方法；一種是如德國專利第884,947號和美國專利第 2，S23,2；37號所述，添加通常至少20〇/。的醇，例如甲醇至甲 越锻料内；另一種則是英國專利第1，〇28,8〇4號所述，添加 安定劑，例如三秦’或是GB專利第93 1，892號所述，將脂 族胺、二胺、第三胺或羥基胺及基本上足以中和溶液之鹼 添加至甲酸水溶液内°至今’只報導過製造三聚甲酸薄片 或塊狀時添加胺類化合物；而需要不同技術製造球時則 不需要。 甲趁的聚合方法據説甚至在形成三聚甲越·薄片或小球後 仍然持續著。因此三聚甲醛的分子量在儲存期間會增加。 此因素因而使得必需的三聚甲醛產物溶解度降低，有時候 在儲存時會降得更快。有報導指出聚合作用抑制劑例如美 國專利第2,519,981號和美國專利第2,519,550號中所述之乙 内醯尿，以及德國專利第1，1 I2,505號中所述之季戊四醇可 以預防此種不必要的熟化過程《其它報導中有效的抑制劑 包括法國專利第1，486,〇60號和德國專利第7〇1〇22號中所述 之脂族和環狀胺及胺基酸。日本專利第73/48-1 7,250和 7 3/48-δ,6 〇3中報導溶於水和溶劑（甲醇）的六亞甲基四胺可 以抑制儲存期間三聚甲醛的聚合作用。 雖然報導了許多抑制熟化效應的方法，但是本藝顯示持 續有必要製造甚至在儲存後溶解時間短而且確實無不溶物 之三聚甲醛。 發明摘要 本發明係關於製造甚至在儲存一段時間後溶解時間短而 -7- 本纸張尺度適用中國國家標準（CNS) 規格（2丨0 χ 297公釐） in . (請先閲讀背面之注意事項再填寫本頁〕 ^- 經濟部中央橾準局員工消費合作社印製 ------- 經濟部中央揉準局員工消費合作社印裝 408149 a? 五、發明説明（1 ) 發明範園 本發明係廣泛關於製造三聚甲醛的方法β 發明背景 本發明係關於製造固態三聚甲醛時對高度濃縮之甲趁的 處理。此技術改善了三聚甲醛的溶解度和儲存期限。本產 物主要使用於油漆和塗料工業。 三聚甲醛是含有80%或以上甲醛的固體型態。典型上甲 趁濃度範圍爲90%至96%。三聚甲膝被認爲是聚（甲齡）乙 —醇，和η = 8-100的HO-(CH2〇)n-H。一般是在減壓下藉由濃 縮熱甲醛水溶液而製造三聚甲醛》冷卻時，所生成的溶液 會固化。以此法製造的三聚甲醛通常時間久了就不安定。 三聚甲醛在製造完成後，立即顯示在水和有機溶劑例如丁 醇中極佳之溶解度。三聚甲醛很容易在水或醇中藉由水解 或解聚而落解生成游離態的甲搭。不過，通常在35 °C以上 的溫度下三聚甲搭在水和溶劑中的溶解度隨著時間或儲存 而減少。此種溶解度的變化據推測可能是由於三聚甲醛的 分子量改變引起。爲了除去這種現象，有人提議使用許多 安定劑和抑制劑。不過’迄今，只有一些能有效地延缓與 三聚甲醛有關的熟化現象。一般來説，溶解度大部份因聚 合作用程度或聚合物的鏈長n而定。因此，必須控制甲醛成 爲三聚甲醛的聚合作用。然而，大部份被試驗的三聚甲醛 中，並非全部皆溶於溶劑内。也就是部份三聚甲醛仍然維 持固態不溶於溶液。這些不溶物咸信是聚（甲醛）乙二醇醚 。此後指的是醚或不溶物。一般認爲這些醚會影響物理性 -4- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公楚） I---------^------II------0 '- C請先閲讀背面之注^事項 ：寫本頁) 第 案 中文說明書修正頁(87年11月） A7 B7 經濟部中央標隼局員工消资合作社印製 五、發明説明（5) 且確實無不溶物之三聚甲醛。業經發現在三聚甲醛的造粒 温度下’將約0.1至約ppm非常不會揮發並會溶於甲 趁和三聚甲醛水溶液的胺，於三聚甲醛造粒和形成期間内 ’在適當時間下添加至甲醛中，會生成溶解時間短且沒有 不溶物之三聚甲醛。所指的胺在化合物中具有約i至約2 〇 個碳原子。該胺可以是Cl.2G脂族胺、Ci.n脂族二胺、1至 约2 0個碳原子的羥基脂族胺、c ^ 2 〇烷氧基脂族胺、第一胺 、第二胺、第三胺和上述各具功能的胺類及其混合物。胺 可以單獨添加或在三聚甲醛製造方法開始時置於溶劑内， 例如當餵料置於約3 7 %甲醢溶液内。大部份低分子量的常 見有機溶劑和水都適用，如水、甲醇、丙酮。水是最佳溶 劑°我們已發現胺可以在約1 〇 〇 或低於該胺的沸點溫度 下倒入熱甲趁液體内。或者也可以藉由噴在確實的三聚甲 態小球上添加胺，因而達到相似效果。本文中的胺通常指 的是如添加劑或安定劑3兩者皆可交換使用。胺也能與鹼 C 1 - 2 〇月曰族醇、C !-〖5脂族煙或芳族烴添加劑胺接觸以改 善胺的安定效果。 本發明之詳細説明 本發明係提供改善前藝製造三聚甲醛小球之方法，而生 成溶解時間短及無不溶物之產物3此發明包括使用含有約i 至約2 0個碳原子之線狀和枝鏈狀胺，製造三聚甲醛小球， 以約6至1 〇個碳原子較佳。 業經發現在三聚甲醛小球中添加少量胺化合物以抑制聚 合作用。抑制聚合作用會使得三聚甲醛小球產物，具有呈 m - m -κ 11 I_ ! In ——.—1 n I i Γ m n _ ! _ nl· J3. / (請先閱讀背面之注意事項再填寫本頁) · _ 8 - 本紙張朗巾關轉準（CNS ) A4%格（210 X297公董） 經濟部中央橾準扃員工消費合作社印装 408149 A7 B7 五、發明説明（2 ) 質，如三聚甲遂的溶解度。此等醚係藉由三聚甲醛和甲醇 在私’例如甲酸存在下反應形成。如前文所述’三聚甲趁 產物必須能快速溶解、很少製造甚或無不溶物，而且在错 存期間不會繼續聚合。有報導指出在聚合作用期間，三聚 甲醛與醇，如甲醇反應形成乙二醇醚β此反應係由酸催化 。典型上甲酸係以低濃度存在於三聚甲醛内，做爲該反應 之催化劑°這些醚不溶於水’因此在三聚甲趁溶解後仍會 維持細微顆粒物質。所以，聚合作用的程度、甲酸濃度和 甲醇屬性直接與二聚曱醒的溶解度和不溶物的問題有關。 二聚曱遂必需具有低聚合作用、高度溶解度、很少或無溶 解物、以及最重要的，不會在35 "C以上的溫度下隨時間或 儲存而改變。 三聚甲搭係由熱濃縮甲酸溶液中製造出來，其中甲兹從 約3 0 %變爲约9 0 % ’最常見爲約8 〇 %甲赵》製造固態三聚 曱醛的各種方法：（1)在反應瓶内利用或不用催化劑，並以 機械方式分散已形成塊狀之固化濃縮的三聚甲醛溶液：（2) 將反應成份傾倒在冰冷表面，如運輸帶上；（3)將反應成份 傾倒在加熱過的滚筒裝置上；（4)利用小球塔，由此將濃縮 甲醛溶液餵進塔内藉由氣流或惰性氣體冷卻。此等方法可 以製成塊狀、薄片狀或球狀固體（也指的是如小球般）。 ΕΡΟ-716 ’ 104Α1。傳统上係藉由眞空蒸發甲醛水溶液製 造三聚甲酸3例如，Sumitomo化學公司利用眞空分館作用 將甲醛溶液濃縮至重量百分比80 %。不過，1961年6月7日， 31111^〇111〇化學公司，英國專利第869,764號中，使得在生成 本紙張尺度適用中國國家標準（CNS ) Α4规格（210Χ297公釐） ----------裝------訂------Μ (^先聞讀背*-之注^^項| .為本頁} 时it 2 ^86112523 5^' 中文說明書修正頁(SS年12月） A7 B7Method; one is as described in German Patent No. 884,947 and U.S. Patent No. 2, S23,2; No. 37, usually adding at least 200 /. Alcohol, such as methanol, into Jiayue forging; the other is the addition of stabilizers, such as San Qin 'or GB Patent No. 93 1,892, as described in British Patent No. 1,028,804. It is stated that aliphatic amines, diamines, tertiary amines, or hydroxylamines and alkalis which are substantially sufficient to neutralize the solution are added to the aqueous formic acid solution. So far, only amine compounds have been reported for the manufacture of trimellitic flakes or lumps; It is not needed when different technologies are needed to make the ball. The polymerization method of formazan is said to be continued even after the formation of the trimer-methoy · flakes or pellets. Therefore the molecular weight of paraformaldehyde increases during storage. This factor therefore reduces the solubility of the necessary paraformaldehyde product, sometimes faster during storage. It has been reported that polymerization inhibitors such as hydantoin as described in U.S. Patent No. 2,519,981 and U.S. Patent No. 2,519,550, and pentaerythritol as described in German Patent No. 1,1 I2,505 can prevent such unnecessary The maturation process "Other inhibitors effective in the report include the aliphatic and cyclic amines and amino acids described in French Patent No. 1,486,060 and German Patent No. 701022. Japanese Patent Nos. 73 / 48-1 7,250 and 7 3 / 48-δ, 603 report that hexamethylenetetramine dissolved in water and solvent (methanol) can inhibit the polymerization of paraformaldehyde during storage. Although many methods have been reported to inhibit the aging effect, the art shows that there is a continuing need to produce paraformaldehyde which has a short dissolution time even after storage and is indeed free of insolubles. Summary of the Invention The present invention is related to the manufacture of a short dissolution time even after storage for a period of time and the paper size is -7- This paper size applies to Chinese National Standard (CNS) specifications (2 丨 0 χ 297 mm) in. (Please read the note on the back first Please fill in this page again for the matters] ^-Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs --------- Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 408149 a? V. Invention Description (1) Invention Park The present invention is broadly related to a method for producing paraformaldehyde. BACKGROUND OF THE INVENTION The present invention is related to the treatment of highly concentrated formaldehyde during the manufacture of solid paraformaldehyde. This technology improves the solubility and shelf life of paraformaldehyde. This product is mainly used In the paint and coating industry. Paraformaldehyde is a solid form containing 80% or more formaldehyde. Typical upper nails have a concentration range of 90% to 96%. Trimer knee is considered to be poly (formaldehyde) ethyl alcohol , And η = 8-100 HO- (CH2〇) nH. Generally, the paraformaldehyde is produced by condensing a hot formaldehyde aqueous solution under reduced pressure. When cooled, the resulting solution will solidify. Acetal is usually long Immediately after manufacture, paraformaldehyde shows excellent solubility in water and organic solvents such as butanol. Paraformaldehyde can easily decompose into free form by hydrolysis or depolymerization in water or alcohol. Parathion. However, the solubility of trimeric parathion in water and solvents generally decreases with time or storage at temperatures above 35 ° C. Such a change in solubility is presumably caused by a change in the molecular weight of paraformaldehyde In order to remove this phenomenon, it has been proposed to use many stabilizers and inhibitors. However, so far, only some can effectively delay the maturation phenomenon related to paraformaldehyde. Generally speaking, the solubility is mostly due to the degree of polymerization or polymerization. The chain length of the product depends on n. Therefore, the polymerization of formaldehyde into paraformaldehyde must be controlled. However, not all of the tested paraformaldehyde is dissolved in the solvent. That is, part of the paraformaldehyde is still dissolved. Maintain a solid insoluble solution. These insolubles are believed to be poly (formaldehyde) glycol ethers. Hereafter referred to as ethers or insolubles. These ethers are generally considered to affect Rational-4- This paper size applies to China National Standard (CNS) Α4 specification (210X297). I --------- ^ ------ II ------ 0 '-C Please First read the note on the back ^ Note: Write this page) Revised page of the Chinese manual for the case (November 87) A7 B7 Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economy Triacetaldehyde. It has been found that at the granulation temperature of paraformaldehyde, 'about 0.1 to about ppm is very non-volatile and will dissolve in amine and aqueous paraformaldehyde amines during the period of granulation and formation of paraformaldehyde' at an appropriate time. If it is added to formaldehyde, it will generate triformaldehyde with short dissolution time and no insoluble matter. The amines referred to have from about i to about 20 carbon atoms in the compound. The amine may be a Cl.2G aliphatic amine, a Ci.n aliphatic diamine, a hydroxyaliphatic amine of 1 to about 20 carbon atoms, a c ^ 2alkoxyaliphatic amine, a first amine, a second Amines, tertiary amines and the above-mentioned functional amines and mixtures thereof. The amine can be added separately or placed in a solvent at the beginning of the paraformaldehyde manufacturing process, for example when the feed is placed in an approximately 37% formamidine solution. Most common low molecular weight organic solvents and water are suitable, such as water, methanol, and acetone. Water is the best solvent. We have found that amines can be poured into hot formic acid at a temperature of about 1,000 or below the boiling point of the amine. Or you can add amine by spraying on the solid trimer spheres to achieve similar effect. An amine herein generally means that, for example, both additive or stabilizer 3 can be used interchangeably. Amines can also be contacted with the bases C 1-2 O alcohols, C!