TW201500389A - Process for incorporating additives into polymers and resulting polymer products - Google Patents

Abstract

Disclosed are a polymer additive apparatus and a process for incorporating additive into a polymer utilizing a polymerization reactor in fluid communication with a primary manifold carrying the polymer. The primary manifold is in fluid communication with at least one secondary manifold comprising an additive injection line. Also disclosed are retrofit options for adding a polymer additive apparatus to an existing polymerization process. The apparatus and process produce varied finished polymer products from one continuous polymerization reactor.

Description

用於將添加劑併入至聚合物之方法及所產生之聚合物產物 Process for incorporating an additive into a polymer and the resulting polymer product 相關申請案之交叉參考Cross-reference to related applications

本申請案主張2013年5月1日申請之美國申請案第61/818,244號之優先權，該美國申請案之全部內容及揭示內容併入在本文中。 The present application claims the benefit of U.S. Application Serial No. 61/818,244, filed on May 1, the entire entire entire entire entire entire entire entire entire entire entire content

本發明係關於一種由一個連續聚合反應器產生複數個聚合物產物之方法。詳言之，本發明係關於藉由使用添加劑注射裝置將不同添加劑注射至在不同部分的液體聚合物而用於產生複數個聚合物的方法。 This invention relates to a process for producing a plurality of polymer products from a continuous polymerization reactor. In particular, the present invention relates to a method for producing a plurality of polymers by injecting different additives into liquid polymers in different portions using an additive injection device.

多種聚合物為此項技術中已知，用於製造成型製品，諸如膜、長絲管、條帶及類似形狀。將常常以固體碎片形式產生之聚合物熔融且擠壓成該等製品。一類重要的聚合物包括聚醯胺，其常用於紡織物、服裝、包裝、輪胎加固、地毯、用於模製汽車、電氣設備、運動裝備及多種工業應用之部件之工程熱塑性塑料。脂族聚醯胺(亦稱為尼龍)可由二羧酸及二胺產生，諸如由二羧酸之鹽溶液及二胺產生。尼龍為用於需要非凡耐用性、耐熱性及韌性之塑料及纖維應用的高效能材料。 A wide variety of polymers are known in the art for use in the manufacture of shaped articles such as films, filament tubes, strips, and the like. The polymer, which is often produced in the form of solid chips, is melted and extruded into the articles. One class of important polymers include polyamines, which are commonly used in textiles, apparel, packaging, tire reinforcement, carpets, engineering thermoplastics for molding automotive, electrical equipment, sports equipment, and components for a variety of industrial applications. Aliphatic polyamines (also known as nylons) can be produced from dicarboxylic acids and diamines, such as from salt solutions of dicarboxylic acids and diamines. Nylon is a high performance material for plastic and fiber applications that require exceptional durability, heat resistance and toughness.

然而，在製造該等聚合物之方法的過程中已遇到許多難題。舉例而言，當成型製品由熔融聚己二醯己二胺(「尼龍6,6」)產生時，聚 醯胺已知在使聚醯胺維持在熔融狀態所需的高溫下分解。分解導致擠壓成型製品變色且傾向於對製品之物理特性具有不希望有的效應。已提出添加熱穩定添加劑至熔融聚合物以解決此問題，例如美國專利第3,121,763號。 However, many difficulties have been encountered in the process of making such polymers. For example, when the shaped article is produced from molten polyhexamethylene adipamide ("nylon 6,6"), The guanamine is known to decompose at the high temperatures required to maintain the polyamine in a molten state. Decomposition results in discoloration of the extruded article and tends to have undesirable effects on the physical properties of the article. It has been proposed to add a heat stabilizing additive to the molten polymer to solve this problem, for example, U.S. Patent No. 3,121,763.

亦已提出用於併入至熔融聚合物之其他添加劑。美國專利第3,824,207號提出將顏料注射至單體反應物料以產生著色的高分子量聚醯胺。Carothers等人美國專利第2,119,584號建議添加調節劑至藉由溶解給定數量聚醯胺所需之大致總數量之二胺及二羧酸於水中形成之溶液。調節劑包括黏度穩定劑、塑化劑、去光劑、顏料及染料。 Other additives for incorporation into the molten polymer have also been proposed. U.S. Patent No. 3,824,207 teaches the injection of a pigment into a monomer reaction mass to produce a colored high molecular weight polyamine. No. 2,119,584 to Carothers et al. suggests the addition of a conditioning agent to a solution of the diamine and dicarboxylic acid formed in water by the dissolution of a given total amount of the desired amount of polyamine. Conditioning agents include viscosity stabilizers, plasticizers, deluters, pigments, and dyes.

然而，迄今提出之將添加劑併入至聚合物之方法存在難題。舉例而言，注射添加劑至反應器上游之聚醯胺聚合過程可降解添加劑，如WO 99/10408中所示。 However, the method proposed to incorporate an additive into a polymer to date has a problem. For example, a polyamine polymerization process that injects an additive to the upstream of the reactor can degrade the additive, as shown in WO 99/10408.

此外，引入添加劑至聚醯胺聚合過程之多個階段(特別在聚合反應器上游)可致使產生符合所需規格之產品的顯著時間延遲。添加劑可使用多種方法併入至聚合物產物，諸如使添加劑以聚合尼龍6,6以物理方式混合、表面翻滾尼龍6,6丸粒與粉狀添加劑、或將添加劑以物理方式併入至熔體擠壓機。 In addition, the introduction of additives to multiple stages of the polyamine polymerization process, particularly upstream of the polymerization reactor, can result in significant time delays in producing products that meet the desired specifications. Additives can be incorporated into the polymer product using a variety of methods, such as physically mixing the additive with polymeric nylon 6,6, surface tumble nylon 6,6 pellets with powdered additives, or physically incorporating the additive into the melt. Extruder.

製造商希望由單個聚合過程及裝置產生多種尼龍等級。前驅物鹽溶液可包含水及己二酸己二胺鹽。前驅物鹽溶液可經蒸發及加熱以產生聚合物。在聚合前注射添加劑包至諸如鹽溶液、蒸發器或連續聚合反應器入口限制可撓性。舉例而言，全部所得聚合物含有注射至鹽溶液中之添加劑且因此妨礙操作者產生複數個聚合物產物。另外，為改變添加劑及聚合物產物，需要相當長的時間切換方法及生產具有不同添加劑的獨立鹽溶液。 Manufacturers desire a variety of nylon grades from a single polymerization process and apparatus. The precursor salt solution may comprise water and a hexanediamine adipate salt. The precursor salt solution can be evaporated and heated to produce a polymer. Injecting the additive package prior to polymerization to an inlet such as a salt solution, an evaporator, or a continuous polymerization reactor limits flexibility. For example, all of the resulting polymers contain additives that are injected into the salt solution and thus prevent the operator from producing a plurality of polymer products. In addition, in order to modify the additives and polymer products, it takes a relatively long time to switch the process and produce separate salt solutions with different additives.

相反地，注射添加劑至連續聚合方法之流出物中帶來許多技術問題。首先，難以均勻且均一地分佈添加劑遍及大部分聚合物。另 外，習知注射閥易於堵塞。同樣，在反應器下游注射添加劑可能致使添加劑降解。 Conversely, injecting additives into the effluent of a continuous polymerization process poses a number of technical problems. First, it is difficult to evenly and uniformly distribute the additive throughout most of the polymer. another In addition, conventional injection valves are prone to blockage. Likewise, injection of additives downstream of the reactor may cause the additive to degrade.

因此，需要經改良之方法及裝置，解決上述難題且同時產生複數個聚合物產物。 Accordingly, there is a need for an improved method and apparatus that addresses the above problems and simultaneously produces a plurality of polymer products.

在第一實施例中，本發明係關於一種用於產生複數個聚合物產物之連續方法，該方法包含：a)將液體聚合物由聚合反應器經由主歧管引導至聚合物凝固器以形成初級成品聚合物產物，其中該主歧管包含至少第一主歧管閥及第二主歧管閥，各在聚合物精整機之上游，b)將第一部分液體聚合物由該主歧管經由該第一主歧管閥引導至第一添加劑注射裝置；c)注射第一添加劑至該第一部分液體聚合物以產生包含該第一添加劑之第一成品聚合物產物；d)將第二部分液體聚合物由該主歧管經由該第二主歧管閥引導至第二添加劑注射裝置；及e)注射第二添加劑以產生包含該第二添加劑之第二成品聚合物產物，其中該第一添加劑不同於該第二添加劑，其中該第一及第二添加劑注射裝置各包含次歧管、連接至該次歧管之至少一個添加劑注射管線、及在該添加劑注射管線下游之與該次歧管流體連通的聚合物凝固器。至少一個添加劑注射管線可包含泵。第一及第二添加劑注射裝置可各另外包含使至少一個添加劑注射管線與次歧管連接的添加劑注射閥。當至少一個添加劑注射閥打開時，至少一個添加劑注射管線可加壓至比次歧管之壓力高的壓力。當至少一個添加劑注射閥打開時，至少一個添加劑注射管線可加壓至比次歧管之壓力高2%至10%的壓力。至少一個添加劑注射閥及第一及第二主歧管閥之每一者之實質上所有部分可包含不鏽鋼。第一及第二主歧管閥之每一者及至少一個添加劑注射閥可為抗堵塞之注射閥。主歧管閥及添加劑注射閥可為交叉桿注射閥、二通閥、三通閥、分流閥或其組合。初級成品聚合物產物可不含第一添加 劑及/或第二添加劑。至少一個添加劑注射裝置可包含兩個添加劑注射管線。主歧管可包含連接於至少一個第三添加劑注射裝置之至少一個第三主歧管閥。次歧管可包含在至少一個添加劑注射管線上游之泵。第一及/或第二添加劑可在實質上等於次歧管中液體聚合物溫度之溫度下添加至添加劑注射管線。至少一個添加劑注射管線另外可包含靜態混合器。主歧管中液體聚合物之溫度可介於265℃與300℃之間。主歧管中液體聚合物之壓力可介於10MPa與31MPa之間。該方法可另外包含將複數個聚合物產物中之至少一者分成實質上固體碎片。該方法可另外包含使二羧酸與二胺縮合形成液體聚合物。二羧酸可選自由乙二酸、丙二酸、丁二酸、戊二酸、庚二酸、己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、順丁烯二酸、戊烯二酸、2-十二烯二酸及已二烯二酸、1,2-或1,3-環己二甲酸、1,2-或1,3-苯二乙酸、1,2-或1,3-環己二乙酸、間苯二甲酸、對苯二甲酸、4,4'-氧基雙苯甲酸、4,4-二苯甲酮二甲酸、2,6-萘二甲酸、對第三丁基間苯二甲酸及2,5-呋喃二甲酸及其混合物組成之群。在一個實施例中，二羧酸為己二酸。二胺可選自由乙醇二胺、三亞甲基二胺、丁二胺、戊二胺、己二胺、2-甲基戊二胺、庚二胺、2-甲基己二胺、3-甲基己二胺、2,2-二甲基戊二胺、辛二胺、2,5-二甲基己二胺、壬二胺、2,2,4-及2,4,4-三甲基己二胺、癸二胺、5-甲基壬二胺、異氟爾酮二胺、十一烷二胺、十二烷二胺、2,2,7,7-四甲基辛二胺、雙(對胺基環己基)甲烷、雙(胺基甲基)降莰烷、視情況經一或多個C1至C4烷基取代之C2-C16脂族二胺、脂族聚醚二胺及呋喃二胺(諸如2,5-雙(胺基甲基)呋喃)及其混合物組成之群。在一個實施例中，二胺為己二胺。在一個實施例中，二羧酸及二胺單體為己二酸及己二胺。第一及第二添加劑可獨立地選自由熱穩定劑、消泡劑、玻璃纖維、潤滑劑、共聚合物、催化劑、阻燃劑、塑化劑、抗衝擊改質劑、填充劑、改變末端 平衡之化合物及其混合物組成之群。第二成品聚合物產物可包含0.1重量%至20重量%之第一添加劑。第三成品聚合物產物可包含0.1重量%至20重量%之第二添加劑。添加劑可添加至在40℃至300℃之溫度下的添加劑注射管線。複數個聚合物產物可具有10,000至50,000道爾頓之分子量。在一個實施例中，無添加劑注射至主歧管。 In a first embodiment, the present invention is directed to a continuous process for producing a plurality of polymer products, the method comprising: a) directing a liquid polymer from a polymerization reactor to a polymer coagulator via a primary manifold to form a primary finished polymer product, wherein the primary manifold comprises at least a first primary manifold valve and a second primary manifold valve, each upstream of the polymer finishing machine, b) a first portion of the liquid polymer from the primary manifold Directing to the first additive injection device via the first main manifold valve; c) injecting the first additive to the first portion of the liquid polymer to produce a first finished polymer product comprising the first additive; d) the second portion The liquid polymer is directed by the primary manifold to the second additive injection device via the second primary manifold valve; and e) injecting a second additive to produce a second finished polymer product comprising the second additive, wherein the first The additive is different from the second additive, wherein the first and second additive injection devices each comprise a secondary manifold, at least one additive injection line connected to the secondary manifold, and under the additive injection line A polymer coagulator that is in fluid communication with the secondary manifold. At least one additive injection line can include a pump. The first and second additive injection devices can each additionally comprise an additive injection valve that connects the at least one additive injection line to the secondary manifold. When the at least one additive injection valve is open, the at least one additive injection line can be pressurized to a higher pressure than the pressure of the secondary manifold. When the at least one additive injection valve is open, the at least one additive injection line can be pressurized to a pressure that is 2% to 10% higher than the pressure of the secondary manifold. Substantially all of the at least one additive injection valve and each of the first and second primary manifold valves may comprise stainless steel. Each of the first and second primary manifold valves and the at least one additive injection valve may be an anti-clogging injection valve. The main manifold valve and the additive injection valve may be a cross rod injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. The primary finished polymer product may not contain the first addition And/or a second additive. The at least one additive injection device can include two additive injection lines. The primary manifold can include at least one third primary manifold valve coupled to the at least one third additive injection device. The secondary manifold can include a pump upstream of the at least one additive injection line. The first and/or second additive can be added to the additive injection line at a temperature substantially equal to the temperature of the liquid polymer in the secondary manifold. The at least one additive injection line may additionally comprise a static mixer. The temperature of the liquid polymer in the main manifold can be between 265 ° C and 300 ° C. The pressure of the liquid polymer in the main manifold can be between 10 MPa and 31 MPa. The method can additionally comprise separating at least one of the plurality of polymer products into substantially solid fragments. The method can additionally comprise condensing a dicarboxylic acid with a diamine to form a liquid polymer. The dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and twelve Alkanedioic acid, maleic acid, glutaconic acid, 2-dodecenedioic acid and dienedicarboxylic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1,2- or 1, 3-benzenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4-benzophenone A group consisting of formic acid, 2,6-naphthalenedicarboxylic acid, p-tert-butylisophthalic acid, and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid is adipic acid. The diamine may be selected from the group consisting of ethanol diamine, trimethylene diamine, butane diamine, pentane diamine, hexamethylene diamine, 2-methyl pentane diamine, heptane diamine, 2-methyl hexane diamine, 3-methyl Hexamethylenediamine, 2,2-dimethylpentanediamine, octanediamine, 2,5-dimethylhexanediamine, decanediamine, 2,2,4- and 2,4,4-trimethyl Hexamethylenediamine, decanediamine, 5-methylindolediamine, isophoronediamine, undecanediamine, dodecanediamine, 2,2,7,7-tetramethyloctanediamine , bis(p-aminocyclohexyl)methane, bis(aminomethyl)norbornane, optionally substituted by one or more C1 to C4 alkyl groups, C2-C16 aliphatic diamine, aliphatic polyether diamine And a group consisting of furan diamines such as 2,5-bis(aminomethyl)furan and mixtures thereof. In one embodiment, the diamine is hexamethylenediamine. In one embodiment, the dicarboxylic acid and diamine monomers are adipic acid and hexamethylene diamine. The first and second additives may be independently selected from the group consisting of heat stabilizers, defoamers, glass fibers, lubricants, copolymers, catalysts, flame retardants, plasticizers, impact modifiers, fillers, and terminal ends. A group of balanced compounds and mixtures thereof. The second finished polymer product may comprise from 0.1% to 20% by weight of the first additive. The third finished polymer product may comprise from 0.1% to 20% by weight of the second additive. Additives can be added to the additive injection line at temperatures between 40 ° C and 300 ° C. The plurality of polymer products may have a molecular weight of from 10,000 to 50,000 Daltons. In one embodiment, no additive is injected to the primary manifold.

在第二實施例中，本發明係關於一種用於產生複數個聚合物產物之連續方法，該方法包含：a)將液體聚合物由聚合反應器經由主歧管引導至聚合物凝固器以形成成品聚合物產物，其中該主歧管包含至少兩個主歧管閥，該等主歧管閥在聚合物精整機之上游，b)將一部分液體聚合物經由該至少兩個主歧管閥之每一者引導至獨立的添加劑注射裝置；及c)注射添加劑至該等獨立的添加劑注射裝置之每一者以形成至少兩個額外成品聚合物產物；其中該等獨立的添加劑注射裝置之每一者包含次歧管、連接至該次歧管之至少一個添加劑注射管線、及在該添加劑注射管線下游之與該次歧管流體連通的聚合物凝固器。 In a second embodiment, the present invention is directed to a continuous process for producing a plurality of polymer products, the method comprising: a) directing a liquid polymer from a polymerization reactor to a polymer coagulator via a primary manifold to form a finished polymer product, wherein the primary manifold comprises at least two primary manifold valves upstream of the polymer finishing machine, b) passing a portion of the liquid polymer through the at least two primary manifold valves Each of which is directed to a separate additive injection device; and c) injecting an additive to each of the separate additive injection devices to form at least two additional finished polymer products; wherein each of the separate additive injection devices One includes a secondary manifold, at least one additive injection line connected to the secondary manifold, and a polymer coagulator in fluid communication with the secondary manifold downstream of the additive injection line.

