TW200823241A - The chlorinated vinyl chloride based resin and the manufacturing method thereof - Google Patents
The chlorinated vinyl chloride based resin and the manufacturing method thereof Download PDFInfo
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- TW200823241A TW200823241A TW95143657A TW95143657A TW200823241A TW 200823241 A TW200823241 A TW 200823241A TW 95143657 A TW95143657 A TW 95143657A TW 95143657 A TW95143657 A TW 95143657A TW 200823241 A TW200823241 A TW 200823241A
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200823241 九、發明說明： 【發明所屬之技術領域】 技術領域 本發明係關於-種氯化氯乙烯系樹脂及其製造方法。 5 【先前技冬好】 背景技術 氯乙烯系樹脂（以下稱為「Pvc」）係機械強度、耐候性 及耐藥品性等均優異之材料，而被用在眾多技術領域中。 然而，因耐熱性不佳，而正在開發一種使Pvc更進—步氯 10化以提高耐熱性之氯化氪乙烯系樹脂（以下稱為「CPVC」）。 CPVC在具有係PVC優點之難燃性、耐候性及耐藥品性 等特徵的同時，並使得被稱為是PVC缺點之高溫下的機械 物性提南’為有用之樹脂而被使用在多方面的用途上。即， CPVC保有PVC之優異難燃性、财候性及耐藥性等，熱變形 15 溫度亦較PVC高出20〜40°c，因此相對於PVC之可用上限溫 度在60〜70°C左右，CPVC在100°C左右仍可使用，而被用在 耐熱管、耐熱片及耐熱工業板等用途上。 然而，CPVC在氣含量達65重量％以上時，產生許多因 附加氯原子之比例提高而產生的不安定結構，因此而有熱 20 安定性惡化之問題。 為了解決此等問題，已有各種用來製造熱安定良好之 CPVC的方法被提出。 舉例而言，已提出一種以特定流速供給氧濃度為 〇·〇5〜0.35容量％之氯，再以55〜80°C之溫度進行氣化，以製 200823241 造熱安定性良好之CPVC的方法（參照如專利文獻。但，於 此種製造方法中，因氧濃度高且於低溫下反應，熱安定性 並未特別優異，無法耐受長期的擠壓成形及射出成形。 而，作為不同的製造方法，已有一種使用氧濃度為 5 2〇〇ppm以下之氯並在紫外線照射下進行氯化的方法（參照 如專利文獻2)被提出，但此種製造方法因係以紫外線照射 之低溫下進行反應，無法獲得熱安定性特別優異之cpvc。 另外，已有使用過氧化氫來控制反應速度的方法被提 出。例如·已提出一種方法，其係於可密閉之容器内使聚 10氯乙烯懸浮於水性溶劑中，並使該容器内部減壓後，將氯 導入容器内，以90~140t之溫度下使聚氯乙稀氣化者；且， 於氯化過程中，在反應中之聚氣乙烯的氯含量達6〇重量％ 以上時，開始以5〜50ppm/hr之速度對$氯乙稀添加過氧化 鼠(麥照如專利文獻3)。‘然而，由於此種方法不論所欲製造 15之CPVC的氯含量，均在到達60重量％之固定氯含量時控制 反應速度，因此，欲製造用在更高耐熱料之cpvc(例如 氯含量達65重量㈣上之CPVQ時，越是提高氯含量，反應 速度即極端地降低，生產性顯著惡化而無法完全兼顧熱安 定性與生產性。 20專利文獻1 :日本特公昭45-30883號公報 專利文獻2:日本特開平9-328518號公報 專利文獻日本特開2001-151815號公報 【潑^明内容^】 發明之揭示 6 200823241 發明欲解決之課題 本發明係鑑於上述習知技術之課題，目的在於提供一 種不安定結構少且熱安定性優異之氯化氣乙烯系樹脂及其 成形體。 5 此外，本發明之目的亦在於提供一種生產性優異且藉 由抑制不安定結構產生而具優異熱安定性之氯化氯乙烯系 樹脂（特別是氣含量達65重量％以上之氯化氣乙烯系樹脂) 的製造方法。 解決課題之手段 10 本發明之氯化氯乙烯系樹脂(CPVC)之特徵在於：氯含 量為65重量％以上而不足69重量％，分子結構中所含之 -CCV為6.2莫耳％以下，·chcm% 〇莫耳％以上，且CI^ 為35.8莫耳％以下。 且’此種€卩¥(：較宜：（1)分子結構中所含之_(：：(：；12_為5.9 15莫耳％以下，_CHC1_為59.5莫耳％以上，且_Ch2_為34 6莫耳 %以下；（2)分子結構中所含之4分子(tetrad)以上的氯乙烯單 位為30.0莫耳％以下；（3)於21611111波長中iUV吸光度為〇8 以下’ (4)於190 C中之脫HC1量到達7〇〇〇ppm所需的時間為 50秒以上。 2〇 此外，就前述CPVC而言，更宜是：於氯乙烯系樹脂懸 浮於水性溶射之狀態下，將液態氯或氣態氯導入反應器 中進行氯化而製得者；且，以該氯化不進行紫外線照射， 而僅藉熱或者熱與過氧化氫以進行氯乙烯系樹脂之結合及 激發氣者尤佳。 200823241 此外，本發明成形體之特徵即在於：係使用前述cpvc 成形而得者。 口口再者，本發明之C P v C之製造方法係於可密閉之反應容 為内使*1乙烯系樹脂分散在水性介質中，再使反應容器内 5部減壓後，將氯導人容器内使氯乙烯系樹脂氯化者；該 pvc之衣這方法包含控制氯消耗速度之步驟，即：於氣化 氯乙烯系樹脂在到達最終氯含量目標還差5重量％的時間 點，以氣消耗速度(原料氯乙烯系樹脂每比§之5分鐘氣消耗 量，以下定義相同）在0·010〜〇.〇2〇kg/pvc_Kg · 5min之範圍 1〇内進行氯化；且，於到達最終氯含量目標還差3重量％的時 間點’以氯消耗速度在〇.〇5〜0.015kg/PVC-Kg· 5min之範圍 内進行氯化。 就該方法而言’宜將氣消耗速度控制成：最終氣含量 (1)為65重量％以上而不足7〇重量％時，於到達目標距5重量 15 %的時間點，以氯消耗速度在0.010〜0.015kg/PVC- Kg · 5min 之範圍内進行氯化 ，而於到達目標距3重量％的時間點，以 氯消耗速度在0.005〜0,010kg/PVC-Kg · 5min之範圍内進行 氯化；或’（2)為70重量％時，於到達目標距5重量％的時間 點’以氯消耗速度在0.015〜0.020kg/PVC- Kg · 5min之範圍 20内進行氯化，而於到達目標距3重量％的時間點，以氣消耗 速度在0·005〜0.015kg/PVC-Kg · 5min之範圍内進行氯化。 發明之效果 本發明可製得一種不安定結構少且具優異熱安定性之 CPVC。 200823241 此外，因其成形體具優異熱安定性，可適於用在建築 組件、建築配管工事機材及住宅材料等用途，特別是♦杀 - 耐熱性及熱安定性之大型耐熱組件。 • #者’可容易且簡便地製造生產性優異且藉由抑制不200823241 IX. Description of the Invention: [Technical Field] The present invention relates to a chlorinated vinyl chloride resin and a method for producing the same. [Background of the prior art] The vinyl chloride resin (hereinafter referred to as "Pvc") is a material excellent in mechanical strength, weather resistance, and chemical resistance, and is used in many technical fields. However, due to poor heat resistance, a ruthenium chloride-based resin (hereinafter referred to as "CPVC") which promotes Pvc to further improve the heat resistance has been developed. CPVC has the characteristics of flame retardancy, weather resistance and chemical resistance of PVC, and it is used as a useful resin in various aspects, which is called a mechanical property at a high temperature called PVC. Use. That is, CPVC retains the excellent flame retardancy, fuel economy and chemical resistance of PVC. The temperature of hot deformation 15 is also 20~40°C higher than that of PVC, so the upper limit temperature of PVC is about 60~70°C. CPVC can be used at around 100 ° C, and is used in heat-resistant tubes, heat-resistant sheets, and heat-resistant industrial boards. However, when the gas content is 65% by weight or more, the CPVC has a lot of unstable structure due to an increase in the proportion of the additional chlorine atoms, and thus there is a problem that the stability of the heat 20 is deteriorated. In order to solve such problems, various methods for producing a heat-stable CPVC have been proposed. For example, a method of supplying chlorine having an oxygen concentration of 〇·〇5 to 0.35 vol% at a specific flow rate and then gasifying at a temperature of 55 to 80 ° C to prepare a CPVC having good thermal stability of 200823241 has been proposed. (Refer to the patent document. However, in such a production method, since the oxygen concentration is high and the reaction is carried out at a low temperature, the thermal stability is not particularly excellent, and it is not possible to withstand long-term extrusion molding and injection molding. In the production method, a method of chlorinating with chlorine having an oxygen concentration of 5 2 〇〇 ppm or less and chlorination under ultraviolet irradiation (refer to Patent Document 2) has been proposed, but the production method is low temperature due to ultraviolet irradiation. The reaction is carried out, and cpvc which is particularly excellent in thermal stability is not obtained. Further, a method of controlling the reaction rate using hydrogen peroxide has been proposed. For example, a method has been proposed which is used to make poly 10 chlorine in a container which can be sealed. Ethylene is suspended in an aqueous solvent, and after decompressing the inside of the vessel, chlorine