-[5 aliphatic smoke or aromatic hydrocarbon additives amines to improve the stability of the amines. Detailed description of the present invention The present invention provides a method for improving the production of paraformaldehyde pellets in the prior art, so as to produce a product with short dissolution time and no insoluble matter. 3 This invention includes the use of a linear shape containing about i to about 20 carbon atoms. And branched chain amines, to produce paraldehyde beads, preferably about 6 to 10 carbon atoms. It has been found that small amounts of amine compounds are added to the paraformaldehyde pellets to inhibit the polymerization. Inhibition of polymerization will cause the product of paraformaldehyde to have m-m -κ 11 I_! In ——.— 1 n I i Γ mn _! _ Nl · J3. / (Please read the precautions on the back before (Fill in this page) · _ 8-This paper is printed in a CNS format (CNS) A4% (210 X297 directors) Printed by the Central Government of the Ministry of Economic Affairs, Zhunxun, Consumer Cooperatives 408149 A7 B7 V. Description of the invention (2) Such as the solubility of trimeric armor. These ethers are formed by the reaction of paraformaldehyde and methanol in the presence of a private solvent such as formic acid. As mentioned before, the 'trimer must take advantage of the fact that the product must dissolve quickly, produce little or no insoluble matter, and not continue to polymerize during staggered periods. It has been reported that during the polymerization, paraformaldehyde reacts with alcohols, such as methanol, to form glycol ether β. This reaction is catalyzed by acids. Formic acid is typically present in paraformaldehyde at a low concentration as a catalyst for the reaction. These ethers are insoluble in water 'and therefore maintain fine particulate matter after the trimer is dissolved. Therefore, the degree of polymerization, formic acid concentration, and methanol properties are directly related to the solubility and insoluble matter of dimerization. Dimerization must then have low polymerization, high solubility, little or no dissolved matter, and most importantly, not change over time or storage at temperatures above 35 ° C. Trimeric metformin is produced from a hot concentrated formic acid solution, in which formazan is changed from about 30% to about 90% 'most common is about 80% metazol.' Various methods of making solid trimeraldehyde: ( 1) Use or not use a catalyst in the reaction bottle, and mechanically disperse the solidified concentrated paraformaldehyde solution that has formed a block: (2) Pour the reaction ingredients on an ice-cold surface, such as a conveyor belt; (3) Pour the reaction The ingredients are poured onto a heated roller device; (4) a small ball tower is used, whereby the concentrated formaldehyde solution is fed into the tower and cooled by a gas stream or an inert gas. These methods can be made into lumps, flakes, or spherical solids (also referred to as pellets). Epo-716 '104A1. Traditionally, triformic acid is produced by evaporating a formaldehyde aqueous solution in the air3 For example, Sumitomo Chemical Company uses the function of the airspace branch to concentrate the formaldehyde solution to 80% by weight. However, on June 7, 1961, 31111 ^ 〇111〇 Chemical Company, British Patent No. 869,764, made the Chinese National Standard (CNS) A4 specification (210 × 297 mm) applicable to the paper size produced ------ ---- Install ------ Order ------ Μ (^ 先 闻 读 背 * -Note of ^^ item |. This page} It 2 ^ 86112523 5 ^ 'Chinese manual correction page (Dec.SS) A7 B7
五、發明説明（7 ) 經濟部中央標準局員工消費合作社印装 進一步聚合和乾燥。 適合的胺類化合物包括第一、第二 '或第三胺' 環狀胺 、二胺或鏈烷醇胺。可做為實施例的胺類包括甲胺、乙胺 、正-丙胺、正-丁胺、異-丁胺、第三丁胺、二甲胺、二乙 胺、二-正-丙胺、二-異-丙胺和二丁胺、三乙胺及三乙醇 胺、六亞甲基四胺（HMTA)、2-乙基己胺（EHA)、2-胺基 丙二醇、己胺（Η A )、乙醇胺、混合型C - 2 0胺、混合型C -10胺、環己胺、1，2 -二甲氧基丙燒胺、三乙胺、乙醇胺 、2 -胺基-1，3 -丙二醇、1-胺基-戊烷、2_甲氧基丙胺。 「混合型」指的是分支枝鏈和直鏈胺類化合物的混合物。 實驗顯示使用同一種胺的混合物與少量的苛性劑（Na〇H) 會使得最終之三聚甲醛產物的不溶物獲得某些改善。較佳 的苛性劑量包括約1〇〇 ppm的苛性劑與胺混合。依濃輪甲醛 溶液的濃度而定，苛性劑與胺形成混合物之範園是約〇 〇 ! 至約1 %。 目前已發現並非所有的胺皆可以同樣操作使得濃縮甲醛 的安定性（其中濃度範圍約60_87%)獲得改善。增加三聚甲 醛溶解度大約二因數的胺類包括乙醇胺、正_丙胺_、2 _乙 基己胺、六亞甲基四胺、二胺基戊烷和已胺（HA)。這些胺 類皆顯示在周園儲存溫度下延長儲存時間時，可以保存 70%或甚至以上的三聚甲醛之安定性。在含有這些胺的濃 縮甲酿樣本中，發現與不含這些胺或安定劑的濃縮甲越相比 ，不溶物減少約一半。也發現雖然觀察到不溶物減少，但是 -10- ΙΊ . II [ . 4本 I ^ (請先閱讀背面之注意事項再填寫本頁) 本紙乐尺度適用中國國家標李（(：”5)八4^洛（2丨0/297公釐 經濟部中央標準局貝工消費合作社印製 408149 A7 _____________ _____ 五、發明説明（3 ) 的產物中快速合成甲酸。 以前，Celanese公司在美國專利第2 568,016號和第 2,568,018號中’申請了持續兩階段眞空蒸發酸鹼値爲約2,9 至約3，5之甲路水溶液的專利。在第—個階段中，在4 5至 7〇(：’於25至1〇〇毫米汞柱下，持續加熱6〇%至8〇%的溶 液。第二個階段，在7〇至90°C間100至2 00毫米汞柱下， 進—步將甲醛溶液加熱濃縮至8 〇至9 0 %。濃縮後的曱醛維 持在100至130。(：下約180分鐘。將所生成的液體送入旋轉 削片機内製造固體片狀三聚甲醛。 文獻中顯示藉由添加催化劑能控制甲醛聚合的速率。美 國專利第2,5 19,550號和德國專利第1，〖12,505號中的兩種酸 ’及美國專利第2,568,018號和美國專利第3,772,392號中的 險據説可以加速該聚合作用。酸性催化劑的實施例有美國 專利第2S519,981號和美國專利第2,519,550號中的硼酸、四 爛酸鈉，以及德國專利第1，1 12,505號中的草酸。 關於控制三聚甲醛分子量的其它努力，有人建議改變濃 縮甲趁的乾燥條件。美國專利第2,568,018號在乾燥方法中 使用含有足以改變三聚甲趑酸鹼値之酸或鹼氣流。例如， 與三乙胺一起處理獲得濕度低於3 %並已分散爲細微顆粒狀 的三聚甲醛。不過，皆無報告指出分子量或聚合物的鏈長 會更低。 這些方法皆可製造高分子量和因而生成低溶解度之三聚 曱酸。所以三聚甲醛會變得有黏性，並且難以流動或儲存 。已有報告指出製造高溶解度或低程度聚合作用之產物的 -6 * 本紙張尺度逍闱中國國家標準（CNS > A4g ( 2ίΟΧ297公釐） I.--------枯衣------1Τ------# (請先閱讀背S-之注意事項ΐ. 為本頁)V. Description of the invention (7) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Further polymerization and drying. Suitable amine compounds include first, second, or third amine cyclic amines, diamines, or alkanolamines. Examples of amines include methylamine, ethylamine, n-propylamine, n-butylamine, iso-butylamine, tertiary butylamine, dimethylamine, diethylamine, di-n-propylamine, and di- Iso-propylamine and dibutylamine, triethylamine and triethanolamine, hexamethylenetetramine (HMTA), 2-ethylhexylamine (EHA), 2-aminopropanediol, hexylamine (ΗA), ethanolamine, Mixed C-20 amine, mixed C-10 amine, cyclohexylamine, 1,2-dimethoxypropanamine, triethylamine, ethanolamine, 2-amino-1,3-propanediol, 1- Amino-pentane, 2-methoxypropylamine. "Mixed type" refers to a mixture of branched and linear amine compounds. Experiments have shown that the use of a mixture of the same amine with a small amount of caustic (NaOH) will result in some improvement in the insolubles of the final paraformaldehyde product. Preferred caustic dosages include about 100 ppm of caustic mixed with amine. Depending on the concentration of the concentrated formaldehyde solution, the range of caustic and amine-forming mixtures is from about 0.00 to about 1%. It has been found that not all amines can be treated the same to improve the stability of concentrated formaldehyde (in which the concentration range is about 60-87%). Amines that increase the solubility of triformaldehyde by approximately two factors include ethanolamine, n-propylamine, 2-ethylhexylamine, hexamethylenetetramine, diaminopentane, and hexamine (HA). These amines have been shown to retain 70% or more of the stability of paraformaldehyde when stored at extended storage temperatures. In concentrated methyl alcohol samples containing these amines, it was found that insoluble matter was reduced by about half compared to concentrated methyl alcohol without these amines or stabilizers. It was also found that although a decrease in insoluble matter was observed, -10- ΙΊ. II [. 