在第三實施例中，本發明係關於一種用於產生複數個聚合物產物之連續方法，該方法包含：a)將液體聚合物由聚合反應器經由主歧管引導至聚合物凝固器以形成初級成品聚合物產物，其中該主歧管包含在聚合物精整機之上游的至少一個主歧管閥，b)將一部分液體聚合物由該主歧管經由第一主歧管閥引導至添加劑注射裝置；及c)注射添加劑至該部分液體聚合物以產生包含第一添加劑之成品聚合物產物；其中該等添加劑注射裝置包含次歧管、連接至該次歧管之至少一個添加劑注射管線、及在該添加劑注射管線下游之與該次歧管流體連通的聚合物凝固器。 In a third embodiment, the present invention is directed to a continuous process for producing a plurality of polymer products, the method comprising: a) directing a liquid polymer from a polymerization reactor to a polymer coagulator via a primary manifold to form a primary finished polymer product, wherein the primary manifold comprises at least one primary manifold valve upstream of the polymer finishing machine, b) a portion of the liquid polymer is directed from the primary manifold to the additive via the first primary manifold valve An injection device; and c) injecting an additive to the portion of the liquid polymer to produce a finished polymer product comprising the first additive; wherein the additive injection device comprises a secondary manifold, at least one additive injection line connected to the secondary manifold, And a polymer coagulator in fluid communication with the secondary manifold downstream of the additive injection line.

在第四實施例中，本發明係關於一種用於產生複數個聚合物產物之裝置，該裝置包含：a)用於提供液體聚合物自聚合反應器至聚合物凝固器以產生第一成品聚合物產物之主歧管，其中該主歧管包含第 一主歧管閥及第二主歧管閥，各在聚合物精整機之上游，b)連接至該第一主歧管閥之第一添加劑注射裝置；及c)連接至該第二主歧管閥之第二添加劑注射裝置；其中該第一添加劑注射裝置及該第二添加劑注射裝置各載送一部分液體聚合物且各包含：i)次歧管；ii)一或多個添加劑注射管線以將添加劑引入至該次歧管中之部分液體聚合物；及iii)下游聚合物凝固器以產生成品聚合物產物。第一添加劑注射裝置及第二添加劑注射裝置可各另外包含添加劑注射閥以使次歧管連接至一或多個添加劑注射管線。第一及第二主歧管閥及各添加劑注射閥之實質上所有部分可包含不鏽鋼。第一及第二主歧管閥及添加劑注射閥可為抗堵塞之注射閥。第一及第二主歧管閥及添加劑注射閥可為交叉桿閥、二通閥、三通閥、分流閥或其組合。次歧管可包含置於第一或第二主歧管閥與添加劑注射閥之間的泵。一或多個添加劑注射管線可各包含壓力控制器以便在添加劑注射閥之每一者打開時，使一或多個添加劑注射管線加壓至比次歧管之壓力高的壓力。較高壓力可為比次歧管之壓力高2%至10%。一或多個添加劑注射管線之每一者可包含添加劑泵。一或多個添加劑注射管線可各包含溫度控制器以使添加劑維持在實質上次歧管中之液體聚合物之溫度下。一或多個添加劑注射管線之每一者可另外包含添加劑儲槽。添加劑儲槽可帶夾套。一或多個添加劑注射管線可包括靜態混合器。該裝置可包含至少一個溫度控制器以使主歧管及次歧管中之液體聚合物維持在265℃與300℃之間的溫度下。主歧管可具有比次歧管之橫剖面內徑大的橫剖面內徑。主歧管可包含壓力控制器以使主歧管內之壓力維持在10MPa與31MPa之間。次歧管可包含壓力控制器以使次歧管內之壓力維持在10MPa與28MPa之間。聚合反應器可藉由使二羧酸與二胺縮合產生液體聚合物。二羧酸可選自由乙二酸、丙二酸、丁二酸、戊二酸、庚二酸、己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、順丁烯 二酸、戊烯二酸、2-十二烯二酸及已二烯二酸、1,2-或1,3-環己二甲酸、1,2-或1,3-苯二乙酸、1,2-或1,3-環己二乙酸、間苯二甲酸、對苯二甲酸、4,4'-氧基雙苯甲酸、4,4-二苯甲酮二甲酸、2,6-萘二甲酸、對第三丁基間苯二甲酸及2,5-呋喃二甲酸及其混合物組成之群。在一個實施例中，二羧酸為己二酸。二胺可選自由乙醇二胺、三亞甲基二胺、丁二胺、戊二胺、己二胺、2-甲基戊二胺、庚二胺、2-甲基己二胺、3-甲基己二胺、2,2-二甲基戊二胺、辛二胺、2,5-二甲基己二胺、壬二胺、2,2,4-及2,4,4-三甲基己二胺、癸二胺、5-甲基壬二胺、異氟爾酮二胺、十一烷二胺、十二烷二胺、2,2,7,7-四甲基辛二胺、雙(對胺基環己基)甲烷、雙(胺基甲基)降莰烷、視情況經一或多個C1至C4烷基取代之C2-C16脂族二胺、脂族聚醚二胺及呋喃二胺(諸如2,5-雙(胺基甲基)呋喃)及其混合物組成之群。在一個實施例中，二胺為己二胺。二羧酸及二胺單體可為己二酸及己二胺。各添加劑可包含熱穩定劑、消泡劑、玻璃纖維、潤滑劑、共聚合物、催化劑、阻燃劑、塑化劑、抗衝擊改質劑、填充劑及/或改變末端平衡之化合物。該裝置可包含三至十個添加劑注射裝置。添加劑注射裝置中之至少一者之次歧管可包含兩個添加劑注射管線。 In a fourth embodiment, the invention relates to a device for producing a plurality of polymer products, the device comprising: a) for providing a liquid polymer from a polymerization reactor to a polymer coagulator to produce a first finished polymerization a main manifold of the product, wherein the main manifold comprises a primary manifold valve and a second primary manifold valve, each upstream of the polymer finishing machine, b) a first additive injection device coupled to the first primary manifold valve; and c) coupled to the second primary a second additive injection device of the manifold valve; wherein the first additive injection device and the second additive injection device each carry a portion of the liquid polymer and each comprise: i) a secondary manifold; ii) one or more additive injection lines a portion of the liquid polymer that introduces the additive into the secondary manifold; and iii) a downstream polymer coagulator to produce the finished polymer product. The first additive injection device and the second additive injection device can each additionally include an additive injection valve to connect the secondary manifold to one or more additive injection lines. Essential portions of the first and second main manifold valves and each additive injection valve may comprise stainless steel. The first and second main manifold valves and the additive injection valve may be anti-clogging injection valves. The first and second main manifold valves and the additive injection valve may be a cross rod valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. The secondary manifold may include a pump disposed between the first or second primary manifold valve and the additive injection valve. The one or more additive injection lines can each include a pressure controller to pressurize the one or more additive injection lines to a higher pressure than the pressure of the secondary manifold when each of the additive injection valves is open. The higher pressure can be 2% to 10% higher than the pressure of the secondary manifold. Each of the one or more additive injection lines can include an additive pump. The one or more additive injection lines can each include a temperature controller to maintain the additive at a temperature of the liquid polymer in the substantially sub-manifold. Each of the one or more additive injection lines may additionally comprise an additive reservoir. The additive reservoir can be jacketed. The one or more additive injection lines can include a static mixer. The apparatus can include at least one temperature controller to maintain the liquid polymer in the primary and secondary manifolds at a temperature between 265 °C and 300 °C. The primary manifold may have a cross-sectional inner diameter that is greater than the inner diameter of the cross-section of the secondary manifold. The primary manifold may include a pressure controller to maintain the pressure within the primary manifold between 10 MPa and 31 MPa. The secondary manifold may include a pressure controller to maintain the pressure within the secondary manifold between 10 MPa and 28 MPa. The polymerization reactor can produce a liquid polymer by condensing a dicarboxylic acid with a diamine. The dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and twelve Alkanoic acid, butene Diacid, glutaconic acid, 2-dodecenedioic acid and dienedicarboxylic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1,2- or 1,3-benzenediacetic acid, 1 , 2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4-benzophenone dicarboxylic acid, 2,6-naphthalene A group consisting of dicarboxylic acid, p-tert-butylisophthalic acid, and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid is adipic acid. The diamine may be selected from the group consisting of ethanol diamine, trimethylene diamine, butane diamine, pentane diamine, hexamethylene diamine, 2-methyl pentane diamine, heptane diamine, 2-methyl hexane diamine, 3-methyl Hexamethylenediamine, 2,2-dimethylpentanediamine, octanediamine, 2,5-dimethylhexanediamine, decanediamine, 2,2,4- and 2,4,4-trimethyl Hexamethylenediamine, decanediamine, 5-methylindolediamine, isophoronediamine, undecanediamine, dodecanediamine, 2,2,7,7-tetramethyloctanediamine , bis(p-aminocyclohexyl)methane, bis(aminomethyl)norbornane, optionally substituted by one or more C1 to C4 alkyl groups, C2-C16 aliphatic diamine, aliphatic polyether diamine And a group consisting of furan diamines such as 2,5-bis(aminomethyl)furan and mixtures thereof. In one embodiment, the diamine is hexamethylenediamine. The dicarboxylic acid and diamine monomers may be adipic acid and hexamethylene diamine. Each additive may comprise a heat stabilizer, an antifoaming agent, a glass fiber, a lubricant, a copolymer, a catalyst, a flame retardant, a plasticizer, an impact modifier, a filler, and/or a compound that alters the terminal balance. The device can contain from three to ten additive injection devices. The secondary manifold of at least one of the additive injection devices can include two additive injection lines.

在第五實施例中，本發明係關於一種用於產生複數個聚合物產物之裝置，該裝置包含：a)用於提供液體聚合物自聚合反應器至聚合物凝固器以產生第一成品聚合物產物之主歧管，其中該主歧管包含在聚合物精整機之上游的主歧管閥，b)連接至該主歧管閥之添加劑注射裝置；及c)其中該添加劑注射裝置載送一部分液體聚合物且包含：i)次歧管；ii)一或多個添加劑注射管線以將添加劑引入至該次歧管中之部分液體聚合物；及iii)下游聚合物凝固器以產生成品聚合物產物。 In a fifth embodiment, the invention relates to a device for producing a plurality of polymer products, the device comprising: a) for providing a liquid polymer from a polymerization reactor to a polymer coagulator to produce a first finished polymerization a primary manifold of the product, wherein the primary manifold includes a primary manifold valve upstream of the polymer finishing machine, b) an additive injection device coupled to the primary manifold valve; and c) wherein the additive injection device carries Delivering a portion of the liquid polymer and comprising: i) a secondary manifold; ii) one or more additive injection lines to introduce an additive to a portion of the liquid polymer in the secondary manifold; and iii) a downstream polymer coagulator to produce the finished product Polymer product.

1‧‧‧聚合方法 1‧‧‧Aggregation method

3‧‧‧先前技術聚合方法 3‧‧‧Previous technical polymerization methods

4‧‧‧先前技術聚合方法 4‧‧‧Previous technical polymerization methods

5‧‧‧儲槽 5‧‧‧ storage tank

6‧‧‧管線 6‧‧‧ pipeline

7‧‧‧蒸發器 7‧‧‧Evaporator

8‧‧‧聚合入口 8‧‧‧Aggregate entrance

9‧‧‧添加劑 9‧‧‧Additives

11‧‧‧管線 11‧‧‧ pipeline

12‧‧‧管線 12‧‧‧ pipeline

13‧‧‧添加劑 13‧‧‧ Additives

14‧‧‧管線 14‧‧‧ pipeline

15‧‧‧泵 15‧‧‧ pump

16‧‧‧液體聚合物 16‧‧‧Liquid polymer

18‧‧‧凝固器 18‧‧‧ coagulator

19‧‧‧成品聚合物產物 19‧‧‧Finished polymer products

20‧‧‧反應器 20‧‧‧Reactor

21‧‧‧主歧管 21‧‧‧Main manifold

22‧‧‧閥 22‧‧‧ Valve

25‧‧‧次歧管 25‧‧‧Management

26‧‧‧泵 26‧‧‧ pump

27‧‧‧添加劑儲槽 27‧‧‧Additive storage tank

71‧‧‧所需位置 71‧‧‧Required location

72‧‧‧所需位置 72‧‧‧Required location

101‧‧‧聚合方法 101‧‧‧ Polymerization method

102‧‧‧聚合物添加劑裝置 102‧‧‧ polymer additive device

108‧‧‧聚合物入口 108‧‧‧ polymer inlet

115‧‧‧泵 115‧‧‧ pump

116‧‧‧聚合物 116‧‧‧ polymer

118‧‧‧聚合物凝固器 118‧‧‧ polymer coagulator

119‧‧‧成品聚合物產物 119‧‧‧Finished polymer products

120‧‧‧聚合反應器 120‧‧‧polymerization reactor

121‧‧‧主歧管 121‧‧‧Main manifold

122‧‧‧主歧管閥 122‧‧‧Main manifold valve

123‧‧‧主歧管閥 123‧‧‧Main manifold valve

124‧‧‧主歧管閥 124‧‧‧Main manifold valve

125‧‧‧次歧管 125‧‧‧Management

126‧‧‧次歧管泵 126‧‧‧ times manifold pump

127‧‧‧添加劑注射儲槽 127‧‧‧Additive injection reservoir

128‧‧‧添加劑注射管線 128‧‧‧Additive injection line

129‧‧‧添加劑注射泵 129‧‧‧Additive syringe pump

130‧‧‧添加劑注射閥 130‧‧‧Additive Injection Valve

131‧‧‧液體聚合物 131‧‧‧Liquid polymer

132‧‧‧具有添加劑之液體聚合物 132‧‧‧Liquid polymer with additives

133‧‧‧聚合物凝固器 133‧‧‧ polymer coagulator

135‧‧‧次歧管 135‧‧‧Management

136‧‧‧次歧管泵 136‧‧‧ times manifold pump

137‧‧‧添加劑注射儲槽 137‧‧‧Additive injection reservoir

138‧‧‧添加劑注射管線 138‧‧‧Additive injection line

139‧‧‧添加劑注射泵 139‧‧‧Additive syringe pump

140‧‧‧添加劑注射閥 140‧‧‧Additive injection valve

141‧‧‧液體聚合物 141‧‧‧Liquid polymer

142‧‧‧具有添加劑之液體聚合物 142‧‧‧Liquid polymer with additives

143‧‧‧聚合物凝固器 143‧‧‧ polymer coagulator

145‧‧‧次歧管 145‧‧‧Management

146‧‧‧次歧管泵 146‧‧‧ times manifold pump

147‧‧‧添加劑注射儲槽 147‧‧‧Additive injection reservoir

148‧‧‧添加劑注射管線 148‧‧‧Additive injection line

149‧‧‧添加劑注射泵 149‧‧‧Additive syringe pump

150‧‧‧添加劑注射閥 150‧‧‧Additive injection valve

152‧‧‧具有添加劑之液體聚合物 152‧‧‧Liquid polymer with additives

153‧‧‧聚合物凝固器 153‧‧‧ polymer coagulator

157‧‧‧第二添加劑儲槽 157‧‧‧Second additive storage tank

158‧‧‧第二添加劑注射管線 158‧‧‧Second additive injection line

159‧‧‧第二添加劑注射泵 159‧‧‧Second additive syringe pump

160‧‧‧第二添加劑注射閥 160‧‧‧Second additive injection valve

161‧‧‧成品聚合物產物 161‧‧‧Finished polymer products

162‧‧‧成品聚合物產物 162‧‧‧Finished polymer products

164‧‧‧成品聚合物產物 164‧‧‧Finished polymer products

201‧‧‧手柄 201‧‧‧handle

202‧‧‧管連接器 202‧‧‧ pipe connector

203‧‧‧止回閥 203‧‧‧ check valve

204‧‧‧供應管線 204‧‧‧Supply pipeline

205‧‧‧注射口 205‧‧ ‧ injection port

207‧‧‧填料 207‧‧‧Filling

208‧‧‧位置 208‧‧‧ position

209‧‧‧螺紋桿 209‧‧‧Threaded rod

210‧‧‧管總成 210‧‧‧ tube assembly

211‧‧‧螺栓 211‧‧‧ bolt

212‧‧‧螺母 212‧‧‧ nuts

213‧‧‧閥體 213‧‧‧ valve body

214‧‧‧入口 214‧‧‧ entrance

215‧‧‧排氣孔 215‧‧‧ venting holes

216‧‧‧口 216‧‧‧ mouth

217‧‧‧塞 217‧‧‧

218‧‧‧出口 218‧‧‧Export

219‧‧‧空隙區 219‧‧‧Void area

220‧‧‧排水管 220‧‧‧Drainage pipe

221‧‧‧分流管線 221‧‧‧Split pipeline

本發明之態樣由以下各圖示意性說明，其中： 圖1為用於製造聚醯胺聚合物之習知裝置。 Aspects of the invention are schematically illustrated by the following figures, wherein: Figure 1 is a conventional apparatus for making a polyamine polymer.

圖2為根據本發明之一個實施例，包含兩個添加劑注射裝置之聚合物添加劑裝置的示意圖。 2 is a schematic illustration of a polymer additive apparatus comprising two additive injection devices, in accordance with one embodiment of the present invention.

圖3為根據本發明之一個實施例，包含三個添加劑注射裝置之聚合物添加劑裝置的示意圖。 3 is a schematic illustration of a polymer additive apparatus comprising three additive injection devices, in accordance with one embodiment of the present invention.