is introduced into the vessel to vaporize the polyvinyl chloride at a temperature of 90 to 140 t; and, in the chlorination process, in the reaction When the chlorine content of the polyethylene in the gas is more than 6% by weight, the peroxide mice are added to the chloroethylene at a rate of 5 to 50 ppm/hr (Mr. Patent Document 3). However, due to this method Regardless of the chlorine content of the CPVC to be manufactured, the reaction rate is controlled at a fixed chlorine content of 60% by weight. Therefore, when it is desired to manufacture a cpvc for a higher heat resistant material (for example, CPVQ having a chlorine content of 65 wt%) When the chlorine content is increased, the reaction rate is extremely lowered, and the productivity is remarkably deteriorated, and thermal stability and productivity cannot be fully achieved. Patent Document 1: Japanese Patent Publication No. Sho 45-30883 Patent Document 2: Japanese Patent Laid-Open No. 9 JP-A-2001-151815, JP-A-2001-151815, JP-A-2001-151815, DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems of the prior art, and aims to provide a less stable structure. Further, it is a chlorinated ethylene-based resin excellent in thermal stability and a molded article thereof. 5 Further, it is an object of the present invention to provide an excellent productivity and excellent in suppressing generation of unstable structures. A method for producing a chlorinated vinyl chloride resin (especially a chlorinated vinyl resin having a gas content of 65% by weight or more). A means for solving the problem 10 Characteristics of a chlorinated vinyl chloride resin (CPVC) of the present invention The chlorine content is 65% by weight or more and less than 69% by weight, and the -CCV contained in the molecular structure is 6.2 mol% or less, ·chcm% 〇mol% or more, and CI^ is 35.8 mol% or less. 'This kind of ¥ ¥ (: is more suitable: (1) contained in the molecular structure _ (:: (:; 12_ is 5.9 15 mol% or less, _CHC1_ is 59.5 mol% or more, and _Ch2_ 4 6 mol% or less; (2) 4 molecules (tetrad) or more of vinyl chloride units contained in the molecular structure is 30.0 mol% or less; (3) iUV absorbance is 〇8 or less at the wavelength of 21611111 ' (4 The time required for the amount of de-HC1 in 190 C to reach 7 〇〇〇 ppm is 50 seconds or more. In addition, in the case of the above-mentioned CPVC, it is more preferable to: obtain the chlorine by introducing liquid chlorine or gaseous chlorine into the reactor for chlorination in a state in which the vinyl chloride resin is suspended in an aqueous solvent; It is preferred that the ultraviolet light is not irradiated, and only the combination of heat and heat with hydrogen peroxide for the vinyl chloride resin and the gas is excited. 200823241 Further, the molded article of the present invention is characterized in that it is obtained by molding the above cpvc. Further, in the method of manufacturing CP v C of the present invention, the *1 vinyl resin is dispersed in an aqueous medium in a closable reaction capacity, and after decompressing five portions in the reaction container, chlorine is introduced. The chlorinated vinyl chloride resin is chlorinated in the container; the method of the pvc garment includes a step of controlling the rate of chlorine consumption, that is, at a time point when the vaporized vinyl chloride resin reaches a final chlorine content target of 5% by weight, Gas consumption rate (the raw material of vinyl chloride resin is the same as the gas consumption of § 5 minutes, the definition is the same). Chlorination is carried out in the range of 0·010~〇.〇2〇kg/pvc_Kg · 5min; The time point at which the final chlorine content target was still 3% by weight was chlorinated at a chlorine consumption rate in the range of 〇.5~0.015 kg/PVC-Kg·5 min. In the case of this method, the gas consumption rate should be controlled such that when the final gas content (1) is 65 wt% or more and less than 7 wt%, the chlorine consumption rate is at the time point when the target reaches 5 wt% and 15%. Chlorination in the range of 0.010~0.015kg/PVC-Kg · 5min, and chlorination in the range of 0.005~0,010kg/PVC-Kg · 5min at the time of reaching the target distance of 3% by weight Or when '(2) is 70% by weight, chlorination is carried out at a chlorine consumption rate in the range of 0.015 to 0.020 kg/PVC-Kg · 5 min at a time point of reaching the target distance of 5% by weight, and reaching the target At a time point of 3% by weight, chlorination was carried out at a gas consumption rate in the range of 0·005 to 0.015 kg/PVC-Kg·5 min. EFFECTS OF THE INVENTION The present invention can produce a CPVC having less unstable structure and excellent thermal stability. 200823241 In addition, due to its excellent thermal stability, it can be used in construction components, construction piping machinery and residential materials, especially for large heat-resistant components such as heat-resistant and heat-stable. • #者' can be easily and easily manufactured with excellent productivity and by suppressing
