and characteristics of such salts (such as melting temperature and melting enthalpy), residual melting enthalpy of intermediates, using the method according to ISO 11357-3 (2009), And the melting temperature of the polymers. The residual enthalpy of enthalpy is used as a control within the conversion for the reaction of the salts and converted to a polyamine (pre)polymer.
就該等測定法而言,係使用一標準熱通量Mettler DSC 823並使用以下條件。以一精密天平稱出約3至10毫克質量之試樣並包封(捲曲)在40微升具有已知質量之鋁坩堝內。以一多孔鋁坩堝蓋密封該鋁坩鍋。該多孔係經機械製成且由50微米的孔寬所組成。使用一相同的空坩堝作為一對照物。以50毫升分鐘-1之速率進行氮沖洗。使用在0至380℃之範圍內具有20℃/分鐘之掃描速率的加熱-冷卻-加熱循環以測定可數字上表示該等經研究材料(呈聚合物形式之這兩種鹽)的熱性質之參數。就該等鹽及聚合物之熔化溫度及殘留熔化焓而言,係使用該第一加熱循環內之熔化尖峰。 For these assays, a standard heat flux Mettler DSC 823 was used and the following conditions were used. A sample of about 3 to 10 milligrams in mass was weighed out on a precision balance and encapsulated (curled) in 40 microliters of aluminum crucible of known quality. The aluminum crucible was sealed with a porous aluminum crucible lid. The porous body was mechanically made and consisted of a pore width of 50 microns. An identical open space was used as a control. Nitrogen flushing was carried out at a rate of 50 ml min -1 . A heating-cooling-heating cycle having a scan rate of 20 ° C/min in the range of 0 to 380 ° C is used to determine the thermal properties that can numerically represent the materials of study (the two salts in polymer form) parameter. The melting peaks in the first heating cycle are used for the melting temperatures of the salts and polymers and the residual melting enthalpy.
藉該根據ISO 9277:2010-藉氣體吸附而測定固體的比表面積-BET方法而測定該等鹽粉末及聚醯胺粉末的BET值。在一Micromeritics TriStar 3000氣體吸附分析儀上分析該等試樣。在進行該等吸附測定前,於100℃下在真空內使該等試樣除氣。 The BET values of the salt powders and the polyamide powders were determined by the specific surface area-BET method for measuring solids by gas adsorption according to ISO 9277:2010. The samples were analyzed on a Micromeritics TriStar 3000 gas adsorption analyzer. The samples were degassed in vacuum at 100 ° C prior to the adsorption measurements.
將61.21克固體對酞酸(0.369莫耳)粉末裝入一1.0升檔板燒瓶內。使該燒瓶與一配備加熱二胺配料容器之旋轉蒸發器連接,藉每小時5克之氮氣滌洗,費時1小時而惰性化。藉以50rpm旋轉該燒瓶而混合該燒瓶內之內容物並保持於氮氣氛(每小時5克)下。使該旋轉燒瓶部份浸沒在維持於65℃下之油浴內藉以使該粉末達到相同溫度。藉在該配料容器內,於60℃(其相當於60℃之配料溫度)下熔化並混合該等二胺而製備含12.67克1,4-丁二胺(0.144莫耳)及26.12克1,6-己二胺(0.225莫耳)之液體混合物。在恆定旋轉下以0.42莫耳%/分鐘之配料速率,在4小時內一滴滴添加該液體混合物至該酸粉末。該配料完成後,藉旋轉而攪拌該反應混合物並於65℃之溫度下使該燒瓶維持在該油浴內,再費時120分鐘。然後使該燒瓶冷卻至室溫並自該燒瓶排出該鹽。如此獲得之該鹽是一種粉末。該鹽之分析特性的結果係示於表1內。 61.21 grams of solid p-citric acid (0.369 moles) powder was charged to a 1.0 liter baffle flask. The flask was connected to a rotary evaporator equipped with a heated diamine batching vessel, and washed with 5 grams of nitrogen per hour, inerting for 1 hour. The contents of the flask were mixed by rotating the flask at 50 rpm and kept under a nitrogen atmosphere (5 g per hour). The rotating flask was partially immersed in an oil bath maintained at 65 ° C to bring the powder to the same temperature. 12.67 g of 1,4-butanediamine (0.144 mol) and 26.12 g of 1, were prepared by melting and mixing the diamine in the batching container at 60 ° C (which corresponds to a compounding temperature of 60 ° C). A liquid mixture of 6-hexanediamine (0.225 mol). The liquid mixture was added dropwise to the acid powder in 4 hours at a batching rate of 0.42 mol%/min under constant rotation. After completion of the batching, the reaction mixture was stirred by rotation and the flask was maintained in the oil bath at a temperature of 65 ° C for a further 120 minutes. The flask was then cooled to room temperature and the salt was drained from the flask. The salt thus obtained is a powder. The results of the analytical properties of the salt are shown in Table 1.