圖4為圖3之聚合物添加劑裝置之示意圖，其中根據本發明之一個實施例，添加劑注射裝置之一個歧管閥關閉。 4 is a schematic illustration of the polymer additive device of FIG. 3, wherein a manifold valve of the additive injection device is closed in accordance with an embodiment of the present invention.

圖5為根據本發明之一個實施例，在添加劑注射裝置中具有兩個添加劑注射管線之聚合物添加劑裝置的示意圖。 Figure 5 is a schematic illustration of a polymer additive apparatus having two additive injection lines in an additive injection device, in accordance with one embodiment of the present invention.

圖6A為根據本發明之一個實施例使用之交叉桿聚合物閥之側面剖視圖。 Figure 6A is a side cross-sectional view of a crossbar polymer valve for use in accordance with one embodiment of the present invention.

圖6B為根據本發明之一個實施例使用之圖6A之交叉桿聚合物閥之一部分的側面剖視圖。 Figure 6B is a side cross-sectional view of a portion of the crossbar polymer valve of Figure 6A used in accordance with one embodiment of the present invention.

圖7為根據本發明之一個實施例使用之I型聚合物閥在允許流經一個出口之位置的側面剖視圖。 Figure 7 is a side cross-sectional view of a Type I polymer valve for use in a position permitting flow through an outlet, in accordance with one embodiment of the present invention.

圖8為根據本發明之一個實施例使用之I型聚合物閥在允許流經兩個出口之位置的側面剖視圖。 Figure 8 is a side cross-sectional view of a Type I polymer valve for use in a position permitting flow through two outlets in accordance with one embodiment of the present invention.

圖9為根據本發明之一個實施例使用之I型聚合物閥在允許流經一個出口之位置的側面剖視圖。 Figure 9 is a side cross-sectional view of a Type I polymer valve for use in a position permitting flow through an outlet, in accordance with one embodiment of the present invention.

圖10為根據本發明之一個實施例使用之II型聚合物閥在不允許流經該閥之位置的側面剖視圖。 Figure 10 is a side cross-sectional view of a Type II polymer valve used in accordance with one embodiment of the present invention where it is not permitted to flow through the valve.

圖11為根據本發明之一個實施例使用之分流聚合物閥在注射位置的側面剖視圖。 Figure 11 is a side cross-sectional view of the split polymer valve used in the injection position in accordance with one embodiment of the present invention.

圖12為根據本發明之一個實施例使用之分流聚合物閥在分流位置的側面剖視圖。 Figure 12 is a side cross-sectional view of the split polymer valve used in the split position, in accordance with one embodiment of the present invention.

圖13為根據本發明之一個實施例，可用聚合物添加劑裝置改裝 之聚合方法的示意圖。 Figure 13 is a modification of a polymer additive device in accordance with one embodiment of the present invention. Schematic diagram of the polymerization process.

圖14為根據本發明之一個實施例，可用聚合物添加劑裝置改裝之聚合方法的示意圖。 Figure 14 is a schematic illustration of a polymerization process that can be retrofitted with a polymer additive device in accordance with one embodiment of the present invention.

本文所用之術語僅用於描述具體實施例之目的且並不意欲限制本發明。如本文所用，除非上下文另外明確指示，否則單數形式「一(a、an)」及「該(the)」亦包括複數形式。另外應瞭解，術語「包含(comprises及/或comprising)」在本說明書中使用時表示存在所陳述之特徵、整數、步驟、操作、元件及/或組件，但不排除存在或添加一或多種其他特徵、整數、步驟、操作、元件組、組分及/或其群組。 The terminology used herein is for the purpose of describing the particular embodiments, As used herein, the singular forms "a", "the" In addition, it should be understood that the term "comprises and/or "comprising" as used in this specification means that there are any stated features, integers, steps, operations, components and/or components, but does not exclude the presence or addition of one or more other Features, integers, steps, operations, component groups, components, and/or groups thereof.

諸如「包括」、「包含」、「具有」、「含有」或「涉及」之語言及其變化形式意欲為廣泛的且涵蓋此後列舉之標的物以及未列舉之等效物及額外標的物。另外，只要組合物、元件組、方法步驟或任何其他表述前有過渡片語「包含」、「包括」或「含有」，應瞭解本文亦涵蓋與過渡片語「基本上由......組成」、「由......組成」或「選自由......組成之群」在前所列舉之組合物、元件組、方法步驟或任何其他表述相同的組合物、元件組、方法步驟或任何其他表述。 Languages such as "including", "including", "having", "comprising" or "comprising" are intended to be broadly encompassed and the subject matter recited herein, and the equivalents and additional subject matter. In addition, as long as there are transitional phrases "including", "including" or "contains" before the composition, component group, method step or any other expression, it should be understood that this article also covers the transitional phrase "basically by ..... Compositions, "composed of" or "groups selected from" are listed above as compositions, component groups, method steps or any other composition that expresses the same, Component group, method step or any other statement.

申請專利範圍中之所有方式之對應結構、材料、行為及等效物或步驟加功能元件(若可用)意欲包括如特定主張之執行功能之任何結構、材料或行為與其他主張元件之組合。本發明之描述已出於說明及描述之目的而提供，但並不意欲為詳盡的或使本發明侷限於所揭示之形式。許多修改及變化在不悖離本發明之範疇及精神的情況下應對一般熟習此項技術者顯而易見。選擇所述實施例且加以描述以便充分闡明本發明之原理及實際應用，及使得一般熟習此項技術者能夠將本發明之具有多種修改之多種實施例理解為適於所涵蓋之具體用途。因此，雖然本發明已依據實施例加以描述，但熟習此項技術者應認識到 本發明可在修改下及在隨附申請專利範圍之精神及範疇中加以實踐。 The corresponding structures, materials, acts, and equivalents or steps and functional elements, if applicable, are intended to include any structure, material, or behavior of a particular claimed function. The description of the present invention has been provided for purposes of illustration and description. Many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention. The embodiments were chosen and described in order to explain the principles of the invention and the embodiments of the invention Thus, although the invention has been described in terms of embodiments, those skilled in the art should recognize The present invention can be practiced in the spirit and scope of the appended claims and the scope of the appended claims.

現將詳細提及所揭示之特定標的物。雖然所揭示之標的物將連同所羅列之申請專利範圍加以描述，但應瞭解該等申請專利範圍並不意欲將所揭示之標的物侷限於此。相反地，所揭示之標的物意欲覆蓋所有替代、修改及等效物，其可包括在如申請專利範圍所定義之目前揭示之標的物的範疇內。 Reference will now be made in detail to the particular subject matter disclosed. It is to be understood that the scope of the invention is to be construed as being limited by the scope of the appended claims. On the contrary, the subject matter disclosed is intended to cover all alternatives, modifications, and equivalents, which are included within the scope of the presently disclosed subject matter as defined by the appended claims.

介紹Introduction

本發明係關於一種聚合物添加劑裝置且關於一種使用該聚合物添加劑裝置產生複數個聚合物產物之方法。本發明亦關於用本文所述之聚合物添加劑裝置改裝現有聚合物產生裝置之方法。聚合物添加劑裝置與包含連續聚合反應器之聚合裝置流體連通。聚合裝置亦可含有閃蒸器及對聚合物進行調節(例如調節分子量)之容器或槽。聚合物添加劑裝置包含主歧管及至少一個添加劑注射裝置，例如至少兩個添加劑注射裝置。主歧管為用於自聚合裝置引導液體聚合物通過聚合反應器排出管線或閃蒸器進料管線之分配管線。在一個實施例中，主歧管將液體聚合物分配至與主歧管接觸之聚合物精整機(例如聚合物凝固器)。主歧管可包含用於控制液體聚合物流動至添加劑注射裝置之主歧管閥。 This invention relates to a polymer additive device and to a method of producing a plurality of polymer products using the polymer additive device. The invention also relates to a method of retrofitting an existing polymer generating device with the polymeric additive device described herein. The polymer additive device is in fluid communication with a polymerization device comprising a continuous polymerization reactor. The polymerization unit may also contain a flasher and a vessel or tank for conditioning (e.g., adjusting molecular weight) the polymer. The polymeric additive device comprises a primary manifold and at least one additive injection device, such as at least two additive injection devices. The primary manifold is a distribution line for directing liquid polymer through the polymerization reactor discharge line or flasher feed line from the polymerization unit. In one embodiment, the primary manifold distributes the liquid polymer to a polymer finishing machine (eg, a polymer coagulator) that is in contact with the primary manifold. The primary manifold can include a primary manifold valve for controlling the flow of liquid polymer to the additive injection device.

添加劑注射裝置包含可載送至少一部分液體聚合物之次歧管。次歧管可與至少一個添加劑注射管線接觸，用於將添加劑進料至次歧管以與液體聚合物組合。該方法可連續運行且具有允許由一個連續方法產生一種以上聚合物產物之優勢。一般，該方法包括形成液體聚合物，自聚合裝置移出液體聚合物，及將至少兩部分液體聚合物引導至獨立的添加劑注射裝置以產生不同聚合物產物。 The additive injection device includes a secondary manifold that can carry at least a portion of the liquid polymer. The secondary manifold can be in contact with at least one additive injection line for feeding the additive to the secondary manifold for combination with the liquid polymer. The process can be run continuously and has the advantage of allowing more than one polymer product to be produced by one continuous process. Typically, the method includes forming a liquid polymer, removing the liquid polymer from the polymerization unit, and directing at least two portions of the liquid polymer to a separate additive injection device to produce a different polymer product.

本發明提供優於先前技術之明顯改良，因為其容許液體聚合物之生產率、產率及速率最大化同時亦允許定製最終產物。舉例而言， 液體聚醯胺可分成多部分且每部分可與不同添加劑組合。第一部分可與阻燃添加劑組合，第二部分可與顏料組合，且第三部分可與熱穩定劑組合。因此，由一種液體聚醯胺產生三種聚醯胺產物。在另一實例中，第一部分液體聚合物自主歧管傳送至聚合物精整機以形成初級成品聚合物產物，而另一部分傳送至添加劑注射裝置以形成包含添加劑之成品聚合物產物。另外，本發明為有利的，因為其減少聚合裝置設備中可由添加劑積聚所造成之污染。因為添加劑可在聚合物已離開聚合裝置後添加，所以聚合裝置無需暴露於添加劑。 The present invention provides a significant improvement over the prior art in that it allows for maximum productivity, yield and rate of liquid polymer while also allowing customization of the final product. For example, The liquid polyamine can be divided into multiple parts and each part can be combined with different additives. The first part can be combined with a flame retardant additive, the second part can be combined with a pigment, and the third part can be combined with a heat stabilizer. Thus, three polyamine products are produced from one liquid polyamine. In another example, the first portion of the liquid polymer autonomous manifold is transferred to the polymer finishing machine to form the primary finished polymer product, and the other portion is passed to the additive injection device to form the finished polymer product comprising the additive. Additionally, the present invention is advantageous because it reduces contamination in the polymerization unit equipment that can be caused by accumulation of additives. Since the additive can be added after the polymer has left the polymerization unit, the polymerization unit need not be exposed to the additive.

本發明亦包括控制添加劑注射管線壓力，以使其在添加劑閥打開時高於次歧管壓力。藉由使用能夠在添加劑流關閉時防止聚合物倒流至添加劑注射管道的適當注射閥來控制壓力。在不存在壓力控制的情況下，溫度可能受到影響且注射閥及管道需要伴熱，因為溫度降低會使聚合物凝固且堵塞裝置。 The invention also includes controlling the additive injection line pressure to be higher than the secondary manifold pressure when the additive valve is open. The pressure is controlled by using a suitable injection valve that prevents the polymer from flowing back to the additive injection conduit when the additive stream is closed. In the absence of pressure control, temperature may be affected and the injection valves and piping require heat, as temperature drops cause the polymer to solidify and block the device.

本發明藉由提供製造商使用包含單個聚合反應器之單個聚合裝置產生複數個聚合物產物之靈活性來克服此缺陷。連續聚合反應器可同時產生多種產物或一次產生一種產物，視指定工廠或操作者之要求而定。本發明避免與添加劑引入至主歧管相關之問題。該裝置亦能夠相對於先前現有裝置及方法在極短時間內產生符合指定聚醯胺產品規格之聚醯胺。可在利用與一或多個添加劑注射裝置組合之一個聚合反應器的單個聚合裝置中製造之不同產物的數目僅受經濟因素限制。本發明之方法亦為可縮放的以便在交付多種聚合物產物方面提供靈活性。 The present invention overcomes this drawback by providing the manufacturer with the flexibility to produce a plurality of polymer products using a single polymerization unit comprising a single polymerization reactor. A continuous polymerization reactor can produce multiple products at the same time or produce one product at a time, depending on the requirements of the designated plant or operator. The present invention avoids the problems associated with the introduction of additives into the main manifold. The device is also capable of producing polyamines that meet the specifications of the specified polyamine product in a very short time relative to prior prior devices and methods. The number of different products that can be made in a single polymerization unit utilizing one polymerization reactor combined with one or more additive injection devices is only limited by economic factors. The method of the invention is also scalable to provide flexibility in delivering a variety of polymer products.

液體聚合物及其製備Liquid polymer and its preparation

如上所論述，液體聚合物經由主歧管自聚合裝置移出。自聚合裝置移出之液體聚合物可不含添加劑。在另一實施例中，自聚合裝置移出之液體聚合物可包含添加劑。然而，一旦液體聚合物組合物自聚 合裝置中移出，當液體聚合物在主歧管中時，不向其中添加添加劑。液體聚合物可為液體形式之任何聚合物(包括熔融聚合物)或可流動形式之聚合物。出於本發明之目的，當聚合物在聚合反應器溫度下為液體形式時，其為液體聚合物。例示性液體聚合物可包括聚醯胺、聚烯烴、聚胺基甲酸酯、聚酯、聚苯乙烯及聚碳酸酯。在較佳實施例中，本發明係關於產生聚醯胺。 As discussed above, the liquid polymer is removed from the polymerization unit via the primary manifold. The liquid polymer removed from the polymerization unit may be free of additives. In another embodiment, the liquid polymer removed from the polymerization unit can comprise an additive. However, once the liquid polymer composition is self-polymerizing The device is removed and no additives are added to the liquid polymer as it is in the main manifold. The liquid polymer can be any polymer in liquid form (including molten polymer) or a polymer in flowable form. For the purposes of the present invention, a polymer is a liquid polymer when it is in liquid form at the polymerization reactor temperature. Exemplary liquid polymers can include polyamines, polyolefins, polyurethanes, polyesters, polystyrenes, and polycarbonates. In a preferred embodiment, the invention relates to the production of polyamines.

用於本發明方法之聚醯胺可由單一單體或兩種或兩種以上不同單體(諸如最初反應形成聚(六亞甲基己二醯胺)之二羧酸及二胺)之混合物獲得。因此，在聚(六亞甲基己二醯胺)之情況下，主要單體為己二胺及己二酸。此類衍生自兩種不同單體之聚醯胺一般使用藉由將二羧酸與二胺以化學計量混合於諸如水之溶劑中所獲得之鹽溶液作為起始物質來製造。在一個實施例中，己二酸與己二胺之莫耳比可為在介於0.8：1與1.2：1之間的範圍內的比率。鹽溶液通常藉由蒸發掉水來濃縮。藉由在高溫及壓力下加熱該鹽溶液以蒸發掉水，而同時避免任何固相形成以避免混合物凝固來獲得聚醯胺。己二酸與己二胺之相對莫耳量可視所需最終產物而變化。 The polyamine used in the process of the present invention can be obtained from a single monomer or a mixture of two or more different monomers, such as a dicarboxylic acid and a diamine which are initially reacted to form poly(hexamethylene hexamethylenediamine). . Therefore, in the case of poly(hexamethylene hexamethylenediamine), the main monomers are hexamethylenediamine and adipic acid. Such polyamines derived from two different monomers are generally produced using a salt solution obtained by stoichiometrically mixing a dicarboxylic acid and a diamine in a solvent such as water as a starting material. In one embodiment, the molar ratio of adipic acid to hexamethylenediamine can be in a range between 0.8:1 and 1.2:1. The salt solution is usually concentrated by evaporation of water. The polyamine is obtained by heating the salt solution under high temperature and pressure to evaporate water while avoiding any solid phase formation to avoid solidification of the mixture. The relative molar amount of adipic acid to hexamethylene diamine can vary depending on the desired end product.

在一些實施例中，液體聚合物可為二羧酸單體與二胺單體之縮合產物。 In some embodiments, the liquid polymer can be a condensation product of a dicarboxylic acid monomer and a diamine monomer.

適用於本發明之二羧酸係選自由乙二酸、丙二酸、丁二酸、戊二酸、庚二酸、己二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、順丁烯二酸、戊烯二酸、2-十二烯二酸及已二烯二酸、1,2-或1,3-環己二甲酸、1,2-或1,3-苯二乙酸、1,2-或1,3-環己二乙酸、間苯二甲酸、對苯二甲酸、4,4'-氧基雙苯甲酸、4,4-二苯甲酮二甲酸、2,6-萘二甲酸、對第三丁基間苯二甲酸及2,5-呋喃二甲酸及其混合物組成之群。在一個實施例中，二羧酸單體包含至少80%己二酸，例如至少95%己二酸。 Dicarboxylic acids suitable for use in the present invention are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecane. Diacid, dodecanedioic acid, maleic acid, glutaconic acid, 2-dodecenedioic acid and dienedicarboxylic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1, 2- or 1,3-benzenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, terephthalic acid, 4,4'-oxybisbenzoic acid, 4,4- A group consisting of benzophenone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, p-tert-butylisophthalic acid, and 2,5-furandicarboxylic acid, and mixtures thereof. In one embodiment, the dicarboxylic acid monomer comprises at least 80% adipic acid, such as at least 95% adipic acid.