4 copies of I ^ (Please read the notes on the back before filling out this page) The paper scale is applicable to Chinese national standard ((: "5) eight 4 ^ Luo (2 丨 0/297 mm printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 408149 A7 _____________ _____ V. Quickly synthesize formic acid from the product of invention description (3). Previously, Celanese Company in US Patent No. 2568,016 No. and No. 2,568,018, 'applied a patent for a two-stage aqueous solution of evaporating acid and base, which is about 2,9 to about 3,5. In the first stage, between 45 and 70 (:' Under the temperature of 25 to 100 mm Hg, continuously heat the solution of 60% to 80%. In the second stage, at 100 to 200 mm Hg at 70 to 90 ° C, further formaldehyde The solution was concentrated by heating to 80 to 90%. The concentrated formaldehyde was maintained at 100 to 130. (: about 180 minutes down. The generated liquid was sent to a rotary chipper to produce solid flake paraformaldehyde. Literature Shows that the rate of formaldehyde polymerization can be controlled by adding a catalyst. U.S. Patent Nos. 2,5,19,550 and The two types of acids in German Patent No. 1, 12,505 and the risks in U.S. Patent No. 2,568,018 and U.S. Patent No. 3,772,392 are said to accelerate the polymerization. Examples of acidic catalysts are U.S. Patent No. 2S519,981 And boric acid, sodium tetradecanoate in U.S. Patent No. 2,519,550, and oxalic acid in German Patent No. 1,1 12,505. Regarding other efforts to control the molecular weight of paraformaldehyde, it has been suggested to change the drying conditions of concentrated formazan. U.S. Patent No. 2,568,018 uses an acid or base gas stream that is sufficient to change the alkali trimeric formamate in the drying method. For example, treatment with triethylamine yields paraformaldehyde having a humidity of less than 3% and dispersed into fine particles. However, there are no reports that the molecular weight or the chain length of the polymer will be lower. These methods can produce high molecular weight and thus produce low solubility trimeric acid. So paraformaldehyde will become sticky and difficult to flow or store . There have been reports indicating the production of products with high solubility or low degree of polymerization. -6 * This paper is based on Chinese National Standards (CNS > A4g ( 2ί〇Χ297mm) I .-------- Without clothes ------ 1Τ ------ # (Please read the precautions for S-back first. For this page)
方法；一種是如德國專利第884,947號和美國專利第 2，S23,2；37號所述，添加通常至少20〇/。的醇，例如甲醇至甲 越锻料内；另一種則是英國專利第1，〇28,8〇4號所述，添加 安定劑，例如三秦’或是GB專利第93 1，892號所述，將脂 族胺、二胺、第三胺或羥基胺及基本上足以中和溶液之鹼 添加至甲酸水溶液内°至今’只報導過製造三聚甲酸薄片 或塊狀時添加胺類化合物；而需要不同技術製造球時則 不需要。 甲趁的聚合方法據説甚至在形成三聚甲越·薄片或小球後 仍然持續著。因此三聚甲醛的分子量在儲存期間會增加。 此因素因而使得必需的三聚甲醛產物溶解度降低，有時候 在儲存時會降得更快。有報導指出聚合作用抑制劑例如美 國專利第2,519,981號和美國專利第2,519,550號中所述之乙 内醯尿，以及德國專利第1，1 I2,505號中所述之季戊四醇可 以預防此種不必要的熟化過程《其它報導中有效的抑制劑 包括法國專利第1，486,〇60號和德國專利第7〇1〇22號中所述 之脂族和環狀胺及胺基酸。日本專利第73/48-1 7,250和 7 3/48-δ,6 〇3中報導溶於水和溶劑（甲醇）的六亞甲基四胺可 以抑制儲存期間三聚甲醛的聚合作用。 雖然報導了許多抑制熟化效應的方法，但是本藝顯示持 續有必要製造甚至在儲存後溶解時間短而且確實無不溶物 之三聚甲醛。 發明摘要 本發明係關於製造甚至在儲存一段時間後溶解時間短而 -7- 本纸張尺度適用中國國家標準（CNS) 規格（2丨0 χ 297公釐） in . (請先閲讀背面之注意事項再填寫本頁〕 ^- 經濟部中央橾準局員工消費合作社印製 ------- 第 案 中文說明書修正頁(87年11月） A7 B7 經濟部中央標隼局員工消资合作社印製 五、發明説明（5) 且確實無不溶物之三聚甲醛。業經發現在三聚甲醛的造粒 温度下’將約0.1至約ppm非常不會揮發並會溶於甲 趁和三聚甲醛水溶液的胺，於三聚甲醛造粒和形成期間内 ’在適當時間下添加至甲醛中，會生成溶解時間短且沒有 不溶物之三聚甲醛。所指的胺在化合物中具有約i至約2 〇 個碳原子。該胺可以是Cl.2G脂族胺、Ci.n脂族二胺、1至 约2 0個碳原子的羥基脂族胺、c ^ 2 〇烷氧基脂族胺、第一胺 、第二胺、第三胺和上述各具功能的胺類及其混合物。胺 可以單獨添加或在三聚甲醛製造方法開始時置於溶劑内， 例如當餵料置於約3 7 %甲醢溶液内。大部份低分子量的常 見有機溶劑和水都適用，如水、甲醇、丙酮。水是最佳溶 劑°我們已發現胺可以在約1 〇 〇 或低於該胺的沸點溫度 下倒入熱甲趁液體内。或者也可以藉由噴在確實的三聚甲 態小球上添加胺，因而達到相似效果。本文中的胺通常指 的是如添加劑或安定劑3兩者皆可交換使用。胺也能與鹼 C 1 - 2 〇月曰族醇、C !-〖5脂族煙或芳族烴添加劑胺接觸以改 善胺的安定效果。 本發明之詳細説明 本發明係提供改善前藝製造三聚甲醛小球之方法，而生 成溶解時間短及無不溶物之產物3此發明包括使用含有約i 至約2 0個碳原子之線狀和枝鏈狀胺，製造三聚甲醛小球， 以約6至1 〇個碳原子較佳。 業經發現在三聚甲醛小球中添加少量胺化合物以抑制聚 合作用。抑制聚合作用會使得三聚甲醛小球產物，具有呈 m - m -κ 11 I_ ! In ——.—1 n I i Γ m n _ ! _ nl· J3. / (請先閱讀背面之注意事項再填寫本頁) · _ 8 - 本紙張朗巾關轉準（CNS ) A4%格（210 X297公董） 經濟部中央標準局貝工消費合作社印製 408149 A7 -------- B7 五、發明説明（6 ) 現容易處理和儲存之乾燥和不黏表面。 —般發現太多胺製造的小球會大黏而且難以處理和傳送 。此外，產物中有大量的胺可能會被視爲不純3然而，胺 的量太少也會導致觀察不到效果。因此以足量的胺製造聚 合作用抑制結果是有必要的。必需的胺量通常依開始例如 3 7%11(：110—1〇〇1)1)111胺、87%11(：}10-~250 卩卩111胺之甲醛濃 度％而定。Method; one is as described in German Patent No. 884,947 and U.S. Patent No. 2, S23,2; No. 37, usually adding at least 200 /. Alcohol, such as methanol, into Jiayue forging; the other is the addition of stabilizers, such as San Qin 'or GB Patent No. 93 1,892, as described in British Patent No. 1,028,804. It is stated that aliphatic amines, diamines, tertiary amines, or hydroxylamines and alkalis which are substantially sufficient to neutralize the solution are added to the aqueous formic acid solution. So far, only amine compounds have been reported for the manufacture of trimellitic flakes or lumps; It is not needed when different technologies are needed to make the ball. The polymerization method of formazan is said to be continued even after the formation of the trimer-methoy · flakes or pellets. Therefore the molecular weight of paraformaldehyde increases during storage. This factor therefore reduces the solubility of the necessary paraformaldehyde product, sometimes faster during storage. It has been reported that polymerization inhibitors such as hydantoin as described in U.S. Patent No. 2,519,981 and U.S. Patent No. 2,519,550, and pentaerythritol as described in German Patent No. 1,1 I2,505 can prevent such unnecessary The maturation process "Other inhibitors effective in the report include the aliphatic and cyclic amines and amino acids described in French Patent No. 1,486,060 and German Patent No. 701022. Japanese Patent Nos. 73 / 48-1 7,250 and 7 3 / 48-δ, 603 report that hexamethylenetetramine dissolved in water and solvent (methanol) can inhibit the polymerization of paraformaldehyde during storage. Although many methods have been reported to inhibit the aging effect, the art shows that there is a continuing need to produce paraformaldehyde which has a short dissolution time even after storage and is indeed free of insolubles. Summary of the Invention The present invention is related to the manufacture of a short dissolution time even after storage for a period of time and the paper size is -7- This paper size applies to Chinese National Standard (CNS) specifications (2 丨 0 χ 297 mm) in. (Please read the note on the back first Please fill in this page again for the matters] ^-Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs --------- Amendment page of the Chinese manual for the case (November 87) A7 B7 Printed 5. Description of the invention (5) and indeed no insoluble matter of paraformaldehyde. It has been found that at the granulation temperature of paraformaldehyde, about 0.1 to about ppm will be very non-volatile and will be soluble in formazan and trimer The amine of an aqueous formaldehyde solution is added to the formaldehyde at the appropriate time during the granulation and formation of the paraformaldehyde, and it will generate triformaldehyde with a short dissolution time and no insoluble matter. The amine referred to in the compound has about 1 to About 20 carbon atoms. The amine may be a Cl.2G aliphatic amine, a Ci.n aliphatic diamine, a hydroxy aliphatic amine of 1 to about 20 carbon atoms, a c ^ 2 alkoxy aliphatic amine , The first amine, the second amine, the third amine, and the above-mentioned functional amines and their mixtures The amine can be added separately or placed in a solvent at the beginning of the paraformaldehyde manufacturing process, for example when the feed is placed in an approximately 37% formamidine solution. Most common low molecular weight organic solvents and water are suitable, such as water , Methanol, acetone. Water is the best solvent. We have found that amines can be poured into hot nails at a temperature of about 1000 or below the boiling point of the amines, or they can be sprayed on the solid trimer. Adding amine to the state pellet, thus achieving a similar effect. The amine in this article generally refers to the use of both additives such as additives or stabilizers 3. The amine can also be used with the bases C 1-2 O group alcohols, C! -[5 Aliphatic smoke or aromatic hydrocarbon additive amine contact to improve the stability of the amine. Detailed description of the present invention The present invention provides a method for improving the process of manufacturing paraformaldehyde pellets, resulting in short dissolution time and no insolubles Product 3 This invention includes the use of linear and branched chain amines containing from about i to about 20 carbon atoms to make paraldehyde beads, preferably from about 6 to 10 carbon atoms. It has been found in paraformaldehyde Add a small amount of amine compound to the pellet to suppress Polymerization. Inhibition of polymerization will make the paraformaldehyde sphere product with m-m -κ 11 I_! In ——.— 1 n I i Γ mn _! _ Nl · J3. / (Please read the back Please fill in this page again for the matters needing attention) · _ 8-This paper is printed in Chinese (CNS) A4% grid (210 X297 public directors) Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 408149 A7 ------- -B7 V. Description of the invention (6) Dry and non-sticky surface which is easy to handle and store now.-Generally, it is found that the pellets made of too much amine will be sticky and difficult to handle and transport. In addition, a large amount of amine in the product may Considered impure3 However, too little amount of amine may also result in no effect being observed. It is therefore necessary to produce a polymerization inhibitory result with a sufficient amount of amine. The required amount of amine is usually determined by the initial formaldehyde concentration of 3 7% 11 (: 110-1001) 1) 111 amine, 87% 11 (:) 10-250 amine 111 amine.