除了使用一2.0升擋板燒瓶,裝填294.18克(1.77莫耳)對酞酸粉末並一滴滴添加215.82克(1.86莫耳)1,6-己二胺(HMDA)及29.74克水之混合物不同外,如實例I所述之步驟製備該鹽。使該HMDA/水混合物維持於80℃之溫度(其係為該配料溫度)下。配料速率為1.0克/分鐘(每分鐘0.3875莫耳%總二胺)。該配料完成後,使該經攪拌粉末之溫度維持於65℃下,費時120分鐘且同時攪拌。然後使該燒瓶冷卻至 室溫且自該燒瓶排放該鹽。獲得該呈粉末之鹽。該鹽之分析特性的結果係示於表1內。 In addition to using a 2.0 liter baffle flask, 294.18 grams (1.77 moles) of citric acid powder was added and a mixture of 215.82 grams (1.86 moles) of 1,6-hexanediamine (HMDA) and 29.74 grams of water was added dropwise. The salt was prepared as described in Example I. The HMDA/water mixture was maintained at a temperature of 80 ° C, which is the temperature of the furnish. The batching rate was 1.0 g/min (0.3875 mol% total diamine per minute). After the batching was completed, the temperature of the stirred powder was maintained at 65 ° C for 120 minutes while stirring. The flask was then cooled to The salt was discharged from the flask at room temperature. The salt of the powder is obtained. The results of the analytical properties of the salt are shown in Table 1.
除了使用一2.0升擋板燒瓶,裝填326.65克(1.97莫耳)對酞酸粉末且一滴滴添加183.35克(2.08莫耳)1,4-丁二胺(DAB)不同外,如實例I所述之步驟製備該鹽。於80℃下維持該DAB之溫度且於65℃下維持將該擋板燒瓶加熱之該油浴的溫度。配料速率為1.0毫升/分鐘(每分鐘0.55莫耳%之總二胺)。該配料完成後,於65℃下維持該經攪拌粉末的溫度,費時120分鐘且同時攪拌。然後使該燒瓶冷卻至室溫且自該燒瓶排放該鹽。獲得呈粉末形式之該鹽。該鹽之分析特性的結果係示於表1內。 Aside from a 2.0 liter baffle flask filled with 326.65 grams (1.97 moles) of citric acid powder and a drop of 183.35 grams (2.08 moles) of 1,4-butanediamine (DAB), as described in Example I This step prepares the salt. The temperature of the DAB was maintained at 80 ° C and the temperature of the oil bath in which the baffled flask was heated was maintained at 65 °C. The batching rate was 1.0 ml/min (0.55 mol% of total diamine per minute). After the formulation was completed, the temperature of the stirred powder was maintained at 65 ° C for 120 minutes while stirring. The flask was then cooled to room temperature and the salt was drained from the flask. The salt is obtained in powder form. The results of the analytical properties of the salt are shown in Table 1.
將228.91先對酞酸裝入1升配備一具有加熱上部之螺旋攪拌裝置的電性加熱圓柱容器內。使該反應器配備一連接至一加熱二胺配料容器(其係藉經每小時5克之氮氣沖洗而情性化)之配料系統。以60rpm混合該反應器內之內容物並藉氮沖洗而惰性化。藉該外套溫度而將該反應器內容物加熱至60℃之溫度,且使該上部溫度維持等於該外套溫度。藉於60℃下在該配料容器內熔化並混合該等二胺而製一含103.26克1,6-己二胺及44.83克1,4-丁二胺(64/36莫耳%/莫耳%)之液體混合物。在恆定旋轉(60rpm)下在5小時內經由該配料系統而一滴滴添加該液體混合物且同時維持該混合物之粉末溫度於60℃下並在添加該等二胺期間及其後, 維持每小時5克之氮流。該等二胺之分配完成後,在一小時內使該反應混合物自60℃加熱至150℃並維持於該溫度下,費時兩小時且允許該等揮發組份離開該反應器。然後,在兩小時內使該反應器內容物冷卻至50℃以下。如此獲得之該鹽為粉末。該鹽之分析結果係示於表1內。該等結果類似實例I之彼等結果。其證明在這兩情況內皆可完全形成鹽,且就實例IV而言,於150℃下進行之該分段處理並未導致二胺的顯著損失、或過早反應。 The 228.91 was first charged with citric acid in a 1 liter electric heating cylindrical vessel equipped with a heated upper stirring device. The reactor was equipped with a dosing system connected to a heated diamine batching container which was conditioned by a nitrogen purge of 5 grams per hour. The contents of the reactor were mixed at 60 rpm and inerted by nitrogen flushing. The reactor contents were heated to a temperature of 60 ° C by the jacket temperature and the upper temperature was maintained equal to the jacket temperature. The diamine was melted and mixed in the batching vessel at 60 ° C to prepare 103.26 g of 1,6-hexanediamine and 44.83 g of 1,4-butanediamine (64/36 mol%/mole). %) liquid mixture. The liquid mixture was added dropwise via the batching system over 5 hours at constant rotation (60 rpm) while maintaining the powder temperature of the mixture at 60 ° C and during and after the addition of the diamines, Maintain a nitrogen flow of 5 grams per hour. After the partitioning of the diamines is completed, the reaction mixture is heated from 60 ° C to 150 ° C in one hour and maintained at this temperature, which takes two hours and allows the volatile components to leave the reactor. The reactor contents were then cooled to below 50 °C within two hours. The salt thus obtained is a powder. The analysis results of the salt are shown in Table 1. These results are similar to those of Example I. It was demonstrated that the salt was completely formed in both cases, and in the case of Example IV, the segmentation treatment at 150 °C did not result in significant loss or premature reaction of the diamine.