己二酸(AA)為最佳二羧酸且以粉末形式使用。AA一般以含有極低量雜質之純形式獲得。典型雜質包括其他酸(一元酸及低碳二元酸)(小於60ppm)、含氮材料、痕量金屬(諸如鐵(小於2ppm)及其他重金屬(小於10ppm))、砷(小於3ppm)及烴油(小於10ppm)。 Adipic acid (AA) is the best dicarboxylic acid and is used in powder form. AA is generally obtained in pure form containing very low levels of impurities. Typical impurities include other acids (monobasic and low carbon dibasic acids) (less than 60 ppm), nitrogenous materials, trace metals (such as iron (less than 2 ppm) and other heavy metals (less than 10 ppm)), arsenic (less than 3 ppm) and hydrocarbons Oil (less than 10ppm).

適用於本發明之二胺係選自由乙醇二胺、三亞甲基二胺、丁二胺、戊二胺、己二胺、2-甲基戊二胺、庚二胺、2-甲基己二胺、3-甲基己二胺、2,2-二甲基戊二胺、辛二胺、2,5-二甲基己二胺、壬二胺、2,2,4-及2,4,4-三甲基己二胺、癸二胺、5-甲基壬二胺、異氟爾酮二胺、十一烷二胺、十二烷二胺、2,2,7,7-四甲基辛二胺、雙(對胺基環己基)甲烷、雙(胺基甲基)降莰烷、視情況經一或多個C₁至C₄烷基取代之C₂-C₁₆脂族二胺、脂族聚醚二胺及呋喃二胺(諸如2,5-雙(胺基甲基)呋喃)及其混合物組成之群。所選二胺可具有高於二羧酸之沸點，且二胺較佳不為二甲苯二胺。在一個實施例中，二胺單體包含至少80%己二胺，例如至少95%己二胺。己二胺(HMD)最常用於製備尼龍6,6。HMD在約42℃下凝固且通常添加水以降低此熔融溫度且易於操作。因此，HMD以例如介於80重量%與100重量%之間或介於92重量%與98重量%之間的濃溶液形式市售。 Diamines suitable for use in the present invention are selected from the group consisting of ethanol diamine, trimethylene diamine, butanediamine, pentane diamine, hexamethylene diamine, 2-methyl pentane diamine, heptane diamine, 2-methyl hexane Amine, 3-methylhexamethylenediamine, 2,2-dimethylpentanediamine, octanediamine, 2,5-dimethylhexanediamine, decanediamine, 2,2,4- and 2,4 ,4-trimethylhexamethylenediamine, decanediamine, 5-methylindolediamine, isophoronediamine, undecanediamine, dodecanediamine, 2,2,7,7-tetra Methyloctanediamine, bis(p-aminocyclohexyl)methane, bis(aminomethyl)norbornane, C ₂ -C ₁₆ aliphatic substituted by one or more C ₁ to C ₄ alkyl groups, as the case may be A group consisting of a diamine, an aliphatic polyether diamine, and a furan diamine such as 2,5-bis(aminomethyl)furan, and mixtures thereof. The diamine selected may have a higher boiling point than the dicarboxylic acid, and the diamine is preferably not xylene diamine. In one embodiment, the diamine monomer comprises at least 80% hexamethylenediamine, such as at least 95% hexamethylenediamine. Hexamethylenediamine (HMD) is most commonly used to prepare nylon 6,6. The HMD solidifies at about 42 ° C and water is typically added to lower this melting temperature and is easy to handle. Thus, the HMD is commercially available, for example, as a concentrated solution between 80% and 100% by weight or between 92% and 98% by weight.

在下文描述中，術語己二酸(AA)及己二胺(HMD)將用於表示二羧酸及二胺。然而，此方法亦適用於如上所指出之其他二羧酸及其他二胺。另外，在下文描述中，術語尼龍6,6及聚醯胺將用於表示液體聚合物。然而，此方法亦適用於如上所指出之其他液體聚合物。 In the following description, the terms adipic acid (AA) and hexamethylenediamine (HMD) will be used to denote dicarboxylic acids and diamines. However, this method is also applicable to other dicarboxylic acids and other diamines as indicated above. Additionally, in the following description, the terms nylon 6,6 and polyamine will be used to denote a liquid polymer. However, this method is also applicable to other liquid polymers as indicated above.

除僅基於二羧酸及二胺之聚醯胺之外，有時宜併入其他單體。當以小於20重量%、例如小於15重量%之比例添加時，此等單體可在不悖離本發明之情況下添加至尼龍鹽溶液。該第三起始物質可包括單官能羧酸，諸如甲酸、乙酸、丙酸、丁酸、戊酸、苯甲酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、肉豆蔻酸、肉豆蔻油 酸、棕櫚酸、棕櫚油酸、十六碳烯酸、硬脂酸、油酸、反油酸、異油酸、亞麻油酸、芥子酸及其類似物。其亦可包括內醯胺，諸如α-乙內醯胺、α-丙內醯胺、β-丙內醯胺、γ-丁內醯胺、δ-戊內醯胺、γ-戊內醯胺、己內醯胺及其類似物。其亦可包括內酯，諸如α-乙內酯、α-丙內酯、β-丙內酯、γ-丁內酯、δ-戊內酯、γ-戊內酯、己內酯及其類似物。其可包括雙官能醇，諸如單乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,5-戊二醇、2-乙基-1,3-己二醇(etohexadiol)、對薄荷烷-3,8-二醇、2-甲基-2,4-戊二醇、1,6-己二醇、1,7-庚二醇及1,8-辛二醇。較高官能分子，諸如甘油、三羥甲基丙烷、三乙醇胺及其類似物，亦可為適用的。合適羥胺亦可選自諸如乙醇胺、二乙醇胺、3-胺基-1-丙醇、1-胺基-2-丙醇、4-胺基-1-丁醇、3-胺基-1-丁醇、2-胺基-1-丁醇、4-胺基-2-丁醇、戊醇胺、己醇胺及其類似物。應瞭解，任何此等單體之摻合物亦可在不悖離本發明之情況下加以利用。 In addition to polyamines based solely on dicarboxylic acids and diamines, it is sometimes desirable to incorporate other monomers. When added in a proportion of less than 20% by weight, for example less than 15% by weight, such monomers may be added to the nylon salt solution without departing from the invention. The third starting material may comprise a monofunctional carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, laurel Acid, myristic acid, nutmeg oil Acid, palmitic acid, palmitoleic acid, hexadecenoic acid, stearic acid, oleic acid, elaidic acid, isooleic acid, linoleic acid, sinapic acid and the like. It may also include indoleamines such as α-acetalamine, α-propionamide, β-propionamide, γ-butyrolactam, δ-valeroinamide, γ-valeroinamide , caprolactam and its analogues. It may also include lactones such as α-lactone, α-propiolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, caprolactone and the like. Things. It may include a difunctional alcohol such as monoethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-ethyl-1,3-hexanediol (etohexadiol), p-menthane -3,8-diol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Higher functional molecules such as glycerol, trimethylolpropane, triethanolamine, and the like, may also be suitable. Suitable hydroxylamines may also be selected from, for example, ethanolamine, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 3-amino-1-butene Alcohol, 2-amino-1-butanol, 4-amino-2-butanol, pentanolamine, hexanolamine and the like. It will be appreciated that any blend of such monomers may also be utilized without departing from the invention.

多種添加劑可用於本發明之實施例。此等添加劑可使用本發明之添加劑注射管線注射。較佳地，此舉允許添加劑併入一部分液體聚合物中。添加劑可包括熱穩定劑，諸如銅鹽、碘化鉀，或此項技術中已知的任何其他抗氧化劑。該等添加劑亦可包括聚合催化劑，諸如金屬氧化物、酸性化合物、含氧磷化合物之金屬鹽或此項技術中已知的其他聚合催化劑。添加劑亦可為去光劑及著色劑，諸如二氧化鈦、碳黑或此項技術中已知的其他顏料、染料及著色劑。所用添加劑可包括消泡劑，諸如二氧化矽分散液、聚矽氧共聚物或此項技術中已知的其他消泡劑。可使用潤滑助劑，諸如硬脂酸鋅、硬脂醯芥酸醯胺、硬脂醇、二硬脂酸鋁、伸乙基雙硬脂醯胺或此項技術中已知的其他聚合物潤滑劑。成核劑可包括在混合物中，諸如煙霧狀二氧化矽或氧化鋁、 二硫化鉬、滑石、石墨、氟化鈣、苯基亞膦酸鹽或此項技術中已知的其他助劑。此項技術中已知的其他常見添加劑，諸如阻燃劑、塑化劑、抗衝擊改質劑及一些類型之填充劑亦可在凝固前添加至熔融不平衡混合物。應瞭解，任何此等添加劑之摻合物亦可在不悖離本文中所揭示之實施例之基本原理的情況下加以利用。在一個實施例中，添加劑及其摻合物包括(但不限於)銅塑化劑、去光劑、顏料、染料、基於銅之穩定劑、顏料(包括無色顏料)、玻璃、玻璃纖維、潤滑劑、共聚合物(諸如尼龍6、尼龍6,10及尼龍6,12)、催化劑及改變末端平衡之化合物(例如胺末端)。在一些實施例中，添加劑以母體混合物形式提供。在一些態樣中，相同添加劑可在多個注射管線中注射，但可與另一添加劑組合、以不同量或其組合添加。 A wide variety of additives can be used in embodiments of the invention. These additives can be injected using the additive injection line of the present invention. Preferably, this allows the additive to be incorporated into a portion of the liquid polymer. Additives can include heat stabilizers such as copper salts, potassium iodide, or any other antioxidant known in the art. Such additives may also include polymerization catalysts such as metal oxides, acidic compounds, metal salts of oxygen-containing phosphorus compounds, or other polymerization catalysts known in the art. The additives may also be matting agents and color formers such as titanium dioxide, carbon black or other pigments, dyes and colorants known in the art. The additives used may include antifoaming agents such as cerium oxide dispersions, polyoxy oxycopolymers or other antifoaming agents known in the art. Lubricating aids such as zinc stearate, stearyl erucamide, stearyl alcohol, aluminum distearate, ethyl bis-stearylamine or other polymers known in the art may be used for lubrication. Agent. A nucleating agent can be included in the mixture, such as fumed ceria or alumina, Molybdenum disulfide, talc, graphite, calcium fluoride, phenylphosphinate or other auxiliaries known in the art. Other common additives known in the art, such as flame retardants, plasticizers, impact modifiers, and some types of fillers may also be added to the molten unbalanced mixture prior to solidification. It will be appreciated that any blend of such additives may also be utilized without departing from the basic principles of the embodiments disclosed herein. In one embodiment, the additives and blends thereof include, but are not limited to, copper plasticizers, matting agents, pigments, dyes, copper-based stabilizers, pigments (including colorless pigments), glass, fiberglass, lubrication Agents, copolymers (such as nylon 6, nylon 6, 10 and nylon 6, 12), catalysts and compounds that alter terminal equilibrium (such as amine ends). In some embodiments, the additive is provided as a parent mixture. In some aspects, the same additive can be injected in multiple injection lines, but can be combined with another additive, in varying amounts, or a combination thereof.

本文所述之聚合物產物可包含0.1重量%至20重量%添加劑、例如0.5重量%至20重量%、1重量%至20重量%、1重量%至15重量%或1重量%至10重量%之添加劑。視待添加至部分液體聚合物之添加劑及量而定，添加劑可維持在40℃至300℃、例如50℃至270℃、60℃至250℃或80℃至220℃之溫度下。應瞭解，調節添加劑之量及添加劑之溫度以保持聚合物流經裝置。因此，添加劑之溫度可小於40℃，諸如在環境溫度下。聚合物產物可具有10,000至50,000道爾頓、諸如12,000至45,000道爾頓或10,000至20,000道爾頓之分子量。 The polymer product described herein may comprise from 0.1% to 20% by weight of additives, for example from 0.5% to 20% by weight, from 1% to 20% by weight, from 1% to 15% by weight or from 1% to 10% by weight. Additives. The additive may be maintained at a temperature of from 40 ° C to 300 ° C, such as from 50 ° C to 270 ° C, from 60 ° C to 250 ° C or from 80 ° C to 220 ° C, depending on the additives and amounts to be added to the portion of the liquid polymer. It will be appreciated that the amount of additive and the temperature of the additive are adjusted to maintain the polymer flow through the device. Thus, the temperature of the additive can be less than 40 °C, such as at ambient temperature. The polymer product can have a molecular weight of from 10,000 to 50,000 Daltons, such as from 12,000 to 45,000 Daltons or from 10,000 to 20,000 Daltons.

液體聚合物可由聚合物鹽溶液，諸如尼龍鹽溶液或已進行脫水(例如蒸發)之尼龍鹽來製備。尼龍鹽溶液可製造成目標鹽含量及二羧酸(例如AA)與二胺(HMD)之目標莫耳比。目標莫耳比可藉由量測尼龍鹽溶液之pH值來計算。尼龍鹽溶液可藉由將AA粉末進料至連續攪拌槽反應器(CSTR)及藉由分別將HMD及水(單獨或組合)進料至CSTR而在CSTR中形成。AA粉末可基於體積或重量而進料至CSTR。由於希望形成與目標鹽含量及pH值具有低變化性的尼龍鹽溶液，AA粉末可 使用失重補償進料器基於重量加以計量。已發現使用失重補償進料器計量AA粉末導致尼龍鹽溶液中之目標鹽含量及pH值之較低變化性，因為AA粉末之容積密度可變化極大。在本發明之例示性實施例中，低可變進料速率可按小於目標進料速度之±5%變化。可接受之失重補償進料器可包括Acrison型號402/404、403、405、406及407；Merrick型號570；K-Tron型號KT20、T35、T60、T80、S60、S100及S500；及Brabender FlexWall®Plus及FlexWall®Classic。 The liquid polymer can be prepared from a polymer salt solution, such as a nylon salt solution or a nylon salt that has been subjected to dehydration (e.g., evaporation). The nylon salt solution can be made to the target salt content and the target molar ratio of the dicarboxylic acid (e.g., AA) to the diamine (HMD). The target molar ratio can be calculated by measuring the pH of the nylon salt solution. The nylon salt solution can be formed in the CSTR by feeding the AA powder to a continuous stirred tank reactor (CSTR) and by feeding HMD and water (alone or in combination) to the CSTR, respectively. The AA powder can be fed to the CSTR based on volume or weight. AA powder can be formed because it is desired to form a nylon salt solution with low variability in target salt content and pH. The weight loss compensation feeder is used to measure based on the weight. It has been found that metering AA powder using a weight loss compensating feeder results in a lower variability in the target salt content and pH in the nylon salt solution, as the bulk density of the AA powder can vary greatly. In an exemplary embodiment of the invention, the low variable feed rate may vary by less than ± 5% of the target feed rate. Acceptable weight loss compensated feeders may include Acrison models 402/404, 403, 405, 406, and 407; Merrick Model 570; K-Tron models KT20, T35, T60, T80, S60, S100, and S500; and Brabender FlexWall® Plus and FlexWall® Classic.

聚合物添加劑方法Polymer additive method

用於製備具有添加劑之聚合物的先前技術方法展示於圖1中。聚合方法1包含將預聚物溶液(亦稱為聚合物鹽溶液)儲存於儲槽5中。當產生足夠聚合物鹽溶液時，或當另外需要形成聚合物時，聚合物鹽溶液經由管線6輸送流經蒸發器7以形成聚合物鹽，聚合物鹽接著經由聚合入口8輸送至聚合反應器20。聚合物16自反應器20中移出且傳送至凝固器18以產生成品聚合物產物119。若需要，添加劑可在聚合方法100之兩個不同部分添加。在一個實施例中，添加劑9經由管線11添加至儲槽5。在另一實施例中，添加劑9隨著聚合物鹽溶液傳至聚合反應器20而經由管線12添加至管線6。在另一實施例(未圖示)中，添加劑9添加至液體聚合物16。在另一實施例中，除添加劑9之外或代替添加劑9，添加劑13經由管線14添加至液體聚合物16。然而，當在反應器20中連續產生液體聚合物時，此等方法之每一者產生一種聚合物產物。 Prior art methods for preparing polymers with additives are shown in Figure 1 . The polymerization method 1 comprises storing a prepolymer solution (also referred to as a polymer salt solution) in the storage tank 5 . When a sufficient polymer salt solution is produced, or when it is additionally desired to form a polymer, the polymer salt solution is transported via line 6 through evaporator 7 to form a polymer salt which is then transported via polymerization inlet 8 to the polymerization reactor. 20 . Polymer 16 is removed from reactor 20 and passed to coagulator 18 to produce finished polymer product 119 . Additives can be added in two different portions of polymerization process 100 , if desired. In one embodiment, the additive 9 is added to the reservoir 5 via line 11 . In another embodiment, additive 9 is added to line 6 via line 12 as the polymer salt solution is passed to polymerization reactor 20 . In another embodiment (not shown), additive 9 is added to liquid polymer 16 . Embodiment, in addition to or instead of the additive than 9 9 additive, the additive 13 is added via line 14 to the liquid polymer 16 in another embodiment. However, when a liquid polymer is continuously produced in reactor 20 , each of these processes produces a polymer product.

