200902542 九、發明說明： 【明所屬之技術領域】 本發明係關於有機膦酸酯寡聚物、有機膦酸酯寡聚物 之混合物、製備有機膦酸酯寡聚物及其混合物之方法，以 及此種有機膦酸酯寡聚物和有機膦酸酯寡聚物之混合物的 用途。 【先前技術】 如今聚胺基甲酸酯發泡體已被用於多種應用上。由於 聚胺基甲酸酯發泡體的廣泛運用，已有許多關於提供此種 發泡體阻燃性質的硏究在進行。爲此，已有無數種阻燃劑 被使用和主張用來提供可揉性聚胺基甲酸酯發泡體所需之 阻燃性質。然而，即使是目前已有許多可取得的阻燃劑， 聚胺基甲酸酯產業對於能勝過現有阻燃劑或是具有更好特 性之阻燃劑的需求仍不斷增加。因此，在阻燃劑技術領域 上的需求在於可有效用於聚胺基甲酸酯發泡體的阻燃劑以 及形成此種阻燃劑的方法。 【發明內容】 此外，本發明人發現：當特定成分以適當的比例及施 以適當反應條件而一起進行反應時，可以產生能夠提供非 常良好品質之阻燃聚胺基甲酸酯發泡體的有機膦酸酯寡聚 物。 因此，在一些實施實例中，本發明係關於一種方法， 其包括： a) 將（i)至少一種三烷基亞磷酸酯，（ii)至少一種聚烷二 200902542 醇，（iii)至少一種丙烯基或甲基化的芳香醇，以及 (iv)選用的至少一種觸媒，一起置放於反應容器中， 在此同時使反應容器內容物的溫度維持在約7 5 °C至 約1 3 0 °C的溫度範圍內，因而形成至少一種烷基亞 磷酸酯寡聚物之混合物； b) 將催化數量的至少一種烷基鹵化物添加至該混合的 烷基亞磷酸酯寡聚物之混合物中，在此同時使反應 容器內容物維持在約6 0 °C至約1 5 0 °C範圍內的一或 多個溫度之下，持續時間約2小時至約1 2小時，因 而將至少一部分的該烷基亞磷酸酯寡聚物之混合物 轉化成烷基膦酸酯寡聚物之混合物；以及 c) 由烷基膦酸酯寡聚物之混合物中去除至少一部分 (較佳爲全部）的任何揮發性物質，因而產生了包含 至少一種有機膦酸酯寡聚物（較佳爲其混合物）之 有機膦酸酯寡聚物產物。 雖然不希望被理論束縛，本發明人相信本發明之方法 可被描述成兩階段的方法，其可描述成1)至少一種三烷 基亞磷酸酯與至少一種聚烷二醇和至少一種丙烯基或甲基 化的芳香醇的轉酯化反應，而產生混合的烷基亞磷酸酯寡 聚物之混合物；以及步驟2)經由以至少一種烷基鹵化物進 行催化的Arbuzov重排反應，使至少一部分的烷基亞磷酸 酯寡聚物之混合物轉化成烷基聚膦酸酯寡聚物之混合物。 在一些實施實例中，在本發明的方法中使用了選用的 觸媒。在一些實施實例中，在本發明的方法中並未使用選 200902542 用的觸媒。 在一些實施實例中，本發明之方法係以批次的方式來 進行，而在其它實施實例中，係以半連續的方式進行，還 有在其它的實施實例中，則是以連續的方式進行。 値得注意的是，在特佳的實施實例中，於製備本發明 之有機膦酸酯寡聚物和有機膦酸酯寡聚物混合物時會使用 非常特定的成分。這些成分爲亞磷酸三甲酯、聚乙二醇和 苯甲醇。由聚丙二醇所製得之類似產物並不適合用來製造 具有良好品質的聚胺基甲酸酯。其它使用亞磷酸三甲酯、 二乙二醇和氯甲苯的方法也同樣可能會產生有毒的氯甲烷 氣體。然而，本發明的發明者已注意到：本發明之方法幾 乎不會產生氯甲烷，通常是沒有氯甲烷，並且在一些較佳 的實施實例中，本發明之方法不會產生任何氣態副產物。 此外，依照本發明所製得之有機膦酸酯寡聚物混合物已被 發現能夠同時提供具有良好品質之聚醚聚胺基甲酸酯和聚 酯聚胺基甲酸酯。同時，由於二乙二醇的可取得性及成本 低廉，因此本發明在實際上亦具有經濟優勢。 發明詳述 在實施本發明時，將（i)至少一種，較佳爲一種三烷基 亞磷酸酯，（Π)至少一種，較佳爲一種聚烷二醇，和（iii)至 少一種，較佳爲一種丙烯基或甲基化的芳香醇，以及選用 的（iv)至少一種，較佳爲一種觸媒一起置放或化合於反應容 器中，因而形成至少一種烷基亞磷酸酯寡聚物之混合物。 値得注意的是，此處所用的反應容器是指最廣義的反應容 200902542 器，這表示可以是任何器皿、容器等，只要在此領域具有 通常技術者認爲可以用來進行本發明之方法即可。 在本文中所使用之（i)至少一種三烷基亞磷酸酯可以選 自任何一種三烷基亞磷酸酯。較佳三烷基亞磷酸酯的非限 制性實例包括亞磷酸三甲酯和亞磷酸三乙酯。在特佳的實 施實例中，至少一種三烷基亞磷酸酯爲亞磷酸三甲酯。 在本文中所使用之（i i)至少一種聚烷二醇可以選自任 何一種聚烷二醇。較佳聚烷二醇的非限制性實例包括三乙 二醇、二乙二醇和二丙二醇。在特佳的實施實例中，至少 —種聚烷二醇爲二乙二醇。 在本文中所使用之（iii)至少一種丙烯基或甲基化的芳 香醇可以選自任何一種丙烯基或甲基化的芳香醇。在特佳 的實施實例中，至少一種丙烯基或甲基化的芳香醇爲苯甲 醇。 (iv)至少一種選用的觸媒可以選自任何一種可有效催 化轉酯化反應的觸媒。適合用於此處之觸媒的非限制性實 例包括鹼金屬烷氧化物，如甲氧化鈉。値得注意的是，本 發明之方法較佳係在沒有選用觸媒的情況下操作。 在實施本發明時，（i)至少一種三烷基亞磷酸酯和（ii) 至少一種聚烷二醇所使用之莫耳比例數量通常爲每莫耳的 (ii)配合使用約0.8至約1 .5莫耳的（i)，較佳的莫耳比例係 介於每莫耳的（ii)配合使用約1.0至約1.2莫耳的（i)之範圍 內。此處所使用（iii)至少一種丙烯基或甲基化的芳香醇之 數量一般爲每莫耳的（ii)配合使用約〇.〇5至約0.3莫耳的 200902542 (i i i)，較佳的莫耳比例係介於每莫耳的（i i)配合使用約0.1 至約〇·2莫耳的（iii)之範圍內。 (i)、（Π)、（iii)和選用的（iv)可以任何順序和任何數量 來組合。舉例來說，一種反應物的一部分或全部可以添加 至一部分或全部的另一種反應物中，依次再將其添加至一 部分或全部的第三種反應物中，這些反應物也可以共同進 料等。然而，在較佳的實施實例中，係將至少一部分（較 佳爲實質上全部）的（i)添加至反應容器中，接著再將（i i) 和（iii)引入反應容器中，較佳爲經過一段時間。在特佳的 實施實例中，實質上全部的（i)被添加至反應容器中’接著 (iii)添力卩至反應容器中，較佳爲經過一段時間，更佳爲經 過約0 · 5小時至約3小時，最佳爲經過約1小時至約2小 時，接著再將（i i)引入反應容器，較佳爲經過一段時間’更 佳爲經過約2小時至約6小時，最佳爲經過約3小時至約 4小時。在這些實施實例中’特佳的情況是（υ爲亞磷酸三 甲酯，（ii)爲二乙二醇，且（iii)爲苯甲醇。 如前所述，在組合（i)、（H)、（⑴）和選用的（iv)期間’ 反應容器內容物的溫度係維持在約75°C至約13〇 °C範圍內 的一或多個溫度之下。在較佳的實施實例中’反應容器的 內容物係維持在約8 5 °C至約1 2 〇 °C範圍內的一或多個溫度 之下。 然而，當本發明方法的操作方式係如上所述在引入 (i i)(較佳爲二乙二醇）和（i i1)(較佳爲苯甲醇）之前將至少部 分（較佳爲實質上全部）的（i)(較佳爲亞磷酸三甲酯）置入反 200902542 應器時，首先將⑴在約7 5 °C至約1 1 〇 °C範圍內加熱到一或 多個溫度，較佳係在約90°C至約1 〇〇°C範圍內加熱到一或 多個溫度。在一些實施實例中，例如當（iii)(較佳爲苯甲醇） 係在（i)(較佳爲亞磷酸三甲酯）之後，但在（i i)(較佳爲二乙 二醇）之前引入反應容器中時，較佳是在添加苯甲醇的期間 使反應容器內容物維持在約75。(：至約110。(：範圍內的一或 多個溫度之下’較佳是維持在約9 0。(：至約1 〇 〇 °C範圍內的 一或多個溫度之下。在這些實施實例中，於（iii)被引入反 應容器之後’在使反應容器內容物之溫度維持在這些範圍 內的同時，接著加入（Π)。値得注意的是，反應容器內容物 的溫度可以經由此領域已知的任何方式和方法來加以維 持。例如’可以對反應器內容物予以加熱以提升溫度，或 者是施加真空壓力以降低煮沸混合物的溫度。在一些實施 實例中’如果施加真空壓力來維持反應容器的溫度，真空 壓力須隨著時間降低，而使得在（i)、（ii)、（iii)和選用的（iv) 引入之後，反應容器的最終壓力介於約1 5 0至約3 3 0毫米 汞柱的範圍內，並且反應容器內容物的最終溫度係介於9 0 °C至約 Π 〇 °C的範圍內。反應溫度和真空壓力及反應時間 的選擇係根據反應所容許達成的聚合度，其可依照反應期 間所產生的甲醇數量來決定。 在實施本發明時，當甲醇由⑴與（ii)和（iii)的轉酯化反 應生成時，最好是將至少部分（較佳爲實質上全部）的甲醇 由反應容器中移除。可藉由任何已知技術將甲醇自反應容 器中移除，但通常可藉著自反應容器收集低沸揮發性成分 -10- 200902542 的方式來有效去除，通常是反應容器溫度維持在上述範圍 內’並且利用蒸餾技術將甲醇分離出來，並且將其中所含 至少一部分（較佳爲實質上全部）的任何亞磷酸三甲酯回送 至反應容器中。 在（i)、（ii)、（iii)和選用的（iv)置放在一起或結合之後， 將催化數量的烷基鹵化物（較佳爲碘甲烷）添加至烷基亞磷 酸酯寡聚物之混合物中，因而將至少一部分（較佳是實質上 全部）的該種烷基亞磷酸酯寡聚物之混合物轉化成烷基膦 酸酯寡聚物之混合物。所謂至少一種烷基鹵化物的催化數 量係指介於約0. 1至約2.0重量％的範圍內，較佳係介於約 0.3至約2.0重量％的範圍內，更佳係介於約〇.3至約1〇 重量％的範圍內，其係以烷基亞磷酸酯寡聚物之混合物的 總重量爲基準。可以將至少一種烷基鹵化物引入含有烷基 亞磷酸酯寡聚物之混合物的反應容器中，或者是將烷基亞 磷酸酯寡聚物之混合物添加至第二反應容器中，選擇性地 含有至少一部分的至少一種烷基鹵化物，接著再引入院基 鹵化物或者是殘留的烷基鹵化物。 在一個特佳的實施實例中，烷基亞磷酸酯寡聚物之混 合物係被引入含有有機隣酸酯混合物（較佳係由本發明前 一回合製程殘留）的第二反應容器中，並且，如有需要，可 添加額外的烷基鹵化物，以使烷基鹵化物的添加量符合前 述的範圍。在這些實施實例中，亦即，當烷基亞磷酸醋寡 聚物之混合物被加入底料（heel)時，烷基亞磷酸酯寡聚物之 混合物較佳是能以約2至約1 6小時的時間來添加，更佳爲 -11- 200902542 約3至約1 0小時。如果烷基亞磷酸酯寡聚物之混合物係依 前述方式來添加時，在添加期間較佳是使反應容器內含物 的溫度維持在約1 2 0 °C至約1 7 〇 °C範圍內的一或多個溫度 之下’較佳是維持在約1 2 0 °C至約1 5 0。(：範圍內的一或多個 溫度之下。 接著由烷基膦酸酯寡聚物之混合物中去除至少一部分 (較佳爲實質上全部）的揮發性物質，因而產生了有機膦酸 酯寡聚物產物。將揮發性物質由烷基膦酸酯寡聚物之混合 物中去除的方法可由任何一種已知可由反應產物混合物中 去除揮發性成分的技術中來選擇。適合方法的非限制性實 例包括汽提、蒸餾或利用刮膜（wipe film)蒸發器。在—些 實施實例中，使用了刮膜蒸發器。 本發明製造之有機膦酸酯寡聚物產物包含至少一種有 機膦酸酯寡聚物，較佳爲有機膦酸酯寡聚物之混合物。這 些由本發明製造的有機膦酸酯寡聚物和有機膦酸酯寡聚物 混合物爲具有適當數量末端羥基的共聚聚膦酸酯’因此使 得它們可被用在聚胺基甲酸酯中做爲反應性阻燃劑。如同 習於本技術領域者已熟知’本發明之有機膦酸醋寡聚物混 合物通常爲個別寡聚物的混合物，由於這些寡聚物爲一系 列反應所生成之個別寡聚物的混合物’產物的描述最多僅 爲大略的敘述。除此之外’以下的描述將可呈現出本發明 所製造有機膦酸酯寡聚物混合物之個別寡聚物的大致結 構： 200902542 ο \200902542 IX. Description of the invention: [Technical field of the invention] The present invention relates to an organic phosphonate oligomer, a mixture of organic phosphonate oligomers, a method for preparing an organic phosphonate oligomer and a mixture thereof, and Use of a mixture of such an organic phosphonate oligomer and an organic phosphonate oligomer. [Prior Art] Polyurethane foams have been used in a variety of applications today. Due to the widespread use of polyurethane foams, many studies have been conducted to provide flame retardant properties of such foams. To this end, a myriad of flame retardants have been used and are claimed to provide the flame retardant properties required for a labile polyurethane foam. However, even though there are many flame retardants available today, the polyurethane industry continues to have an increasing demand for flame retardants that outperform existing flame retardants or have better properties. Accordingly, a need in the field of flame retardant technology is a flame retardant which can be effectively used for a polyurethane foam and a method of forming such a flame retardant. SUMMARY OF THE INVENTION Further, the inventors have found that when a specific component is reacted together in an appropriate ratio and under appropriate reaction conditions, a flame-retardant polyurethane foam capable of providing a very good quality can be produced. Organic phosphonate oligomers. Accordingly, in some embodiments, the present invention is directed to a method comprising: a) (i) at least one trialkyl phosphite, (ii) at least one polyalkane 200902542 alcohol, (iii) at least one propylene The base or methylated aromatic alcohol, and (iv) at least one catalyst selected, are placed together in the reaction vessel while maintaining the temperature of the contents of the reaction vessel at about 75 ° C to about 1 30 a temperature range of ° C, thus forming a mixture of at least one alkyl phosphite oligomer; b) adding a catalytic amount of at least one alkyl halide to the mixture of mixed alkyl phosphite oligomers At the same time maintaining the contents of the reaction vessel below one or more temperatures in the range of from about 60 ° C to about 150 ° C for a period of from about 2 hours to about 12 hours, thus at least a portion of Converting a mixture of the alkyl phosphite oligomers to a mixture of alkylphosphonate oligomers; and