除了使用2.0升擋板燒瓶,裝填280.26克(1.687莫耳)對酞酸粉末並一滴滴添加藉於60℃下熔化並混合該等二胺而製成之含117.65克(1.012莫耳)1,6-己二胺、24.87克(0.282莫耳)1,4-丁二胺及87.22克(0.506莫耳)1,10-癸二胺的液體混合物不同外,如實例I內所述的步驟製成該鹽。於60℃下維持該二胺混合物之溫度並使將該擋板燒瓶加熱之該油浴的溫度維持於65℃下。配料速率為1.0克/分鐘。該配料完成後,使該油浴之溫度維持於65℃下,費時120分鐘且同時攪拌。然後使該燒瓶冷卻至室溫並自該燒瓶排出該鹽。獲得如粉末形式的該鹽。該鹽之分析特性的結果係示於表1內。 In addition to using a 2.0 liter baffle flask, 280.26 g (1.687 mol) of citric acid powder was charged and added dropwise with 117.65 g (1.012 mol) 1 by melting at 60 ° C and mixing the diamines. The procedure described in Example I was followed by a liquid mixture of 6-hexanediamine, 24.87 grams (0.282 moles) of 1,4-butanediamine, and 87.22 grams (0.506 moles) of 1,10-decanediamine. Into the salt. The temperature of the diamine mixture was maintained at 60 ° C and the temperature of the oil bath in which the baffled flask was heated was maintained at 65 °C. The batching rate was 1.0 g/min. After the batching was completed, the temperature of the oil bath was maintained at 65 ° C, and it took 120 minutes while stirring. The flask was then cooled to room temperature and the salt was drained from the flask. The salt is obtained as a powder. The results of the analytical properties of the salt are shown in Table 1.
除了使用2.0升擋板燒瓶,裝填238.21克(1.434莫耳)對酞酸粉末及38.46克(0.263莫耳)己二胺,然後一滴滴添 加一藉於60℃下熔化並混合該等二胺而製成之含144.87克(1.247莫耳)1,6-己二胺及45.27克(0.514莫耳)1,4-丁二胺的液體混合物不同外,如實例I內所述的步驟製成該鹽。使該二胺混合物之溫度維持於60℃下並使將該擋板燒瓶加熱之該油浴的溫度維持於65℃下。配料速率為1.0克/分鐘。該配料完成後,使該油浴之溫度維持於65℃下,費時120分鐘且同時攪拌。然後使該燒瓶冷卻至室溫且自該燒瓶排放該鹽。獲得如粉末形式的該鹽。該鹽之分析特性的結果係示於表1內。該等DSC測定法顯示兩熔化尖峰。 In addition to using a 2.0 liter baffle flask, charge 238.21 grams (1.434 moles) of citric acid powder and 38.46 grams (0.263 moles) of hexamethylenediamine, then add one drop A liquid containing 144.87 g (1.247 mol) of 1,6-hexanediamine and 45.27 g (0.514 mol) of 1,4-butanediamine prepared by melting and mixing the diamine at 60 ° C. The salt was prepared as described in Example I, except for the mixture. The temperature of the diamine mixture was maintained at 60 ° C and the temperature of the oil bath in which the baffled flask was heated was maintained at 65 °C. The batching rate was 1.0 g/min. After the batching was completed, the temperature of the oil bath was maintained at 65 ° C, and it took 120 minutes while stirring. The flask was then cooled to room temperature and the salt was drained from the flask. The salt is obtained as a powder. The results of the analytical properties of the salt are shown in Table 1. These DSC assays show two melting peaks.
除了將一含75克對酞酸及40.4克己二酸(62/38莫耳/莫耳%)之物理混合物裝入該1.0升擋板燒瓶內,並一滴滴添加液體1,6-己二胺(86.6克)於其中不同外,如實例I內所述之步驟製成該鹽。獲得呈粉末形式之該鹽。該鹽之分析特性的結果係示於表1內。該等DSC測定法顯示兩熔化尖峰。 In addition to a physical mixture containing 75 grams of citric acid and 40.4 grams of adipic acid (62/38 moles per mole %) was charged into the 1.0 liter baffle flask and the liquid hexamethylenediamine was added dropwise. (86.6 g) was prepared in the same manner as described in Example I. The salt is obtained in powder form. The results of the analytical properties of the salt are shown in Table 1. These DSC assays show two melting peaks.