本發明之聚合方法101展示於圖2、3及4中且包括聚合物添加劑裝置102。聚合方法101包含聚合物鹽儲槽105、蒸發器107、輸送管線106、聚合反應器120及聚合物入口108。聚合入口108(包含聚合物鹽及添加用來調節聚合物鹽之化學計量的任何單體)將聚合物鹽進料至聚合反應器120。聚合物鹽可視情況包含如上所論述之添加劑。聚合 物鹽在連續聚合反應器120中以縮合反應聚合形成聚合物116。聚合物116自聚合反應器120中移出至主歧管121，通過泵115且進入聚合物添加劑裝置102。在離開聚合反應器120之前，聚合物116可進料至閃蒸器(未圖示)及/或用於調節聚合物分子量之容器(未圖示)。該容器可包含混合籃及螺旋泵。該容器可為水平或垂直的，且可在真空下操作。聚合物添加劑裝置102包含主歧管121、主歧管泵115、聚合物凝固器118及主歧管閥122及123。聚合物添加劑裝置102亦包含至少一個，例如至少兩個添加劑注射裝置。如圖2中所示，兩個添加劑注射裝置包含次歧管125及135、次歧管泵126及136、添加劑注射儲槽127及137、添加劑注射管線128及138、添加劑注射泵129及139、添加劑注射閥130及140、以及聚合物凝固器133、143，與主歧管121流體連通。成品聚合物產物161、162及119接著自聚合物凝固器133、143及118中移出。雖然圖2、3及4中展示一個泵、閥及注射管線，但可能存在額外泵、閥及注射管線以及溫度控制器及感測器、壓力控制器及感測器及視情況選用之靜態混合器。 The polymerization process 101 of the present invention is shown in Figures 2 , 3 and 4 and includes a polymer additive device 102 . The polymerization process 101 includes a polymer salt storage tank 105 , an evaporator 107 , a transfer line 106 , a polymerization reactor 120, and a polymer inlet 108 . Polymerization inlet 108 (comprising a polymer salt and any monomer added to adjust the stoichiometry of the polymer salt) feeds the polymer salt to polymerization reactor 120 . The polymeric salt may optionally comprise an additive as discussed above. The polymer salt is polymerized in a continuous polymerization reactor 120 by a condensation reaction to form a polymer 116 . Polymer 116 is removed from polymerization reactor 120 to main manifold 121 , through pump 115 and into polymer additive unit 102 . Prior to exiting polymerization reactor 120 , polymer 116 can be fed to a flasher (not shown) and/or a vessel (not shown) for adjusting the molecular weight of the polymer. The container can include a mixing basket and a screw pump. The container can be horizontal or vertical and can be operated under vacuum. The polymer additive device 102 includes a main manifold 121 , a main manifold pump 115 , a polymer coagulator 118, and main manifold valves 122 and 123 . The polymer additive device 102 also includes at least one, for example at least two, additive injection devices. As shown in FIG. 2, the injection device comprises two secondary additive manifolds 125 and 135, secondary manifolds 136 and pump 126, and 127 inject the additive reservoir 137, line 128 and 138 inject the additive, the additive injection pump 129 and 139, Additive injection valves 130 and 140 , and polymer coagulators 133 , 143 are in fluid communication with main manifold 121 . The finished polymer products 161 , 162 and 119 are then removed from the polymer coagulators 133 , 143 and 118 . Although a pump, valve, and injection line are shown in Figures 2 , 3, and 4 , there may be additional pumps, valves, and injection lines as well as temperature controllers and sensors, pressure controllers and sensors, and static mixing as appropriate. Device.

本發明考慮到複數個聚合物產物之產生。本發明亦考慮到有效的添加劑注射裝置修改及/或置換。在習知方法中，為將第一添加劑切換為第二添加劑且產生具有第二添加劑之聚合物產物，該方法可耗時3至12小時。時間需求歸因於設備(添加劑儲槽)之物理切換、移除包含第一添加劑之所有液體聚合物、添加第二添加劑及產生包含所需量第二添加劑之聚合物產物。本發明之方法方便地在1小時內、例如在30分鐘內、在15分鐘內、在5分鐘內或在1分鐘內將第一添加劑切換成第二添加劑且產生包含所需量第二添加劑之聚合物產物。 The present invention contemplates the production of a plurality of polymer products. The present invention also contemplates modification and/or replacement of effective additive injection devices. In a conventional method, to switch the first additive to the second additive and produce a polymer product having the second additive, the process can take from 3 to 12 hours. The time requirement is due to physical switching of the equipment (additive reservoir), removal of all liquid polymers comprising the first additive, addition of the second additive, and production of a polymer product comprising the desired amount of the second additive. The method of the present invention conveniently switches the first additive to the second additive within 1 hour, such as within 30 minutes, within 15 minutes, within 5 minutes, or within 1 minute, and produces a second additive comprising the desired amount. Polymer product.

在一些實施例中，成品聚合物產物119可實質上不含添加劑。在一些實施例中，成品聚合物產物119可實質上不含添加劑注射儲槽127及/或添加劑儲槽137中之添加劑。添加劑注射儲槽127中之添加劑可 為與添加劑儲槽137中之添加劑不同的添加劑。另外，一種以上添加劑可以添加劑混合物形式儲存於每一添加劑儲槽中。各成品聚合物產物161、162及119可為不同的成品聚合物產物。 In some embodiments, the finished polymer product 119 can be substantially free of additives. In some embodiments, the finished polymer product 119 can be substantially free of additives in the additive injection reservoir 127 and/or additive reservoir 137 . The additive in the additive injection reservoir 127 can be an additive that is different from the additive in the additive reservoir 137 . Additionally, more than one additive may be stored in the additive reservoir as an additive mixture. Each finished polymer product 161 , 162, and 119 can be a different finished polymer product.

聚合物116在足以使聚合物維持液體形式之溫度下流經主歧管121及次歧管125及135。在一些實施例中，對於聚醯胺而言，液體聚合物之溫度可介於265℃與300℃之間。在主歧管121中，壓力可介於10與31兆帕(MPa)之間。各次歧管中之壓力可等於或小於主歧管中之壓力，例如介於10MPa與31MPa之間或介於10MPa與28MPa之間。主歧管及次歧管可帶夾套或以其他方式加熱或絕緣，以便維持使聚合物保持液體形式所需之主歧管及次歧管之溫度。另外，主歧管及次歧管可各包含溫度控制器以便量測液體聚合物之溫度及(若需要)調節該溫度。主歧管及次歧管亦可各包含壓力控制器以便量測及調節液體聚合物之壓力。 The polymer 116 flows through the primary manifold 121 and the secondary manifolds 125 and 135 at a temperature sufficient to maintain the polymer in liquid form. In some embodiments, for polyamines, the temperature of the liquid polymer can be between 265 ° C and 300 ° C. In the main manifold 121 , the pressure can be between 10 and 31 megapascals (MPa). The pressure in each manifold may be equal to or less than the pressure in the primary manifold, such as between 10 MPa and 31 MPa or between 10 MPa and 28 MPa. The primary and secondary manifolds may be jacketed or otherwise heated or insulated to maintain the temperature of the primary and secondary manifolds required to maintain the polymer in liquid form. Additionally, the primary manifold and the secondary manifold may each include a temperature controller to measure the temperature of the liquid polymer and, if desired, adjust the temperature. The primary manifold and the secondary manifold may each also include a pressure controller to measure and adjust the pressure of the liquid polymer.

主歧管閥122及123在如圖2中所示打開時提供主歧管121與次歧管125及135之間的流體連通。主歧管121之內徑可等於或大於次歧管125及135之內徑。在一些實施例中，次歧管之內徑相對於主歧管121之內徑可用於控制次歧管中液體聚合物之流動及壓力。 A main manifold valve 122 and 123 provide primary and the secondary manifold 121 in fluid communication between the manifold 125 and 135 as shown in Figure 2 when opened. The inner diameter of the main manifold 121 may be equal to or greater than the inner diameter of the secondary manifolds 125 and 135 . In some embodiments, the inner diameter of the secondary manifold relative to the inner diameter of the primary manifold 121 can be used to control the flow and pressure of the liquid polymer in the secondary manifold.

雖然主歧管121經展示在歧管中具有90°角，但主歧管121可為連續聚合反應器120之直管、曲管或彎管或可與連續聚合反應器120成任何合適角度。 While the main manifold 121 having a 90 ° angle through the display in the manifold, but the primary manifold 121 may be a continuous polymerization reactor of 120 straight pipe, bent pipe or elbow or a continuous polymerization reactor 120 and in any suitable angle.

主歧管及次歧管可具有圓形、橢圓形、矩形或任何其他合適截面，視各設施及方法之要求而定。在一個實施例中，主歧管可為圓柱形管。主歧管121之內徑可在25毫米(mm)與650mm之間、例如在50mm與300mm之間或在50mm與200mm之間變化。次歧管125與135之內徑可在25mm與300mm之間、例如在50mm與250mm之間或在50mm與150mm之間變化。對於主歧管或次歧管，「內徑」意指主歧管 或次歧管之截面的最長內徑，不考慮歧管之形狀。主歧管121可包含限制鐵溶解於聚合物中之耐腐蝕材料。實例包括奧氏體不鏽鋼(austenitic stainless steel)，諸如304、304L、316及316L。次歧管125及135可包含與主歧管之使用材料類似的材料。雖然次歧管125及135經展示與主歧管121成90°角，但其可為彎曲、成曲線的或可與主歧管121成任何合適角度。另外，雖然次歧管125及135經展示平行且來自主歧管121之同一側，但其可處於主歧管121之相對側或以其他方式排列。 The primary and secondary manifolds can have a circular, elliptical, rectangular or any other suitable cross-section depending on the requirements of each facility and method. In one embodiment, the primary manifold can be a cylindrical tube. The inner diameter of the main manifold 121 can vary between 25 millimeters (mm) and 650 mm, such as between 50 mm and 300 mm or between 50 mm and 200 mm. The inner diameter of the secondary manifolds 125 and 135 can vary between 25 mm and 300 mm, such as between 50 mm and 250 mm or between 50 mm and 150 mm. For the primary or secondary manifold, "inner diameter" means the longest inner diameter of the section of the primary or secondary manifold, regardless of the shape of the manifold. The primary manifold 121 can include a corrosion resistant material that limits the dissolution of iron into the polymer. Examples include austenitic stainless steels such as 304, 304L, 316 and 316L. Secondary manifolds 125 and 135 may comprise materials similar to those used for the primary manifold. While the secondary manifolds 125 and 135 are shown at an angle of 90 to the primary manifold 121 , they may be curved, curved, or may be at any suitable angle to the primary manifold 121 . Further, although the secondary manifold 125 and the display 135 via parallel and from the same side of the main manifold 121, but may be at opposite sides of the main manifold 121, or arranged in other ways.

各次歧管及添加劑注射管線可視情況安裝有一或多個靜態混合器(未圖示)以保證均勻混合。例示性靜態混合器進一步描述於Perry,Robert H.，及Don W.Green.Perry's Chemical Engineers' Handbook.第7版New York：McGraw-Hill,1997：18-25至18-34，在此以引用的方式併入。 Each manifold and additive injection line may optionally be fitted with one or more static mixers (not shown) to ensure uniform mixing. Exemplary static mixers are further described in Perry, Robert H., and Don W. Green. Perry's Chemical Engineers' Handbook. 7th Edition New York: McGraw-Hill, 1997: 18-25 to 18-34, hereby incorporated by reference. The way to merge.

添加劑注射儲槽可用於儲存呈純液體、熔融之純固體、液體母體混合物或固體母體混合物形式之添加劑供應物。視需要，各添加劑儲槽可包括合適設備用於維持添加劑供應容器在所需溫度下。在一些實施例中，添加劑儲存在實質上與液體聚合物在進入次歧管時之溫度相同的高溫下。舉例而言，若液體聚合物116在進入次歧管125時在300℃之溫度下，添加劑儲槽127可使用加熱裝置維持在約300℃之溫度下。添加劑儲槽可能夠使用具有熱傳遞管道之夾套、電伴熱、布加熱、夾套裝置、帶式加熱器或電伴熱維持及調節溫度。若使用熱傳遞管道，可使用合適熱傳遞流體，諸如聯苯與二苯醚之混合物(由Dow Chemical Company以商品名DOWTHERM® A銷售)。此等裝置亦可用於夾套及/或加熱主歧管及次歧管以及主歧管閥及添加劑注射閥。 The additive injection reservoir can be used to store an additive supply in the form of a neat liquid, a molten pure solid, a liquid parent mixture or a solid parent mixture. Each additive reservoir may include suitable equipment for maintaining the additive supply container at the desired temperature, as desired. In some embodiments, the additive is stored at a substantially elevated temperature that is substantially the same as the temperature of the liquid polymer as it enters the secondary manifold. For example, if the liquid polymer 116 enters the secondary manifold 125 at a temperature of 300 ° C, the additive reservoir 127 can be maintained at a temperature of about 300 ° C using a heating device. The additive reservoir can be maintained and conditioned using a jacket with a heat transfer conduit, electric heat tracing, cloth heating, jacketing, band heater or electric heat tracing. If a heat transfer conduit is used, a suitable heat transfer fluid such as a mixture of biphenyl and diphenyl ether (sold by the Dow Chemical Company under the trade name DOWTHERM® A) can be used. These devices can also be used to jacket and/or heat the primary and secondary manifolds as well as the primary manifold valves and additive injection valves.

在其他實施例中，添加劑注射管線中添加劑之溫度可介於40℃與300℃之範圍內。添加劑之溫度可基於添加至液體聚合物之添加劑 之量加以選擇。舉例而言，若成品聚合物產物包含0.1重量%添加劑，添加劑溫度對於液體聚合物之影響最小且添加劑可在不同溫度(例如低於次歧管中液體聚合物之溫度)下注射至次歧管。 In other embodiments, the temperature of the additive in the additive injection line can range from 40 °C to 300 °C. The temperature of the additive can be based on an additive added to the liquid polymer The amount is chosen. For example, if the finished polymer product contains 0.1% by weight of additive, the additive temperature has minimal effect on the liquid polymer and the additive can be injected into the secondary manifold at different temperatures (eg, below the temperature of the liquid polymer in the secondary manifold) .

添加劑注射管線128及138經加壓以提供添加劑，亦即在比液體聚合物131及141高的壓力下。此有助於改良添加劑與液體聚合物混合及防止添加劑回流至添加劑儲存器。當開始使用聚合物添加劑裝置102時，使添加劑注射管線恢復至目標壓力，隨後打開添加劑注射閥。接著，打開主歧管閥，使液體聚合物流經次歧管。接著打開添加劑注射閥且添加劑經由該閥泵送至次歧管。次歧管中液體聚合物之壓力可介於10MPa與31MPa之範圍內。在一些實施例中，添加劑注射管線壓力可比次歧管中液體聚合物壓力大至少2至10%。 Additive injection lines 128 and 138 are pressurized to provide an additive, i.e., at a higher pressure than liquid polymers 131 and 141 . This helps to improve the mixing of the additive with the liquid polymer and to prevent the additive from flowing back to the additive reservoir. When the polymer additive device 102 is initially used, the additive injection line is returned to the target pressure, and then the additive injection valve is opened. Next, the main manifold valve is opened to allow the liquid polymer to flow through the secondary manifold. The additive injection valve is then opened and the additive is pumped through the valve to the secondary manifold. The pressure of the liquid polymer in the secondary manifold can be in the range of 10 MPa and 31 MPa. In some embodiments, the additive injection line pressure can be at least 2 to 10% greater than the liquid polymer pressure in the secondary manifold.

在一些實施例中，如圖3及4中所示，聚合物添加劑裝置102包含三個閥122、123及124，當打開時，提供主歧管121與次歧管125、135及145之間的流體連通。應瞭解，聚合物添加劑裝置102可包含三個以上閥及添加劑注射裝置，例如四個以上、五個以上或六個以上，視需要由該裝置產生之聚合物產物的數目而定。在一些實施例中，聚合物添加劑裝置102包含三至十個添加劑注射裝置。次歧管145包含次歧管泵146、添加劑注射儲槽147、添加劑注射管線148、添加劑注射泵149、添加劑注射閥150、聚合物凝固器153及成品聚合物產物164。 In some embodiments, as shown in FIGS. 3 and 4, the device 102 comprises a polymer additive three valves 122, 123 and 124, when open, provides primary manifold 121 and the secondary manifold 125, between 135 and 145 Fluid communication. It will be appreciated that the polymeric additive device 102 can include more than three valves and additive injection devices, such as four or more, five or more, or more than six, depending on the number of polymer products produced by the device, as desired. In some embodiments, the polymer additive device 102 includes three to ten additive injection devices. The secondary manifold 145 includes a secondary manifold pump 146 , an additive injection reservoir 147 , an additive injection line 148 , an additive injection pump 149 , an additive injection valve 150 , a polymer coagulator 153, and a finished polymer product 164 .

在圖2中，主歧管閥122及123經展示處於打開位置，例如完全打開或部分打開以允許流經該閥，且添加劑注射閥130及140經展示處於打開位置。因此，液體聚合物116流經主歧管121至次歧管125及135及至聚合物凝固器118。另外，因為添加劑注射閥130及140經展示處於打開位置，且所以添加劑自添加劑儲槽127及137流入次歧管125及135。 In FIG. 2 , main manifold valves 122 and 123 are shown in an open position, such as fully open or partially open to allow flow through the valve, and additive injection valves 130 and 140 are shown in an open position. Thus, liquid polymer 116 flows through primary manifold 121 to secondary manifolds 125 and 135 and to polymer coagulator 118 . Additionally, because additive injection valves 130 and 140 are shown in an open position, and therefore additives flow from additive reservoirs 127 and 137 into secondary manifolds 125 and 135 .