c) removing at least a portion (preferably all) of the mixture of alkylphosphonate oligomers Volatile matter, thus resulting in inclusion An organic phosphonate oligomer product of at least one organic phosphonate oligomer, preferably a mixture thereof. While not wishing to be bound by theory, the inventors believe that the process of the present invention can be described as a two-stage process which can be described as 1) at least one trialkyl phosphite with at least one polyalkylene glycol and at least one propenyl group or a transesterification reaction of a methylated aromatic alcohol to produce a mixture of mixed alkyl phosphite oligomers; and a step 2) of at least a portion of the Arbuzov rearrangement reaction catalyzed by at least one alkyl halide The mixture of alkyl phosphite oligomers is converted to a mixture of alkyl polyphosphonate oligomers. In some embodiments, an optional catalyst is used in the method of the present invention. In some embodiments, the catalyst used in 200902542 is not used in the method of the present invention. In some embodiments, the methods of the present invention are performed in batches, while in other embodiments, in a semi-continuous manner, and in other embodiments, in a continuous manner. . It is noted that in a particularly preferred embodiment, very specific ingredients are used in preparing the mixture of the organophosphonate oligomer and the organophosphonate oligomer of the present invention. These components are trimethyl phosphite, polyethylene glycol and benzyl alcohol. Similar products made from polypropylene glycol are not suitable for use in the manufacture of polyurethanes of good quality. Other methods using trimethyl phosphite, diethylene glycol, and chlorotoluene may also produce toxic methyl chloride gas. However, the inventors of the present invention have noted that the process of the present invention produces substantially no methyl chloride, typically no methyl chloride, and in some preferred embodiments, the process of the present invention does not produce any gaseous by-products. Furthermore, the organophosphonate oligomer mixtures prepared in accordance with the present invention have been found to provide both good quality polyether polyurethanes and polyester polyurethanes. At the same time, the present invention also has an economic advantage in fact due to the availability and low cost of diethylene glycol. DETAILED DESCRIPTION OF THE INVENTION In the practice of the invention, (i) at least one, preferably a trialkyl phosphite, at least one, preferably a polyalkylene glycol, and (iii) at least one Preferably, a propylene- or methylated aromatic alcohol, and optionally at least one, preferably a catalyst, is placed or combined in a reaction vessel to form at least one alkyl phosphite oligomer a mixture. It should be noted that the reaction vessel as used herein refers to the most general reaction volume 200902542, which means that it can be any vessel, container, etc., as long as there is a method in the art that can be used to carry out the invention. Just fine. As used herein, (i) at least one trialkyl phosphite may be selected from any of the trialkyl phosphites. Non-limiting examples of preferred trialkyl phosphites include trimethyl phosphite and triethyl phosphite. In a particularly preferred embodiment, at least one trialkyl phosphite is trimethyl phosphite. (i i) at least one polyalkylene glycol used herein may be selected from any of the polyalkylene glycols. Non-limiting examples of preferred polyalkylene glycols include triethylene glycol, diethylene glycol, and dipropylene glycol. In a particularly preferred embodiment, at least one of the polyalkylene glycols is diethylene glycol. (iii) At least one propylene-based or methylated aromatic alcohol used herein may be selected from any one of propylene-based or methylated aromatic alcohols. In a particularly preferred embodiment, the at least one propylene or methylated aromatic alcohol is benzyl alcohol. (iv) At least one of the selected catalysts may be selected from any of the catalysts which are effective in catalyzing the transesterification reaction. Non-limiting examples of catalysts suitable for use herein include alkali metal alkoxides such as sodium methoxide. It should be noted that the method of the present invention preferably operates without the use of a catalyst. In the practice of the invention, the molar ratio of (i) at least one trialkyl phosphite and (ii) at least one polyalkylene glycol is typically from about 0.8 to about 1 per mole of (ii) combined use. The .5 molar (i), preferred molar ratio is in the range of (i) from about 1.0 to about 1.2 moles per mole of (ii) combined use. The amount of (iii) at least one acryl-based or methylated aromatic alcohol used herein is generally (ii) 20090 42 (iii) per mole of (ii) combined use of about 〇.〇5 to about 0.3 moles, preferably Mo. The ear ratio is in the range of (iii) per mole of (ii) combined use of from about 0.1 to about 2 moles (iii). (i), (Π), (iii) and optional (iv) may be combined in any order and in any quantity. For example, a part or all of a reactant may be added to some or all of the other reactants, and then added to some or all of the third reactants in turn, and these reactants may also be fed together. . However, in a preferred embodiment, at least a portion (preferably substantially all) of (i) is added to the reaction vessel, followed by introduction of (ii) and (iii) into the reaction vessel, preferably After awhile. In a particularly preferred embodiment, substantially all of (i) is added to the reaction vessel and then (iii) is added to the reaction vessel, preferably over a period of time, more preferably after about 0.5 hours. Up to about 3 hours, preferably from about 1 hour to about 2 hours, and then (ii) is introduced into the reaction vessel, preferably over a period of time, more preferably from about 2 hours to about 6 hours, preferably as a pass. About 3 hours to about 4 hours. In these examples, 'extraordinary cases are (trimethyl phosphite, (ii) diethylene glycol, and (iii) benzyl alcohol. As described above, in combination (i), (H) The temperature of the contents of the reaction vessel during the period of (1) and (iv) is maintained at one or more temperatures in the range of from about 75 ° C to about 13 ° C. In a preferred embodiment. 