除了使用2.0升擋板燒瓶,裝填263.7克(1.59莫耳)對酞酸粉末,然後一滴滴添加一藉於60℃下熔化並混合該等二胺而製成之含95.1克(0.82莫耳)1,6-己二胺及41.3克(0.47莫耳)1,4-丁二胺的液體混合物不同外,如實例I內所述之步驟製成該鹽。使該二胺混合物之溫度維持於60℃下並使將該擋板燒瓶加熱之該油浴的溫度維持於65℃下。配料速率為1.0克/分鐘。該配料完成後,使該油浴之溫度維持於65℃下,費時120分鐘並同時攪拌。然後,使該燒瓶冷卻至 室溫且自該燒瓶排放該鹽。獲得呈粉末形式之該鹽。該鹽之分析特性的結果係示於表1內。 In addition to using a 2.0 liter baffle flask, 263.7 g (1.59 mol) of citric acid powder was charged, and then one drop was added, and 95.1 g (0.82 m) was prepared by melting and mixing the diamine at 60 ° C. The salt was prepared as described in Example I, except that the liquid mixture of 1,6-hexanediamine and 41.3 g (0.47 mol) of 1,4-butanediamine was used. The temperature of the diamine mixture was maintained at 60 ° C and the temperature of the oil bath in which the baffled flask was heated was maintained at 65 °C. The batching rate was 1.0 g/min. After the ingredients were completed, the temperature of the oil bath was maintained at 65 ° C for 120 minutes while stirring. Then, the flask is cooled to The salt was discharged from the flask at room temperature. The salt is obtained in powder form. The results of the analytical properties of the salt are shown in Table 1.
將2380克對酞酸粉末及385克己二酸裝入一配備一通過冷凝器之氣體入口及氣體出口的15升犂頭混合機內。在一維持於50℃之溫度下的套容器內製成一含453克1,4-丁二胺及1449克1,6-己二胺的混合物。使2.25克次磷酸鈉單水合物溶解在13克水中並添加至該二胺混合物。於實驗開始時,將該等固體酸裝入該混合機內並經氮沖洗而惰性化。然後,以30毫升/分鐘之速率將該二胺混合物分配至該混合機內且以60RPM進行該攪拌器之攪拌。該胺混合物經分配後,使該混合機加熱至100℃並在3分鐘內添加90毫升之額外水。將該外套之溫度設定於110℃且允許該系統回流40分鐘。然後將該外套之溫度設定於150℃且使所有水及過量胺蒸發。打開後,該混合機含有鹽顆粒之混合物。 2380 grams of citric acid powder and 385 grams of adipic acid were charged into a 15 liter plowshare mixer equipped with a gas inlet and gas outlet through the condenser. A mixture of 453 grams of 1,4-butanediamine and 1449 grams of hexamethylenediamine was prepared in a kit maintained at a temperature of 50 °C. 2.25 g of sodium hypophosphite monohydrate was dissolved in 13 g of water and added to the diamine mixture. At the beginning of the experiment, the solid acid was charged into the mixer and inerted by nitrogen flushing. Then, the diamine mixture was dispensed into the mixer at a rate of 30 ml/min and the stirrer was stirred at 60 RPM. After the amine mixture was dispensed, the mixer was heated to 100 ° C and 90 ml of additional water was added over 3 minutes. The temperature of the jacket was set at 110 ° C and the system was allowed to reflux for 40 minutes. The temperature of the jacket was then set at 150 ° C and all water and excess amine were evaporated. After opening, the mixer contains a mixture of salt particles.
添加61.21克對酞酸(0.369莫耳)及112克去礦質水至250立方厘米之攪拌容器內。在第二步驟內,係添加12.67克1,4-丁二胺(0.144莫耳)及26.12克1,6-己二胺(0.225莫耳)。使該溫度增至95℃並混合以得到一透明水性鹽溶液。所形成鹽溶液之pH為7.4。然後添加1.368克次磷酸鈉單水合物(催化劑)至該鹽溶液。於50毫巴之真空下,在旋轉蒸發器內濃縮所形成該透明溶液且自該容器移除所形成固體白色鹽並於60℃及20毫巴下在真空烘箱內經乾燥至小於0.1重 量%之水含量。藉在一研缽內壓碎而使所形成該鹽均質化,並分析。該分析特性之結果係示於表1內。 61.21 grams of citric acid (0.369 moles) and 112 grams of demineralized water were added to a stirred vessel of 250 cubic centimeters. In the second step, 12.67 grams of 1,4-butanediamine (0.144 moles) and 26.12 grams of 1,6-hexanediamine (0.225 moles) were added. The temperature was increased to 95 ° C and mixed to obtain a clear aqueous salt solution. The pH of the salt solution formed was 7.4. Then 1.368 g of sodium hypophosphite monohydrate (catalyst) was added to the salt solution. The clear solution was concentrated in a rotary evaporator under a vacuum of 50 mbar and the solid white salt formed was removed from the vessel and dried in a vacuum oven at 60 ° C and 20 mbar to less than 0.1 weight. The amount of water in %. The salt formed was homogenized by crushing in a mortar and analyzed. The results of this analytical property are shown in Table 1.
重複比較實驗A共4次且合併所得到之鹽數量。 Comparative experiment A was repeated 4 times and the amount of salt obtained was combined.