Thigpen (美國專利第 4550213號）和 Derivados (EP 0716104 A1)參考文獻中揭示將包括胺之三聚甲醛配方與酸或鹼性催 化劑一起使用。這些參考文獻並未揭示了解小球黏性或黏 著度的問題，以及後續在處理和儲存期間面臨之流動性的 困難。雖然本藝提及使用胺作爲催化劑，但本藝並不了解 在沒有酸或鹼性催化劑時，使用胺抑制製造三聚甲醛小球 的熟化難題。 因此本發明之具體實施例係關於製造三聚甲趁小球的方 法，其包含爲： a) 提供至少37%甲醛的甲醛溶液，而且使甲醛溶液接觸與 胺類安定劑； b) 加熱步驟（a)之混合物至溫度範圍约70°C到約13(TC。 c) 使混合物熟化一段充份時間使該甲醛混合物聚合，而形 成三聚甲醛。 d) 經由噴嘴傳送三聚甲醛以形成小球，使其落在塔内的反 向氣流中進一步聚合和固化。 固化作用後，將小球傳送至分離驟冷小瓶内，其中該小球 本紙張尺度適用中國國家標準（CNS ) Α4現格（210Χ297公釐〉 I---------装--------1T------^ (請先閲讀背赴之注意事項V 冩本貰) 时it 2 ^86112523 5^' 中文說明書修正頁(SS年12月） A7 B7Thigpen (U.S. Patent No. 4,550,213) and Derivados (EP 0716104 A1) references disclose the use of a paraformaldehyde formulation including an amine with an acid or basic catalyst. These references do not reveal the problems of understanding the viscosity or tackiness of the spheres and the subsequent difficulties of fluidity during handling and storage. Although this art mentions the use of amines as catalysts, this art does not understand the difficulty of using amines to inhibit the maturation of making paraformaldehyde pellets in the absence of acid or basic catalysts. Therefore, a specific embodiment of the present invention relates to a method for manufacturing trimer pellets, which comprises: a) providing a formaldehyde solution of at least 37% formaldehyde, and contacting the formaldehyde solution with an amine stabilizer; b) a heating step ( The mixture of a) to a temperature range of about 70 ° C. to about 13 (TC. c) The mixture is matured for a sufficient time to polymerize the formaldehyde mixture to form paraformaldehyde. d) The paraformaldehyde is transferred through the nozzle to form pellets, which are further polymerized and solidified in the reverse air flow falling inside the tower. After curing, the pellets are transferred to a separate quenching vial. The paper size of the pellets is in accordance with the Chinese National Standard (CNS) A4 (210 × 297 mm) I ---------- pack-- ------ 1T ------ ^ (Please read the precautions for going back V 冩 本 贳) when it 2 ^ 86112523 5 ^ 'Chinese manual correction page (SS year December) A7 B7
五、發明説明（7 ) 經濟部中央標準局員工消費合作社印装 進一步聚合和乾燥。 適合的胺類化合物包括第一、第二 '或第三胺' 環狀胺 、二胺或鏈烷醇胺。可做為實施例的胺類包括甲胺、乙胺 、正-丙胺、正-丁胺、異-丁胺、第三丁胺、二甲胺、二乙 胺、二-正-丙胺、二-異-丙胺和二丁胺、三乙胺及三乙醇 胺、六亞甲基四胺（HMTA)、2-乙基己胺（EHA)、2-胺基 丙二醇、己胺（Η A )、乙醇胺、混合型C - 2 0胺、混合型C -10胺、環己胺、1，2 -二甲氧基丙燒胺、三乙胺、乙醇胺 、2 -胺基-1，3 -丙二醇、1-胺基-戊烷、2_甲氧基丙胺。 「混合型」指的是分支枝鏈和直鏈胺類化合物的混合物。 實驗顯示使用同一種胺的混合物與少量的苛性劑（Na〇H) 會使得最終之三聚甲醛產物的不溶物獲得某些改善。較佳 的苛性劑量包括約1〇〇 ppm的苛性劑與胺混合。依濃輪甲醛 溶液的濃度而定，苛性劑與胺形成混合物之範園是約〇 〇 ! 至約1 %。 目前已發現並非所有的胺皆可以同樣操作使得濃縮甲醛 的安定性（其中濃度範圍約60_87%)獲得改善。增加三聚甲 醛溶解度大約二因數的胺類包括乙醇胺、正_丙胺_、2 _乙 基己胺、六亞甲基四胺、二胺基戊烷和已胺（HA)。這些胺 類皆顯示在周園儲存溫度下延長儲存時間時，可以保存 70%或甚至以上的三聚甲醛之安定性。在含有這些胺的濃 縮甲酿樣本中，發現與不含這些胺或安定劑的濃縮甲越相比 ，不溶物減少約一半。也發現雖然觀察到不溶物減少，但是 -10- ΙΊ . II [ . 4本 I ^ (請先閱讀背面之注意事項再填寫本頁) 本紙乐尺度適用中國國家標李（(：”5)八4^洛（2丨0/297公釐 經濟部中央橾準局員工消費合作社印製 408149 at _B7五、發明説明（8 ) 長鏈的胺'枝鏈的胺和一些第三胺對於減少濃縮甲醛樣本 中的不溶物效果較差。 胺的濃度以約〇. 1至約1 000 ppm較佳，約150-400 ppm尤 佳，而以約200-300 ppm最佳。在形成小球前，胺可以直接 與濃縮甲醛接觸，或噴在三聚甲醛小球上。胺可以直接倒 入濃縮甲醛，如80_89 %三聚甲醛，或37 %甲醛内。本藝 已揭示胺的用途，不過本藝一般步驟包括藉由冷卻含有聚 合作用調節劑之濃縮甲醛溶液或與藉由胺一起乾燥濃縮的 三聚甲醛粉末而製造三聚甲醛（美國專利第2,568,018號；美 國專利第3,772,392號）》此外，本藝揭示胺在製造三聚甲醢 薄片而非小球之用途。本發明係將胺直接與濃縮曱醛接觸 ’因此不需要三聚甲醛粉末和或冷卻該溶液。實驗室的结 果顯示依選用的胺種類不同，添加劑的較佳濃度是約2〇〇_ 300 ppm β 本發明之具體實施例包括胺和熱濃縮甲搭接觸。已發現 約8 7 %濃縮熱甲醛與胺添加劑混合後作用良好。一旦胺與 甲醛混合，利用噴嘴將胺傳送到經由塔傳送或掉入之甲醛 混合物而形成小球。以反向氣流與惰性氣體（例如氮氣）維 持該塔。所形成的小球掉入塔的底部，然後直接至骤冷瓶内。 本發明另一個具體實施例包括形成胺安定劑混合物，其 中胺與低級烷醇，如Ci—4 ’最好是曱醇混合或接觸。醇可 以添加至胺和熱甲醛液體内。據發現醇添加劑能幫助安定 二聚甲越產物。本藝之甲搭配方中揭示了甲醇的用途，但 是只以甲醛餵料濃度範圍4 %以上爲主。將醇添加劑以低於 ----------t------π------m (請先閲讀背面之注冩本頁) -11- 本紙乐^!適用中關家標準（CNS) M规格（21()><297公董） 經濟部中央標準局貝工消費合作社印製 408149 A7 A7 一.___B7 ____ 五、發明説明（9 ) 4%的範圍添加至胺較佳，而最好低於2 %。胺也可以與驗 ’例如N a Ο Η混合，同樣地總添加劑低於4 %。其他的添加 劑包括(^-2 0脂族醇、C5-! 5脂族烴、芳族烴、或是鹼性添 加劑，而實施例中的添加劑包括環己烷、丙酮、曱基乙酮 、氫氧化鈉、乙醇、甲醇、丁醇、乙基乙酯、丁基乙酯和 其類似物。 本發明另一個具體實施例係關於三聚甲醛的製造方法， 其包含爲： a) 提供至少37 %的甲醛溶液： b) 加熱步驟（a)中的混合物至溫度範圍約70°C至約130°C ; c) 以充份時間熟化混合物，以使曱醛混合物聚合並形成三 聚甲醛； d) 經由噴嘴傳送三聚甲醢以形成小球，使其掉入塔内的反 向氣流中進一步聚合和固化。 通常接著將小球傳送至分離的驟冷小瓶内，其中小球在 約室溫至約3 0 0 C下’進一步骤合並乾燥達約1至約2 〇小時 ，以約2至約9小時較佳。其後該小球與噴在上面的胺類安 定劑接觸。 以傳統步驟噴灑小球，將胺溶液喷在Γ冷的」固態小球 上以便能塗上胺。通常，胺溶液會溶解於常見的有機、會 揮發的溶劑中，例如C〗，2〇脂族醇、C 5 _ i 5脂族烴、芳族烴 或鹼9實施例中的溶劑包括甲醇、丁醇、乙醇、甲基乙明、 丙酮、環己烷、乙酸乙酯、乙酸丁酯和其類似物。 與胺和曱醛混合物有關的加熱步驟一般是在溫度範圍約 -12- 本紙張尺度適用中國國家標準（CNS ) A4规格（210 X 297公釐） -----^------#------1T------^ (4先閲讀背面之注意事項tv+杓本頁) 408149 A7 經濟部中央橾準局員工消費合作杜印装 _B7五、發明説明（i〇) 7 0。(：至约1 3 0 °C，最好是從約8 0 °C至約1 0 〇 °C下傳導a該 混合物典型上在約〇 . 1至約3小時的時間内熟化（在經由噴嘴 傳送前），約20至約40分鐘較佳’而最好是約20至約分 鐘。 實施例 製備實驗室研究用的樣本。利用混合胺和熱、高度濃度 的甲醛完成胺類添加劑的比較。添加至甲醛的胺量是約i Οι 0 0 0 ppm 3 實驗室的結 果顯示依所選用的胺量不同 ，較佳 的添加劑濃度是介於200-300 ppm之間。爲了要確定聚合作 用反應已經停止’將胺和甲醢的混合物冷卻至_ 5 2 r。然後 在試驗前先將該固體溶液磨成細微粉末。在六個月期間内 所有的樣本皆儲存於溫度約2 5 - 7 0 °C的範圍内。爲了評佑 儲存期限，在五週期間樣本皆維持在溫度35-40。(：下。數 據顯示儲存在較高溫度五週與三聚甲醛產物實際儲存在室 溫下一年相近》樣本經儲存五週後，試驗其溶解度、不溶 物、間苯二酚反應、平均分子量、曱醇、酸和其它物理性 質。 實施例1 三聚甲趁的製造基本上與美國專利2568016，2568017， 2568018號中所揭示的類似。經由連續眞空蒸發作用濃縮 3 7 %甲趁水溶液。其固體產物含有9丨％或9 5 %甲醛9爲了 觀察添加劑的效果，在蒸發的最後階段使用86%至89〇/〇甲 趁°從三聚甲醛的製造裝置中收集大約5〇〇克所生成之 86%溶液。將該溶液維持在6〇τ;的溫度以上，立即將〇 〇5 ί^先閱讀背面之注意事項-Η本頁) ______ -13 - 本錄尺度通财關家標準（CNS) Α4·獻297公 408149 at B7 五、發明説明（11 ) 克或100 ppm的胺加至甲醛溶液内充份混合。然後將該溶液 在乾冰中冷凍至溫度約-5 6 °C以利傳送。一旦冷卻，該溶液 會固化成爲三聚甲醛。然後在實驗室中將生成的固體磨成 500-700微米的細微粉末。分析該粉末中的胺、甲醛、甲 醇和水濃度、平均分子量、溶解度、不溶物和間苯二驗反 應。利用微庫倫分析法確定樣本中氮和胺的量。 緊接著以上的步驟，評估嘗試改善三聚甲醛溶解度之各 種添加劑。在3 5 °C下儲存3 5天後的試驗結果顯示於表1。 表1 -----^------^— (請先®讀背面之注意事項jph本頁) 經濟部中央標準局員工消費合作社印製 在3 5 °C下含1 0 0 p p m添加劑的三聚甲醛儲存3 5天之試驗 添加劑 (100 ppm) 測得的胺 (PPm) 在35°C下第0天 在35°C下第35天 溶解度(％) 不溶物(ppm) 溶解度(％) 不溶物(ppm) 六亞甲基四胺 85 100 33 65 65 乙醇胺 70 100 17 60 85 2-己基己胺 87 100 0 57 100 正丙胺 100 96 30 51 51 己胺 75 100 17 48 132 六亞甲基二胺 95 89 20 34 34 混合的c-20胺 98 85 67 35 100 56%甲醇， 22%甲瑤 0 77 33 28 245 12%甲醇， 27%曱醛 0 22 148 15 196 異丙胺 56 89 65 30 67 己胺，10 ppm <1.0 91 17 0 119 混合的c-10胺 65 82 49 0 138 不含添加劑的 甲膝 0 76 54 35 213 訂 -14- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） 9 4 Ti 8 ο 4 五、發明説明（π ) 實施例2 利用實施例1的步驟，評估五種胺類添加劑。每種添加劑 的量是1 0 0 ppm。所評估的添加劑包括己胺、環己胺、1， 2-二曱氧基丙烷、三乙胺和己二醇。將含有添加劑的樣本 儲存於3 5 °C的烤箱内五週。其結果摘錄於表2 »在測試化 學物質時，胺的結果最好。所評估的各種胺包括線狀、枝 鏈狀、烷基、芳基和短及長鏈胺。短枝鏈第三胺所獲得的 結果較差。相反地，較長鏈的第一和第二胺產生的溶解度 結果較佳。 如表2所見，已胺甚至在3 5 °C儲存5週後，會使得9 6 %的 樣本溶於水。不含胺時，40%的三聚甲醛會溶於水。儲存 前的三聚甲醛最初的溶解度爲97 % => 除了第一胺之外，據發現第二胺和二胺也會促進溶解度 。相反地，環狀第三胺和二醇獲得的效果較差。 —---------^-- (.請先閏讀背面之注意事項V 舄本頁) 訂 經濟部中央標準局負工消費合作社印製 表2 添加劑 35°C下第0天 35°C下第35天 不含添加劑之甲醛 97% 40% 己胺 100% 96% 環己胺 95% 76% 1，2-二甲氧基丙烷 99% 47%' 三乙胺 97% 44% 己二醇 74% 36% 線 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局貝工消费合作社印製 408^49 A7 —____ B7 五、發明説明（13 ) 一 - 實施例3 利用實施例1之步驟’許估四種添加劑。添加劑的濃度是 WO ppm。在35T下儲存樣本15天。儲存試驗中樣本之溶 解度顯示於表3。添加劑包括己胺、二胺基戊拔 '氫氧化納 和己二醇。己胺和二胺基戍烷都會使98%的樣本，甚至在 儲存後溶於水不含添加劑，三聚甲醛的溶解度爲2丨％ e 本結果確認了實施例2中所提及己胺的較佳操作性。已胺 和二胺基戊烷會改善三聚甲醛的溶解度。相反地，在35。〇 下15天後，氫氧化鈉和己二醇會獲得較差的結果^ 表3 添加劑 —35°C下第0天 35°C下第15天 不含添加劑之甲醛 56% 21% 己胺 100% 98% 二胺基戊娱： 99% 98% 己二醇 51% 17% 氫氧化鈉 52% 33% 實施例4 重覆實施例1的步驟，使用4 0 0 ppm的胺。該胺包括六亞 甲基四胺、2-乙基己胺、2-胺基-丙二醇和己胺。在35 °C 下儲存5週後，這些胺仍維持著62 %至68 %的溶解度。不溶 物的範圍從50至100 ppm。其結杲敘述於表4。與實施例3 相似，己胺的操作效果較佳》此外，六亞甲基四胺、2 -乙 基己胺和2 -胺基-丙二醇的溶解度也會明顯地增加3 -16- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ----^------^------ΐτ------^ (_請先閱讀背面之注意事項/ Η本頁) 408149 A7 --------B7 五、發明説明（14 ) 表4 胺的種類 {添加400 ppm) 測得的胺 (ppm) 在 35°Cl^ 溶解⑥函 ------. 0天 「 -— 在35°C下第35天 不落物(DDirfl 溶解度 不?容物fnrMTi) 苎亞曱基四胺 280 99 60 68 」 50 2-乙基己胺 323 100 17 63 1 ft] 2·胺基丙二醇 360 100 0 62 83 己胺 350 100 0 64 100 不含添加劑的 甲醛 0 100 33 35 213 實施例5 重覆實施例1的步驟，使用1 000 ppm的胺，該胺包括六 亞甲基四胺、2 -乙基己胺、乙醇胺、己胺和甲氧基丙胺。 在35 °C下儲存5週後，除了甲氧基丙胺外的所有胺之溶解 度都改善至7 0 % - S 5 % ’而且不溶物保持低於丨〇 〇 p p m。 其結果敘述於表5 » {'請先W讀背面之注意事項'.5?本頁) -裝_ 訂 經濟部中央標牟局員工消費合作社印裝 表5 胺的種類 (添加 1000 ppm) 測得的胺 (PPm) 在35 C下第〇天 在35°C下第35天 溶解度(％) 不溶物(ppm) 溶解度(％) 不溶物fppnO 六亞甲基四胺 800 99 33 85 60 2-乙基己胺 790 100 17 78 83 己胺 1290 100 33 72 67 乙醇胺 750 100 17 80 17 不含添加劑的 甲醛 0 76 54 35 213 2-曱氧基丙胺 1000 100 0 56 0 添加胺類添加劑會改變二聚曱醛的性質a其結果列於表6 。例如，2 -乙基己胺和六亞甲基四胺，藉由降低平均分子 量而促進三聚曱醛的溶解度。 