'The contents of the reaction vessel are maintained below one or more temperatures in the range of from about 85 ° C to about 1 2 ° C. However, when the method of operation of the method of the invention is introduced as described above (ii) (preferably diethylene glycol) and (i i1) (preferably benzyl alcohol) are placed at least partially (preferably substantially all) of (i) (preferably trimethyl phosphite) in the opposite 200902542 In the case of the device, first (1) is heated to one or more temperatures in the range of about 75 ° C to about 1 1 ° C, preferably in the range of about 90 ° C to about 1 ° C. One or more temperatures. In some embodiments, for example, when (iii) (preferably benzyl alcohol) is after (i) (preferably trimethyl phosphite), but at (ii) (preferably Two When the diol) is previously introduced into the reaction vessel, it is preferred to maintain the contents of the reaction vessel at about 75 during the addition of benzyl alcohol. (: to about 110. (: below one or more temperatures in the range). It is maintained at a temperature of about 90° (. to one or more temperatures in the range of about 1 〇〇 ° C. In these examples, after (iii) is introduced into the reaction vessel, 'the contents of the reaction vessel are made While the temperature is maintained within these ranges, it is then added (Π). It is noted that the temperature of the contents of the reaction vessel can be maintained by any means and method known in the art. For example, the contents of the reactor can be Heating to raise the temperature, or applying a vacuum pressure to lower the temperature of the boiling mixture. In some embodiments, 'if vacuum pressure is applied to maintain the temperature of the reaction vessel, the vacuum pressure must decrease over time such that (i), After (ii), (iii) and (iv) are introduced, the final pressure of the reaction vessel is in the range of from about 150 to about 3,000 mm Hg, and the final temperature of the contents of the reaction vessel Between 90 ° C and about Π 〇 ° C. The reaction temperature and vacuum pressure and reaction time are selected according to the degree of polymerization allowed by the reaction, which can be determined according to the amount of methanol produced during the reaction. In the practice of the invention, when methanol is formed by the transesterification of (1) with (ii) and (iii), it is preferred to remove at least a portion (preferably substantially all) of the methanol from the reaction vessel. Methanol is removed from the reaction vessel by any known technique, but can generally be effectively removed by collecting the low boiling volatile component-10-200902542 from the reaction vessel, usually with the reaction vessel temperature maintained within the above range' and The methanol is separated by distillation techniques and any at least a portion (preferably substantially all) of any trimethyl phosphite contained therein is returned to the reaction vessel. A catalytic amount of an alkyl halide (preferably methyl iodide) is added to the alkyl phosphite oligomer after (i), (ii), (iii) and optionally (iv) are placed together or combined. Of such a mixture, at least a portion (preferably substantially all) of a mixture of such alkyl phosphite oligomers is converted to a mixture of alkylphosphonate oligomers. The catalytic amount of at least one alkyl halide is in the range of from about 0.1 to about 2.0% by weight, preferably in the range of from about 0.3 to about 2.0% by weight, more preferably in the range of from about 0.3 to about 2.0% by weight. From the range of from 3 to about 1% by weight, based on the total weight of the mixture of alkyl phosphite oligomers. At least one alkyl halide may be introduced into the reaction vessel containing the mixture of alkyl phosphite oligomers, or a mixture of alkyl phosphite oligomers may be added to the second reaction vessel, optionally containing At least a portion of the at least one alkyl halide is then reintroduced into the pendant halide or the residual alkyl halide. In a particularly preferred embodiment, the mixture of alkyl phosphite oligomers is introduced into a second reaction vessel containing a mixture of organic orthoesters, preferably remaining in the previous round of the process of the invention, and, for example, If necessary, an additional alkyl halide may be added so that the amount of the alkyl halide added is within the aforementioned range. In these embodiments, that is, when a mixture of alkyl phosphite oligopolymers is added to the heel, the mixture of alkyl phosphite oligomers preferably ranges from about 2 to about 16. Hours of time to add, more preferably -11-200902542 about 3 to about 10 hours. If the mixture of alkyl phosphite oligomers is added as described above, it is preferred to maintain the temperature of the contents of the reaction vessel in the range of from about 1 2 0 ° C to about 1 7 ° C during the addition. Below one or more temperatures, it is preferably maintained at about 1 20 ° C to about 1 50. (: below one or more temperatures in the range. Next, at least a portion (preferably substantially all) of volatile matter is removed from the mixture of alkylphosphonate oligomers, thereby producing an organic phosphonate oligomer Polymer product. The method of removing volatile materials from a mixture of alkyl phosphonate oligomers can be selected from any of the techniques known to remove volatile components from the reaction product mixture. Non-limiting examples of suitable methods This includes stripping, distillation or using a wipe film evaporator. In some embodiments, a wiped film evaporator is used. The organic phosphonate oligomer product produced by the present invention comprises at least one organic phosphonate oligomer a polymer, preferably a mixture of organic phosphonate oligomers. These organophosphonate oligomers and organophosphonate oligomer mixtures prepared by the present invention are copolymerized polyphosphonates having an appropriate number of terminal hydroxyl groups. Therefore, they can be used as a reactive flame retardant in polyurethanes. As is well known in the art, the organic phosphonic acid vinegar oligomer mixture of the present invention is known. As a mixture of individual oligomers, the description of the mixture of individual oligomers produced by these oligomers as a series of reactions is at most abbreviated. In addition, the following description will present this book. The general structure of the individual oligomers of the organic phosphonate oligomer mixture produced by the invention: 200902542 ο
其中每一個Ri係獨立選自甲基、苯甲基或具有1至10個 碳原子之分枝或直鏈（較佳爲分枝）之末端羥基烷基；每一 個El可相同或相異，並且爲H0C2H40C2H4-或甲基；η爲整 數或是分數。在一些實施實例中，一·個£!爲HOC2H4OC2H，’ 另一個E!爲甲基。在一些實施實例中，末端羥基的烷基爲 具有2至5個碳原子的分枝一級或二級醇。在其它的實施 實例中，每一個R!爲甲基或苯甲基。在這些實施實例中’ 甲基和苯甲基存在的數値比例爲每一個苯甲基約有3個甲 基至每一個苯甲基約有10個甲基。在這些較佳的實施實例 中，甲基和苯甲基存在的數値比例爲每一個苯甲基約有3 個甲基至每一個苯甲基約有8個甲基。 一般而言，η爲約2 0或更少，較佳爲約1 0或更少’ 並且這些數値可以是平均數値，因爲產物通常爲寡聚物的 混合物。如果是寡聚物的混合物，η的平均値通常係介於 約1至約1 〇的範圍內；在一些實施實例中，係介於約1至 約5的範圍內；在一些實施實例中，係介於約2至約3的 範圍內；在其它的實施實例中，則是介於約5至約1 0的範 圍內。如前所述’至少一部分的Ε,Ο含有末端羥基。上式 並未企圖針對寡聚物做任何特殊立體異構組態之描述’上 式亦不會構成有關寡聚物之幾何組態的任何圖像，更不用 200902542 說是限制了。 在一些實施實例中，本發明之有機膦酸酯寡聚物混合 物還包含其中每一個£】爲甲基的有機膦酸酯寡聚物。 在任何既定的產物中，可藉由標準分析程序來決定羥 基數。一般而言，依照本發明所製造的聚膦酸酯寡聚物具 有的羥基數係介於約1 0至約1 00的範圍內，但具有的羥基 數可介於0至100的範圍內。 本發明所製造之有機膦酸酯寡聚物混合物的特徵在於 符合以下至少兩項情況，在一些實施實例會符合兩項以 上’並且在其它實施實例會符合全部：υ以凝固點下降法 ("FPD”）所測得之平均分子量介於約400至約1 200克/克莫 耳的範圍內，在一些實施實例中係介於約5 0 0至約9 0 0克/ 克莫耳的範圍內；Π)在25°C下的黏度介於約2,000至約 30,〇〇〇厘泊的範圍內，在一些實施實例中係介於約3000 至約9 0 0 〇厘泊的範圍內；i i i)以感應耦合電漿法（” I C P ”）所 測得之磷含量介於約1 5至約2 0重量％的範圍內，在一些 實施實例中係介於約1 6至約1 8重量％的範圍內；v)酸値介 於約0.5至1.5毫克KOH/克溶液；iv)TGA(熱重分析）數據 爲： 5 重量％TGArC) 10重量％丁0八(°〇 在約210至約240°的範圍內 在約235-260°的範圍內 本發明所製造之有機膦酸酯寡聚物混合物可在許多應 用方面用來做爲阻燃劑。在一些實施實例中’本發明所製 -14- 200902542 造的有機膦酸酯寡聚物混合物被用來做爲聚胺基甲酸酷發 泡體中的阻燃劑。爲了形成本發明之阻燃聚胺基甲酸醋發 泡體’所使用的基本成分爲異氰酸酯、多元醇和本發明之 有機膦酸酯寡聚物混合物。多元醇爲聚醚多元醇或聚醋多 元醇。在有發泡劑（例如水、揮發性烴類、鹵碳化合物或 鹵烴’或是兩種或以上此類材料所形成之混合物）存在的 況下’於室溫下很谷易發生此種反應。用來進行此反應 的觸媒包括胺觸媒、錫-系觸媒、鉍-系觸媒或其它有機金 { 屬觸媒寺。爲了維持聚合系統中單元的均質性，通常會使 用如經取代之聚矽氧化合物之類的界面活性劑。可以使用 受阻酚抗氧化劑，例如2，6 -二·三級丁基-對甲酚和亞甲雙 (2，6 -二-三級丁酚）來進一步協助安定化，以抵抗氧化降 解。這些和其它可被使用的組成分、比例及其使用的方式 皆報載於文獻中。