將20克實例I之鹽粉末裝入一具有10毫米內壁之圓柱形玻璃管內並使其兩側經玻璃棉密封以將該粉末保留在該管內。將該管放在一玻璃珠填充床內。使5公斤/小時之氮流通過該玻璃珠填充床。使該管內之粉末經1克/小時 之氮流惰性化,費時3小時。在後續加熱及冷卻步驟期間,使該氮流維持於本位準下。藉預熱該等氮氣流而在1小時內將該粉末及包圍的玻璃珠填充床加熱至120℃且接著在3小時內加熱至260℃之溫度。使該溫度維持於260℃下,費時3小時,然後在1小時內冷卻至50℃以下之溫度。獲得呈微黃色固體聚合物粉末之該聚合物(產率17.28克,99.6%理論產率)。藉DSC而表示所獲得該聚合物的特性。該第一加熱掃描顯示等於一聚合物之吸熱熔化尖峰特性且其溫度高於原有的鹽尖峰。未偵測出微量之殘留未經反應鹽。該DSC曲線清楚地顯示缺乏被記錄為該起始物質之鹽尖峰。該等分析結果係示於表2內。 Twenty grams of the salt powder of Example I was placed in a cylindrical glass tube having an inner wall of 10 mm and both sides were sealed with glass wool to retain the powder in the tube. The tube was placed in a glass bead packed bed. A nitrogen flow of 5 kg/hr was passed through the glass bead packed bed. Make the powder in the tube pass 1 g / h The nitrogen stream is inertized and takes 3 hours. The nitrogen flow is maintained at the local level during subsequent heating and cooling steps. The powder and the enclosed glass bead packed bed were heated to 120 ° C in 1 hour by preheating the nitrogen stream and then heated to a temperature of 260 ° C in 3 hours. This temperature was maintained at 260 ° C for 3 hours and then cooled to a temperature below 50 ° C in 1 hour. The polymer was obtained as a yellowish solid polymer powder (yield 17.28 g, 99.6% theoretical yield). The properties of the obtained polymer are represented by DSC. The first heating scan shows an endothermic melting spike characteristic equal to a polymer and its temperature is higher than the original salt spike. A small amount of residual unreacted salt was not detected. This DSC curve clearly shows the lack of salt spikes recorded as the starting material. The results of these analyses are shown in Table 2.
除了使用比較實驗A之該6T/4T鹽粉末不同外,重複實例I-a。在該玻璃管內之所得到的產物(產率17.1克;98.6%理論產率)係由大褐色的固體塊所組成。該等分析結果係示於表2內。 Example I-a was repeated except that the 6T/4T salt powder of Comparative Experiment A was used. The product obtained in the glass tube (yield 17.1 g; 98.6% theoretical yield) consisted of a large brown solid block. The results of these analyses are shown in Table 2.
在一雙層式1升電加熱金屬反應器內進行該聚合反應,該反應器配備一螺旋形攪拌裝置、一惰性氣體入口及一使該惰性氣體及冷凝氣體離開該反應器的出口、以及測量該反應器器壁及反應器內容物的溫度之溫度計。將鹽粉末裝入該反應器內。攪拌該鹽粉末並施加每小時5克之氮氣滌洗物以使該反應器內容物惰性化。然後,藉施加一程式控制之 溫度分佈加熱該反應器器壁而加熱該反應器內容物並監測該粉末床內之該反應器內容物的溫度,同時持續進行該氮氣沖洗且攪拌該反應器內容物。 The polymerization is carried out in a two-layer, one-liter electric heating metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for leaving the inert gas and condensed gas out of the reactor, and measuring A thermometer for the temperature of the reactor wall and the contents of the reactor. A salt powder was charged into the reactor. The salt powder was stirred and 5 grams of nitrogen scrubbing per hour was applied to inertize the reactor contents. Then, by applying a program control The temperature profile heats the reactor wall to heat the reactor contents and monitor the temperature of the reactor contents within the powder bed while continuing the nitrogen purge and agitating the reactor contents.
使用300克實例II之鹽。安排該氮氣沖洗,並於室溫下維持在每小時5克的氣體體積下。在開始該加熱分佈前,在3小時內使該反應器內容物惰性化。在180分鐘內使該反應器內容物自25℃加熱至245℃。然後在90分鐘內進一步使該溫度上升至260℃。使該溫度維持於260℃下,費時90分鐘。然後在110分鐘內,使該反應器內容物自260℃冷卻至50℃以下。所得到產物(260克,97.0%理論產率)係由具有少量小塊狀物之主要含粉末的微著色材料所組成。分析結果係示於表2內。 300 grams of the salt of Example II was used. The nitrogen purge was arranged and maintained at a gas volume of 5 grams per hour at room temperature. The reactor contents were inerted within 3 hours before starting the heating profile. The reactor contents were heated from 25 ° C to 245 ° C over 180 minutes. The temperature was then further increased to 260 ° C over 90 minutes. This temperature was maintained at 260 ° C and took 90 minutes. The reactor contents were then cooled from 260 ° C to below 50 ° C in 110 minutes. The product obtained (260 g, 97.0% theoretical yield) consisted of a predominantly powder-containing micro-colored material with a small amount of small cakes. The results of the analysis are shown in Table 2.