5安定結構產生而具有優異熱安定性之CPVC(特別是氯人曰 達65重量 ％iCPVC)。 S L實施方式]I 0 實施本發明之最佳形態 本發明之氯化氯乙烯系樹脂(CPVC)係氯乙稀系樹脂 10 (PVC)氯化而成者。 PVC可列舉如氯乙烯單聚體、具有可與氣乙烯單體共 聚合之不飽和鍵的單體與氯乙烯單體（含有50重量％為佳） 之共聚物、及使聚合物與氯乙烯單體作接枝共聚合之接枝 共聚物等。該等聚合物可單獨使用亦可併用2種以上。 15 具有可與前述氯乙烯單體共聚合之不飽和鍵的單體可 φ 列舉如·乙烯、丙烯及丁烯等α-烯烴類；乙酸乙烯酯及丙 酸乙烯酯等乙烯醋類；丁基乙晞S旨及錄蠘基乙烯醋等乙烯 ~ s曰類’（甲基)丙烯酸甲酉旨、(甲基)丙烯酸乙ί旨、丙烯酸丁酉旨 - 及甲基丙烯酸苯酉旨等（甲基)丙稀酸醋類；苯乙稀、(X-甲基苯 2〇乙稀等芳香族乙稀類；氯化亞乙婦、說化亞乙稀等齒化乙 烯乙烯類，Ν-苯基馬來醯亞胺、Ν_環己基馬來醯亞胺等Ν_ 取代馬來醯亞胺類；（甲基)丙稀酸；馬來酸酐 ;及，丙浠腈。 該等可單獨使用，亦可併用兩種以上。 使月述氯乙埽作接枝共聚合之聚合物僅需為可使氯乙 200823241 烯作接枝聚合者即可，未特別受限，舉例而言，可列舉如 乙烯醋一氧化碳共聚 物、乙烯-丙烯酸乙罐物、乙歸沔烯酸丁醋共聚物、乙 烯-丙烯酸丁醋一氧化碳編、乙埽甲基丙烯酸甲醋共 聚物、乙稀·丙烯共聚物、丙騎_Tq共聚物、聚胺基甲 酸酿、氯化聚乙烯及氣化聚丙烯等。該等可單獨使用，亦 可併用兩種以上。 刖述PVC之平肖聚合度亚未特別受到限制，宜為通常 使用之400〜3000,更宜為_〜1500。此夕卜，pvc之平均粒 10徑考慮操作及氣化反應所需時間，宜為賺〜雇叫。 impvc之聚合方法未受特別限制，可列舉如迄今已 知之水懸浮聚合、塊狀聚合、溶液聚合及乳化聚合等。聚 體而言，例如，於聚合器中加入氯乙婦系單體、水性溶劑、 /刀散劑及聚合起始劑，升溫到預定聚合溫度進行聚合反 15應，使氯乙烯系單體之聚合轉化率達70〜90重量％之預定比 例後，進行冷卻、排氣及脫單體之處理，而獲得含Pvc之 水料’再將該漿料脫水乾燥而至得PVC。 分散劑可列舉如：曱基纖維素、乙基纖維素、羥乙基 、素及^丙基甲基纖維素等水熔性纖維素類；部分束化 20 聚乙烯ϋ、_ 1 π 氣化Λ畏乙稀、丙烯酸聚合物及明膠等水溶性高 ’山梨糖醇酐單月桂酸酯及聚氧乙烯山梨糖醇 桂酸_等水溶性乳化劑。 ^ :合起始劑可列舉如··過氧十二醯；過氧碳酸二異丙 曰I乙基己基過氧碳酸酯、二乙氧基乙基過氡碳酸酯 10 200823241 等過氧碳酸r日化合物；過氧新葵酸α，香_、過氧 第三丁醋、過氧三甲乙酸第三丁酷、過氧新葵‘三= 等過氧化自旨化合物；2,2-偶氮異丁腈、2, 2偶氮雙从二甲曰 基戊猜、2，2-偶氣雙(‘甲氣基-2, 4-二甲其士、昧、& 甲基戊腈）等偶氮化合 物0 再者，亦可添加通常被用在氯乙稀之聚合上的聚合調 整劑、連鎖移動劑、ΡΗ調整劑、交聯劑、安定劑、充填劑、 抗氧化劑及出垢防止劑等。 /ή 本發明之CPVC之氯含率宜為65重量％以上，若氯含率 10不足65重量％則有而t熱性提高不足的傾向。此外，在需要 特別高之耐熱性時，宜為69重量％或70重量％以上，成形加 工性亦隨之變得良好。 此時，較佳地，分子結構中所含之_CC12_宜為17 〇莫耳 %以下，-CHC1-宜為46.0莫耳％以上且_CH2_宜為37 〇莫耳％ 15 以下。 分子結構中所含之-CC12_、_CHCK^_CH广之比例反映 出PVC氯化時被導入氯的部分。氯化前之pvc在理想上大 致呈-CClr為0莫耳％、_CHC1_為50莫耳％、CH2 j5〇莫耳 -0 伴隨氯化進行(隨著氯化度提高）而-CH2-減少，-CC12- 及-CHC1·增加。此時，因立體結構妨礙甚大且不安定之 _CH2—過度增加，若在CPVC之同一分子内受到氯化的部分 與未叉氯化的部分偏頗，則氯化狀態之不均勻性增加，而 使熱女疋性大為受損。因此，分子結構中之各成分宜於前 11 200823241 述範圍内。 特別疋cpvc的氣含率更宜為⑴65重量％以上而不足 69 ^量％ ’或是⑵66重量％以上而不足的重量％，或是⑶的 重里％以上，或者⑷69重量％以上且不足72重量％。 5 氯含率為⑴或⑵時，-卿-宜為6.2莫耳％以下、_CHC1_ 宜為58.0莫耳％以上且（Hr宜為％ 8莫耳％以下。這是為了 使不均勻氯化之影響停留在最小限度，以提高熱安定性。 此外，若-CC12-為5.9莫耳％以下、_CHC1•為59 5莫耳％以上 且-CH2-為34.6莫耳％以下，熱安定性將更佳，故而更為理 10 想。 氯a率為(3)或⑷時，分子結構中所含_CC12_宜為17 〇 莫耳％以下、-CHC1-宜為46.〇莫耳％以上且CH2宜為37 〇 莫耳％以下。雖然CPVC隨著其氯化程度提高而有{肥增 加、氣化狀態不均勻性更增大的傾向，但可藉由使其呈前 15述範圍而更提高熱安定性。此外，若-CC12-為16.0莫耳％以 下、-CHC1-為53.5莫耳％以上且-CHr為3〇 5莫耳％以下，更 為理想。 本發明之CPVC在分子結構中所含4分子(tetrad)以上之 氯乙烯單位（以下稱為「VC單位」）宜於3〇 〇莫耳％以下，更 20 宜為28.0莫耳％以下。 特別是在本發明之CPVC氯含率為(3)及(4)時，該cpvc 在分子結構中所含4分子以上之氯乙烯單位宜在18 〇莫耳％ 以下。 存在於CPVC之VC單位將成為脫HC1的起點，且若該 12 200823241 VC單位連續，將容易引起被稱為連鎖反應之連續脫HC1& 應。意即，該4分子以上之VC單位量越大，越容易引起脫 HC1反應’使熱安定性降低。 此外，前述VC單位係指未氯化之PVC單位，為 5 -CH2-CHC1-，4分子以上之VC單位係指4個以上VC單位連續 結合而成之單位。 此外，本發明之CPVC在216nm波長中之UV吸光度宜為 8.0以下。特別在本發明之CPVC之氯含率為（1)及(2)時，宜 為0.8以下。 ίο 就cpvc而言，可藉UV吸光值使氯化反應時之分子鏈 的異種結構定量化，而作為熱安定性之指標。在CPVC中， 因附著在呈雙鍵結合之碳原子所相鄰之碳原子上的氯原子 不安定，而將以其為起點發生脫HC1。即，UV吸光度越大， 越容易發生脫HCL，熱安定性越低。 15 一般而言，為製得氯化度高之CPVC，氣化時將長時間 暴露在催化劑或紫外線中，或是在高溫中放置長時間，因 此而有CPVC分子鏈中之異種結構增加，導致熱安定性大為 受損的傾向。 UV吸光度之值係以下述方法測定者，即：測定紫外線 20吸收圖譜，再讀取CPVC中之異種結構_CH=CH-C(=0)j -CH=CH-CH=CH-可吸收的波長216nm之UV吸光度值。 前述CPVC於190°c中之脫HC1量到達7000ppm所需的 時間宜為50秒以上，較宜為60秒以上，而更宜為7〇秒以上。 特別是，在本發明CPVC的氯含率為(3)及(4)時，於19〇 13 200823241 °C中之脫HC1量到達7000ppm所需的時間宜為1〇〇秒以上， 車父且為120秒以上’更宜為140秒以上。 • 就CPVC而言，可藉於DOt：中之脫HC1量到達7000ppm 所需的時間而作為熱安定性之指標。若CPVC暴露於高溫將 5引起熱分解，此時將發生HC1氣體。亦即，於19〇t中之脫 HC1量到達7000ppm所需的時間越短，熱安定性越低。 cpvc隨著其氯化程度提高，未氯化Pvc單位之▽。單 _ 位將減少，因此其脫HC1量有減少的傾向。然而，同時將引 起不均勻的氣化狀態及異種結構增加，熱安定性降低，因 10 此需將脫HC1量抑制為較少。 本發明之CPVC係PVC氣化而成之樹脂，氣化可藉習用 公知之任何方法進行。例如，宜於反應器中5l pVc呈释 浮於水性溶劑中之狀態，再將液態氯或氣態氯導入反應器 内進行氯化。 15 舉例來說，反應容器宜為裝設有攪拌裝置、加熱裝置、 Φ 冷卻裝置、減壓裝置及照光裝置等之可密閉耐壓容器。該 反應谷裔之材質可應用施有玻璃櫬裡之不鏽鋼製、鈦製等 - 一般使用的材質。 - 將Pvc調整為懸浮狀態的方法並未特別受到限制，可 20使用係令聚合後之pvc作脫單體處理而成的塊（cake)狀 PVC，亦可使經乾燥之PVC再度懸浮化於水性溶劑中。或 是，亦可使用從聚合系統中除去不宜氯化反應之物質的懸 浮液。其中，以使用係令聚合後之PVC作脫單體處理而成 的塊狀樹脂為佳。裝入反應器中之水性溶劑量並未特別限 14 200823241 制，一般而言，相對於100重量份Pvc宜為2〜1〇重量份。 氯未受到特別限制，可以液態或氣態等狀態導入。製 程上，使用液態氯較有效率，但亦可為了反應中途之壓力 調整或伴隨氯化反應之氯補給，而更適當地吹入氯氣^宜 5使用氣中之氧濃度為1〇〇ppm以下，更宜為1〇咖以下的氯。 反應器内之大氣壓力並未特別受限，但因氯壓越高氯 越容易浸透至㈣粒子内部，魏3〜2Mpa之範圍為佳。 >此外’在導人氯之前，宜先使反應容器内部減壓並除 去孔。若存有多量之氧，將妨礙氯化反應之控制，故而宜 10使反應容器内之氧量減壓至1〇〇ppm以下。此時，若氯之供 給減少則氣化反應之進行速度緩慢，增多則反應結束後殘 留多Ϊ未反應之氯而不經濟，因此宜供至使反應容器内之 氣分壓為0.03〜0.5MPa。 使pvc氯化之方法並未特別限制，可列舉如：藉由熱 15使PVC之結合及激發氣，以促進氯化的方法（以下稱為熱氯 化），…、射光而光反應性地促進氯化的方法（以下稱為光氯 化）；及，一邊加熱同時照射光之方法等。 藉熱能進行氯化時之加熱方法並未特別受限，舉例來 A ’以來自反應&、壁之外部套件方式所進行之加熱甚有效 20果肖別疋’僅以加熱進行氯化時，一旦反應溫度降低氣 化速度即有降低的傾向，若過高職氯減應並行地發生 脫鹽酸反應，導致所得CPVC有著色傾向，因此反應溫度宜 為70〜14(TC，更宜為1〇〇〜135Τ。 再者’使用紫外光線等光能時，需要在高溫高壓條件 15 200823241 下可作紫外線照射等之光能照射的裝¥。止* i 九氧反應時，氣 化反應溫度為40〜80°C。 ' 氯化時亦可不照射光而添加過氧化氫。過氧化氣之添 加量若減少則有使氯化速度提高之效果減少的傾向，且若 5增多則有使所得PVC之耐熱性降低的傾向，因此宜對pv^ 以每1小時5〜500ppm的量添加。因添加過氧化气可使氯化 速度提高，添加過氧化氫時之反應溫度宜為6〇〜14〇1，更 宜為65〜ll〇°C。 於上述氯化方法中，以不進行紫外線照射之熱氯化法 10為彳土’及’以僅藉熱或熱與過氧化氫使氯乙烯樹脂結合並 激發氯而促進氯化反應的方法為佳。 以紫外線進行氯化反應時，PVC氯化所需之光能大小 受到PVC與光源間之距離影響甚大。因此，Pvc粒子之表 面與内部因該能量大小的差異而產生不同，更難進行均句 15之氯化。相對於此，不進行紫外線照射而僅藉熱或熱與過 氧化氫使PVC結合及激發氣以進行氯化的方法可實現更均 勻之氯化反應，進而提高CPVC之熱安定性。 氯化若速度減緩將有生產性降低的傾向，加快則有發 生脫鹽酸反應而使所得CPVC著色，耐熱性亦降低的傾向。 20因此，於本發明中，宜在PVC氯化時控制氯化速度（即氣消 耗速度）。 氯消耗速度之控制方法可列舉如控制光之照射量、反 應速度及添加過氧化氫等。 光知、射Bji者知射距離延長而損失能量，因此僅有光照 16 200823241 射裝置附近容易進行反應，而難以維持反應均勻化。為克 服此一問題，必須大幅提高攪拌效率，因而需要改造設備。 - 此外，欲增加光照射強度時，需要增強光照射裝置之能力。 , 這需要設備大型化或增設光照射裝置，因此難以輕易變 5 更，並不經濟。 令溫度較反應初期更高溫(PVC之玻璃轉移溫度以上） 時，氯化速度將加速，但同時PVC本身亦將發生脫鹽酸反 ^ 應，而須設定在對熱安定性等不造成不良影響的範圍内， 因而使反應溫度之控制範圍更為狹窄。更何況，將產生許 10 多如準備可耐高溫之反應容器及週邊設備等的設備擴充， 甚不經濟。 因氯化之進行狀況不同，氯化速度即使在相同條件下 亦不同。這是因為隨著氯化進行，將從PVC結構中容易附 加氯的部分優先進行反應，到一定之氣含量以上時，在結 15構上附加氯所需的能量增加，且不安定之氯將發生脫鹽酸 _ 反應專’附加氯以外的反應亦將同時發生，因而伴隨著複 雜反應。 - 由此可知’在氣化反應初期中’即使僅藉光照射及加 熱溫度，一般來說即可使氣化速度維持甚高，但在氯化反 2〇應中期至後期，該等能源即告不足，使得氯化速度極端降 低。為彌補此-現象，可添加過氧化氯等過氧化物作為催 化劑，藉此提高反應速度。 曲將過氧化氫用作氣化反應之催化_，可藉過氧化氣 之濃度、添加速度來控制反應速度。牲 ^将別疋，過氧化氫可 17 200823241 、穿声㈣地分散在水媒介中。可觀等而容㈣控制添 • 力：因:^_於配合氯化所進行之控制。 ^匕反應初期中投人過氧化氫時，反應速度當然會 • 加速到較—^船A Wi 又马快，可使氯化反應時間本身縮短。然而， -逮度過快，將引起發熱反應，通常發生在氯化反應 cpV(：^欲駄反應等變得容易從初期就開始發生，故而 有般情況更多之雙鍵及分枝等不安定結 # I重要之初期著色性及熱安定性等之性能降低。 氯化反應中期至後期可藉由如添加過氧化氫而控制成 10 ^應速度不減緩。未添加時，到達製品氯含量為止所需之 長生產性大幅惡化。即使欲維持生產性而提高加 熱/皿度5其效果亦不佳，且氯化反應時間中所受之加熱過 程增加，導致熱安定性降低。 由此了知，可藉由如添加過氧化氫而控制氣化之進行 15狀態（氣含量)及氯消耗速度，提高生產性、抑制不安定結構 • 產生及使承受之熱經歷最小化，進而製得熱安定性優異之 CPVC。 * 習知技術中之CPVC製造方法(如參照專利文獻1}係於 氣含量成為60重量％之時間點上控制氯消耗速度，藉此實 2〇 現生產性與初期著色性之改善。但是，對氯含量達65重量 %以上之製品同樣應用該方法時，對於熱安定性等性能雖 有發揮效果，但在生產性上，氯含量越高則越是降低。這 是因為即使在反應中變化pvc之氣含量，卻未隨著配合控 制反應速度。 18 200823241 本發明係以CPVC之氣含量來階段性地控制氯消耗速 度，藉此可在確保生產性之同時，確實抑制不安定結構之 發生。 可列舉如，以氣消耗速度在0.005〜0 05kg · PVC —Kg · 5 min之範圍内，以到達所欲製造之CPVC之的最終氯含量目 標還差5重量％及還差3重量％的兩階段來進行控制的方法。 此種cpvc之製造方法特別適於製造氯含量達65重量 %以上之CPVC，但氯含量愈高，生產性隨之降低。此外， 因產生許多不安定結構而亦發生熱安定性降低。欲兼顧生 10產性及熱安定性，需將氯化速度作更精密的控制。 因此，在進行PVC氯化之際，且欲製得最終氯含量為 65重量％以上而不足70重量％iCPVC時，宜作下述控制： 在到達隶終氣含量目標還差5重量％的時間點，以氯消耗速 度（原料氣乙炸糸樹脂每1kg之5分鐘氣消耗量）在 15 0·010〜〇.〇15kg/PVC-Kg · 5min之範圍内進行氯化；且，於 到達最終氣含量目標還差3重量％的時間點，以氣消耗速度 在0·005〜0.010kg/PVC-Kg · 5miri之範圍内進行氯化。 再者’欲製得最終氯含量為70重量％以上，且較佳不 足72重量％iCPVC時，宜作下述控制：在到達最終氯含量 20目標還差5重量％的時間點，以氯消耗速度在 0.015〜0.020kg/PVC- Kg · 5min之範圍内進行氯化；且， 到達最終氯含量目標還差3重量％的時間點，以氯消耗速声 在0.005〜0.015kg/PVC-Kg · 5min之範圍内進行氯化。 