例如可參閱：Herrington和Hock，^揉浮 聚胺基甲酸酯發泡體{Flexible Polyurethane Foams、、腐氏H學 公司 ’ 1991 ’ 9.25-9.27 或 Roegler，M ASlabstock Foams@ ;聚 \ MS Ψ ^ Se Ψ- 0 (Polyurethane Handbook) ； Oertel, G., Ed.;HanserEach of the Ri is independently selected from a methyl group, a benzyl group or a branched or straight chain (preferably branched) terminal hydroxyalkyl group having 1 to 10 carbon atoms; each of the El groups may be the same or different, And is H0C2H40C2H4- or methyl; η is an integer or a fraction. In some embodiments, one is £! is HOC2H4OC2H, and the other E! is methyl. In some embodiments, the alkyl group of the terminal hydroxyl group is a branched primary or secondary alcohol having 2 to 5 carbon atoms. In other embodiments, each R! is methyl or benzyl. In these examples, the ratio of the number of methyl groups and benzyl groups present is about 3 methyl groups per benzyl group to about 10 methyl groups per benzyl group. In these preferred embodiments, the methyl and benzyl groups are present in a number of from about 3 methyl groups per benzyl group to about 8 methyl groups per benzyl group. In general, η is about 20 or less, preferably about 10 or less' and these numbers can be average 値 because the product is typically a mixture of oligomers. If it is a mixture of oligomers, the average enthalpy of η is typically in the range of from about 1 to about 1 Torr; in some embodiments, it is in the range of from about 1 to about 5; in some embodiments, The range is from about 2 to about 3; in other embodiments, it is in the range of from about 5 to about 10. As described above, at least a portion of the oxime contains a terminal hydroxyl group. The above formula does not attempt to describe any particular stereoisomeric configuration of the oligomer. The above formula does not constitute any image relating to the geometric configuration of the oligomer, and it is not limited to 200902542. In some embodiments, the organophosphonate oligomer mixture of the present invention further comprises an organophosphonate oligomer in which each of the methyl groups is methyl. In any given product, the number of hydroxyl groups can be determined by standard analytical procedures. In general, the polyphosphonate oligomers produced in accordance with the present invention have a hydroxyl number in the range of from about 10 to about 100, but may have a hydroxyl number in the range of from 0 to 100. The organophosphonate oligomer mixture produced by the present invention is characterized by meeting at least two of the following conditions, in some embodiments, it will meet two or more 'and in other embodiments will conform to all: υ to freeze point drop method (" The average molecular weight measured by FPD") is in the range of from about 400 to about 1 200 grams per gram of mole, and in some embodiments is in the range of from about 50,000 to about 9000 grams per gram of mole. The viscosity at 25 ° C is in the range of from about 2,000 to about 30, 〇〇〇 centipoise, and in some embodiments, in the range of from about 3,000 to about 9000 psi; Iii) the phosphorus content measured by inductively coupled plasma ("ICP") is in the range of from about 15 to about 20% by weight, and in some embodiments from about 16 to about 18 weight. Within the range of %; v) acid strontium is between about 0.5 and 1.5 mg KOH/g solution; iv) TGA (thermogravimetric analysis) data is: 5 wt% TGARC) 10 wt% butyl 0 八 (° 〇 at about 210 至The organic phosphonate oligomer mixture produced by the present invention may be in many ranges in the range of about 235-260° in the range of about 240°. The aspect is used as a flame retardant. In some embodiments, the organic phosphonate oligomer mixture produced by the invention of the invention is used as a flame retardant in a polyurethane foam. The essential component used in forming the flame-retardant polyurethane foam of the present invention is an isocyanate, a polyol, and an organic phosphonate oligomer mixture of the present invention. The polyol is a polyether polyol or a polyester. Polyol. In the presence of a blowing agent (such as water, volatile hydrocarbons, halocarbons or halocarbons) or a mixture of two or more such materials, it is very easy at room temperature. This reaction occurs. The catalyst used to carry out the reaction includes an amine catalyst, a tin-based catalyst, a ruthenium-based catalyst or other organic gold. In order to maintain the homogeneity of the unit in the polymerization system, usually A surfactant such as a substituted polyoxo compound may be used. A hindered phenol antioxidant such as 2,6-di-tertiary butyl-p-cresol and methylene bis (2,6-di-) may be used. Third-grade butanol) to further assist in stabilization to resist oxidation These and other components and ratios that can be used and the manner in which they are used are reported in the literature. For example, see: Herrington and Hock, ^ Polyfoam Foams, Flexible Polyurethane Foams, , Roche H's company '1991' 9.25-9.27 or Roegler, M ASlabstock Foams@; poly \ MS Ψ ^ Se Ψ - 0 (Polyurethane Handbook); Oertel, G., Ed.; Hanser
Munich，1 985，176-1 77或Woods，G.矽猱沒聚废基伊麽磨發泡 鐙，化學范犮銜；應用科學出版社，倫敦，1982，2 5 7 -260。 在利用本發明所形成之有機膦酸酯寡聚物來形成阻燃 聚胺基甲酸酯時，通常所使用本發明之有機膦酸酯寡聚物 混合物的數量係介於約4至約1 5重量％的範圍內，其係以 聚胺基甲酸酯調配物的總重量爲基準。 本發明所製造之有機膦酸酯寡聚物產物通常爲無色或 200902542 是淡淡的灰白色。淡的顏色較爲有利，因爲它可以簡化最 終使用者在確保以寡聚物產品提供阻燃功能之物品在色澤 一致性上所要承擔的工作。 本發明所製造之有機膦酸酯寡聚物混合物也可用於聚 胺基甲酸酯樹脂及複合物、剛性聚胺基甲酸酯發泡體、酚 樹脂 '塗料、清漆和紡織品中做爲阻燃劑，或者是和它們 一起使用。 此外，本發明之有機膦酸酯寡聚物混合物可以用於具 有其它可燃性材料的調配物中，做爲添加的阻燃劑。可燃 性材料可以爲巨分子，例子，纖維質材料或聚合物。聚合 物的示範性實例爲：烯烴聚合物、交聯和其它（例如）乙烯、 丙烯和丁烯的同元聚合物；兩種或更多種此類烯單體的共 聚物和一或多種此類烯單體與其它可共聚單體的共聚物， 例如’乙烯/丙烯共聚物、乙烯/丙烯酸乙酯共聚物和乙 烯/丙烯共聚物、乙烯/丙烯酸酯共聚物和乙烯/醋酸乙 烯酯共聚物；烯烴不飽和單體的聚合物，例如，聚苯乙烯 - (如耐衝擊性聚苯乙烯）和苯乙烯共聚物；聚醯胺；聚醯 亞胺；聚碳酸酯；聚醚；丙烯酸樹脂；聚酯，特別是聚（對 酞酸乙二酯）和聚（對酞酸丁二酯）；熱固物，例如環氧樹脂； 彈性體，例如丁二烯/苯乙烯共聚物和丁二烯/丙烯腈共 聚物；丙烯腈、丁二烯和苯乙烯的三元共聚物；天然橡膠； 丁基橡膠和聚矽氧烷。可視適當情況，以化學或是照射的 方式來使聚合物交聯。本發明之有機膦酸酯寡聚物產物也 可以用於紡織品的應用上，如乳膠系的背膠。 -16- 200902542 用於調配物中由本發明所製造之有機膦酸酯寡聚物混 合物的數量需爲達到所設定防燃效果所需的數量。習於本 技術領域者將可清楚的了解，在所有的情形中，調配物中 的產品比例不會有單一的精確數値，因爲這種比例會隨著 所使用的特殊可燃性材料、其它添加劑的存在和任何既定 用途中所設定的防燃效果而改變。此外，要達成特殊調配 物中所設定防燃效果所需使用的比例將會受到調配物所製 成物品（例如’電氣絕緣、管道、電子機櫃和薄膜）形狀 的影響’這些物品的運作方式皆不相同。然而，調配物和 所得產物通常可含有約1至約3 0重量％本發明所製造之有 機膦酸酯寡聚物混合物，以約5至約2 5重量％爲較佳。含 有本發明之有機膦酸酯寡聚物混合物的聚合物母粒 (masterbatch)，其係與額外數量的基材聚合物摻合在一 起’通常含有還要更高濃度的本發明有機膦酸酯寡聚物混 合物，例如，高達5 0重量％或以上。 本發明之寡聚阻燃劑可以搭配使用數種傳統上用於熱 塑性調配物之添加劑中的任何一種，依其各自的傳統用量 來使用，例如，塑化劑、抗氧化劑、塡料、顏料、U V安定 劑等。 由含有熱塑性聚合物和本發明之寡聚產物的調配物所 形成之熱塑性物品可以依照傳統方式來製造，例如，以射 出成型、擠製成型、壓縮成型等。在一些特定的例子中， 吹出成型也可能是適當的製造方法。 本發明的實際應用和優點可由以下的示範性實施例得 -17- 200902542 到更清楚的瞭解。這些實施例並非企圖將本發明限縮於所 描述內容之範疇。 【實施方式】 實施例 實施例 1 (9 1 5 3 - 1 9 7) 在安裝有上方攪拌器、加料漏斗、溫度計和蒸餾頭的 2升圓底夾套的Pyrex反應燒瓶中裝入亞磷酸三甲酯 ("TMPi”）（992.8克；8.0莫耳）。在加入TMPi之後，將反應 器內容物加熱至9 5 °C，並且以1 · 2小時的時間來進料苯甲 醇（"BzOH" )(134.8克；1.25莫耳）。在添加苯甲醇的期間， 反應混合物的溫度係在92-95 °C之間變動。接下來，以5 小時的時間將二乙二醇（"DEG")(724克；6.82莫耳）進料至 反應器中。在添加二乙二醇的期間，反應器的溫度係維持 在約8 2 - 9 2 °C之間，並且收集低沸的副產物。在二乙二醇完 全添加之後，使反應混合物在反應容器中停留約6小時， 在這段期間內，使反應容器的壓力由約7 6 0托的起始壓力 逐漸下降至約1 6 4托的最終壓力，並且持續去除低沸的副 產物。當壓力到達164托時，反應容器的溫度爲約i〇2t：。 在冷卻時，以31P-NMR來分析反應容器中的烷基亞磷酸醋 寡聚物之混合物，結果發現其含有95.2莫耳％的亞磷酸甲 酯和苯甲酯、1 . 1莫耳％的H-膦酸酯和3.3莫耳％的膦酸醋。 由反應容器移除的低沸副產物經稱重爲486.7克，並且發 現其含有92.5重量％的甲醇（"MeOH")和7.5重量。/。的亞磷 酸三甲酯，兩者皆是以所去除之低沸副產物的總重量爲基 -18- 200902542 準。 將碘甲烷（6.7克；0.047克莫耳）（"Mel")添加至含有來 自先前反應之底料（heel)(192克）的第二反應容器（2升的 Pyrex反應燒瓶）中。此底料含有97.7%的膦酸酯；1.8%的 H-膦酸酯；和0.5 %的膦酸酯；並且具有的酸値爲0.73毫克 KOH/克。將底料加熱至130°C，接著在4小時的時間內將 1 3 5 0.5克的烷基亞磷酸酯寡聚物混合物添加至第二反應容 器中，同時使第二反應容器的內容物維持在約1 3 0 °C。