除了使用300克實例III之該4T鹽,並使用262℃以取代260℃不同外,重複實例II-b。所形成該產物(255克,96.9%理論產率)係由微著色粉末狀材料所組成。該等分析結果係示於表2內。 Example II-b was repeated except that 300 grams of the 4T salt of Example III was used and 262 ° C was used instead of 260 ° C. The product formed (255 g, 96.9% theoretical yield) consisted of a micro-colored powdery material. The results of these analyses are shown in Table 2.
除了以下不同外,重複實例III-b步驟:使用300克實例IV之6T/4T鹽且當達262℃時,係以10分鐘添加8克1,6-己二胺及4克1,4-丁二胺之液體混合物。然後使該溫度維持於262℃以下,再費時90分鐘。然後在110分鐘內,使該反應器內容物自262℃冷卻至50℃以下。產率258克(98.5%理論最大產率)。所形成該聚醯胺粉末具有0.76米2/克之BET值及19.7 微米的d10、140微米的d50、602微米的d90、及2.64的跨度之粒度分佈。 The procedure of Example III-b was repeated except that 300 grams of the 6T/4T salt of Example IV was used and when 262 ° C was reached, 8 grams of 1,6-hexanediamine and 4 grams of 1,4- were added over 10 minutes. A liquid mixture of butane diamine. This temperature was then maintained below 262 ° C and took another 90 minutes. The reactor contents were then cooled from 262 ° C to below 50 ° C in 110 minutes. Yield 258 g (98.5% theoretical maximum yield). The polyamine powder formed had a BET value of 0.76 m 2 /g and a particle size distribution of d10 of 19.7 micrometers, d50 of 140 micrometers, d90 of 602 micrometers, and a span of 2.64.
除了使用300克實例V之該6T/4T/10T鹽不同外,重複實例II-b的步驟。獲得呈粉末形式之該聚合物。產率為262.5克(97.4%理論最大產率)。 The procedure of Example II-b was repeated except that the 6T/4T/10T salt of 300 grams of Example V was used. The polymer is obtained in powder form. The yield was 262.5 g (97.4% theoretical maximum yield).
除了使用300克實例VI之該46/66/4T/6T鹽不同外,重複實例II-b的步驟。在3小時內,使該反應器內容物自25℃加熱至215℃,維持於215℃下,費時3小時,在5小時內加熱至235℃,在1.5小時內加熱至265℃,維持於265℃下,費時1小時。然後於265℃下,在1小時內,添加含2克1,4-丁二胺及6克1,6-己二胺的混合物(其係已於60℃下維持熔態)6克。於265℃下再經2小時後,在110分鐘內使該反應器內容物自265℃冷卻至50℃以下之溫度。產率為263.0克(95.3%理論最大產率)粉末狀材料。該產物具有1.7之BET值及具有d10=50.5微米、d50=146微米及d90=572微米、以及跨度2.30之粒度分佈。其它分析結果示於表2內。 The procedure of Example II-b was repeated except that the 46/66/4T/6T salt of 300 grams of Example VI was used. The reactor contents were heated from 25 ° C to 215 ° C in 3 hours, maintained at 215 ° C, took 3 hours, heated to 235 ° C in 5 hours, heated to 265 ° C in 1.5 hours, maintained at 265 At °C, it takes 1 hour. Then, 6 g of a mixture containing 2 g of 1,4-butanediamine and 6 g of 1,6-hexanediamine (which was maintained at 60 ° C) was added at 265 ° C for 1 hour. After a further 2 hours at 265 ° C, the reactor contents were cooled from 265 ° C to temperatures below 50 ° C in 110 minutes. The yield was 263.0 g (95.3% theoretical maximum yield) of powdered material. The product had a BET value of 1.7 and a particle size distribution with d10 = 50.5 microns, d50 = 146 microns and d90 = 572 microns, and a span of 2.30. Other analysis results are shown in Table 2.
除了以下不同外,重複實例II-b之步驟:使用300克實例VII之該66/6T鹽,且在3小時內使該反應器內容物自25 ℃加熱至220℃,維持於220℃下,費時3小時,在5小時內加熱至250℃,維持於250℃下,費時5小時,然後在110分鐘內使該反應器內容物自250℃冷卻至50℃以下之溫度。所形成該產物(268克,97.1%理論產率)係由微著色粉末狀材料所組成。該等分析結果係示於表2內。 Repeat the procedure of Example II-b except that 300 grams of the 66/6T salt of Example VII was used and the reactor contents were made from 25 within 3 hours. °C heated to 220 ° C, maintained at 220 ° C, took 3 hours, heated to 250 ° C in 5 hours, maintained at 250 ° C, took 5 hours, then cooled the reactor contents from 250 ° C in 110 minutes To a temperature below 50 °C. The product formed (268 g, 97.1% theoretical yield) consisted of a micro-colored powdery material. The results of these analyses are shown in Table 2.