線 17- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 408149 A7 B7 五、發明説明（I5 ) 表6 儲存試驗的第0天含有添加劑之三聚甲醛的性質 添加劑 間苯二酚反 平均分子量 平均鏈長 溶解度 不溶物 應(秒） (克/莫耳） (%) (ppm) 2-乙基己胺 82 164 4.9 100 33 六亞甲基四胺 109 166 4.9 100 0 正己胺 97 175 5.2 100 17 不含添加劑 126 167 5.0 76 54 之三聚甲眵 實施例6 除了胺的種類之外，據發現胺的量也會影響溶解度和不 溶物°按照實施例1的步驟，對含有1 0至1 0 0 0 p p m的三聚 甲醛進行儲存試驗。表7的數據顯示已胺明顯地改善了三聚 甲醛。含有1000 ppm己胺時，產物在試驗的第35天後仍 維持1 0 0 %的溶解度和1 3 0 p p m。 表7 f-- (請先閱讀背面之注意事項.寫本頁) 訂 經濟部中央標準局員工消費合作社印裂 己胺對三聚甲醛的效果 己胺的量 (PPm) 在35°C下第0天 在35°C下第35天 溶解度(％) 不溶物(ppm) 溶解度(％) 不溶物(ppm) 10 91 17 0 119 50 95 25 48 119 100 100 0 34 132 500 100 0 64 100 1000 100 33 85 67 -18- 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） —_ 408149__b7____ 五、發明説明（16 ) 實施例7 重覆實施例1的步驟，使用含有最多1〇〇〇 pprn之2 -乙基 己胺的樣本。由表8和9的結果顯示乙基己胺會增加產物的 溶解度以及減少不溶物。溶解度的増加與分子量的減少有 關。在40。(： 14天後，含有150 ppm之2 -乙基已胺樣本溶 解度85%’而不落物爲63 ppm。其平均分子量爲181克/ 莫耳3不含胺時，樣本的溶解度爲62%和83 ppm 3熟化樣 本的平均分子量爲192克/莫耳。 表8 ί^-- (請先閏讀背面之注意事項H r本頁) 訂 經濟部中央標準局員工消費合作社印裝 在40°C下儲存含有乙基己胺之三聚甲醛2週 添加的乙基己胺量 溶解度(62%) 不溶物(83 ppm) 平均分子量(克/莫耳） 0天 14天 0天 14天 0天 14天 0 92 62 60 83 167 192 100 99 76 33 17 161 181 150 99 87 83 63 162 181 300 99 88 67 50 159 186 500 100 89 17 50 154 150 -19- 本紙張尺度適用中國國家標準（CNS } A4规格（2丨0 X 297公釐） 五、發明説明（17 408149 a? B7 經濟部中央標準局員工消費合作社印製 表9 在4 (TC下儲存含有乙基己胺之三聚甲醛5週 添加的胺量 測得的胺 溶解度(62。/。） 不溶物(83 ppm) 平均分子量(克/莫 耳） 0天 35天 0天 35天 0天 35天 0 0 92 35 54 221 167 2 13 100 79 99 53 33 68 161 180 150 87 99 57 83 70 162 205 300 210 99 60 67 92 159 177 500 323 100 63 17 81 154 166 1000 790 100 78 17 130 154 160 實施例8 以美國專利第2566016 ’ 2566017，2566018號中揭示的類 似方法製造三聚甲醛小球樣本。藉由陸續眞空蒸發作用濃 縮3 7 %甲遂的溶液’然後利用喷嘴傳送製造出小球β該固 尨產物含有9 1 - 9 5 %間的甲搭。典型上，在經由喷嘴傳送三 聚甲醛則先添加約丨00-200 ppm的胺至濃縮甲醛溶液内， 以形成小球’使其掉入塔内的反向氣流内以進行聚合和固 化。典型上’由三聚甲愁的製造裝置中收集5〇〇克所生成 的91-95 %三聚甲醛小球。然後在下儲存該三聚甲醛小 球，直到可以分析爲止。分析該小球中的胺、甲醛、甲醇 和水濃度，平均分子量、溶解度和不溶物及間苯二酚反應 。利用微庫侖分析法測定出樣本中氮和胺的量。在35。〇下 儲存3 5天後的試驗結果顯示於表1〇和11。 -20- 表紙張尺度適用中國圏家標準（CNS )从· ( 2丨〇><297公羡 1.--------^------.玎------0 (_請先閱讀背面之注意事項r舄本頁) 408149 a7 B7 五、發明説明（IS ) 不含苛性劑的胺經試驗會增加三聚甲醛的溶解度及減少 不溶物。試驗苛性劑和胺的量後，三聚甲醛小球的溶解度 稍微有改善，而且不溶物也減少了。 表1 0 (含胺類的安定劑） 三聚甲醛 小球的樣 本 測得的胺 在35°C下第0天 在35°C下第35天 溶解度(％) 不溶物(ppm) 溶解度(％) 不溶物(ppm) 91% 0 71 83 7 3 3 3 樣本1 167 89 17 46 33 樣本2 176 89 34 37 42 樣本3 170 91 50 29 40 樣本4 178 98 17 33 50 樣本5 173 98 33 62 50 95% 0 46 350 25 83 2 樣本6 109 91 42 44 20 樣本7 84 90 33 50 66 樣本8 93 89 17 23 3 3 (，請先閲讀背面之注意事項， 裝-- iC本頁) 訂 線 經濟部中央標準局員工消費合作社印製 -21 - 本紙張尺度適用中國國家標準（CNS > A4規格（2[0Χ2?7公釐） A7408149 B7 五、發明説明（l9 ) 表1 1 (含胺+ N a Ο Η安定劑混合物） 三聚甲醢 小球的樣 本 測得的 胺 測得的 納 在35Ϊ下第0天 在35UC下第35天 溶解度(％) 不溶物(ppm) 溶解度(％) 不溶物tppm) 91% 0 1.275 71 83 7 ^ *C.F„ 87% 183 0.924 73 166 43 樣本1 107 0.848 81 17 33 17 樣本2 119 0.887 86 17 24 0 樣本3 119 0.906 87 33 25 9 樣本4 106 0.824 87 17 28 17 95% 0 0.996 46 350 25 832 樣本5 46 0.599 87 17 17 25 樣本6 38 0.589 90 9 21 42 樣本7 27 0.37 87 41 41 17 ----------裝-- (請先閲讀背Φ.之注意事項.?r本頁) 訂 經濟部中央標準局員工消費合作社印策 * C . F .=濃縮甲醛 實施例9 利用實施例1的步驟，將200 ppm 2 -乙基己胺和0.2 p p m 1氧化鈉混合後添加至甲酸溶液内。於4 0 °C下儲存樣 本2週。在試驗期間後，含有胺或胺和氫氧化鈉混合物的樣 本生成約7 5 %至8 3 %的溶解度値。兩種樣本的不溶物皆減 少至約1 0 0 ppm。相反地，最初不含添加劑的樣本含有1 7 3 p p m不溶物和4 1 %溶解度。 -22 本紙乐尺度適用中國國家標率（CMS ) A4現格（210 X 297公釐） 408149 A7 B7五、發明説明（2〇 ) 表12 樣本 溶解度(％) 不溶物(ppm) 平均分子量(克/莫耳） 〇天 1 4天 0天 1 4天 0天 14天 不含恭加劑之甲醛 92 41 116 173 163 200 +200 ppm EHA 98 83 17 83 161 161 +200 ppm EHA +0.2 ppm NaOH 99 75 33 100 161 172 +1 ppm NaOH 90 52 $0 110 150 - +10 ppm NaOH 6S 12 0 86 170 - 經濟部中央標準局|工消費合作社印| 爲了了解不溶物的形成，將不溶物分離出來並加以確認 °根據發現，該不溶物是平均鏈長爲8的甲醛乙二醇醚。有 許多分析技術可以用來記述該不溶物的特性。這些技術包 括固態核磁共振法、液上氣體層析法、質譜分析法、差示 掃描量熱法和紅外光譜法。 溶解度試驗 使用重量分析法來測定三聚曱醛的溶解度。此方法包括 在70°C下將10%三聚甲醛溶於水中15分鐘。試驗後，藉由 秤重測定產物中不溶部份的溶解度。利用Micro-Miller研磨 器將固態三聚甲醛樣本磨成400-700微米的粉末。然後將 三聚曱醛和90±0.01克經去離子及蒸餾過的水置於裝有濃 编器的圓底燒瓶内。將該燒瓶置於常溫浴内。當溶液溫度 達到7 0 °C時，將1 0 ± 0.0 1克三聚曱醛加至該溶液中。以 2 0 0 rpm的速度激烈攪拌混合物1 5分鐘。定期以上清液濕 潤燒瓶周圍以確定所有的固體都能浸到溶液。熱過濾該混 -23 - ---;------1------1T------^ (.請先閲讀背面之注意事項寫本頁) 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 408149 A7 B7 五、發明説明（21 ) 合物。使用Micron Separations公司出售的0.45微米，鐵弗 龍濾紙。以5 0克冷水洗滌濾液，並在室溫約2 0 〇毫米水銀 拄的眞空下乾燥其固體1小時。在室溫下以乾氮氣噴射濾液 。秤出不溶物的重量且分析其甲醛成份和分子量。根據下 式計算溶解度： %溶解度=[1 -(濾液重量)/{(三聚甲醛重量）*曱趑分析値}]* 1 〇〇% 舉例來説’某一個實驗中，由第四階段蒸發器中獲得的 10，U45克三聚甲醛溶解於90.1950克水中。15分鐘後，其 溶解度是76%。 % 溶解度=[1-{(2,4975·0.〇936)/10.114}]*ΐ〇〇=(ΐ〇〇·23.76)=76.2% 此方法比另一種使用亞硫酸鈉和硫酸滴定的方法受人歡 迎’而獲得的結果也相似》關於上述實施例，以滴定測得 的溶解度是78.5%。 不溶物試驗 經清部中央標準局負工消費合作社印製 {‘請先閎讀背面之注意事項，.·"本頁) 此方法係利用秤重測定經酸鹼値調整後之三聚曱膝中不 的量。因此’應小心預防任何小顆粒，如灰塵 和其它空氣中顆粒的污染。乾燥條件，如溫度和時間對試 驗的一致性也很重要。利用Micro-Miner研磨器將固態三聚 甲路樣本磨成4〇〇_700微米的粉末。覆蓋該樣本並且置於 一旁。在70 眞空烤箱内乾燥該樣本2〇分鐘。使用Micr〇n Separations公司出售的0 45微米，鐵弗龍濾紙。將乾燥後 的遽紙健存於乾燥器内，並由乾燥濾紙上秤得其本身的重 量。將已知重量且乾燥後之濾紙插入Millip〇re濾器中。在 250圓底燒瓶内約1〇〇»c下加熱24克酸鹼値9的緩衝液至回 .24· 私紙張尺度適财關家標準（CNS) Α4· (21料297公 408149 經濟部中央標準局員工消費合作社印製 五、發明説明（22 ) 流。酸鹼値/9 Fisher Scientific緩衝液 #SR 114-20 是 0-1 莫耳硼酸、氯化鉀、氫氧化鈉的溶液，將6 + 〇 〇1克三聚甲 胺加至裝有濃縮器的圓底燒瓶内。在約〗0 0 1下加熱該溶 液至回流並以1 5 0 rpm的速度攪拌。定期以上清液濕潤燒瓶 的周園以確定所有的固體皆能浸入溶液中。保持熱的狀沉 下’取出並過濾混合物。以50克水洗滌該濾液，然後以50 克試劑分離出丙酮。在室溫約200毫米水銀柱的眞空下乾 燥其固體1小時。在室溫下以乾氮氣噴射該濾液。秤不溶物 的重量且分析其甲醛成份和分子量。以pprn記錄不溶物的 重量。 例如’將5.8926克粉末狀三聚甲搭溶解於24.0325克緩衝 溶液中。1小時後，回收0.0010克《亦即，樣本含有17〇 ppm ° 1%相當於 10,〇〇〇 ppm。 不溶物=0.0010/5.9829=0.01697%= 170 ppm 平均分予量 根據美國專利第3772392號中揭示的方法，藉由測定全部 和游離的水中所獲得之三聚甲醛的平均分子量。 間苯二酚反應 藉由本藝中廣爲人知，如美國專利第2,5 19,550和第 2,519,981號中的方法測定間苯二酚反應。 甲醛濃度： 本試驗中所應用的滴定步驟敛述了以測定每A. s . 丁. Μ .方 法D 2 1 94-84中的甲醛成份。 -25- 本紙張尺度適用中國國家標準（CNS ) Μ规格（2丨〇Χ；297公釐） ί ,------^------,?τ---^---0 (請先閱讀背’面之注意事坏 ；寫本頁)V. Description of the invention (7) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Further polymerization and drying. Suitable amine compounds include first, second, or third amine cyclic amines, diamines, or alkanolamines. Examples of amines include methylamine, ethylamine, n-propylamine, n-butylamine, iso-butylamine, tertiary butylamine, dimethylamine, diethylamine, di-n-propylamine, and di- Iso-propylamine and dibutylamine, triethylamine and triethanolamine, hexamethylenetetramine (HMTA), 2-ethylhexylamine (EHA), 2-aminopropanediol, hexylamine (ΗA), ethanolamine, Mixed C-20 amine, mixed C-10 amine, cyclohexylamine, 1,2-dimethoxypropanamine, triethylamine, ethanolamine, 2-amino-1,3-propanediol, 1- Amino-pentane, 2-methoxypropylamine. "Mixed type" refers to a mixture of branched and linear amine compounds. Experiments have shown that the use of a mixture of the same amine with a small amount of caustic (NaOH) will result in some improvement in the insolubles of the final paraformaldehyde product. Preferred caustic dosages include about 100 ppm of caustic mixed with amine. Depending on the concentration of the concentrated formaldehyde solution, the range of caustic and amine-forming mixtures is from about 0.00 to about 1%. It has been found that not all amines can be treated the same to improve the stability of concentrated formaldehyde (in which the concentration range is about 60-87%). Amines that increase the solubility of triformaldehyde by approximately two factors include ethanolamine, n-propylamine, 2-ethylhexylamine, hexamethylenetetramine, diaminopentane, and hexamine (HA). These amines have been shown to retain 70% or more of the stability of paraformaldehyde when stored at extended storage temperatures. In concentrated methyl alcohol samples containing these amines, it was found that insoluble matter was reduced by about half compared to concentrated methyl alcohol without these amines or stabilizers. It was also found that although a decrease in insoluble matter was observed, -10- ΙΊ. II [. 4 copies of I ^ (Please read the notes on the back before filling out this page) The paper scale is applicable to Chinese national standard ((: "5) eight 4 ^ Luo (2 丨 0/297 mm printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 408149 at _B7 V. Description of the invention (8) Long-chain amines' branched amines and some tertiary amines for reducing concentrated formaldehyde The insoluble matter in the sample is less effective. The amine concentration is preferably about 0.1 to about 1 000 ppm, more preferably about 150-400 ppm, and most preferably about 200-300 ppm. Before the pellets are formed, the amine can Direct contact with concentrated formaldehyde, or spray on the paraformaldehyde pellets. The amine can be poured directly into concentrated formaldehyde, such as 80_89% paraformaldehyde, or 37% formaldehyde. The use of amines has been disclosed in this art, but the general steps of this art Including the production of paraformaldehyde by cooling a concentrated formaldehyde solution containing a polymerization regulator or drying the concentrated paraformaldehyde powder with an amine (U.S. Patent No. 2,568,018; U.S. Patent No. 3,772,392) "In addition, the present disclosure Amines are making trimeridine instead of The use of pellets. The present invention directly contacts the amine with concentrated formaldehyde, so no paraformaldehyde powder and or cooling the solution is required. The laboratory results show that the preferred concentration of the additive is about 2 depending on the type of amine selected. 