經 過在1 3 0 °C下後加熱4小時之後，31P-NMR確認了亞磷酸酯 已完全轉化成膦酸酯。 所得之烷基膦酸酯寡聚物混合物經稱重爲1 5 5 7.9克， 並且移出178.8克的烷基膦酸酯寡聚物混合物，以用來做 爲實施例2的底料。利用2 ”的刮膜蒸發器將其餘烷基膦酸 酯寡聚物混合物中的揮發性物質予以汽提，其係在絕對壓 力爲0.62托的真空下操作，並且夾套溫度爲130 °C，因而 生成了有機膦酸酯寡聚物產物。 此種有機膦酸酯寡聚物產物的特徵在於： 2 5 °C下的黏度：1 0，5 2 8厘泊 平均分子量：964克/克莫耳（以凝固點下降法來量測） 酸値：0.74毫克KOH /克 羥基値：22毫克KOH /克 P含量：1 7.4重量％ (以ICP來量測） TGA: 5重量％時爲238 °C ’ 1〇重量％時爲263 °C 膦酸甲酯和苯甲酯（以31P-NMR來量測）：9 7莫耳％ 200902542 產率：8 1 %，其係以P爲基準 實施例2 ( 9 1 9 4 - 3 ) 在安裝有上方攪拌器、加料漏斗、熱電偶和蒸餾頭的 2升圓底夾套的？7“乂反應器中裝入丁1^丨（1〇14.8克；8.18 莫耳）。在加入TMPi之後’將反應器內容物加熱至95。〇， 並且以1小時的時間來進料Bz〇H( 127.4克；1.18莫耳）。 在添加Β ζ Ο Η的期間’反應混合物的溫度係在9 5 · 9 7 °C之間 變動。接下來，以5.5小時的時間將DEG (743_9克；7.01 莫耳）進料至反應器中。在添加DEG的期間，反應器的溫 度係維持在8 5 - 9 5 °C之間’並且收集低沸的副產物。在d E G 完全添加之後，使反應混合物在反應容器中停留約7.5小 時’在這段期間內’使反應容器的壓力由約7 6 〇托的起始 壓力逐漸下降至約1 5 0托的最終壓力，並且持續去除低沸 的副產物。當壓力到達i 5 〇托時，反應容器的溫度爲約1 1 2 °C。在冷卻時，以3iP_NMR來分析反應容器中的烷基亞磷 酸酯寡聚物之混合物，結果發現其含有94.3莫耳％的亞磷 酸醋、3.6莫耳％的膦酸酯、〇 _ 5莫耳％的磷酸酯和1 · 6莫耳 H-0H酸醋。由反應容器移除的低沸副產物經稱重爲48〇 克’並且包含95.1重量％的MeOH和4.7重量％的TMPi， Μ #皆1U所去除之低沸副產物的總重量爲基準。 將Mel(6.7克；0.047莫耳）添加至含有179克來自實 施例1之底料的第二反應容器（2升的Pyrex反應燒瓶）中。 將底料加熱至1 3 0 °C，接著在4小時的時間內將1 3 7 1克的 太完基亞隣酸醋寡聚物混合物添加至第二反應容器中，同時 -20 - 200902542 使第二反應容器的內容物維持在約13 0 °c。經過在13 0 °c下 後加熱8小時之後’ 31P_NMR確認了亞磷酸酯已完全轉化成 膦酸酯。 所得之烷基膦酸酯寡聚物混合物經稱重爲1 5 5 5 · 1克’ 並且移出173克的烷基膦酸酯寡聚物混合物’以用來做爲 實施例3的底料。利用2 "的刮膜蒸發器將其餘烷基膦酸酯 寡聚物混合物中的揮發性物質予以汽提，其係在絕對壓力 爲0.66托的真空下操作，並且夾套溫度爲130 °C，因而生 成了有機膦酸酯寡聚物產物。 此種有機膦酸酯寡聚物產物的特徵在於： 25°C下的黏度：13,43 6厘泊 平均分子量：1〇7〇克/克莫耳（以凝固點下降法來量測） 酸値·_ 0.59毫克KOH/克 羥基値：20毫克KOH/克 P含量：1 7.4重量％ (以IC P來量測） T G A : 5重量％時爲2 2 3 °C，1 0重量％時爲2 5 3 °C 膦酸甲酯和苯甲酯（以31P-NMR來量測）：9 8莫耳％ 產率：8 3 %，其係以P爲基準 實施例3 (9194-7) 在安裝有上方攪拌器、加料漏斗、熱電偶和蒸餾頭的 2升圓底夾套的Pyrex反應器中裝入TMPi (1010克；8.15 莫耳）。在加入TMPi之後’將反應器內容物加熱至92。〇， 並且以1.3小時的時間來進料Bz〇H(128克；1.18莫耳）。 在添加Β ζ Ο Η的期間，反應混合物的溢度係在9 2 - 9 9 °C之間 200902542 變動。接下來，以5 · 7小時的時間將D E G ( 7 4 7.4克；7 · 0 4 莫耳）進料至反應器中。在添加DEG的期間，反應器的溫 度係維持在8 2 -1 〇 〇 °C之間，並且收集低沸的副產物。在D E G 完全添加之後，使反應混合物在反應容器中停留約3小 時，在這段期間內’使反應容器的壓力由約7 6 0托的起始 壓力逐漸下降至約100托的最終壓力，並且持續去除低沸 的副產物。當壓力到達1 0 〇托時，反應容器的溫度爲約1 1 3 °c。在冷卻時，以31p-nmr來分析反應容器中的烷基亞磷 酸酯寡聚物之混合物，結果發現其含有9 8 . 1莫耳％的亞磷 酸酯、0.7莫耳％的膦酸酯、0.57莫耳％的磷酸酯和〇_71莫 耳％的Η -膦酸酯。由反應容器移除的低沸副產物經稱重爲 496克，並且包含93.8重量％的MeOH和5.1重量％的 Τ Μ P i，兩者皆是以所去除之低沸畐[J產物的總重量爲基準。 將碘甲烷（6.53克；0.046莫耳）添加至含有173克來自 實施例2之底料的第一反應容器（2升的圓底夾套Pyrex反 應燒瓶）中。將底料加熱至1 3 0 °C，接著在4.3小時的時間 內將1317克的烷基亞磷酸酯寡聚物混合物添加至第二反 應容器中，同時使第二反應容器的內容物維持在約1 3 0 t。 經過在1 4 0 °C下後加熱4小時之後，31P-NMR確認了亞磷酸 酯已完全轉化成膦酸酯。 所得之烷基膦酸酯寡聚物混合物經稱重爲1 4 9 3克，並 且有2 1 8克的烷基膦酸酯寡聚物混合物被移除。利用2，，的 刮膜蒸發器將其餘烷基膦酸酯寡聚物混合物中的揮發性物 質予以汽提，其係在絕對壓力爲〇·7托的真空下操作，並 -22 - 200902542 且夾套溫度爲130 °C，因而生成了有機膦酸酯寡聚物產物。 此種有機膦酸酯寡聚物產物的特徵在於： 2 5 °C下的黏度：2 9，5 8 4厘泊 平均分子量：1 196克/克莫耳（以凝固點下降法來量測） 酸値：1.1毫克KOH /克 羥基値：8_6毫克KOH /克 P含量：1 7 · 2重量％ (以IC P來量測） T G A : 5重量％時爲2 4 0 °C，1 0重量％時爲2 6 1 °C 膦酸甲酯和苯甲酯（以31P-NMR來量測）：9 8 · 7莫耳％ 產率：82%，其係以P爲基準 實施例 4 (9194-24) 在安裝有上方攪拌器、加料漏斗、熱電偶和蒸餾頭的 2升圓底夾套的Pyrex反應器中裝入TMPi ( 1 03 6克；8.35 莫耳）。在加入TMPi之後，將反應器內容物加熱至94°C， 並且以1 · 3小時的時間來進料Β ζ Ο Η (1 4 1 . 5克；1 . 3 1莫耳）。 在添加ΒζΟΗ的期間，反應混合物的溫度係在94-96 °C之間 變動。接下來，以4.3小時的時間將DEG (822克；7.74莫 耳）進料至反應器中。在添加DEG的期間，反應器的溫度 係維持在81-9 3 °C之間，並且收集低沸的副產物。在DEG 完全添加之後，使反應混合物在反應容器中停留約1 · 3小 時，在這段期間內，使反應容器的壓力由約760托的起始 壓力逐漸下降至約240托的最終壓力，並且持續去除低沸 的副產物。當壓力到達240托時，反應容器的溫度爲約9 1 °C，並且此反應含有約1 544克烷基亞磷酸酯寡聚物之混合 -23 - 200902542 物。由反應容器移除的低沸副產物經稱重爲4 5 6 包含9 3 _ 1重量％的μ e Ο Η和6.8重量％的Τ Μ P i， 以所去除之低沸副產物的總重量爲基準。 將碘甲烷（7.5克；〇.〇53莫耳）添加至含有1: 先前反應之底料的第二反應容器（2升的圓底夾套 應燒瓶）中。此底料含有9 7 · 5莫耳％的鱗酸酯、2 的H-膦酸酯和0·2莫耳％的酯。在將底料加熱到 後，在4 · 5小時的時間內將1 5 2 8克的烷基亞磷酸 混合物添加至第二反應容器中，同時使第二反應 容物維持在約1 25 - 1 27°C。經過在130°C下後加熱 後，31P-NMR確認了亞磷酸酯已完全轉化成膦酸酿 將所得之烷基膦酸酯寡聚物混合物首先予 提，而在最終條件爲1 3 8托及1 2 7 °c的情況·下去p 的揮發性物質。經過"預先汽提”之後，烷基膦酸 之混合物經稱重爲1 6 3 3克’其中有2 5 8克被移 2 ··的刮膜蒸發器將其餘烷基膦酸酯寡聚物混合物 性物質予以汽提’其係在絕對壓力爲〇 . 4 5托的 作，並且夾套溫度爲130 °C ’因而生成了有機膦 物產物。 此種有機膦酸酯寡聚物產物的特徵在於： 25r下的黏度：4，286厘泊 平均分子量：762克/克莫耳（以凝固點下降妇 酸値：1.2毫克KOH /克 經基値：56.9暈克KOH /克 克，並且 兩者皆是 59克來自 Pyrex 反 .2莫耳％ 125°C 之 酯寡聚物 容器的內 4小時之 卜 以批次汽 余35.7克 酯寡聚物 除。利用 中的揮發 真空下操 酸酯寡聚 來量測） -24- 200902542 P含量：1 6.5重量％ (以IC P來量測） T (3 A : 5重量％時爲2 1 9 °C，1 0重量％時爲2 4 6 °C 膦酸甲酯和苯甲酯（以31P-NMR來量測）：96.8莫耳％ 產率：80%，其係以P爲基準 實施例 5 (9 1 94-47) 在安裝有上方攪拌器、加料漏斗、熱電偶和蒸餾頭的 2升圓底夾套的Pyrex反應器中裝入TMPi ( 1 005克；8.1 莫耳）。在加入TMPi之後，將反應器內容物加熱至95°C， 並且以1 . 3小時的時間來進料Β ζ Ο Η (1 2 6克；1 · 1 7莫耳）。 在添加ΒζΟΗ的期間，反應混合物的溫度係在95-97 °C之間 變動。接下來，以4小時的時間將DEG (818克；7.7莫耳） 進料至反應器中。在添加DEG的期間，反應器的溫度係維 持在8 3 - 9 2 °C之間，並且收集低沸的副產物。在d E G完全 添加之後’使反應混合物在反應容器中停留約1 . 5小時， 在這段期間內’使反應容器的壓力由約7 6 0托的起始壓力 逐漸下降至約1 4 5托的最終壓力，並且持續去除低沸的副 產物。當壓力到達〗4 5托時，反應容器的溫度爲約1 〇〗t。 在冷卻時’以31 P_NMR來分析反應容器中的烷基亞磷酸酯 寡聚物之混合物’結果發現其含有98.0莫耳％的亞磷酸 醋、0.8莫耳％的膦酸酯、〇·3莫耳％的磷酸酯和〇 8莫耳％ 的H-鱗酸酷。由反應容器移除的低沸副產物經稱重爲5〇6 克’並且包含92重量％的Me〇H和7·5重量％的TMPi，兩 者皆是以所去除之低沸副產物的總重量爲基準。 和蛛甲k(7.1克；005莫耳）添加至含有228克來自先 -25- 200902542 前反應之底料的第二反應容器（2升的圓底夾套Pyrex反應 燒瓶）中。此底料含有9 8 · 8莫耳％的膦酸酯、1 ·丨莫耳％的 Η -膦酸酯和〇 . 2莫耳％的酯。將底料加熱至} 3 〇乞，接著在 4小時的時間內將1 4 0 2克的烷基亞磷酸酯寡聚物混合物添 加至第一反應容器中，同時使第二反應容器的內容物維持 在約1 3 0 C。經過在1 3 0。(：下後加熱4小時之後’ 31P-NMR確 認了亞磷酸酯已完全轉化成膦酸酯。 所得之烷基膦酸酯寡聚物混合物經稱重爲1 6 3 7克，並 且有361克的烷基膦酸酯寡聚物混合物被移除。利用2,，的 刮膜蒸發器將其餘烷基膦酸酯寡聚物混合物中的揮發性物 質予以汽提’其係在絕對壓力爲0.75托的真空下操作，並 且夾套溫度爲130 °C，因而生成了有機膦酸酯寡聚物產物。 此種有機隣酸酯寡聚物產物的特徵在於： 25°C下的黏度：Π，556厘泊 平均分子量·· 8 9 5克/克莫耳（以凝固點下降法來量測） 酸値：0.9 1毫克KOH/克 羥基値：28毫克KOH/克 P含量：1 7.0重量％ (以IC P來量測） TGA: 5重量％時爲229 °C，1〇重量％時爲252 °C 膦酸甲酯和苯甲酯（以31P-NMR來量測）：97.7莫耳％ 產率：7 8 %，其係以P爲基準 實施例 6 (9194-38) 在安裝有上方攪拌器、加料漏斗、熱電偶和蒸餾頭的 2升圓底夾套的Pyrex反應器中裝入TMPi (1000克；8.06 -26- 200902542 莫耳）。在加入TMPi之後，將反應器內容物加熱至95°C， 並且以1小時的時間來進料BzOH(129.2克；1.29莫耳）。 在添加Β ζ Ο Η的期間，反應混合物的溫度係在9 5 - 9 8。(：之間 變動。在添加了 ΒζΟΗ之後，使25重量％的甲氧化鈉（1.45 克）溶液與反應器內容物混合。接下來，以4小時的時間將 DEG (732克；6.9莫耳）進料至反應器中。在添加DEG的期 間’反應器的溫度係維持在8 3 -95 °C之間，並且收集低沸的 副產物。在DEG完全添加之後，使反應混合物在反應容器 ' 中停留約2.5小時，在這段期間內，使反應容器的壓力由 約7 6 0托的起始壓力逐漸下降至約400托的最終壓力，並 且持續去除低沸的副產#。當壓力到達4 0 0托時，反應容 器的溫度爲約99°C，並且此反應含有約1 470克的烷基亞 磷酸酯寡聚物混合物。由反應容器移除的低沸副產物經稱 重爲394.4克，並且包含94.8重量％的MeOH和5.2重量·/ο 的TM P i ’兩者皆是以所去除之低沸副產物的總重量爲基 準。 移除一部分（1 1 02克）的烷基亞磷酸酯寡聚物混合物》 將碘甲烷（1.62克）添加至反應器的其餘烷基亞磷酸酯寡聚 物中。將反應器內容物在1 3 0 °C下加熱3小時，以產生膦 酸酯寡聚物之混合物底料。接著將5.8克的碘甲烷添加至 底料中。接著在4小時的時間內將1 1 02克的烷基亞磷酸酯 寡聚物混合物添加至反應容器中，同時使反應容器內容物 維持在1 3 0 °C。經過在1 3 0 °C下後加熱4小時之後，31P-NMR 確認了亞磷酸酯已完全轉化成膦酸酯。 -27 - 200902542 將所得之烷基膦酸酯寡聚物混合物首 提，而在最終條件爲49托及126 °C的情況下 揮發性物質，並且接著利用2 "的刮膜蒸發器 留的揮發性物質，其係在絕對壓力爲 0.46 作，並且夾套溫度爲130 °C，因而生成了有 物產物。 此種有機膦酸酯寡聚物產物的特徵在於 2 5。〇下的黏度：2，6 6 8厘泊 平均分子量：619克/克莫耳（以凝固點Ί 酸値：4.0毫克ΚΟΗ/克 經基値：48毫克ΚΟΗ/克 Ρ含量：1 7.2重量％ (以IC Ρ來量測） T G A : 5重量％時爲2 1 2 °C ’ 1 〇重量。時 膦酸甲_和苯甲酯（以31p_NMR來量測）： 產率：7 7 %，其係以P爲基準 先予以批次汽 去除5 4.3克的 來去除所有殘 托的真空下操 機膦酸酯寡聚 降法來量測） 爲 23 8 °C 9 7.6莫耳％ -28 -Munich, 1 985, 176-1 77 or Woods, G. 