藉此’可獲得氯化狀態不均勻性較少且熱安定性優異 19 200823241 之CPVC。 此外，前述氯消耗速度之控制可階段性或極快地進 行，但仍以徐徐進行為佳。 本發明之成形體係將上述CPVC成形而製得者。 成形體之製造方法可採用習用公知之任意製造方法， 例如擠壓成形法及射出成形法等。所得成形體之熱安定性 優異。5 CPVC (especially chlorhexidine 65 wt% iCPVC) produced by a stable structure with excellent thermal stability. S L embodiment] I 0 BEST MODE FOR CARRYING OUT THE INVENTION The chlorinated vinyl chloride resin (CPVC) of the present invention is a chlorinated vinyl chloride resin 10 (PVC). The PVC may, for example, be a vinyl chloride monomer, a monomer having an unsaturated bond copolymerizable with a gas ethylene monomer, a copolymer of a vinyl chloride monomer (preferably containing 50% by weight), and a polymer and a vinyl chloride. The monomer is a graft copolymer copolymerized by a graft copolymerization or the like. These polymers may be used alone or in combination of two or more. 15 A monomer having an unsaturated bond copolymerizable with the above vinyl chloride monomer φ exemplifies an α-olefin such as ethylene, propylene, and butene; an ethylene vinegar such as vinyl acetate or vinyl propionate; and a butyl group;晞 晞 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 甲基 甲基 甲基 甲基 甲基Acetate vinegar; styrene, (X-methyl benzene 2 〇 ethylene and other aromatic ethene; chlorinated acetylene, acetylated ethylene, etc., styrene-phenyl Maleic imine, Ν_cyclohexylmaleimide, etc. 取代 substituted maleimide; (meth)acrylic acid; maleic anhydride; and acrylonitrile. These can be used alone, The polymer which is used for the graft copolymerization of the chloroethyl hydrazine may be used only for the graft polymerization of the chloroethylene 200823241 olefin, and is not particularly limited, and examples thereof include, for example, ethylene. Vinegar carbon monoxide copolymer, ethylene-acrylic acid ethyl can, ethyl ruthenium butyl acrylate copolymer, ethylene-acrylic acid butyl vinegar carbon monoxide, acetonitrile methyl propyl a methacrylate copolymer, an ethylene/propylene copolymer, a propylene-Tq copolymer, a polyurethane, a chlorinated polyethylene, a vaporized polypropylene, etc. These may be used singly or in combination of two or more. The fact that the degree of polymerization of PVC is not particularly limited is preferably 400 to 3000, more preferably _~1500. In addition, the average particle size of pvc considers the time required for operation and gasification reaction. The polymerization method of impvc is not particularly limited, and examples thereof include water suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, and the like which have hitherto been known. For the polymerization, for example, it is added to the polymerization vessel. a vinyl chloride monomer, an aqueous solvent, a knife powder, and a polymerization initiator, and the temperature is raised to a predetermined polymerization temperature to carry out a polymerization reaction, and the polymerization conversion ratio of the vinyl chloride monomer reaches a predetermined ratio of 70 to 90% by weight. The process of cooling, venting, and de-monomerization is performed to obtain a water-containing material containing Pvc, and then the slurry is dehydrated and dried to obtain PVC. Examples of the dispersing agent include mercapto cellulose, ethyl cellulose, and hydroxy group. Water-melting properties such as ethyl, ketone and propylmethylcellulose Vitamins; partially bundled with 20 PTFE, _ 1 π gasified acetophenone, acrylic polymer and gelatin such as water-soluble high sorbitol monolaurate and polyoxyethylene sorbitan cin Water-soluble emulsifier etc. ^ : The starting agent can be exemplified by ··········································· 200823241 and other peroxycarbonated r-day compounds; peroxynonic acid α, fragrant _, peroxy third butyl vinegar, peroxytriacetic acid third butyl, peroxy new sunflower 'three = and other peroxidation of the compound; 2 , 2-azoisobutyronitrile, 2, 2 azo double from dimethyl hydrazine, 2, 2- bis double ('methyl ketone-2, 4- dimethyl ketone, oxime, & A Azo compound such as valeronitrile) Further, a polymerization regulator, a chain shifting agent, a ruthenium adjusting agent, a crosslinking agent, a stabilizer, a filler, and an antioxidant which are usually used in the polymerization of vinyl chloride may be added. And scale inhibitors, etc. / C. The chlorine content of the CPVC of the present invention is preferably 65% by weight or more, and if the chlorine content is less than 65% by weight, the increase in t heat tends to be insufficient. Further, when heat resistance is required to be particularly high, it is preferably 69% by weight or more, and the moldability is also improved. In this case, preferably, _CC12_ contained in the molecular structure is preferably 17 〇 mol% or less, -CHC1- is preferably 46.0 mol% or more, and _CH2_ is preferably 37 〇 mol% 15 or less. The ratio of -CC12_, _CHCK^_CH contained in the molecular structure reflects the portion of the chlorine into which chlorine is introduced during chlorination. The pvc before chlorination is ideally -CClr is 0 mol%, _CHC1_ is 50 mol%, CH2 j5〇mol-0 is accompanied by chlorination (as the degree of chlorination increases) and -CH2- decreases , -CC12- and -CHC1· increase. At this time, since the three-dimensional structure hinders the large and unstable _CH2-excessive increase, if the chlorinated portion and the un-chlorinated portion are biased in the same molecule of the CPVC, the unevenness of the chlorinated state increases, and The hot girl is greatly damaged. Therefore, the components in the molecular structure are suitable for the range of the previous 11 200823241. In particular, the gas content of cpvc is preferably (1) 65 wt% or more and less than 69 μg% 'or (2) 66 wt% or more and insufficient wt%, or (3) wt% or more, or (4) 69 wt% or more and less than 72 wt%. %. 