〇〇_ 300 ppm β Specific embodiments of the present invention include contact between amine and hot concentrated methyl formaldehyde. It has been found that about 87% of the concentrated hot formaldehyde mixed with amine additive works well. Once the amine and formaldehyde are mixed, the amine is delivered to the nozzle The formaldehyde mixture transferred or dropped through the tower forms pellets. The tower is maintained with a counter current and an inert gas (such as nitrogen). The formed pellets fall into the bottom of the tower and then directly into the quench bottle. Another specific example includes forming an amine stabilizer mixture where the amine is mixed or contacted with a lower alkanol, such as Ci-4 ', preferably methanol. Alcohols can be added to amines and hot formaldehyde liquids. Alcohol additives have been found to help Diazepam dimethylate product. The use of methanol is disclosed in the formula of the art, but only the concentration range of formaldehyde feed is above 4%. The alcohol additive is lower than -------- --t ------ π ------ m (Please read the note on the back of this page first) -11- This paper music ^! Applies to the Zhongguanjia Standard (CNS) M specification (21 () > < 297 public directors) Printed by the Central Standards Bureau of the Ministry of Economy, Shellfish Consumer Cooperative, 408149 A7 A7 I. ___B7 ____ V. Description of the invention (9) It is better to add 4% of the range to the amine, and the best is less than 2%. Amine can also be mixed with test materials such as Na O Η, and the total additive is less than 4%. Other additives include (^ -2 0 aliphatic alcohol, C5-! 5 aliphatic hydrocarbon, aromatic hydrocarbon, or alkali Additives, and the additives in the examples include cyclohexane, acetone, methyl ethyl ketone, sodium hydroxide, ethanol, methanol, butanol, ethyl ethyl ester, butyl ethyl ester, and the like. Another specific embodiment of the present invention relates to a method for manufacturing paraformaldehyde, comprising: a) providing at least 37% formaldehyde solution: b) heating the mixture in step (a) to a temperature range of about 70 ° C to about 130 ° C; c) mature the mixture for a sufficient time to polymerize the formaldehyde mixture to form paraformaldehyde; d) transfer the trimer formamidine through a nozzle to form a pellet and drop it into the reverse air flow in the tower to further Polymerize and cure. The pellets are usually then transferred to a separate quench vial, where the pellets are further combined and dried at about room temperature to about 300 ° C for about 1 to about 20 hours, compared with about 2 to about 9 hours. good. The pellet was then contacted with the amine stabilizer sprayed thereon. Spray the pellets in the traditional procedure, spraying the amine solution onto the "cold" solid pellets so that they can be coated with amine. Generally, the amine solution will be dissolved in common organic, volatile solvents, such as C, 20 aliphatic alcohols, C 5-i 5 aliphatic hydrocarbons, aromatic hydrocarbons or bases. The solvents in the embodiments include methanol, Butanol, ethanol, methylacetamine, acetone, cyclohexane, ethyl acetate, butyl acetate, and the like. The heating step related to the mixture of amine and formaldehyde is generally in the temperature range of about -12- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- ^ ------ # ------ 1T ------ ^ (4 Read the precautions on the back first tv + 杓 this page) 408149 A7 Consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed equipment_B7 V. Invention Description (i 〇) 7 0. (: To about 130 ° C, preferably from about 80 ° C to about 100 ° C. The mixture is typically matured over a period of about 0.1 to about 3 hours (after passing through a nozzle Before transmission), about 20 to about 40 minutes is preferred, and most preferably about 20 to about minutes. Examples Prepare samples for laboratory research. Comparison of amine additives was performed using mixed amines and hot, high concentrations of formaldehyde. The amount of amine added to formaldehyde is about 10 μm 0 0 0 ppm 3 Laboratory results show that depending on the amount of amine used, the preferred additive concentration is between 200-300 ppm. To determine that the polymerization reaction has been Stop 'Chill the mixture of amine and formamidine to _ 5 2 r. Then grind the solid solution into a fine powder before testing. All samples are stored at a temperature of about 2 5-7 0 ° for a period of six months In the range of C. In order to evaluate the shelf life, the samples were maintained at a temperature of 35-40 during the five-week period. (: Bottom. The data shows that the product was stored at a higher temperature for five weeks and the paraformaldehyde product was actually stored at room temperature for one year. Similar samples were tested for solubility and insolubility after being stored for five weeks. Compounds, resorcinol reaction, average molecular weight, methanol, acid, and other physical properties. Example 1 The production of trimerol is basically similar to that disclosed in U.S. Patent Nos. 2568016, 2568017, 2568018. Evaporation via continuous airspace Concentrate 37% formic acid in water solution. Its solid product contains 9 丨% or 95% formaldehyde. 9 In order to observe the effect of the additives, use 86% to 89 ％ / formaldehyde in the final stage of evaporation from the manufacture of paraformaldehyde. Collect about 500 grams of the 86% solution produced in the device. Maintain the solution at a temperature above 60 τ; immediately read 〇005 ^^ First read the notes on the back-this page) ______ -13- Standards for Financial Records (CNS) A4 · Xian 297, 408149 at B7 5. Description of the invention (11) g or 100 ppm of amine is added to the formaldehyde solution and mixed thoroughly. Then the solution is frozen in dry ice to The temperature is about -5 6 ° C to facilitate transportation. Once cooled, the solution will solidify into paraformaldehyde. Then the generated solid is ground into a fine powder of 500-700 microns in the laboratory. The amine and formaldehyde in the powder are analyzed , Methanol and water concentrations, Molecular weight, solubility, insoluble matter, and isophthalene test. Determine the amount of nitrogen and amine in the sample by micro-coulometry. Following the above steps, evaluate various additives that try to improve the solubility of paraformaldehyde. At 3 5 ° C The test results after 3 to 5 days of storage are shown in Table 1. Table 1 ----- ^ ------ ^ — (Please read the precautions on the back of this page jph first page) Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printed with paraformaldehyde containing 100 ppm additive at 35 ° C. Test additive (100 ppm) stored for 3 to 5 days. Measured amine (PPm) at 35 ° C on day 0 at 35 ° C. 35 days solubility (%) insoluble matter (ppm) solubility (%) insoluble matter (ppm) hexamethylenetetramine 85 100 33 65 65 ethanolamine 70 100 17 60 85 2-hexylhexylamine 87 100 0 57 100 n-propylamine 100 96 30 51 51 Hexylamine 75 100 17 48 132 Hexamethylene diamine 95 89 20 34 34 Mixed c-20 amine 98 85 67 35 100 56% methanol, 22% methylamine 0 77 33 28 245 12% methanol, 27% acetaldehyde 0 22 148 15 196 isopropylamine 56 89 65 30 67 hexylamine, 10 ppm < 1.0 91 17 0 119 mixed c-10 amine 65 82 49 0 138 without additives Nail of the agent 0 76 54 35 213 Order -14- This paper size applies to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 9 4 Ti 8 ο 4 5. Description of the invention (π) Example 2 The procedure of Example 1 evaluated five amine additives. The amount of each additive was 100 ppm. The evaluated additives include hexylamine, cyclohexylamine, 1,2-dimethoxypropane, triethylamine and hexanediol. Store samples containing additives in an oven at 35 ° C for five weeks. The results are summarized in Table 2 »Amine has the best results when testing chemicals. The various amines evaluated included linear, branched, alkyl, aryl, and short and long chain amines. The results obtained with short-chain tertiary amines are poor. In contrast, longer chain first and second amines yield better solubility