聚 聚 聚 基 基 基 发泡 发泡 发泡 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学When the organic phosphonate oligomer formed by the present invention is used to form a flame-retardant polyurethane, the amount of the organophosphonate oligomer mixture of the present invention generally used is from about 4 to about 1. Within the range of 5% by weight, based on the total weight of the polyurethane formulation. The organic phosphonate oligomer product produced by the present invention is typically colorless or 200902542 is a pale grayish white. The lighter color is advantageous because it simplifies the work that the end user must do to ensure the color consistency of the article providing the flame retardant function of the oligomer product. The organophosphonate oligomer mixture produced by the present invention can also be used as a barrier in polyurethane resin and composites, rigid polyurethane foams, phenolic resins, paints, varnishes and textiles. Burning agents, or use them with them. Further, the organophosphonate oligomer mixture of the present invention can be used in a formulation having other flammable materials as an added flame retardant. The flammable material can be a macromolecule, an example, a fibrous material or a polymer. Illustrative examples of polymers are: olefin polymers, cross-linking and other homopolymers of, for example, ethylene, propylene and butene; copolymers of two or more such olefinic monomers and one or more of this Copolymers of olefin monomers with other copolymerizable monomers, such as 'ethylene/propylene copolymers, ethylene/ethyl acrylate copolymers and ethylene/propylene copolymers, ethylene/acrylate copolymers and ethylene/vinyl acetate copolymers a polymer of an olefinically unsaturated monomer, for example, polystyrene- (such as impact-resistant polystyrene) and a styrene copolymer; polyamine; polyimine; polycarbonate; polyether; acrylic resin; Polyesters, especially poly(ethylene phthalate) and poly(butylene phthalate); thermosets such as epoxy resins; elastomers such as butadiene/styrene copolymers and butadiene / acrylonitrile copolymer; terpolymer of acrylonitrile, butadiene and styrene; natural rubber; butyl rubber and polyoxyalkylene. The polymer may be crosslinked by chemical or illuminating, as appropriate. The organophosphonate oligomer product of the present invention can also be used in textile applications such as latex based backings. -16- 200902542 The amount of the organophosphonate oligomer mixture produced by the present invention in the formulation is required to achieve the desired amount of flame retardant effect. It will be apparent to those skilled in the art that, in all cases, there will be no single precise number of products in the formulation, as this ratio will vary with the particular flammable materials, other additives used. The presence and the flame retardant effect set in any given application vary. In addition, the proportions required to achieve the flame retardant effect of a particular formulation will be affected by the shape of the article (eg, 'electrical insulation, piping, electronics cabinets, and membranes'). Not the same. However, the formulations and the resulting product may generally contain from about 1 to about 30% by weight of the organophosphonate oligomer mixture of the present invention, preferably from about 5 to about 25 percent by weight. A polymer masterbatch containing a mixture of the organophosphonate oligomers of the present invention, which is blended with an additional amount of substrate polymer 'usually containing a higher concentration of the organic phosphonate of the invention. The oligomer mixture, for example, is up to 50% by weight or more. The oligomeric flame retardant of the present invention can be used in combination with any of a variety of additives conventionally used in thermoplastic formulations, for example, plasticizers, antioxidants, tanning agents, pigments, UV stabilizers, etc. The thermoplastic article formed from the formulation comprising the thermoplastic polymer and the oligomeric product of the present invention can be produced in a conventional manner, for example, by injection molding, extrusion molding, compression molding, and the like. In some specific examples, blow molding may also be a suitable manufacturing method. The practical application and advantages of the present invention can be more clearly understood from the following exemplary embodiments -17-200902542. These examples are not intended to limit the invention to the scope of the description. EXAMPLES Example 1 (9 1 5 3 - 1 9 7) A Pyrex reaction flask equipped with a 2 liter round bottom jacket equipped with an upper stirrer, an addition funnel, a thermometer and a distillation head was charged with phosphorous acid tri Methyl ester ("TMPi") (992.8 g; 8.0 mol). After the addition of TMPi, the reactor contents were heated to 95 ° C and the benzyl alcohol was fed in a period of 1.2 hours ("BzOH") (134.8 g; 1.25 mol). During the addition of benzyl alcohol, the temperature of the reaction mixture was varied between 92 and 95 ° C. Next, diethylene glycol was added over a period of 5 hours ("DEG") (724 g; 6.82 mol) was fed to the reactor. During the addition of diethylene glycol, the temperature of the reactor was maintained between about 8 2 - 9 2 ° C and low boiling was collected. By-product. After the diethylene glycol is completely added, the reaction mixture is allowed to stand in the reaction vessel for about 6 hours, during which the pressure of the reaction vessel is gradually decreased from about 75 Torr to about 1 Torr. 6 4 Torr of final pressure and continuous removal of low boiling by-products. When the pressure reaches 164 Torr, The temperature of the reaction vessel was about i〇2t: Upon cooling, the mixture of the alkyl phosphite oligopolymer in the reaction vessel was analyzed by 31P-NMR, and it was found to contain 95.2 mol% of methyl phosphite and Benzyl methyl ester, 1.1 mol% H-phosphonate and 3.3 mol% phosphonic acid vinegar. The low boiling by-product removed from the reaction vessel was weighed to 486.7 g and found to contain 92.5% by weight. Methanol ("MeOH") and 7.5 wt% trimethyl phosphite, both based on the total weight of the low boiling by-products removed -18-200902542. Methyl iodide (6.7 g) ; 0.047 gram of mol) ("Mel") was added to a second reaction vessel (2 liters of Pyrex reaction flask) containing the heel (192 grams) from the previous reaction. This primer contained 97.7%. Phosphonate; 1.8% H-phosphonate; and 0.5% phosphonate; and having a strontium of 0.73 mg KOH/g. The base is heated to 130 ° C, followed by a 4 hour period 1 3 5 0.5 g of the alkyl phosphite oligomer mixture is added to the second reaction vessel while making the contents of the second reaction vessel It was maintained at about 130 ° C. After heating at 130 ° C for 4 hours, 31 P-NMR confirmed that the phosphite had been completely converted to the phosphonate. The resulting alkyl phosphonate oligomer mixture It was weighed to 1 5 5 7.9 g, and 178.8 g of the alkylphosphonate oligomer mixture was removed for use as the primer of Example 2. The volatiles in the remaining alkylphosphonate oligomer mixture were stripped using a 2" wiped film evaporator operating at a vacuum of 0.62 Torr absolute and a jacket temperature of 130 °C. Thus, an organic phosphonate oligomer product is produced. The organic phosphonate oligomer product is characterized by: viscosity at 25 ° C: 10, 5 2 8 cps average molecular weight: 964 g / gram Mo Ear (measured by the freezing point drop method) Acid strontium: 0.74 mg KOH / gram hydroxy hydrazine: 22 mg KOH / gram P content: 1 7.4% by weight (measured by ICP) TGA: 238 ° C at 5 wt% '1〇% by weight is 263 °C methyl phosphonate and benzyl ester (measured by 31P-NMR): 9 7 mol % 200902542 yield: 8 1 %, based on P as the reference example 2 ( 9 1 9 4 - 3 ) In a 7 liter reactor equipped with a 2 liter round bottom jacket with an upper stirrer, addition funnel, thermocouple and distillation head, 1 〇 1 丨 (1 〇 14.8 g; 8.18 Moore). The reactor contents were heated to 95 after the addition of TMPi. 