5 When the chlorine content is (1) or (2), -qing is preferably 6.2 mol% or less, _CHC1_ is preferably 58.0 mol% or more and (Hr is preferably % 8 mol% or less. This is for uneven chlorination. The effect is kept to a minimum to improve the thermal stability. In addition, if -CC12- is 5.9 mol% or less, _CHC1 is 59 5 mol% or more, and -CH2- is 34.6 mol% or less, the thermal stability will be more Preferably, when the chlorine a ratio is (3) or (4), the _CC12_ contained in the molecular structure is preferably 17 〇 mol% or less, and -CHC1 is preferably 46. 〇 mol% or more. CH2 is preferably 37 〇 mol% or less. Although CPVC has a tendency to increase in fertilizer and increase in gasification state unevenness as the degree of chlorination increases, it can be made to be in the range of the first 15 Further, it is more preferable that -CC12- is 16.0 mol% or less, -CHC1- is 53.5 mol% or more, and -CHr is 3〇5 mol% or less. The vinyl chloride unit (hereinafter referred to as "VC unit") of four or more molecules (hereinafter referred to as "VC unit") is preferably 3 〇〇 mol% or less, and more preferably 20 8.0 mol% or less. When the chlorine content of the CPVC of the present invention is (3) and (4), the cpvc containing more than 4 molecules of the vinyl chloride unit in the molecular structure is preferably less than 18 〇 mol%. The VC unit present in the CPVC will be It becomes the starting point for the removal of HC1, and if the 12 200823241 VC unit is continuous, it will easily cause a continuous deHC1 & called a chain reaction. That is, the larger the VC unit amount of more than 4 molecules, the more likely the HC1 reaction is caused. 'The above-mentioned VC unit means an unchlorinated PVC unit, which is 5-CH2-CHC1-, and a VC unit of 4 or more molecules means a unit in which four or more VC units are continuously combined. The UV absorbance of the CPVC of the present invention at a wavelength of 216 nm is preferably 8.0 or less. Particularly, when the chlorine content of the CPVC of the present invention is (1) and (2), it is preferably 0.8 or less. ίο In terms of cpvc, it is possible to borrow The UV absorbance value quantifies the heterogeneous structure of the molecular chain during the chlorination reaction, and serves as an indicator of thermal stability. In CPVC, the chlorine atom attached to the carbon atom adjacent to the carbon atom bonded by the double bond is not Stability, and will take off HC1 as its starting point. That is, the greater the UV absorbance The more prone to de-HCL, the lower the thermal stability. 15 In general, in order to obtain CPVC with high chlorination degree, it will be exposed to catalyst or ultraviolet light for a long time during gasification, or it may be left at a high temperature for a long time. However, the heterogeneous structure in the CPVC molecular chain increases, which leads to a great tendency for thermal stability to be impaired. The value of UV absorbance is determined by the following method: measuring the ultraviolet 20 absorption spectrum, and then reading the heterogeneous structure in CPVC_ CH=CH-C(=0)j -CH=CH-CH=CH- absorbable UV absorbance at a wavelength of 216 nm. The time required for the amount of de-HC1 of the CPVC to reach 7000 ppm at 190 ° C is preferably 50 seconds or more, more preferably 60 seconds or more, and more preferably 7 seconds or more. In particular, when the chlorine content of the CPVC of the present invention is (3) and (4), the time required for the amount of de-HC1 to reach 7000 ppm in 19〇13 200823241 °C is preferably 1 sec or more, the father and the It is more than 120 seconds' more preferably 140 seconds or more. • In the case of CPVC, it can be used as an indicator of thermal stability by the time required for the amount of de-HC1 in DOt to reach 7000 ppm. If the CPVC is exposed to high temperatures, 5 will cause thermal decomposition, and HC1 gas will occur at this time. That is, the shorter the time required for the amount of dehydrogenated HC1 to reach 7000 ppm in 19 〇t, the lower the thermal stability. As cpvc increases with its degree of chlorination, it does not chlorinate Pvc units. The single _ bit will decrease, so there is a tendency for the amount of deHC1 to decrease. However, at the same time, an uneven gasification state and an increase in heterogeneous structure are caused, and the thermal stability is lowered, so that the amount of de-HC1 is required to be suppressed to be small. The CPVC-based PVC gasified resin of the present invention can be gasified by any method known in the art. For example, it is preferred that 5 l of pVc is released in an aqueous solvent in the reactor, and liquid chlorine or gaseous chlorine is introduced into the reactor for chlorination. For example, the reaction vessel is preferably a hermetic pressure-resistant container equipped with a stirring device, a heating device, a Φ cooling device, a pressure reducing device, and an illuminating device. The material of the reaction grain can be applied to stainless steel made of glass crucible, titanium, etc. - generally used materials. - The method of adjusting the Pvc to the suspension state is not particularly limited, and the cake PVC which is obtained by depolymerizing the polymerized pvc may be used, and the dried PVC may be resuspended again. In an aqueous solvent. Alternatively, a suspension in which a substance which is not suitable for chlorination is removed from the polymerization system can also be used. Among them, a block resin obtained by subjecting the polymerized PVC to de-monomerization is preferred. The amount of the aqueous solvent to be charged into the reactor is not particularly limited to 14 200823241, and is generally 2 to 1 part by weight