在圖3中，主歧管閥122、123及124經展示處於打開位置且添加 劑注射閥130、140及150經展示處於打開位置。因此，液體聚合物116流經主歧管121。至少一部分液體聚合物116流入次歧管125、135及145。至少一部分液體聚合物116流入聚合物凝固器118。另外，添加劑注射閥130、140及150經展示處於打開位置，且因此添加劑自添加劑儲槽127、137及147流入次歧管。具有添加劑之液體聚合物132、142及152接著經由次歧管125、135及145進料至聚合物凝固器133、143及153。 In FIG. 3 , main manifold valves 122 , 123, and 124 are shown in an open position and additive injection valves 130 , 140, and 150 are shown in an open position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 , 135, and 145 . At least a portion of the liquid polymer 116 flows into the polymer coagulator 118 . Additionally, additive injection valves 130 , 140, and 150 are shown in an open position, and thus additives flow from additive reservoirs 127 , 137, and 147 into the secondary manifold. Liquid polymers 132 , 142 and 152 with additives are then fed to polymer coagulators 133 , 143 and 153 via sub-manifolds 125 , 135 and 145 .

在圖4中，主歧管閥122及123經展示處於打開位置且添加劑注射閥130及140經展示處於打開位置。主歧管閥124及添加劑注射閥150經展示處於閉合位置。因此，液體聚合物116流經主歧管121。至少一部分液體聚合物116流入次歧管125及135，但不流入次歧管145。另外，添加劑注射閥130及140經展示處於打開位置，且因此添加劑自添加劑儲槽127及137流入次歧管125及135。具有添加劑之液體聚合物132及142接著經由次歧管125及135進料至聚合物凝固器133及143。 In FIG. 4 , main manifold valves 122 and 123 are shown in an open position and additive injection valves 130 and 140 are shown in an open position. Main manifold valve 124 and additive injection valve 150 are shown in a closed position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 and 135 but does not flow into the secondary manifold 145 . Additionally, additive injection valves 130 and 140 are shown in an open position, and thus additives flow from additive reservoirs 127 and 137 into secondary manifolds 125 and 135 . Liquid polymers 132 and 142 with additives are then fed to polymer coagulators 133 and 143 via sub-manifolds 125 and 135 .

在圖5中，次歧管145含有第二添加劑儲槽157、第二添加劑注射管線158、第二添加劑注射泵159及第二添加劑注射閥160。添加劑儲槽157中之添加劑不同於添加劑儲槽147中之添加劑。雖然在次歧管145中展示兩個不同添加劑儲槽，但應瞭解任何及/或全部次歧管可具有一個以上的添加劑注射管線以及操作添加劑注射管線所需之添加劑泵、閥及其他元件。主歧管閥122、123及124經展示處於打開位置，且添加劑注射閥130、140及150經展示處於打開位置。因此，液體聚合物116流經主歧管121。至少一部分液體聚合物116流入次歧管125、135及145。至少一部分液體聚合物116流入聚合物凝固器118。另外，添加劑注射閥130、140、150及160經展示處於打開位置，且因此添加劑自添加劑儲槽127、137、147及157流入次歧管。具有添加劑之液體聚合物132、142及152接著經由次歧管125、135及145進料至聚合物凝 固器133、143及153。 In FIG. 5 , the secondary manifold 145 includes a second additive reservoir 157 , a second additive injection line 158 , a second additive injection pump 159, and a second additive injection valve 160 . The additive in the additive reservoir 157 is different from the additive in the additive reservoir 147 . While two different additive reservoirs are shown in the secondary manifold 145 , it should be understood that any and/or all of the secondary manifolds may have more than one additive injection line and additive pumps, valves, and other components required to operate the additive injection line. Main manifold valves 122 , 123, and 124 are shown in an open position, and additive injection valves 130 , 140, and 150 are shown in an open position. Therefore, the liquid polymer 116 flows through the main manifold 121 . At least a portion of the liquid polymer 116 flows into the secondary manifolds 125 , 135, and 145 . At least a portion of the liquid polymer 116 flows into the polymer coagulator 118 . Additionally, additive injection valves 130 , 140 , 150, and 160 are shown in an open position, and thus additives flow from additive reservoirs 127 , 137 , 147, and 157 into the secondary manifold. Liquid polymers 132 , 142 and 152 with additives are then fed to polymer coagulators 133 , 143 and 153 via sub-manifolds 125 , 135 and 145 .

主歧管泵115及次歧管泵126、136及146可為選自由葉輪泵、活塞泵、撓性構件泵、多葉泵、齒輪泵、離心泵、環形活塞泵及螺旋泵組成之群之泵。 The main manifold pump 115 and the sub-manifold pumps 126 , 136 and 146 may be selected from the group consisting of an impeller pump, a piston pump, a flexible member pump, a multi-leaf pump, a gear pump, a centrifugal pump, a ring piston pump, and a screw pump. Pump.

主歧管閥122、123及124及添加劑注射閥130、140、150及160可包括抗堵塞之注射閥，諸如圖6A及6B中示意性說明之交叉桿注射閥，圖7、8、9及10中示意性說明之I型及/或II型聚合物閥，及圖11及12中示意性說明之分流閥。雖然各閥之功能經描述為如同其為添加劑注射閥，但各閥亦可充當主歧管閥，當打開時允許液體聚合物流入次歧管或當關閉時阻斷流動。 Main manifold valves 122 , 123, and 124 and additive injection valves 130 , 140 , 150, and 160 may include anti-clogging injection valves, such as the cross-bar injection valves illustrated schematically in Figures 6A and 6B , Figures 7 , 8 , 9 and The Type I and / or Type II polymer valve schematically illustrated in 10 , and the diverter valve illustrated schematically in Figures 11 and 12 . While the function of each valve is described as being an additive injection valve, each valve can also act as a primary manifold valve that allows liquid polymer to flow into the secondary manifold when open or to block flow when closed.

如圖6A及6B中所示，交叉桿注射閥包含閥體213、手柄201、填料外殼207、注射口205(一部分液體聚合物經由其流經次歧管)及包括螺紋桿209之管總成210。管總成210包括供應管線204，添加劑經由供應管線204輸送至閥。管總成210在位置208處***閥底部。管總成210包括僅允許在一個方向上流動的止回閥203。管連接器202連接兩個管。填料207藉由螺母及螺栓總成211、212固定位以防止洩漏。 As and shown in FIG. 6A 6B, the cross bar injection valve comprises a valve body 213, a handle 201, packing casing 207, an injection port 205 (a portion of the liquid polymer through which flows through the secondary manifold) and comprises a threaded rod pipe assembly 209 of 210 . Tube assembly 210 includes a supply line 204, fed to the additive supply line 204 via a valve. Tube assembly 210 is inserted into the bottom of the valve at position 208 . The tube assembly 210 includes a check valve 203 that only allows flow in one direction. The tube connector 202 connects the two tubes. The packing 207 is held in place by the nut and bolt assemblies 211 , 212 to prevent leakage.

如圖7中所示，I型聚合物閥(亦稱為二通閥)允許液體聚合物於空隙區219流入閥且隨後允許打開兩口中之一者。I型聚合物閥具有入口214及出口218及塞217。入口214在打開時允許添加劑流入次歧管。出口218允許添加劑加液體聚合物流經次歧管。塞217旋轉以保持一個口始終打開(部分或完全)且另一口關閉。在圖7中，口218打開且口214關閉。無添加劑可經由口214注射且液體聚合物流經該閥。如所示，該閥為帶夾套的。熱量經由口216傳遞至該閥。排氣孔215可連接至真空以移除不可凝結的氣體。排水管220移除冷凝物及任何其他液體。I型聚合物閥亦可用作主歧管閥以允許液體聚合物自主歧管流動至次歧管。 As shown therein, the polymer valve 7 Type I (also referred to as a two-way valve) to allow liquid polymer to flow into the void region 219 is then allowed to open the valve and the mouth of one of those two. The Type I polymer valve has an inlet 214 and an outlet 218 and a plug 217 . The inlet 214 allows the additive to flow into the secondary manifold when opened. The outlet 218 allows the additive plus liquid polymer to flow through the secondary manifold. The plug 217 is rotated to keep one opening open (partial or complete) and the other closed. In Figure 7 , port 218 is open and port 214 is closed. No additives can be injected via port 214 and the liquid polymer flows through the valve. As shown, the valve is jacketed. Heat is transferred to the valve via port 216 . The vent 215 can be connected to a vacuum to remove non-condensable gases. Drain 220 removes condensate and any other liquid. The Type I polymer valve can also be used as a primary manifold valve to allow the liquid polymer autonomous manifold to flow to the secondary manifold.

如圖8、9及10中所示，II型聚合物閥(亦稱為三通閥)允許液體聚合物在空隙區219流入該閥且隨後允許i)口214及218打開(圖8)、ii)口218打開及口214關閉(圖9)、或iii)口214及218關閉(圖10)。II型聚合物閥可用作主歧管閥以允許液體聚合物自主歧管流動至次歧管。 As FIG. 8, 9 and shown, Type II polymer valve 10 (also referred to as a three-way valve) to allow liquid polymer to flow into the valve gap region 219 and then allowed to i) ports 214 and 218 open (FIG. 8), Ii) Port 218 is open and port 214 is closed ( Fig. 9 ), or iii) ports 214 and 218 are closed ( Fig. 10 ). Type II polymer valves can be used as primary manifold valves to allow liquid polymer autonomous manifolds to flow to the secondary manifold.

分流閥展示於圖11及12中。如圖11中所示，分流閥允許注射位置(液體聚合物在此處流經空隙區219)垂直於添加劑注射平面。添加劑可流經入口214。如圖12中所示，入口214可藉由機械方式分流至分流管線221。分流閥可用作主歧管閥或添加劑注射閥。 The diverter valve is shown in Figures 11 and 12 . As shown in FIG. 11, the shunt valve allows the injection position (where the liquid polymer flows through the gap region 219) plane perpendicular to the additive injection. Additives can flow through inlet 214 . As shown in Figure 12, inlet 214 may be diverted to the bypass line 221 by mechanical means. The diverter valve can be used as a primary manifold valve or as an additive injection valve.

本文所述之每一閥及其全部部件可為抗堵塞的且包含不鏽鋼。 Each of the valves described herein and all of its components may be clogging resistant and comprise stainless steel.

聚合物凝固器133、143、153及118可包含濕式旋轉器、乾式旋轉器、熔體旋轉器、擠壓旋轉器、直接旋轉器、凝膠旋轉器、電旋轉器或粒化機。聚合物凝固器133、143、153及118之每一者可為不同聚合物凝固器，視最終所需聚合物產物而定。各聚合物可為纖維級聚合物及/或可隨後分成實質上固體碎片，例如薄片或丸粒。 Polymer coagulators 133 , 143 , 153, and 118 can include wet rotators, dry rotators, melt rotators, extrusion rotators, direct rotators, gel rotators, electric rotators, or granulators. Each of the polymer coagulators 133 , 143 , 153, and 118 can be a different polymer coagulator depending on the final desired polymer product. Each polymer can be a fiber grade polymer and/or can be subsequently separated into substantially solid pieces, such as flakes or pellets.

先前技術聚合方法之改裝Modification of prior art polymerization methods

本發明係關於用於再組態現有聚合方法以使用本文所述之聚合物添加劑裝置的改裝方法。先前技術聚合方法3展示於圖13中。此方法經由入口8將預聚物或聚合物鹽引入聚合反應器20。液體聚合物16自聚合反應器20抽取至主歧管21，主歧管21充當用於引導液體聚合物自聚合反應器20至聚合物凝固器18之管道。在聚合方法3中，主歧管21為該方法中存在之唯一歧管。主歧管21具有兩個開口：一個開口用於連接至聚合反應器20之排出管線且一個開口用於連接至聚合物凝固器18。視情況，聚合方法3可包含泵15。在預聚物或聚合物鹽進入入口8之前，先前技術聚合方法3可包含額外步驟及設備以製備用於聚合之預聚物或聚合物鹽。此等步驟可包括鹽形成反應器、蒸發器、預聚合反應器、預聚物/氣體分離、閃蒸器及其類似物。如圖13中所示， 聚合方法3在液體聚合物離開聚合反應器20後不向液體聚合物添加添加劑。液體聚合物16流經主歧管21至聚合物凝固器18且回收成品聚合物產物19。 This invention relates to a retrofit process for reconfiguring existing polymerization processes to use the polymer additive devices described herein. The prior art polymerization method 3 is shown in FIG . This process introduces a prepolymer or polymer salt into polymerization reactor 20 via inlet 8 . 16 the liquid polymer from the polymerization reactor 20 is drawn into the main manifold 21, the main manifold 21 acts as a guide for the liquid polymer from the polymerization reactor 20 through conduit 18 of coagulated polymer. In polymerization method 3 , main manifold 21 is the only manifold present in the process. The main manifold 21 has two openings: one for connection to the discharge line of the polymerization reactor 20 and one for connection to the polymer coagulator 18 . The polymerization method 3 may include a pump 15 as appropriate . Prior art polymerization process 3 may include additional steps and equipment to prepare a prepolymer or polymer salt for polymerization prior to entering the prepolymer or polymer salt into inlet 8 . These steps may include a salt forming reactor, an evaporator, a prepolymerization reactor, a prepolymer/gas separation, a flasher, and the like. As illustrated in FIG. 13, the liquid polymer in the polymerization process 3 leaving the polymerization reactor to the liquid additive is not added after the polymer 20. The liquid polymer 16 flows through the main manifold 21 to the polymer coagulator 18 and recovers the finished polymer product 19 .

先前技術聚合方法3可藉由修改主歧管21而用聚合物添加劑裝置改裝。改裝方法可包含用改裝歧管置換開口上游用於連接至聚合物凝固器18之一部分主歧管121。改裝歧管可藉由在所需位置71及72切割主歧管21且將改裝歧管焊接至主歧管21來添加。應瞭解，此等位置可基於現有主歧管21位置、長度及方法組態加以選擇。改裝歧管包含複數個歧管閥，該複數個歧管閥包括第一歧管閥及第二歧管閥。在一些實施例中，改裝歧管可包含二至十個歧管閥。改裝歧管可包含至少一個連接管用於將改裝歧管固定至主歧管21。連接管可為壓合接頭、螺紋連接管、鑽孔連接器、魯爾整體鎖環(luer integral lock ring)等。密封墊可安置於至少一個連接管與主歧管21之間以在主歧管21與改裝歧管之間形成實質上密封連接。另外，改裝歧管可使用螺母、螺栓、螺桿或其他連接構件固定至主歧管。 The prior art polymerization process 3 can be retrofitted with a polymer additive device by modifying the main manifold 21 . The retrofitting method can include replacing a portion of the primary manifold 121 upstream of the opening for coupling to the polymer coagulator 18 with a modified manifold. The retrofit manifold can be added by cutting the main manifold 21 at desired locations 71 and 72 and welding the retrofit manifold to the main manifold 21 . It should be appreciated that such locations may be selected based on the existing primary manifold 21 position, length, and method configuration. The retrofit manifold includes a plurality of manifold valves including a first manifold valve and a second manifold valve. In some embodiments, the retrofit manifold can include from two to ten manifold valves. The retrofit manifold can include at least one connecting tube for securing the retrofit manifold to the main manifold 21 . The connecting pipe may be a press fitting, a threaded connecting pipe, a drilled connector, a luer integral lock ring, or the like. A gasket may be disposed between the at least one connecting tube and the main manifold 21 to form a substantially sealed connection between the main manifold 21 and the retrofit manifold. Alternatively, the retrofit manifold can be secured to the main manifold using nuts, bolts, screws or other connecting members.

改裝歧管可具有與主歧管21實質上類似或相等的形狀及內徑。改裝歧管、歧管閥及添加劑注射閥之實質上所有部分可包含不鏽鋼，例如奧氏體不鏽鋼，諸如304、304L、316及316L。歧管閥可為本文所述之主歧管閥，包括交叉桿注射閥、二通閥、三通閥、分流閥或其組合。改裝歧管內液體聚合物之壓力及溫度實質上與主歧管21內之溫度及壓力相同，例如溫度介於65℃與300℃之間且壓力介於10MPa與31MPa之間。 The retrofit manifold can have a shape and an inner diameter that are substantially similar or equal to the main manifold 21 . Essential portions of the modified manifold, manifold valve, and additive injection valve may comprise stainless steel, such as austenitic stainless steels such as 304, 304L, 316, and 316L. The manifold valve can be a primary manifold valve as described herein, including a crossbar injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. The pressure and temperature of the liquid polymer in the modified manifold are substantially the same as the temperature and pressure in the main manifold 21 , for example, the temperature is between 65 ° C and 300 ° C and the pressure is between 10 MPa and 31 MPa.

改裝方法可另外包含將第一添加劑注射裝置連接至第一歧管閥，將第一部分液體聚合物自改裝閥引導至第一添加劑注射裝置，及將第一添加劑注射至第一部分液體聚合物以產生包含添加劑之第一成品聚合物產物。如圖2、3、4及5中所示，第一添加劑注射裝置包含次 歧管125、次歧管泵126、添加劑注射儲槽127、添加劑注射管線128、添加劑注射泵129、添加劑注射閥130及在添加劑注射管線128下游之與次歧管125流體連通的聚合物凝固器133。添加劑注射儲槽127中之添加劑可選自由消泡劑、潤滑助劑、成核劑、阻燃劑、塑化劑、抗衝擊改質劑、玻璃纖維、基於銅之穩定劑、潤滑劑、去光劑、共聚合物、催化劑、改變末端平衡之化合物及其混合物組成之群。額外添加劑可包括顏料及染料。添加劑注射管線128可另外包含靜態混合器(未圖示)。成品聚合物產物161及119接著自聚合物凝固器133及118中移出。各成品聚合物產物161及119可為不同的成品聚合物產物。 The retrofitting method can additionally include connecting the first additive injection device to the first manifold valve, directing the first portion of the liquid polymer from the retrofit valve to the first additive injection device, and injecting the first additive to the first portion of the liquid polymer to produce A first finished polymer product comprising an additive. As shown in FIG. 3, 4 and 5, the additive injection means comprises a first secondary manifold 125, manifold pump 126 times, the additive injection tank 127, line 128 inject the additive, the additive injection pump 129, the additive injection valve 130 And a polymer coagulator 133 in fluid communication with the secondary manifold 125 downstream of the additive injection line 128 . The additive in the additive injection storage tank 127 can be selected from a defoaming agent, a lubricating agent, a nucleating agent, a flame retardant, a plasticizer, an impact modifier, a glass fiber, a copper-based stabilizer, a lubricant, and A group of light agents, copolymers, catalysts, compounds that alter the terminal balance, and mixtures thereof. Additional additives may include pigments and dyes. The additive injection line 128 can additionally include a static mixer (not shown). The finished polymer products 161 and 119 are then removed from the polymer coagulators 133 and 118 . Each finished polymer product 161 and 119 can be a different finished polymer product.