results. As can be seen in Table 2, even after 5 weeks of storage at 35 ° C, hexylamine dissolved 96% of the samples in water. Without amine, 40% of paraformaldehyde is soluble in water. The initial solubility of paraformaldehyde before storage was 97% => In addition to the first amine, it was found that the second and diamines also promote solubility. In contrast, the effects obtained by cyclic third amines and diols are poor. —--------- ^-(. Please read the precautions on the back of the page V 舄 this page) Order the printed form of the Central Consumer Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives, and print the table 2 Additive 0th day at 35 ° C Formaldehyde without additives at 35 ° C on day 35 97% 40% hexylamine 100% 96% cyclohexylamine 95% 76% 1,2-dimethoxypropane 99% 47% 'triethylamine 97% 44% Hexylene glycol 74% 36% Line -15- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 408 ^ 49 A7 —____ B7 V. Description of the invention (13) One-Example 3 The procedure of Example 1 was used to estimate four kinds of additives. The concentration of the additive is WO ppm. The samples were stored at 35T for 15 days. The solubility of the samples in the storage test is shown in Table 3. Additives include hexylamine, diaminopentalbene 'sodium hydroxide and hexanediol. Both hexylamine and diaminoxanthene will make 98% of the samples, even after storage, soluble in water without additives, and the solubility of paraformaldehyde is 2 丨%. E This result confirms the hexylamine mentioned in Example 2. Better operability. Hexylamine and diaminopentane improve the solubility of paraformaldehyde. Instead, at 35. After 15 days, poor results will be obtained with sodium hydroxide and hexanediol ^ Table 3 Additives—Day 0 at 35 ° C Day 15 at 35 ° C Additive-free formaldehyde 56% 21% Hexylamine 100% 98 % Diaminopentanol: 99% 98% Hexanediol 51% 17% Sodium hydroxide 52% 33% Example 4 The procedure of Example 1 was repeated using 400 ppm of amine. The amine includes hexamethylenetetramine, 2-ethylhexylamine, 2-amino-propylene glycol, and hexylamine. After 5 weeks of storage at 35 ° C, these amines still maintain a solubility of 62% to 68%. Insolubles range from 50 to 100 ppm. The results are described in Table 4. Similar to Example 3, the operation of hexylamine is better. In addition, the solubility of hexamethylenetetramine, 2-ethylhexylamine and 2-amino-propanediol will also increase significantly. 3 -16- Paper size Applicable to China National Standard (CNS) Α4 specification (210X297 mm) ---- ^ ------ ^ ------ ΐτ ------ ^ (_Please read the precautions on the back / (ΗPage) 408149 A7 -------- B7 V. Description of the invention (14) Table 4 Types of amines (add 400 ppm) The measured amines (ppm) are dissolved at 35 ° Cl ^ ⑥ Function --- ---. 0 days "--No dropping at 35 ° C at 35 ° C (DDirfl solubility fnrMTi) fluorenylenetetramine 280 99 60 68" 50 2-ethylhexylamine 323 100 17 63 1 ft] 2. Aminopropanediol 360 100 0 62 83 Hexylamine 350 100 0 64 100 Additive-free formaldehyde 0 100 33 35 213 Example 5 The procedure of Example 1 was repeated using 1 000 ppm of amine, which Amine includes hexamethylenetetramine, 2-ethylhexylamine, ethanolamine, hexylamine and methoxypropylamine. After 5 weeks of storage at 35 ° C, the solubility of all amines except methoxypropylamine improved to 70%-S5 %% 'and insolubles remained below 丨 00 p p m. The results are described in Table 5 »('Please read the Precautions on the back'. 5? This page)-Equipment _ Orders printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperatives Table 5 Types of amines (1000 ppm added) Obtained amine (PPm) on day 0 at 35 ° C on day 35 at 35 ° C solubility (%) insoluble matter (ppm) solubility (%) insoluble matter fppnO hexamethylenetetramine 800 99 33 85 60 2- Ethylhexylamine 790 100 17 78 83 Hexylamine 1290 100 33 72 67 Ethanolamine 750 100 17 80 17 Additive-free formaldehyde 0 76 54 35 213 2-Methoxypropylamine 1000 100 0 56 0 The properties a of polyacetal are shown in Table 6 below. For example, 2-ethylhexylamine and hexamethylenetetramine promote the solubility of trimeraldehyde by reducing the average molecular weight. Line 17- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 408149 A7 B7 V. Description of the invention (I5) Table 6 Properties of the additive paraformaldehyde, m-phenylene, on the 0th day of the storage test Phenol anti-average molecular weight average chain length solubility insoluble matter (sec) (g / mole) (%) (ppm) 2-ethylhexylamine 82 164 4.9 100 33 hexamethylenetetramine 109 166 4.9 100 0 n-hexylamine 97 175 5.2 100 17 Additive-free 126 167 5.0 76 54 Trimethylformamidine Example 6 In addition to the type of amine, it was found that the amount of amine also affects the solubility and insoluble matter. According to the procedure of Example 1, 10 to 100 ppm of paraformaldehyde was tested for storage. The data in Table 7 shows that hexylamine significantly improved paraformaldehyde. With 1000 ppm hexylamine, the product maintained a 100% solubility and 130 p p m after the 35th day of the test. Table 7 f-- (Please read the notes on the back first. Write this page) Order the effect of hexamethamine on paraformaldehyde by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The amount of hexamylamine (PPm) at 35 ° C 0 day at 35 ° C Solubility (%) Insoluble matter (ppm) Solubility (%) Insoluble matter (ppm) 10 91 17 0 119 50 95 25 48 119 100 100 0 34 132 500 100 0 64 100 1000 100 33 85 67 -18- The size of this paper applies to China National Standard (CNS) A4 (210X297 mm) — 408 149__b7____ 5. Description of the invention (16) Example 7 Repeat the steps of Example 1 and use a maximum of 10%. 00pprn of 2-ethylhexylamine. The results in Tables 8 and 9 show that ethylhexylamine increases the solubility of the product and reduces insolubles. The increase in solubility is related to the decrease in molecular weight. At 40. (: After 14 days, a sample containing 150 ppm of 2-ethylhexylamine has a solubility of 85% 'without dropping to 63 ppm. Its average molecular weight is 181 g / mol. 3 Without amine, the sample has a solubility of 62% The average molecular weight of the cured samples at 83 ppm and 3 ppm is 192 g / mol. Table 8 ί ^-(Please read the precautions on the back of this page H r first page) Ordered by the Central Bureau of Standards of the Ministry of Economic Affairs, the consumer cooperative is printed at 40 ° Ethylhexylamine added in trioxane containing ethylhexylamine at 2 weeks C Solubility (62%) Insoluble matter (83 ppm) Average molecular weight (g / mole) 0 days 14 days 0 days 14 days 0 days 14 days 0 92 62 60 83 167 192 100 99 76 33 17 161 181 150 99 87 83 63 162 181 300 99 88 67 50 159 186 500 100 89 17 50 154 150 -19- This paper size applies Chinese National Standard (CNS} A4 specifications (2 丨 0 X 297 mm) V. Description of the invention (17 408149 a? B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Table 9 Stores paraformaldehyde containing ethylhexylamine for 5 weeks at 4 (TC Amine solubility as measured by the amount of amine added (62%). Insoluble matter (83 ppm) Average molecular weight (g / mole) 0 days 35 days 0 days 35 days 0 days 35 days 0 0 92 35 54 221 167 2 13 100 79 99 53 33 68 161 180 150 87 99 57 83 70 162 205 300 210 99 60 67 92 159 177 500 323 100 63 17 81 154 166 1000 790 100 78 17 130 154 160 Example 8 A paraformaldehyde pellet sample was produced in a similar manner as disclosed in U.S. Patent Nos. 2566016 '2566017, 2566018. A 37% solution of formazan was concentrated by successive evaporations and then used Nozzles are produced to produce small particles β. The solid product contains 9 1-95% of methyl formaldehyde. Typically, when delivering paraformaldehyde through a nozzle, approximately 00-200 ppm of amine is added to the concentrated formaldehyde solution. In order to form pellets, it is dropped into the reverse air flow in the tower for polymerization and curing. Typically, the 91-95% paraformaldehyde produced by collecting 500 g of trioxane in a manufacturing device is collected. Sphere. Then store the paraformaldehyde pellet underneath until it can be analyzed. Analyze the amine, formaldehyde, methanol and water concentrations, average molecular weight, solubility and insolubles and resorcinol in the pellet. The amount of nitrogen and amine in the sample was determined by microcoulometry. At 35. The test results after 3 to 5 days of storage are shown in Tables 10 and 11. -20- The paper size of the table is applicable to the Chinese Standard (CNS) from · (2 丨 〇) < 297 Public Envy 1 .