based on 100 parts by weight of Pvc. Chlorine is not particularly limited and can be introduced in a liquid or gaseous state. In the process, the use of liquid chlorine is more efficient, but it can also be adjusted for the pressure in the middle of the reaction or the chlorine supply accompanying the chlorination reaction, and the chlorine gas is more appropriately blown into the gas. The concentration of oxygen in the gas is 1 〇〇ppm or less. More preferably, it is chlorine below 1 〇 coffee. The atmospheric pressure in the reactor is not particularly limited, but the higher the chlorine pressure, the more easily the chlorine penetrates into the interior of the (IV) particles, and the range of Wei 3 to 2 Mpa is preferred. > In addition, it is preferred to depressurize the inside of the reaction vessel and remove the pores before introducing chlorine. If a large amount of oxygen is present, the control of the chlorination reaction is hindered. Therefore, it is preferable to reduce the amount of oxygen in the reaction vessel to 1 〇〇 ppm or less. At this time, if the supply of chlorine is decreased, the progress of the gasification reaction is slow, and if the amount of chlorine is unreacted after the completion of the reaction, it is not economical, so it is preferable to supply the gas partial pressure in the reaction vessel to 0.03 to 0.5 MPa. . The method for chlorinating pvc is not particularly limited, and examples thereof include a method of promoting the chlorination by heat 15 and an excitation gas to promote chlorination (hereinafter referred to as thermal chlorination), ..., and photoreactively. A method of promoting chlorination (hereinafter referred to as photochlorination); and a method of simultaneously irradiating light while heating. The heating method for chlorination by thermal energy is not particularly limited. For example, A 'heating by means of an external kit from the reaction & wall, is effective. 20 When chlorination is only performed by heating, Once the reaction temperature is lowered, the gasification rate tends to decrease. If the dechlorination reaction occurs in parallel with the high-level chlorine reduction, the resulting CPVC has a tendency to color. Therefore, the reaction temperature is preferably 70 to 14 (TC, more preferably 1〇). 〇~135Τ. In addition, when using light energy such as ultraviolet light, it is necessary to irradiate light energy such as ultraviolet radiation under high temperature and high pressure conditions 15 200823241. When the reaction is zero, the gasification reaction temperature is 40. ~80 ° C. 'In the case of chlorination, hydrogen peroxide may be added without illuminating the light. If the amount of the peroxide gas is decreased, the effect of increasing the chlorination rate tends to decrease, and if the amount of 5 is increased, the resulting PVC may be used. The heat resistance tends to decrease, so it is preferable to add pv^ in an amount of 5 to 500 ppm per hour. The chlorination rate can be increased by adding peroxygen gas, and the reaction temperature when hydrogen peroxide is added is preferably 6 〇 14 14 〇 1 More preferably 65~ll〇°C. In the above chlorination method, the thermal chlorination method 10 which does not perform ultraviolet irradiation is the alumina 'and the method of promoting the chlorination reaction by combining the vinyl chloride resin only by heat or heat and hydrogen peroxide to excite chlorine. When chlorination by ultraviolet light, the light energy required for chlorination of PVC is greatly affected by the distance between PVC and the light source. Therefore, the surface and interior of Pvc particles are different due to the difference in the amount of energy, which is more difficult. The chlorination of the phrase 15. In contrast, the method of merging only by heat or heat with hydrogen peroxide to combine PVC and excite the gas for chlorination can achieve a more uniform chlorination reaction, thereby improving CPVC. Thermal stability. If the chlorination rate is slowed down, there is a tendency for productivity to decrease. When the chlorination is accelerated, the dechlorination reaction may occur to color the obtained CPVC, and the heat resistance tends to decrease. 20 Therefore, in the present invention, it is preferred to chlorinate in PVC. The chlorination rate (that is, the gas consumption rate) is controlled. The control method of the chlorine consumption rate includes, for example, the amount of irradiation of the control light, the reaction rate, and the addition of hydrogen peroxide, etc. Loss of energy, so only the light 16 200823241 near the launching device is easy to react, and it is difficult to maintain the reaction uniformity. To overcome this problem, the stirring efficiency must be greatly improved, and thus the equipment needs to be modified. - In addition, when increasing the light irradiation intensity There is a need to enhance the ability of the light-irradiating device. This requires a large-scale device or a light-increasing device, so it is difficult to easily change it. It is not economical. When the temperature is higher than the initial stage of the reaction (above the glass transition temperature of PVC), chlorine The rate of oxidation will accelerate, but at the same time, the PVC itself will undergo dehydrochlorination, and it must be set within a range that does not adversely affect the thermal stability, thus making the control range of the reaction temperature narrower. What's more, it will not be economical to create more than 10 equipments such as reactors and peripherals that can withstand high temperatures. The chlorination rate is different even under the same conditions due to the different conditions of chlorination. This is because as the chlorination proceeds, the portion