除了使用300克實例VIII該4T/6T鹽不同外,重複實例II-b之步驟。於260℃下經1小時後,使該反應混合物冷卻至230℃,於該溫度下在30分鐘內分配一含26.6克(0.23莫耳)1,6-己二胺及11.0克(0.13莫耳)1,4-丁二胺之混合物。該分配步驟完成後,使該反應混合物經加熱至240℃並維持於該溫度下,費時2小時。使該反應混合物冷卻至230℃並在15分鐘內分配一含13.3克(0.115莫耳)1,6-己二胺及5.8克(0.065莫耳)1,4-二胺基丁烷之混合物。該分配步驟完成後,再使該反應混合物經加熱至240℃並維持於該溫度下,費時6小時,然後在2小時內使該反應器內容物冷卻至50℃以下的溫度。所形成該產物係由微著色粉末狀材料所組成。該等分析結果係示於表2內。 The procedure of Example II-b was repeated except that 300 g of the 4T/6T salt of Example VIII was used. After 1 hour at 260 ° C, the reaction mixture was cooled to 230 ° C, at which temperature 26.6 g (0.23 mol) of 1,6-hexanediamine and 11.0 g (0.13 mol) were dispensed within 30 minutes. a mixture of 1,4-butanediamine. After the partitioning step was completed, the reaction mixture was heated to 240 ° C and maintained at this temperature for 2 hours. The reaction mixture was cooled to 230 ° C and a mixture of 13.3 g (0.115 mol) of 1,6-hexanediamine and 5.8 g (0.065 mol) of 1,4-diaminobutane was partitioned over 15 minutes. After the dispensing step was completed, the reaction mixture was heated to 240 ° C and maintained at this temperature for 6 hours, then the reactor contents were cooled to a temperature below 50 ° C over 2 hours. The product formed consists of a microcolored powdered material. The results of these analyses are shown in Table 2.
收集3批實例IX之鹽顆粒並裝入100升配備一冷凝器及惰性氣體入口的雙層轉筒式乾燥機內。藉另外使用10毫巴絕對真空及氮氣沖洗而使該乾燥器返回常壓。於常壓在氮氣氛下,在3小時內,使該乾燥機自室溫逐漸加熱至170℃,進一步在7小時內加熱至190℃,且進一步在20小時加熱至 260℃,並使該轉筒乾燥機保持旋轉。經由該氣相而移除自該聚縮合反應所排出的水並收集在該冷凝器內。在本熱處理方法期間,並未發現顆粒的黏附現象。該等分析結果係示於表2內。 Three batches of salt particles of Example IX were collected and charged into a 100 liter double drum dryer equipped with a condenser and an inert gas inlet. The dryer was returned to normal pressure by additionally using a 10 mbar absolute vacuum and nitrogen flushing. The dryer was gradually heated from room temperature to 170 ° C under normal pressure under a nitrogen atmosphere for 3 hours, further heated to 190 ° C in 7 hours, and further heated to 20 hours. 260 ° C, and the drum dryer kept rotating. Water discharged from the polycondensation reaction is removed via the gas phase and collected in the condenser. No adhesion of the particles was observed during the heat treatment method. The results of these analyses are shown in Table 2.
該鹽製法及聚合反應係在雙層式1升電加熱金屬反應器內進行。該反應器配備一螺旋形攪拌裝置、一惰性氣體入口及一用於使該惰性氣體及冷凝氣體離開該反應器的出口、及測定該反應器器壁與該反應器內容物的溫度計。將183.63克固體對酞酸(1.106莫耳)粉末裝入該反應器內。攪拌該對酞酸粉末且使用每小時5克之氮氣沖洗以在3小時內使該反應器內容物惰性化。在連續攪拌該反應器內容物並在75rpm之恆定轉動下,進行另外步驟,同時持續該氮氣沖洗。藉使用一程式控制性溫度分佈並監測該粉末床內之反應器內容物的溫度而在30分鐘內將該反應器器壁自25℃加熱至65℃以加熱該反應器內容物。藉在一配料容器內於65℃(其等於該二胺混合物之分配溫度(65℃))下熔化並混合該等二胺而製成一含40.01克1,4-丁二胺(0.454莫耳)及81.37克1,6-己二胺(0.700莫耳)之液體混合物。以0.42莫耳%/分鐘之配料速率一滴滴添加該液體混合物至該對酞酸粉末床,且使該反應器內容物維持在85℃以下的溫度。該分配步驟完成後,再使該反應器內容物維持於85℃之溫度下,費時120分鐘。其後,在180分鐘內使該反應器內容物自85℃加熱至245℃,然後在 90分鐘內自245℃加熱至260℃。使該溫度維持於260℃下,費時90分鐘。然後在110分鐘內使該反應器內容物自260℃冷卻至50℃以下之溫度。所形成該產物(257克,97%理論最大產率)係由微著色粉末材料所組成。分析結果係示於表2內。 The salt production process and the polymerization reaction were carried out in a two-layer, one-liter electric heating metal reactor. The reactor is equipped with a spiral stirring device, an inert gas inlet, and an outlet for leaving the inert gas and condensed gas out of the reactor, and a thermometer for measuring the reactor wall and the contents of the reactor. 183.63 grams of solid p-citric acid (1.106 moles) powder was charged to the reactor. The pair of citric acid powders were stirred and flushed with 5 grams of nitrogen per hour to inertize the reactor contents within 3 hours. The reactor contents were continuously stirred and subjected to a constant rotation at 75 rpm for an additional step while continuing the nitrogen purge. The reactor contents were heated from 25 ° C to 65 ° C in 30 minutes by using a programmed temperature profile and monitoring the temperature of the reactor contents in the powder bed to heat the reactor contents. 40.01 g of 1,4-butanediamine (0.454 mol) was prepared by melting and mixing the diamine in a batching vessel at 65 ° C (which is equal to the dispensing temperature of the diamine mixture (65 ° C)). And a liquid mixture of 81.37 grams of 1,6-hexanediamine (0.700 mole). The liquid mixture was added dropwise to the bed of the p-citric acid powder at a compounding rate of 0.42 mol%/min, and the reactor contents were maintained at a temperature below 85 °C. After the dispensing step was completed, the reactor contents were maintained at a temperature of 85 ° C for a period of 120 minutes. Thereafter, the reactor contents were heated from 85 ° C to 245 ° C in 180 minutes, then Heat from 245 ° C to 260 ° C in 90 minutes. This temperature was maintained at 260 ° C and took 90 minutes. The reactor contents were then cooled from 260 ° C to temperatures below 50 ° C in 110 minutes. The product formed (257 g, 97% theoretical maximum yield) consisted of a micro-colored powder material. The results of the analysis are shown in Table 2.