-------- ^ ------. 玎 ---- --0 (_Please read the precautions on the back of this page r 舄 this page) 408149 a7 B7 V. Description of the Invention (IS) Amine containing no caustic agent will increase the solubility of paraformaldehyde and reduce insoluble matter after testing. Test caustic agent After the amount of amine and the amount of amine, the solubility of the paraformaldehyde pellets was slightly improved, and the insoluble matter was also reduced. Table 10 0 (Stabilizers containing amines) The sample of paraformaldehyde pellets measured the amine at 35 ° C. Next day 0 at 35 ° C Solubility (%) Insoluble matter (ppm) Solubility (%) Insoluble matter (ppm) 91% 0 71 83 7 3 3 3 Sample 1 167 89 17 46 33 Sample 2 176 89 34 37 42 Sample 3 170 91 50 29 40 Sample 4 178 98 17 33 50 Sample 5 173 98 33 62 50 95% 0 46 350 25 83 2 Sample 6 109 91 42 44 20 Sample 7 84 90 33 50 66 Sample 8 93 89 17 23 3 3 (Please read the precautions on the back first, install-iC page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives-21-This paper size applies to Chinese national standards (CNS > A4 regulations) (2 [0 × 2? 7 mm) A7408149 B7 V. Description of the invention (l9) Table 1 1 (containing amine + N a Ο stabilizer) Mixture of trimethylmethacrylate beads measured by amine Day 0 at 35 ° C Day 35 at 35UC Solubility (%) Insolubles (ppm) Solubility (%) Insolubles tppm 91% 0 1.275 71 83 7 ^ * CF „87% 183 0.924 73 166 43 Sample 1 107 0.848 81 17 33 17 Sample 2 119 0.887 86 17 24 0 Sample 3 119 0.906 87 33 25 9 Sample 4 106 0.824 87 17 28 17 95% 0 0.996 46 350 25 832 Sample 5 46 0.599 87 17 17 25 Sample 6 38 0.589 90 9 21 42 Sample 7 27 0.37 87 41 41 17 ---------- Equipment-(Please read the precautions on the back Φ.? This page) Order the policy of the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs * C.F. = Concentrated formaldehyde Example 9 Using the procedure of Example 1, 200 ppm 2-ethylhexylamine and 0.2 ppm sodium oxide were mixed and added to the formic acid solution. Store the samples at 40 ° C for 2 weeks. After the test period, samples containing amines or mixtures of amines and sodium hydroxide produced a solubility of about 75 to 83%. The insolubles in both samples were reduced to approximately 100 ppm. In contrast, the original sample without additives contained 17 3 p p m insolubles and 41 1% solubility. -22 The paper scale is applicable to the Chinese National Standard (CMS) A4 standard (210 X 297 mm) 408149 A7 B7 V. Description of the invention (20) Table 12 Sample solubility (%) Insoluble matter (ppm) Average molecular weight (g / Mol) 〇Day 1 4 days 0 days 1 4 days 0 days 14 days Formaldehyde without admixture 92 41 116 173 163 200 +200 ppm EHA 98 83 17 83 161 161 +200 ppm EHA +0.2 ppm NaOH 99 75 33 100 161 172 +1 ppm NaOH 90 52 $ 0 110 150-+10 ppm NaOH 6S 12 0 86 170-Central Standards Bureau of the Ministry of Economy | Industrial and Consumer Cooperatives | In order to understand the formation of insolubles, separate and dissolve the insolubles It was confirmed that the insoluble matter was formaldehyde glycol ether having an average chain length of 8 based on the findings. There are many analytical techniques that can be used to characterize the insolubles. These technologies include solid-state nuclear magnetic resonance, liquid chromatography, mass spectrometry, differential scanning calorimetry, and infrared spectroscopy. Solubility test The gravimetric method is used to determine the solubility of trimeraldehyde. This method involves dissolving 10% paraformaldehyde in water at 70 ° C for 15 minutes. After the test, the solubility of the insoluble portion in the product was determined by weighing. Micro-Miller mills were used to grind solid paraformaldehyde samples into 400-700 micron powder. Trimeraldehyde and 90 ± 0.01 grams of deionized and distilled water were then placed in a round bottom flask equipped with a thick kneader. The flask was placed in a normal temperature bath. When the temperature of the solution reached 70 ° C, 10 ± 0.0 1 g of trimeraldehyde was added to the solution. The mixture was stirred vigorously at 2000 rpm for 15 minutes. Regularly moisten the flask around with the supernatant to make sure that all solids can be immersed in the solution. Heat filter the mixture -23----; ------ 1 ------ 1T ------ ^ (. Please read the precautions on the back first to write this page) This paper is suitable for China National Standard (CNS) A4 Specification (210X297 mm) 408149 A7 B7 V. Description of Invention (21) Compound. A 0.45 micron, Teflon filter paper sold by Micron Separations was used. The filtrate was washed with 50 g of cold water, and the solid was dried under an atmosphere of about 200 mm of mercury at room temperature for 1 hour. The filtrate was sparged with dry nitrogen at room temperature. The weight of the insolubles was weighed and analyzed for formaldehyde content and molecular weight. Calculate the solubility according to the following formula:% Solubility = [1-(Weight of filtrate) / {(Weight of paraformaldehyde) * 曱 趑 Analysis 値}] * 1 〇 ％ For example, in a certain experiment, evaporation from the fourth stage 45 g of paraformaldehyde obtained in the device was dissolved in 90.1950 g of water. After 15 minutes, its solubility was 76%. % Solubility = [1-{(2,4975 · 0.0936) /10.114}] * ΐ〇〇 = (〇〇〇 · 23.76) = 76.2% This method is better than another method using sodium sulfite and sulfuric acid titration "Welcome and the results obtained are similar." Regarding the above examples, the solubility measured by titration was 78.5%. The insoluble matter test is printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Justice {' Please read the precautions on the back first. · &Quot; This page) This method uses a weight to determine the trimer after adjusting for pH Amount not in the knee. So 'care should be taken to prevent any small particles, such as dust and other airborne particles. Drying conditions such as temperature and time are also important for test consistency. Micro-Miner mill was used to grind the solid trimer sample into 400-700 micron powder. Cover the sample and set aside. The samples were dried in a 70-degree oven for 20 minutes. A 45 micron, Teflon filter paper sold by the company Micron Separations was used. Store the dried paper in a desiccator, and weigh it by weighing it on the dry filter paper. A known weight and dried filter paper was inserted into the Millipor filter. In a 250 round-bottomed flask, heat 24 g of the acid-base 値 9 buffer solution back to about 100 »c. 24 · Private paper size suitable financial standards (CNS) Α4 · (21 material 297 public 408 149 Central Ministry of Economic Affairs Printed by the Bureau of Standards Consumer Cooperatives V. Invention Description (22) Flow. Acid-base 値 / 9 Fisher Scientific Buffer #SR 114-20 is a solution of 0-1 mol boronic acid, potassium chloride, and sodium hydroxide. + 001 g of trimeramine was added to a round bottom flask equipped with a concentrator. The solution was heated to reflux at about 0.001 and stirred at a speed of 150 rpm. Periodically, the flask was wet with the above liquid Zhou Yuan determined that all solids could be immersed in the solution. Sink while hot and take out and filter the mixture. The filtrate was washed with 50 g of water and then 50 g of reagent was used to separate acetone. At room temperature about 200 mm of mercury column Dry the solid for 1 hour in the air. Spray the filtrate with dry nitrogen at room temperature. Weigh the insolubles and analyze the formaldehyde composition and molecular weight. Record the weight of the insolubles in pprn. For example, '5.8926 grams of powdered trimer Dissolve in 24.0325 grams of buffer solution. After 1 hour, Recovered 0.0010 g. That is, the sample contained 170 ppm ° 1% which is equivalent to 10,000 ppm. Insoluble matter = 0.0010 / 5.9829 = 0.01697% = 170 ppm. The average dose was calculated according to the method disclosed in US Patent No. 3772392 The resorcinol reaction is well known in the art, such as the methods described in US Patent Nos. 2,5 19,550 and 2,519,981. Diphenol reaction. Formaldehyde concentration: The titration procedure used in this test summarizes the determination of formaldehyde content per A. s. D. M. Method D 2 1 94-84. -25- This paper scale applies to China Standard (CNS) M specifications (2 丨 〇 ×; 297 mm) ί, ------ ^ ------ ,? τ --- ^ --- 0 (Please read the Beware of things bad; write this page)