改裝方法可另外包含將第二添加劑注射裝置連接至第二歧管閥，將第二部分液體聚合物自改裝歧管引導至第二添加劑注射裝置，及將第二添加劑注射至第二部分液體聚合物以產生包含第二添加劑之第二成品聚合物產物。如圖2、3、4及5中所示，第二添加劑注射裝置包含次歧管135、次歧管泵136、添加劑注射儲槽137、添加劑注射管線138、添加劑注射泵139、添加劑注射閥140及在添加劑注射管線128下游之與次歧管135流體連通的聚合物凝固器143。添加劑注射儲槽137中之添加劑可選自由熱穩定劑、消泡劑、玻璃纖維、潤滑劑、共聚合物、催化劑、阻燃劑、塑化劑、抗衝擊改質劑、填充劑、改變末端平衡之化合物及其混合物組成之群。在一個實施例中，第一添加劑注射裝置中之添加劑不同於第二添加劑注射裝置中之添加劑。添加劑注射管線138可另外包含靜態混合器(未圖示)。成品聚合物產物161、162及119接著自聚合物凝固器133、143及118中移出。各成品聚合物產物161、162及119可為不同的成品聚合物產物。 The retrofitting method can additionally include connecting the second additive injection device to the second manifold valve, directing the second portion of the liquid polymer from the retrofit manifold to the second additive injection device, and injecting the second additive to the second portion of the liquid polymerization To produce a second finished polymer product comprising a second additive. As shown in FIG. 3, 4 and 5, a second means comprising a secondary additive injection manifold 135, manifold pump 136 times, the additive injection tank 137, line 138 inject the additive, the additive injection pump 139, the additive injection valve 140 And a polymer coagulator 143 in fluid communication with the secondary manifold 135 downstream of the additive injection line 128 . The additive in the additive injection reservoir 137 may be selected from the group consisting of a heat stabilizer, a defoaming agent, a glass fiber, a lubricant, a copolymer, a catalyst, a flame retardant, a plasticizer, an impact modifier, a filler, and a terminal change. A group of balanced compounds and mixtures thereof. In one embodiment, the additive in the first additive injection device is different than the additive in the second additive injection device. The additive injection line 138 can additionally include a static mixer (not shown). The finished polymer products 161 , 162 and 119 are then removed from the polymer coagulators 133 , 143 and 118 . Each finished polymer product 161 , 162, and 119 can be a different finished polymer product.

改裝方法可另外包含添加或修改圖13及14之泵15。若泵15不存在，其可添加。若泵之材料不足以與所需液體聚合物一起使用，或若泵並非所需泵之類型，泵15可經如本文所述之泵115置換。一般，泵 115可為葉輪泵、活塞泵、撓性構件泵、多葉泵、齒輪泵、離心泵、環形活塞泵或螺旋泵。 The retrofitting method may additionally include adding or modifying the pump 15 of Figures 13 and 14 . If pump 15 is not present, it can be added. If the pump material is not sufficient for use with the desired liquid polymer, or if the pump is not of the type required, the pump 15 can be replaced by a pump 115 as described herein. In general, the pump 115 can be a vane pump, a piston pump, a flexible member pump, a multi-leaf pump, a gear pump, a centrifugal pump, a ring piston pump, or a screw pump.

如圖14中所示，先前技術聚合方法4與先前技術聚合方法3類似，除了先前技術聚合方法4包含次歧管25用於將添加劑儲槽27之添加劑經由次歧管25注射至主歧管21中之液體聚合物中。主歧管21視情況包含可打開或關閉以控制添加劑自次歧管25流入主歧管21之閥22。次歧管25視情況包含泵26。 As shown in FIG. 14, the prior art polymerization process 4 and 3 prior art polymerization process is similar except that the polymerization method of the prior art comprises four sub manifold 25 Additives for the reservoir 27 via the secondary manifold 25 is injected into the main manifold In the liquid polymer of 21 . The main manifold 21 optionally includes a valve 22 that can be opened or closed to control the flow of additive from the secondary manifold 25 into the main manifold 21 . Secondary manifold 25 includes pump 26 as appropriate .

先前技術聚合方法4可藉由修改主歧管21及次歧管25而用聚合物添加劑裝置改裝。改裝方法可包含將聚合物凝固器連接至次歧管25，及將至少一個添加劑注射管線連接至聚合物凝固器(現稱為主要聚合物凝固器)上游之次歧管25。改裝方法可另外包含將第一部分液體聚合物自主歧管引導至次歧管25，及將第一添加劑經由至少一個添加劑注射管線注射至第一部分液體聚合物。包含添加劑之液體聚合物可隨後引導至添加劑聚合物凝固器以產生包含第一添加劑之第一成品聚合物。添加劑聚合物凝固器可直接連接至次歧管。與次歧管接觸之添加劑聚合物凝固器因此未連接至主歧管21。在改裝方法中，一旦部分液體聚合物流入次歧管，該方法已經改裝且第一添加劑不再注射至主歧管21，而實際上流入次歧管25及添加劑聚合物凝固器。應瞭解，雖然先前技術聚合方法4僅展示一個次歧管125，但若存在額外次歧管，每一者可如本文所述加以改裝。 The prior art polymerization process 4 can be retrofitted with a polymer additive device by modifying the primary manifold 21 and the secondary manifold 25 . The retrofitting method can include connecting the polymer coagulator to the secondary manifold 25 and connecting at least one additive injection line to the secondary manifold 25 upstream of the polymer coagulator (now referred to as the primary polymer coagulator). The retrofitting method can additionally include directing the first portion of the liquid polymer autonomous manifold to the secondary manifold 25 and injecting the first additive to the first portion of the liquid polymer via the at least one additive injection line. The liquid polymer comprising the additive can then be directed to the additive polymer coagulator to produce a first finished polymer comprising the first additive. The additive polymer coagulator can be directly connected to the secondary manifold. The additive polymer coagulator in contact with the secondary manifold is therefore not connected to the primary manifold 21 . In the retrofitting process, once a portion of the liquid polymer has flowed into the secondary manifold, the process has been modified and the first additive is no longer injected into the primary manifold 21 , but actually flows into the secondary manifold 25 and the additive polymer coagulator. It should be appreciated that while prior art polymerization process 4 only shows one secondary manifold 125 , if additional secondary manifolds are present, each can be retrofitted as described herein.

若先前技術聚合方法4中之主歧管21不包含歧管閥或若該閥不足以用於改裝聚合方法，可添加或置換該閥。合適閥及閥材料描述於本文。另外，添加劑注射管線之合適材料描述於本文。若先前技術聚合方法4中之次歧管25不包含泵26，可添加泵。 If the primary manifold 21 in prior art polymerization process 4 does not contain a manifold valve or if the valve is not sufficient for retrofitting the polymerization process, the valve may be added or replaced. Suitable valve and valve materials are described herein. Additionally, suitable materials for the additive injection line are described herein. If the secondary manifold 25 in prior art polymerization method 4 does not include pump 26 , a pump can be added.

如本文所述添加添加劑注射管線、添加劑注射儲槽、閥、泵及靜態混合器。另外，一個以上添加劑注射管線可添加至次歧管125， 例如二至十個添加劑注射管線及相應添加劑儲槽、閥、泵及靜態混合器。 Additive injection lines, additive injection reservoirs, valves, pumps, and static mixers are added as described herein. Additionally, more than one additive injection line can be added to the secondary manifold 125 , such as two to ten additive injection lines and corresponding additive reservoirs, valves, pumps, and static mixers.

先前技術聚合方法4之改裝可另外包含用一個添加劑注射裝置改裝主歧管21以產生如圖2中所示之裝置，或用兩個添加劑注射裝置改裝主歧管21以產生如圖3及4中所示之裝置。如關於先前技術聚合方法3之改裝所述，用於添加添加劑注射裝置之改裝方法包含用具有改裝歧管閥之改裝歧管置換聚合物凝固器上游之一部分主歧管，將添加劑注射裝置連接至改裝歧管閥，及將一部分液體聚合物自主歧管引導至添加劑注射裝置以產生成品聚合物產物。 Prior art polymerization method may further comprise converting four of additive injection device with a modified primary manifold 21 to produce the device shown in Figure 2, with two or additive injection means adapted to generate a primary manifold 21 as shown in Figure 3 and 4 The device shown. As described in relation to the modification of prior art polymerization method 3 , a retrofit method for adding an additive injection device includes replacing one of the main manifolds upstream of the polymer coagulator with a modified manifold having a modified manifold valve, connecting the additive injection device to The manifold valve is modified and a portion of the liquid polymer autonomous manifold is directed to the additive injection device to produce the finished polymer product.

實例Instance 實例1Example 1

產生包含尼龍6,6之連續聚合產物。連續聚合產物在介於265℃與300℃之間的溫度下及在介於10MPa與31MPa之間的壓力下流經主歧管。主歧管經由兩個主歧管閥與兩個次歧管流體連通。打開每一主歧管閥以使得一部分液體聚合物在介於265℃與300℃之間的溫度下及在介於10MPa與31MPa之間的壓力下流經每一次歧管。每一次歧管與不同添加劑注射管線流體連通。每一添加劑注射管線與添加劑來源流體連通。為製備包含添加劑之尼龍6,6聚合物，將添加劑自添加劑儲槽引入至添加劑注射管線。添加劑注射管線中添加劑之壓力積聚達到至少液體聚合物流經次歧管之壓力。添加劑注射管線中添加劑之溫度可介於40℃與300℃之間。接著打開添加劑注射閥。設定目標成品聚合物產物且為達成此目標，允許介於0.1重量%至20重量%之範圍內的值的添加劑流經添加劑注射閥以與次歧管中之液體聚合物組合。 A continuous polymerization product comprising nylon 6,6 is produced. The continuous polymerization product flows through the main manifold at a temperature between 265 ° C and 300 ° C and at a pressure between 10 MPa and 31 MPa. The primary manifold is in fluid communication with the two secondary manifolds via two primary manifold valves. Each of the main manifold valves is opened such that a portion of the liquid polymer flows through each of the manifolds at a temperature between 265 ° C and 300 ° C and at a pressure between 10 MPa and 31 MPa. Each manifold is in fluid communication with a different additive injection line. Each additive injection line is in fluid communication with an additive source. To prepare the nylon 6,6 polymer containing the additive, the additive is introduced from the additive reservoir to the additive injection line. The pressure build-up of the additive in the additive injection line reaches at least the pressure at which the liquid polymer flows through the secondary manifold. The temperature of the additive in the additive injection line can be between 40 ° C and 300 ° C. The additive injection valve is then opened. The target finished polymer product is set and to achieve this goal, an additive having a value in the range of 0.1% to 20% by weight is allowed to flow through the additive injection valve to combine with the liquid polymer in the secondary manifold.

接著將具有添加劑之液體聚合物進料至聚合物凝固器以使聚合物旋轉或粒化且回收成品聚合物產物。另外，將至少一部分液體聚合物傳送至與主歧管流體連通之聚合物凝固器且回收成品尼龍6,6聚合 物。因此，至少兩種不同成品尼龍6,6聚合物由此自裝置中移出。向添加劑注射管線提供添加劑來源與移出包含達到目標添加劑含量之添加劑的尼龍6,6聚合物之間的時間小於1小時。 The liquid polymer with the additive is then fed to a polymer coagulator to spin or granulate the polymer and recover the finished polymer product. Additionally, at least a portion of the liquid polymer is transferred to a polymer coagulator in fluid communication with the main manifold and the finished nylon 6,6 is recycled. Things. Thus, at least two different finished nylon 6,6 polymers are thereby removed from the apparatus. The time between the supply of the additive to the additive injection line and the removal of the nylon 6,6 polymer containing the additive to the target additive level is less than one hour.

實例2Example 2

如實例1中產生連續聚合產物且如實例1添加添加劑。主歧管與三個次歧管接觸，每一次歧管連接至不同添加劑注射管線。阻斷與主歧管接觸之凝固器，導致無來自凝固器之成品聚合物產物。包含去光劑之第一添加劑經由第一添加劑注射管線注射至第一次歧管且與液體聚合物組合以形成聚合物產物。包含玻璃纖維之第二添加劑經由第二添加劑注射管線注射至第二次歧管且與液體聚合物組合以形成聚合物產物。關閉連接第三添加劑注射管線與第三次歧管之添加劑注射閥。各產物進料經過與相應次歧管接觸之聚合物凝固器以產生成品聚合物產物。該方法因此由一種連續聚合方法產生三種聚合物產物：具有去光劑之聚合物產物A、具有玻璃纖維之聚合物產物B及無添加劑之聚合物產物C。因為不存在添加劑或液體聚合物自相應次歧管回流至主歧管，所以聚合物產物A及C無玻璃纖維且聚合物產物B無去光劑。 A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each connected to a different additive injection line. Blocking the coagulator in contact with the main manifold results in no finished polymer product from the coagulator. A first additive comprising a matting agent is injected into the first manifold via a first additive injection line and combined with the liquid polymer to form a polymer product. A second additive comprising glass fibers is injected into the second manifold via a second additive injection line and combined with the liquid polymer to form a polymer product. The additive injection valve connecting the third additive injection line and the third manifold is closed. Each product feed is passed through a polymer coagulator in contact with a corresponding secondary manifold to produce a finished polymer product. The process thus produces three polymer products from a continuous polymerization process: a polymer product A with a matting agent, a polymer product B with glass fibers, and a polymer product C without additives. Since no additive or liquid polymer is refluxed from the corresponding secondary manifold to the main manifold, polymer products A and C are free of glass fibers and polymer product B has no matting agent.

實例3Example 3

如實例1中產生連續聚合產物且如實例1添加添加劑。主歧管與三個次歧管接觸，每一次歧管連接至不同添加劑注射管線。包含20meq/kg胺末端之第一添加劑經由第一添加劑注射管線注射至第一次歧管且與液體聚合物組合以形成聚合物產物。包含40meq/kg胺末端之第二添加劑經由第二添加劑注射管線注射至第二次歧管且與液體聚合物組合以形成聚合物產物。包含60meq/kg胺末端之第三添加劑經由第三添加劑注射管線注射至第三次歧管且與液體聚合物組合以形成聚合物產物。各產物進料經過與相應次歧管接觸之聚合物凝固器以產生成品聚合物產物。該方法因此由一種連續聚合方法產生三種聚合物產 物：每一者具有不同胺末端含量且因此每一者具有不同可染性。染料及/或顏料可添加至聚合物產物下游或由最終使用者添加。 A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each connected to a different additive injection line. A first additive comprising 20 meq/kg of amine end is injected into the first manifold via a first additive injection line and combined with a liquid polymer to form a polymer product. A second additive comprising 40 meq/kg of amine end is injected via a second additive injection line to a second manifold and combined with a liquid polymer to form a polymer product. A third additive comprising 60 meq/kg amine end is injected via a third additive injection line to a third manifold and combined with the liquid polymer to form a polymer product. Each product feed is passed through a polymer coagulator in contact with a corresponding secondary manifold to produce a finished polymer product. The method thus produces three polymers produced by a continuous polymerization process Matters: Each has a different amine end content and therefore each has a different dyeability. Dyes and/or pigments may be added downstream of the polymer product or added by the end user.

實例4Example 4

如實例1中產生連續聚合產物且如實例1添加添加劑，主歧管與三個次歧管接觸，每一次歧管連接至不同添加劑注射管線。包含尼龍6之第一添加劑經由第一添加劑注射管線注射至第一次歧管且與液體聚合物組合以形成聚合物產物。包含尼龍6,12之第二添加劑經由第二添加劑注射管線注射至第二次歧管且與液體聚合物組合以形成聚合物產物。包含尼龍6,10之第三添加劑經由第三添加劑注射管線注射至第三次歧管且與液體聚合物組合以形成聚合物產物。各產物進料經過與相應次歧管接觸之聚合物凝固器以產生成品聚合物產物。該方法因此由一種連續聚合方法產生三種聚合物產物，每一者具有不同成品聚合物。 As in Example 1, a continuous polymerization product was produced and as in Example 1, an additive was added, the primary manifold was in contact with three secondary manifolds, each manifold being connected to a different additive injection line. The first additive comprising nylon 6 is injected into the first manifold via a first additive injection line and combined with the liquid polymer to form a polymer product. A second additive comprising nylon 6,12 is injected into the second manifold via a second additive injection line and combined with the liquid polymer to form a polymer product. A third additive comprising nylon 6, 10 is injected into the third manifold via a third additive injection line and combined with the liquid polymer to form a polymer product. Each product feed is passed through a polymer coagulator in contact with a corresponding secondary manifold to produce a finished polymer product. The process thus produces three polymer products from one continuous polymerization process, each having a different finished polymer.