〇, and Bz〇H (127.4 g; 1.18 mol) was fed in 1 hour. During the addition of Β Ο Η ’, the temperature of the reaction mixture fluctuated between 9 5 · 9 7 °C. Next, DEG (743_9 g; 7.01 mol) was fed to the reactor over a period of 5.5 hours. During the addition of DEG, the temperature of the reactor was maintained between 8 5 - 95 ° C and the low boiling by-products were collected. After the complete addition of d EG, the reaction mixture was allowed to stand in the reaction vessel for about 7.5 hours ' during this period' to gradually reduce the pressure of the reaction vessel from the initial pressure of about 76 Torr to about 150 Torr. Pressure and continuous removal of low boiling by-products. When the pressure reached i5 Torr, the temperature of the reaction vessel was about 1 1 2 °C. Upon cooling, the mixture of alkyl phosphite oligomers in the reaction vessel was analyzed by 3iP_NMR, and it was found to contain 94.3 mol% of phosphite sulfate, 3.6 mol% of phosphonate, and 〇 5 mol. % phosphate and 1.6 mol H-0H vinegar. The low-boiling by-product removed from the reaction vessel was weighed to 48 gram' and contained 95.1% by weight of MeOH and 4.7% by weight of TMPi, based on the total weight of the low-boiling by-product removed by 11U. Mel (6.7 g; 0.047 mol) was added to a second reaction vessel (2 liter Pyrex reaction flask) containing 179 g of the base from Example 1. The bottom material was heated to 130 ° C, and then 137 μg of the taiji phthalate oligomer mixture was added to the second reaction vessel over a period of 4 hours while -20 - 200902542 The contents of the second reaction vessel were maintained at about 130 °C. After 31 hours of heating at 130 ° C, <31P_NMR confirmed that the phosphite had been completely converted to the phosphonate. The resulting alkylphosphonate oligomer mixture was weighed to 1 5 5 5 · 1 g' and 173 g of the alkylphosphonate oligomer mixture was removed for use as the primer of Example 3. The volatiles in the remaining alkylphosphonate oligomer mixture were stripped using a 2 " wiped film evaporator operating at a vacuum of 0.66 Torr absolute and a jacket temperature of 130 °C Thus, an organic phosphonate oligomer product is formed. The organic phosphonate oligomer product is characterized by: viscosity at 25 ° C: 13,43 6 cps average molecular weight: 1 〇 7 gram / gram of mol (measured by the freezing point drop method) ·_ 0.59 mg KOH / g hydroxy hydrazine: 20 mg KOH / g P content: 1 7.4 wt% (measured by IC P) TGA: 2 2 3 ° C at 5 wt%, 2 at 10 wt% 5 3 °C methylphosphonate and benzyl ester (measured by 31P-NMR): 9 8 mol% yield: 83% based on P as Example 3 (9194-7) at installation A 2 liter round bottom jacketed Pyrex reactor with an agitator, addition funnel, thermocouple and distillation head was charged with TMPi (1010 g; 8.15 mol). The reactor contents were heated to 92 after the addition of TMPi. 〇, and Bz〇H (128 g; 1.18 mol) was fed in 1.3 hours. During the addition of Β ζ Η ,, the overflow of the reaction mixture was between 9 2 - 9 9 °C and 200902542. Next, D E G (7 4 7.4 g; 7 · 0 4 mole) was fed to the reactor over a period of 5 · 7 hours. During the addition of DEG, the temperature of the reactor was maintained between 8 2 -1 〇 C °C and low boiling by-products were collected. After the DEG is completely added, the reaction mixture is allowed to stand in the reaction vessel for about 3 hours, during which time the pressure of the reaction vessel is gradually decreased from a starting pressure of about 760 Torr to a final pressure of about 100 Torr, and The low boiling by-products are continuously removed. When the pressure reached 10 Torr, the temperature of the reaction vessel was about 1 13 °c. Upon cooling, the mixture of alkyl phosphite oligomers in the reaction vessel was analyzed at 31 p-nmr and found to contain 9.8 mol% phosphite, 0.7 mol% phosphonate, 0.57 mol% of phosphate and 〇71 mol% of ruthenium-phosphonate. The low-boiling by-product removed from the reaction vessel was weighed to 496 g and contained 93.8% by weight of MeOH and 5.1% by weight of ΤP i, both of which were removed by the low boiling enthalpy [J product total The weight is the benchmark. Methyl iodide (6.53 g; 0.046 moles) was added to a first reaction vessel (2 liter round bottom jacketed Pyrex reaction flask) containing 173 grams of the base from Example 2. The bottom material was heated to 130 ° C, and then 1317 grams of the alkyl phosphite oligomer mixture was added to the second reaction vessel over a period of 4.3 hours while maintaining the contents of the second reaction vessel at About 1 3 0 t. After heating at 140 ° C for 4 hours, 31 P-NMR confirmed that the phosphite had been completely converted into a phosphonate. The resulting alkylphosphonate oligomer mixture was weighed to 14.93 g, and 218 g of the alkylphosphonate oligomer mixture was removed. The volatiles in the remaining alkylphosphonate oligomer mixture are stripped using a 2,, wiper evaporator, operating at a vacuum of 〇·7 Torr, and -22 - 200902542 and The jacket temperature was 130 °C, thus producing an organic phosphonate oligomer product. The organic phosphonate oligomer product is characterized by: Viscosity at 25 ° C: 2 9,5 8 4 cps Average molecular weight: 1 196 g / g mole (measured by the freezing point drop method)値: 1.1 mg KOH / gram of hydroxy hydrazine: 8_6 mg KOH / gram P content: 1 7 · 2% by weight (measured by IC P) TGA : 2 4 0 ° C at 5 wt%, 10% by weight Methylphosphonate and benzyl ester at 2 6 1 °C (measured by 31P-NMR): 9 8 · 7 mol % yield: 82% based on P as Example 4 (9194-24) ) A TMPi (1 03 6 g; 8.35 mol) was charged in a 2 liter round bottom jacketed Pyrex reactor equipped with an overhead stirrer, addition funnel, thermocouple and distillation head. After the addition of TMPi, the reactor contents were heated to 94 ° C and fed Β ζ Η (1 4 1.5 g; 1.3 1 mol) for 1.3 hours. During the addition of hydrazine, the temperature of the reaction mixture varied between 94 and 96 °C. Next, DEG (822 g; 7.74 mol) was fed to the reactor over a period of 4.3 hours. During the addition of DEG, the temperature of the reactor was maintained between 81 and 3 °C and low boiling by-products were collected. After the DEG is completely added, the reaction mixture is allowed to stand in the reaction vessel for about 1.3 hours, during which the pressure of the reaction vessel is gradually lowered from a starting pressure of about 760 Torr to a final pressure of about 240 Torr, and The low boiling by-products are continuously removed. When the pressure reached 240 Torr, the temperature of the reaction vessel was about 91 ° C, and the reaction contained about 1 544 grams of a mixture of alkyl phosphite oligomers -23 - 200902542. The low-boiling by-product removed from the reaction vessel is weighed to 4 5 6 containing 9 3 _ 1% by weight of μ e Ο Η and 6.8% by weight of Τ Μ P i to the total weight of the low-boiling by-product removed As the benchmark. Methyl iodide (7.5 g; 〇. 〇 53 mol) was added to a second reaction vessel (2 liter round bottom jacketed flask) containing 1: the base of the previous reaction. This primer contained 97. 