which is easily added with chlorine from the PVC structure is preferentially reacted. When the gas content is above a certain gas content, the energy required to add chlorine to the structure of the structure 15 is increased, and the unstable chlorine will be Dehydrochlorination occurs. Reactions other than the addition of chlorine will also occur simultaneously, thus accompanying complex reactions. - It can be seen that 'in the initial stage of the gasification reaction', even if only by light irradiation and heating temperature, the gasification rate can be maintained at a high level, but in the middle to late stages of the chlorination reaction, the energy is Insufficient, the chlorination rate is extremely reduced. To compensate for this phenomenon, a peroxide such as chlorine peroxide can be added as a catalyst to increase the reaction rate. The use of hydrogen peroxide as a catalyst for the gasification reaction allows the reaction rate to be controlled by the concentration and rate of addition of the oxidizing gas. The animals will not be embarrassed, hydrogen peroxide can be dispersed in the water medium by sound (4). Appreciable and equal (4) Controlling the force: Because: ^_ is controlled by chlorination. ^ When the hydrogen peroxide is injected in the initial stage of the reaction, the reaction rate will of course be accelerated to a higher speed than the ship A Wi, which will shorten the chlorination reaction time itself. However, if the catch is too fast, it will cause an exothermic reaction, usually occurring in the chlorination reaction cpV (: ^ 駄 駄 reaction, etc. becomes easy to occur from the beginning, so there are more cases of double bonds and branches, etc. Anding knot # I important performance of initial coloring and thermal stability, etc. The chlorination reaction can be controlled to 10 ^ by the addition of hydrogen peroxide in the middle to the end. The speed should not be slowed. When not added, the chlorine content of the product is reached. The long-term productivity required so far has been greatly deteriorated. Even if it is desired to maintain the productivity and increase the heating/dishness 5, the effect is not good, and the heating process in the chlorination reaction time is increased, resulting in a decrease in thermal stability. It is known that the gasification can be controlled by the addition of hydrogen peroxide to control the state of 15 (gas content) and the rate of chlorine consumption, thereby improving productivity, suppressing unstable structures, generating and minimizing the heat experience, and thereby producing heat. CPVC which is excellent in stability. * The CPVC manufacturing method in the prior art (for example, refer to Patent Document 1) controls the chlorine consumption rate at a time when the gas content is 60% by weight, thereby realizing the productivity and the initial stage. However, when the method is applied to a product having a chlorine content of 65% by weight or more, although it has an effect on properties such as heat stability, the higher the chlorine content, the lower the productivity. This is because even if the gas content of pvc is changed during the reaction, the reaction rate is not controlled with the mixing. 18 200823241 The present invention controls the chlorine consumption rate step by step with the gas content of CPVC, thereby ensuring productivity while ensuring productivity. It does suppress the occurrence of unstable structures. For example, the gas consumption rate is in the range of 0.005~0 05kg · PVC - Kg · 5 min, and the final chlorine content of the CPVC to be manufactured is still 5% by weight. And a method of controlling in two stages of 3% by weight. The method for producing cpvc is particularly suitable for producing CPVC having a chlorine content of 65% by weight or more, but the higher the chlorine content, the lower the productivity. A lot of unstable structures are produced and thermal stability is also reduced. In order to take into account the productivity and thermal stability of the raw materials, the chlorination rate needs to be controlled more precisely. Therefore, when PVC is chlorinated, When the final chlorine content is 65% by weight or more and less than 70% by weight of iCPVC, the following control should be adopted: At the time point when the target gas content is 5 wt%, the chlorine consumption rate (raw material B-expanded resin) Chlorination per 5 kg of gas consumption) chlorination in the range of 15 0. 010 〇 〇 〇 15 kg / PVC-Kg · 5 min; and, at the time point when the final gas content target is still 3% by weight, The gas consumption rate is chlorinated in the range of 0.005~0.010kg/PVC-Kg · 5miri. Further, if the final chlorine content is 70% by weight or more, and preferably less than 72% by weight of iCPVC, it is preferable to use it. The following control: chlorination at a chlorine consumption rate of 0.015 to 0.020 kg/PVC-Kg · 5 min at a time point when the final chlorine content of 20 is still 5 wt%; and, reaching the final chlorine content target At a time point of 3% by weight difference, chlorination was carried out at a speed of 0.005 to 0.015 kg/PVC-Kg·5 min with a chlorine consumption speed. Thereby, it is possible to obtain CPVC which has less chlorination state unevenness and excellent thermal stability 19 200823241. Further, the control of the chlorine consumption rate can be carried out stepwise or extremely fast, but it is preferably carried out slowly. The molding system of the present invention is obtained by molding the above-mentioned CPVC. The manufacturing method of the molded body can be any conventionally known manufacturing method, such as an extrusion molding method and an injection molding method. The obtained molded body was excellent in thermal stability.