實例5Example 5

如實例1中產生連續聚合產物且如實例1添加添加劑。主歧管與三個次歧管接觸，每一次歧管連接至不同添加劑注射管線。包含潤滑劑之第一添加劑經由第一添加劑注射管線注射至第一次歧管且與液體聚合物組合以形成聚合物產物。包含基於銅之穩定劑包之第二添加劑經由第二添加劑注射管線注射至第二次歧管且與液體聚合物組合以形成聚合物產物。包含阻燃劑之第三添加劑經由第三添加劑注射管線注射至第三次歧管且與液體聚合物組合以形成聚合物產物。各產物進料經過與相應次歧管接觸之聚合物凝固器以產生成品聚合物產物。該方法因此由一種連續聚合方法產生三種聚合物產物：包含潤滑劑之聚合物產物A、包含基於銅之穩定劑包的聚合物產物B及包含阻燃劑之聚合物產物C。 A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each connected to a different additive injection line. A first additive comprising a lubricant is injected to the first manifold via a first additive injection line and combined with the liquid polymer to form a polymer product. A second additive comprising a copper based stabilizer package is injected via a second additive injection line to a second manifold and combined with the liquid polymer to form a polymer product. A third additive comprising a flame retardant is injected to the third manifold via a third additive injection line and combined with the liquid polymer to form a polymer product. Each product feed is passed through a polymer coagulator in contact with a corresponding secondary manifold to produce a finished polymer product. The process thus produces three polymer products from a continuous polymerization process: a polymer product A comprising a lubricant, a polymer product B comprising a copper-based stabilizer package, and a polymer product C comprising a flame retardant.

實例6Example 6

如實例1中產生連續聚合產物且如實例1添加添加劑。主歧管與三個次歧管接觸，每一次歧管連接至不同添加劑注射管線。包含第一量之尼龍6之第一添加劑經由第一添加劑注射管線注射至第一次歧管且與液體聚合物組合以形成聚合物產物。包含第二量(其不同於第一量)之尼龍6之第二添加劑經由第二添加劑注射管線注射至第二次歧管且與液體聚合物組合以形成聚合物產物。包含第三量之尼龍6(其不同於第一或第二量之尼龍6)之第三添加劑經由第三添加劑注射管線注射至第三次歧管且與液體聚合物組合以形成聚合物產物。各產物進料經過與相應次歧管接觸之聚合物凝固器以產生成品聚合物產物。該方法因此由一種連續聚合方法產生三種聚合物產物，每一者含有不同量之尼龍6。 A continuous polymerization product was produced as in Example 1 and an additive was added as in Example 1. The primary manifold is in contact with three secondary manifolds, each connected to a different additive injection line. A first additive comprising a first amount of nylon 6 is injected into the first manifold via a first additive injection line and combined with a liquid polymer to form a polymer product. A second additive comprising a second amount (which is different than the first amount) of nylon 6 is injected into the second manifold via a second additive injection line and combined with the liquid polymer to form a polymer product. A third additive comprising a third amount of nylon 6 (which differs from the first or second amount of nylon 6) is injected via a third additive injection line to a third manifold and combined with the liquid polymer to form a polymer product. Each product feed is passed through a polymer coagulator in contact with a corresponding secondary manifold to produce a finished polymer product. The process thus produces three polymer products from a continuous polymerization process, each containing varying amounts of nylon 6.

比較實例AComparison example A

使用添加劑在介於265℃與300℃之間的溫度下及在介於10MPa與31MPa之間的壓力下產生包含尼龍6,6之連續聚合產物。在進入聚合反應器之前，形成尼龍鹽溶液。尼龍鹽溶液接著傳送至蒸發器以移除水且隨後傳送至聚合反應器。添加添加劑至尼龍鹽溶液，隨後將該溶液傳送至蒸發器。設定目標成品聚合物產物且為達成此目標，將介於0.1重量%至20重量%範圍內之值的添加劑添加至尼龍鹽溶液。向尼龍鹽溶液提供添加劑與移出包含達到目標添加劑含量之添加劑的尼龍6,6聚合物之間的時間為8至12小時。若需要具有與第一聚合物產物不同的添加劑的第二聚合物產物，離線採用聚合裝置且清潔以自蒸發器、聚合反應器、蒸發器與反應器之間的管道及反應器排出管線移除任何積聚的添加劑。在清潔後接著需要額外8至12小時以產生符合目標規格之第二聚合物產物。 The continuous polymerization product comprising nylon 6,6 is produced using an additive at a temperature between 265 ° C and 300 ° C and at a pressure between 10 MPa and 31 MPa. A nylon salt solution is formed prior to entering the polymerization reactor. The nylon salt solution is then passed to an evaporator to remove water and then transferred to the polymerization reactor. The additive is added to the nylon salt solution, which is then transferred to the evaporator. The target finished polymer product is set and to achieve this goal, an additive having a value ranging from 0.1% by weight to 20% by weight is added to the nylon salt solution. The time between the supply of the additive to the nylon salt solution and the removal of the nylon 6,6 polymer containing the additive to the target additive level is from 8 to 12 hours. If a second polymer product having an additive different from the first polymer product is desired, the polymerization unit is taken offline and cleaned to remove the tubes from the evaporator, the polymerization reactor, the evaporator and the reactor, and the reactor discharge line. Any accumulated additive. An additional 8 to 12 hours is required after cleaning to produce a second polymer product that meets the target specifications.

比較實例BCompare example B

使用添加劑在介於265℃與300℃之間的溫度下及在介於10MPa 與31MPa之間的壓力下產生包含尼龍6,6之連續聚合產物。在進入蒸發器移除水之前及在聚合反應器之前，形成尼龍鹽溶液。接著將尼龍鹽溶液傳送至儲槽儲存直至需要為止。設定目標成品聚合物產物且為達成此目標，將介於0.1重量%至20重量%範圍內之值的添加劑添加至儲槽中之尼龍鹽溶液。向儲槽中之尼龍鹽溶液提供添加劑與移出包含達到目標添加劑含量之添加劑的尼龍6,6聚合物之間的時間為8至12小時。若需要具有與第一聚合物產物不同的添加劑的第二聚合物產物，離線採用聚合裝置且清潔以自儲槽、蒸發器、聚合反應器、儲槽與蒸發器之間的管道、蒸發器與反應器之間的管道及反應器排出管線移除任何積聚的添加劑。在清潔後接著需要額外8至12小時以產生符合目標規格之第二聚合物產物。 Use additives at temperatures between 265 ° C and 300 ° C and at 10 MPa A continuous polymerization product comprising nylon 6,6 was produced at a pressure of between 31 MPa. A nylon salt solution was formed before entering the evaporator to remove water and before the polymerization reactor. The nylon salt solution is then transferred to a reservoir for storage until needed. The target finished polymer product is set and to achieve this goal, an additive having a value ranging from 0.1% by weight to 20% by weight is added to the nylon salt solution in the storage tank. The time between providing the additive to the nylon salt solution in the storage tank and removing the nylon 6,6 polymer containing the additive to the target additive content is 8 to 12 hours. If a second polymer product having an additive different from the first polymer product is required, the polymerization unit is taken offline and cleaned from the storage tank, the evaporator, the polymerization reactor, the piping between the storage tank and the evaporator, the evaporator and The piping between the reactors and the reactor discharge line remove any accumulated additives. An additional 8 to 12 hours is required after cleaning to produce a second polymer product that meets the target specifications.

比較實例CComparative example C

產生包含尼龍6,6之連續聚合產物。連續聚合產物在介於265℃與300℃之間的溫度下及在介於10MPa與31MPa之間的壓力下流經主歧管。主歧管與添加劑注射管線流體連通。設定目標成品聚合物產物且為達成此目標，允許介於0.1重量%至20重量%之範圍內的值的添加劑流經添加劑注射管線以與主歧管中之液體聚合物組合。向儲槽中之主歧管提供添加劑與移出包含達到目標添加劑含量之添加劑的尼龍6,6聚合物之間的時間為3至6小時。若需要具有與第一聚合物產物不同的添加劑的第二聚合物產物，離線採用聚合裝置且清潔主歧管以自主歧管移除任何積聚的添加劑。在清潔後接著需要額外3至6小時以產生符合目標規格之第二聚合物產物。 A continuous polymerization product comprising nylon 6,6 is produced. The continuous polymerization product flows through the main manifold at a temperature between 265 ° C and 300 ° C and at a pressure between 10 MPa and 31 MPa. The primary manifold is in fluid communication with the additive injection line. The target finished polymer product is set and to achieve this goal, an additive having a value in the range of 0.1% to 20% by weight is allowed to flow through the additive injection line to combine with the liquid polymer in the primary manifold. The time between supplying the additive to the main manifold in the storage tank and removing the nylon 6,6 polymer containing the additive to the target additive content is 3 to 6 hours. If a second polymer product having an additive different from the first polymer product is desired, the polymerization unit is taken offline and the main manifold is cleaned to remove any accumulated additives from the autonomous manifold. An additional 3 to 6 hours is required after cleaning to produce a second polymer product that meets the target specifications.

雖然已詳細描述本發明，但在本發明之精神及範疇內之修改應易於對熟習此項技術者顯而易見。以上論述之所有公開案及參考文獻以引用的方式併入本文中。此外，應瞭解，本發明之態樣與部分所列舉之多種實施例及多種特徵可完全或部分組合或互換。在多種實施例 之以上描述中，提及另一實施例之彼等實施例可適當地與其他實施例組合，如熟習此項技術者應瞭解。此外，熟習此項技術者應理解，以上描述僅舉例而言，且並不意欲限制本發明。 Although the present invention has been described in detail, modifications of the present invention should be readily apparent to those skilled in the art. All publications and references discussed above are hereby incorporated by reference. In addition, it should be understood that the various aspects and various features of the invention may be combined or interchanged in whole or in part. In various embodiments In the above description, reference to other embodiments of another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. In addition, those skilled in the art should understand that the above description is by way of example only and is not intended to limit the invention.

101‧‧‧聚合方法 101‧‧‧ Polymerization method

102‧‧‧聚合物添加劑裝置 102‧‧‧ polymer additive device

108‧‧‧聚合物入口 108‧‧‧ polymer inlet

115‧‧‧泵 115‧‧‧ pump

116‧‧‧聚合物 116‧‧‧ polymer

118‧‧‧聚合物凝固器 118‧‧‧ polymer coagulator

119‧‧‧成品聚合物產物 119‧‧‧Finished polymer products

120‧‧‧聚合反應器 120‧‧‧polymerization reactor

121‧‧‧主歧管 121‧‧‧Main manifold

122‧‧‧主歧管閥 122‧‧‧Main manifold valve

123‧‧‧主歧管閥 123‧‧‧Main manifold valve

125‧‧‧次歧管 125‧‧‧Management

126‧‧‧次歧管泵 126‧‧‧ times manifold pump

127‧‧‧添加劑注射儲槽 127‧‧‧Additive injection reservoir

128‧‧‧添加劑注射管線 128‧‧‧Additive injection line

129‧‧‧添加劑注射泵 129‧‧‧Additive syringe pump

130‧‧‧添加劑注射閥 130‧‧‧Additive Injection Valve

131‧‧‧液體聚合物 131‧‧‧Liquid polymer

132‧‧‧具有添加劑之液體聚合物 132‧‧‧Liquid polymer with additives

133‧‧‧聚合物凝固器 133‧‧‧ polymer coagulator

135‧‧‧次歧管 135‧‧‧Management

136‧‧‧次歧管泵 136‧‧‧ times manifold pump

137‧‧‧添加劑注射儲槽 137‧‧‧Additive injection reservoir

138‧‧‧添加劑注射管線 138‧‧‧Additive injection line

139‧‧‧添加劑注射泵 139‧‧‧Additive syringe pump

140‧‧‧添加劑注射閥 140‧‧‧Additive injection valve

141‧‧‧液體聚合物 141‧‧‧Liquid polymer

142‧‧‧具有添加劑之液體聚合物 142‧‧‧Liquid polymer with additives

143‧‧‧聚合物凝固器 143‧‧‧ polymer coagulator

161‧‧‧成品聚合物產物 161‧‧‧Finished polymer products

162‧‧‧成品聚合物產物 162‧‧‧Finished polymer products

Claims (15)

一種用於產生複數個聚合物產物之連續方法，該方法包含：a)將液體聚合物由聚合反應器經由主歧管引導至聚合物凝固器以形成初級成品聚合物產物，其中該主歧管包含至少第一主歧管閥及第二主歧管閥，其各在聚合物精整機之上游，b)將第一部分液體聚合物由該主歧管經由該第一主歧管閥引導至第一添加劑注射裝置；c)注射第一添加劑至該第一部分液體聚合物以產生包含第一添加劑之第一成品聚合物產物；d)將第二部分液體聚合物由該主歧管經由該第二主歧管閥引導至第二添加劑注射裝置；及e)注射第二添加劑以產生包含該第二添加劑之第二成品聚合物產物，其中該第一添加劑不同於該第二添加劑，其中該等第一及第二添加劑注射裝置各包含次歧管、連接至該次歧管之至少一個添加劑注射管線、及在該添加劑注射管線下游之與該次歧管流體連通的聚合物凝固器；及其中該等第一及第二添加劑係獨立地選自由消泡劑、潤滑助劑、成核劑、阻燃劑、塑化劑、抗衝擊改質劑、玻璃纖維、基於銅之穩定劑、潤滑劑、去光劑、共聚合物、催化劑、改變末端平衡之化合物及其混合物組成之群。 A continuous process for producing a plurality of polymer products, the method comprising: a) directing a liquid polymer from a polymerization reactor to a polymer coagulator via a primary manifold to form a primary finished polymer product, wherein the primary manifold Including at least a first primary manifold valve and a second primary manifold valve, each upstream of the polymer finishing machine, b) directing a first portion of liquid polymer from the primary manifold via the first primary manifold valve to a first additive injection device; c) injecting a first additive to the first portion of the liquid polymer to produce a first finished polymer product comprising a first additive; d) passing a second portion of the liquid polymer from the primary manifold via the first The second main manifold valve is directed to the second additive injection device; and e) the second additive is injected to produce a second finished polymer product comprising the second additive, wherein the first additive is different from the second additive, wherein The first and second additive injection devices each include a secondary manifold, at least one additive injection line coupled to the secondary manifold, and a fluid in fluid communication with the secondary manifold downstream of the additive injection line And the first and second additives are independently selected from the group consisting of defoamers, lubricating agents, nucleating agents, flame retardants, plasticizers, impact modifiers, fiberglass, based on A group of copper stabilizers, lubricants, deluters, copolymers, catalysts, compounds that alter the terminal balance, and mixtures thereof. 如請求項1之方法，其中該至少一個添加劑注射管線包含泵。 The method of claim 1, wherein the at least one additive injection line comprises a pump. 如請求項1之方法，其中該等第一及第二添加劑注射裝置各另外包含用於使該至少一個添加劑注射管線與該次歧管連接之添加劑注射閥。 The method of claim 1, wherein the first and second additive injection devices each additionally comprise an additive injection valve for connecting the at least one additive injection line to the secondary manifold. 如請求項3之方法，其中該至少一個添加劑注射管線在該至少一 個添加劑注射閥打開時經加壓至比該次歧管之壓力高的壓力。 The method of claim 3, wherein the at least one additive injection line is at least one When the additive injection valve is opened, it is pressurized to a pressure higher than the pressure of the secondary manifold. 如請求項3之方法，其中該至少一個添加劑注射管線在該至少一個添加劑注射閥打開時經加壓至比該次歧管之壓力高2%至10%的壓力。 The method of claim 3, wherein the at least one additive injection line is pressurized to a pressure that is 2% to 10% higher than the pressure of the secondary manifold when the at least one additive injection valve is opened. 如請求項3之方法，其中該至少一個添加劑注射閥及該等第一及第二主歧管閥之每一者之實質上所有部分包含不鏽鋼。 The method of claim 3, wherein substantially all of the at least one additive injection valve and each of the first and second primary manifold valves comprise stainless steel. 如請求項3之方法，其中該等第一及第二主歧管閥之每一者及該至少一個添加劑注射閥為抗堵塞之注射閥。 The method of claim 3, wherein each of the first and second primary manifold valves and the at least one additive injection valve are anti-clogging injection valves. 如請求項1之方法，其中該等主歧管閥及添加劑注射閥為交叉桿注射閥、二通閥、三通閥、分流閥或其組合。 The method of claim 1, wherein the main manifold valve and the additive injection valve are a cross rod injection valve, a two-way valve, a three-way valve, a diverter valve, or a combination thereof. 如請求項1之方法，其中該至少一個添加劑注射裝置包含兩個添加劑注射管線。 The method of claim 1, wherein the at least one additive injection device comprises two additive injection lines. 如請求項1之方法，其中該主歧管包含連接至至少一個第三添加劑注射裝置之至少一個第三主歧管閥。 The method of claim 1, wherein the primary manifold comprises at least one third primary manifold valve coupled to the at least one third additive injection device. 如請求項1之方法，其中該次歧管包含在該至少一個添加劑注射管線上游之泵。 The method of claim 1, wherein the secondary manifold comprises a pump upstream of the at least one additive injection line. 如請求項1之方法，其中該第一及/或第二添加劑係在實質上等於該次歧管中液體聚合物溫度之溫度下添加至該添加劑注射管線。 The method of claim 1, wherein the first and/or second additive is added to the additive injection line at a temperature substantially equal to the temperature of the liquid polymer in the secondary manifold. 如請求項1之方法，其中該至少一個添加劑注射管線另外包含靜態混合器。 The method of claim 1, wherein the at least one additive injection line additionally comprises a static mixer. 如請求項1之方法，其中該主歧管中液體聚合物之溫度係在265℃與300℃之間，且其中該主歧管中液體聚合物之壓力係在10MPa與31MPa之間。 The method of claim 1, wherein the temperature of the liquid polymer in the main manifold is between 265 ° C and 300 ° C, and wherein the pressure of the liquid polymer in the main manifold is between 10 MPa and 31 MPa. 如請求項1之方法，其中該添加劑係在介於40℃與300℃之間的溫度下添加至該添加劑注射管線。 The method of claim 1, wherein the additive is added to the additive injection line at a temperature between 40 ° C and 300 ° C.