5 mol% of squarate, 2 of H-phosphonate and 0.2 mol% of ester. After heating the primer, a mixture of 1558 grams of alkylphosphite is added to the second reaction vessel over a period of 4.5 hours while maintaining the second reaction vessel at about 1 25 -1 27 ° C. After post-heating at 130 ° C, 31 P-NMR confirmed that the phosphite had been completely converted to the phosphonic acid. The resulting alkylphosphonate oligomer mixture was firstly extracted, and the final condition was 138 Torr. And in the case of 1 2 7 °c, go to the volatile substance of p. After "pre-stripping, the mixture of alkylphosphonic acids was weighed to 163 3 grams, of which 2,58 grams were removed by a wiper evaporator to oligomerize the remaining alkylphosphonates. The mixture of substances is stripped 'at an absolute pressure of 〇 45 Torr and the jacket temperature is 130 ° C ' and thus produces an organic phosphine product. The organic phosphonate oligomer product It is characterized by: viscosity at 25r: 4,286 centipoise average molecular weight: 762 g / gram of molar (decreased by freezing point: 1.2 mg KOH / gram base 値: 56.9 克 KOH / gram, and both All were 59 g of the ester oligomer container from Pyrex anti-2 mol % 125 ° C for 4 hours, except for 35.7 g of ester oligomers in batches. Aggregate measurement) -24- 200902542 P content: 1 6.5 wt% (measured by IC P) T (3 A : 2 1 9 °C at 5 wt%, 2 4 6 ° at 10 wt%) C methyl phosphonate and benzyl ester (measured by 31P-NMR): 96.8 mol% yield: 80% based on P as Example 5 (9 1 94-47) A 2 liter round bottom jacketed Pyrex reactor with a square stirrer, addition funnel, thermocouple and distillation head was charged with TMPi (1 005 g; 8.1 mol). After addition of TMPi, the reactor contents were heated to 95. °C, and feed Β Ο Η Η (1 2 6 g; 1 · 1 7 mol) for 1.3 hours. During the addition of hydrazine, the temperature of the reaction mixture is 95-97 °C. The change was followed. Next, DEG (818 g; 7.7 mol) was fed to the reactor over a period of 4 hours. During the addition of DEG, the temperature of the reactor was maintained between 8 3 - 9 2 °C. And collecting low boiling by-products. After the d EG is completely added, 'the reaction mixture is allowed to stand in the reaction vessel for about 1.5 hours, during which the pressure of the reaction vessel is started from about 760 Torr. The pressure gradually drops to a final pressure of about 145 Torr and the low boiling by-products are continuously removed. When the pressure reaches 〖45 Torr, the temperature of the reaction vessel is about 1 〇 t. When cooled, '31 P_NMR Analysis of the mixture of alkyl phosphite oligomers in the reaction vessel was found to contain 98.0 moles. % of phosphite sorbate, 0.8 mol% of phosphonate, 〇·3 mol% of phosphate and 〇8 mol% of H-quaternary acid. Low-boiling by-products removed from the reaction vessel are weighed It is 5 〇 6 grams' and contains 92% by weight of Me 〇 H and 7.5 % by weight of TMPi, both based on the total weight of the low boiling by-products removed. And spider K (7.1 g; 005 mol) was added to a second reaction vessel (2 liter round bottom jacketed Pyrex reaction flask) containing 228 grams of the base from the previous -25-200902542 reaction. This primer contained 9 8 · 8 mol% of phosphonate, 1 · mol% of bismuth-phosphonate and 2 mol% of ester. The bottom material was heated to 3 Torr, and then 1,420 grams of the alkyl phosphite oligomer mixture was added to the first reaction vessel over a period of 4 hours while the contents of the second reaction vessel were made Maintain at about 1 30 C. After passing at 1 3 0. (: After heating for 4 hours) '31P-NMR confirmed that the phosphite had been completely converted to the phosphonate. The obtained alkylphosphonate oligomer mixture was weighed to 167 g and had 361 g. The alkylphosphonate oligomer mixture was removed. The volatiles in the remaining alkylphosphonate oligomer mixture were stripped using a 2,, wiped film evaporator at an absolute pressure of 0.75. The operation was carried out under vacuum and the jacket temperature was 130 ° C, thus producing an organic phosphonate oligomer product. This organic orthoester oligomer product is characterized by: viscosity at 25 ° C: Π, 556 cps average molecular weight · · 8 9 5 g / g mole (measured by the freezing point drop method) strontium: 0.9 1 mg KOH / gram hydroxy hydrazine: 28 mg KOH / gram P content: 1 7.0% by weight IC P to measure) TGA: 229 °C at 5 wt%, 252 °C at 1 wt% methyl phosphinate and benzyl ester (measured by 31P-NMR): 97.7 mol% yield : 7 8 %, based on P Example 6 (9194-38) 2 liter round bottom clamp with top stirrer, addition funnel, thermocouple and distillation head The Pyrex reactor was charged with TMPi (1000 g; 8.06 -26-200902542 Mohr). After the addition of TMPi, the reactor contents were heated to 95 ° C and BzOH (129.2 g was fed over 1 hour). 1.29 moles. During the addition of Β ζ Ο ,, the temperature of the reaction mixture was between 9 5 and 9 8 ((): after adding hydrazine, 25% by weight of sodium methoxide (1.45 g) The solution was mixed with the reactor contents. Next, DEG (732 g; 6.9 m) was fed to the reactor over a period of 4 hours. During the addition of DEG, the temperature of the reactor was maintained at 8 3 - Between 95 ° C, and collecting low boiling by-products. After the DEG is completely added, the reaction mixture is allowed to stand in the reaction vessel for about 2.5 hours, during which the pressure of the reaction vessel is about 760 Torr. The initial pressure gradually drops to a final pressure of about 400 Torr, and the low boiling by-product # is continuously removed. When the pressure reaches 400 Torr, the temperature of the reaction vessel is about 99 ° C, and the reaction contains about 1 470. Alkyl phosphite oligomer mixture. by reaction vessel The low boiling by-products were weighed to 394.4 grams and contained 94.8% by weight of MeOH and 5.2 weights of TM P i 'based on the total weight of the low boiling by-products removed. Except for a portion (1 1 02 g) of the alkyl phosphite oligomer mixture, methyl iodide (1.62 g) was added to the remaining alkyl phosphite oligomer of the reactor. The reactor contents were at 1 3 Heating at 0 °C for 3 hours to produce a mixture of phosphonate oligomers. Next, 5.8 grams of methyl iodide was added to the bottom. Then, 1102 g of the alkyl phosphite oligomer mixture was added to the reaction vessel over a period of 4 hours while maintaining the contents of the reaction vessel at 130 °C. After post-heating at 130 °C for 4 hours, 31 P-NMR confirmed complete conversion of the phosphite to the phosphonate. -27 - 200902542 The resulting alkylphosphonate oligomer mixture was first extracted, and the volatiles were obtained at a final condition of 49 Torr and 126 ° C, and then retained by a 2 " wiped film evaporator The volatile material was produced at an absolute pressure of 0.46 and the jacket temperature was 130 °C, thus producing a product. Such an organic phosphonate oligomer product is characterized by 25 . Viscosity of the underarm: 2,6 6 8 cps Average molecular weight: 619 g / gram of mol (with freezing point bismuth citrate: 4.0 mg ΚΟΗ / gram base 値: 48 mg ΚΟΗ / gram Ρ content: 1 7.2% by weight ( Measured by IC )) TGA: 2 1 2 °C '1 〇 by weight at 5 wt%. A and phenyl methyl phosphonate (measured by 31p_NMR): Yield: 7 7 %, Based on P, the batch steam removal of 5 4.3 grams was used to remove all the residual vacuum under the vacuum of the phosphonate oligomerization method to measure) 23 8 ° C 9 7.6 mol % -28