除了使用300克CE-B之該6T/4T鹽不同外,重複實例II-b之步驟。當達到238℃時,由於高扭矩形成,所以中止該實驗,且在110分鐘內使該反應器內容物冷卻至50℃以下的溫度。 The procedure of Example II-b was repeated except that the 6T/4T salt was used in combination with 300 grams of CE-B. When 238 ° C was reached, the experiment was aborted due to high torque formation and the reactor contents were cooled to a temperature below 50 ° C in 110 minutes.
就根據本發明之該等實驗而言,在該等黏度測定法內並未發現凝膠。文中之凝膠係意指不溶性顆粒之存在,當使該聚合物溶解在一典型溶劑(例如H2SO4)內時,該不溶性顆粒之存在不能進行可靠的溶液黏度測定。 For the experiments according to the invention, no gel was found in the viscosity measurements. The paper-based gel is meant the presence of insoluble particles when the polymer is dissolved in a Typical solvents (e.g. H 2 SO 4) within which the insoluble particles present in the solution viscosity can not be measured reliably.
將6克實例IV之鹽粉末裝入一無銷且具有預穿孔之蓋子(50微米孔)的40微升鋁DSC試樣坩鍋內。將本試樣坩鍋放在Mettler TGA-DSC 1自動系統上。本儀器之爐台係經一恆溫水浴系統冷卻。本儀器之TGA-DSC 1爐係經流率為50毫升/分鐘之無水氮氣沖洗。在後續加熱及冷卻步驟期間,使該氮流維持於本位準下。以每分鐘15℃之速率將該粉末加熱至150℃。使該溫度維持於150℃下,費時5分鐘,並接著以每分鐘1℃之速率加熱至260℃。使該溫度維持於260℃下,費時4小時,然後冷卻至室溫。自該加熱方案開始進行後140分鐘,發現8.1重量%損失率,其相當於61%之轉化率。 Six grams of the salt powder of Example IV was placed in a 40 microliter aluminum DSC sample crucible without a pin and having a pre-perforated lid (50 micron holes). The sample crucible was placed on a Mettler TGA-DSC 1 automated system. The furnace of the instrument is cooled by a constant temperature water bath system. The TGA-DSC 1 furnace of this instrument was flushed with anhydrous nitrogen at a flow rate of 50 ml/min. The nitrogen flow is maintained at the local level during subsequent heating and cooling steps. The powder was heated to 150 ° C at a rate of 15 ° C per minute. This temperature was maintained at 150 ° C for 5 minutes and then heated to 260 ° C at a rate of 1 ° C per minute. This temperature was maintained at 260 ° C for 4 hours and then cooled to room temperature. 140 minutes after the start of the heating protocol, a loss rate of 8.1% by weight, which corresponds to a conversion of 61%, was found.
除了使用實例III之鹽粉末以取代IV之鹽粉末不同外,重複實例XI之步驟。自該加熱方案開始進行後140分鐘,發現僅2.8重量%損失率,其相當於20%之轉化率。 The procedure of Example XI was repeated except that the salt powder of Example III was used in place of the salt powder of IV. 140 minutes after the start of the heating protocol, a loss rate of only 2.8% by weight was found, which corresponds to a conversion of 20%.
以上實例XI及XII顯示經由使用根據本發明之該方法,一共聚醯胺的形成速度比一均聚物之形成顯著地快。因此,本發明該方法特別適於製備共聚醯胺。 The above Examples XI and XII show that the formation rate of a copolyamide is significantly faster than the formation of a homopolymer by using the method according to the invention. Thus, the process of the invention is particularly suitable for the preparation of copolymerized guanamines.
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