10 1510 15
20 可依需要而在成形體中添加安定劑、潤滑劑、加工助 劑、衝擊改值劑、耐熱提高劑、抗氧化劑、紫外線吸收劑、 光安定劑、充填劑及顏料等之添加劑。 安定劑並未受到特別限制，可列舉如熱安定劑及熱安 定化助劑等。熱安定龍切财限，可列舉㈣基二丁 基錫、巯基二辛基錫，基二甲基錫、巯二丁基錫、二丁 基缚馬來酸醋、二丁基錫馬來動旨聚合物、二辛基錫馬來 酸竭、二辛基錫馬來_旨聚合物、二丁基錫月桂酸醋、二 丁基錫月桂酸酯聚合物等有機锡安定劑；㈣賴、二元 亞磷酸鉛、三元硫酸鉛等糾备^ 、’σ系文定劑；釣-鋅系安定劑；鋇 、辞系安定劑；及，鋇-鎘系 _ 系女疋劑等。該等可單獨使用，亦 可併用2種以上。 安定化助劑並未特別受限，可列舉如乙氧基化大豆 ^由、磷酸酯、多元醇、篆7h、，、 .. 久艰鎂鉋石及沸石等。該等可單獨 使用，亦可併用2種以上。 滑劑可列舉如内部滑劑及外部滑劑。 内部滑劑係以降低成飛^ -加工時之溶融樹脂的動黏度及 20 200823241 防止摩擦發熱為目 的而使用。内部滑劑並未特 列舉如硬脂酸丁酯、 ^ 、 J又限τ 月才土基醇、硬脂基释、™旬 一 甘油單硬脂酸酯、# 、虱大丑油、 亦可併用2種以上。 j早獨使用 外部滑劑係以撻古 一 Ν成形加工牯熔融樹脂與金屬面間之 凋滑效果為目的而係20 Additives such as stabilizers, lubricants, processing aids, impact modifiers, heat-resistant improvers, antioxidants, UV absorbers, light stabilizers, fillers, and pigments may be added to the molded body as needed. The stabilizer is not particularly limited, and examples thereof include a thermal stabilizer and a thermal stabilizer. The heat and stability of the dragon cut, can be cited as (iv) dibutyltin, decyldioctyltin, dimethyltintin, bismuth butyl hydride, dibutyl conjugated maleic acid vinegar, dibutyltin malay kinetic polymer, dioctane Organotin stabilizers such as base tin maleic acid, dioctyltin malay-polymer, dibutyltin laurate, dibutyltin laurate polymer; (iv) lead, binary lead phosphite, lead ternary sulfate Waiting for correction ^, 'σ system fixed agent; fishing - zinc system stabilizer; 钡, rhythm stabilizer; and, 钡-cadmium _ system female sputum. These may be used alone or in combination of two or more. The stabilizer is not particularly limited, and examples thereof include ethoxylated soybeans, phosphates, polyhydric alcohols, hydrazines 7h, and . These may be used alone or in combination of two or more. Examples of the slip agent include internal slip agents and external slip agents. The internal slip agent is used for the purpose of reducing the dynamic viscosity of the molten resin during the processing and the prevention of frictional heat generation. The internal slip agents are not specifically listed as butyl stearate, ^, J, and τ ̄ ̄ 土 才 土 、 、 硬 硬 硬 硬 硬 TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM TM Use two or more types. j used alone in the early days, the external slip agent is used for the purpose of forming a smelting effect between the molten resin and the metal surface.
舉如石壌、聚烯_,卜部滑劑並未特別受限，可列 亦可併用2種以上。1日減褐煤壤等。該等可單獨使用， 加工助劑並未特別受限，舉例而言可列舉如重量平均 取子:10萬〆200萬之兩婦酸烧基醋甲基丙婦酸烧基醋共 κ物等之丙烯酸系加工助劑。前述丙烯酸系加卫助劑並未 特別受限，可列舉如甲基丙締酸正丁醋甲基丙稀酸甲醋共 聚物、2-乙基己基丙埽酸醋甲基丙稀酸甲醋甲基丙稀酸丁 酉曰來物#該等可單獨使用，亦可併用2種以上。 5 ㈣改貝劑亚未特別受限，可列舉如甲基丙烯酸甲醋_ 丁二烯-乙稀共聚物_s)、氯化聚乙稀及丙稀酸橡膠等。 耐熱提〶劑並未特別受限，可列舉如α·甲基笨乙歸 系、N-苯基馬來醯胺系樹脂等。 抗氧化劑亚未特別受限，可列舉如紛系抗氧化劑。 20 料線吸收劑並未特別受限，可列舉如水楊S㈣系、 二苯甲酮(benzophenone)系、笨并***系及氰基丙烯酸輯系 等之紫外線吸收劑。 光安定劑並未特別受限，舉例而言可列舉如受阻胺 (hindered amine)系等光安定劑等。 21 200823241 充填劑並未特別受限，可列舉如碳酸鈣及滑石等 顏料並未特別受限，可列舉如偶氮系、鈦菁 (phthalocyaniiie)系、士林(threne)系、麗基(lake)系染料等有 基顏料；氧化物系、鉻酸鉬系、硫化物·；6西化物系、鐵氧 5花菁（ferr〇cyanine)系等無機顏料。 以提高成形時之加工性為目的，可於成形體中添加可 塑劑，但可能使成形體耐熱性降低，而不宜多量使用。可 塑劑並無特別受限，可列舉如二丁基鄰苯二甲酸酯、二-2-乙基己基鄰苯二甲酸酯、二乙基己基己二酸等。 10 再者，以提高施工性為目的，亦可於成形體中添加熱 塑性彈性體。該熱可塑性彈性體並未特別受限，可列舉如·· 丙烯腈、丁二烯共聚物（NBR)、乙烯/乙酸乙烯酯共聚物 (EVA)、乙烯乙酸乙烯_一氧化碳共聚物(evac〇)、氯乙 烯-乙酸乙烯酯共聚物及氯乙烯-亞乙烯氯共聚物等氯乙烯 15系熱可塑性彈性體、求乙稀系熱可塑性彈性體、梯燥系熱 可塑性彈性體、聚胺酯系熱可塑性彈性體、聚酯系熱玎塑 性彈性體、聚醯胺系熱可塑性彈性體等。該等熱$塑性彈 性體可單獨使用，亦可併用2種以上。 於CPVC中混合添加劑之方法並未特別受限，{列舉如 20 熱摻合法及冷摻合法等。 兹就本發明之CPVC、其成形體及cpvc之製造方法的 實施例說明於T，但本發不·於下述各例。 (實施例1) ° 蓋i化氣乙缔樹脂之調繫 22 200823241 於内容積300公升之玻璃襯裡製反應容器中供給離子 父換水200重量份與平均聚合度1000之PVC50重量份，攪拌 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 氧’同時升溫至90°c。 5 該氯化步驟中未照射紫外線。 其-人，將氣供至反應容器中使氯分壓成為0.4Mpa，一 邊以每1小時1重量份(320Ppm/小時）添加〇2重量％過氧化 氫k進行氯化反應，反應進行至經氣化之氯乙烯樹脂的 氯含量達62重量％為止。 10 接著，在經氯化之氯乙烯樹脂的氯含量達到62重量 %(離目標還差5重量％)時，使〇·2重量％過氧化氫之添加量 減少至每1小時0.1重量份(200ppm/小時），使平均氯消耗速 度調整為0.012kg/PVC-Kg · 5min再進行氯化，並在達到料 重量％(離目標還差3重量％)時，使〇·2重量％過氧化氫之添 15加量減少至每1小時15〇PPm/小時，使平均氯消耗速度調整 為0.008kg/PVC-Kg · 5min後進行氯化，而製得氯含量66 9 重量％之氯化氯乙烯樹脂。 gpvc成形體之f柞 於所得氯化氯乙烯樹脂100重量份中添加有機錫安定 20劑（二共有機合成社製，商品名「ONZ-100F」）1.5重量份、 衝擊改貝劑(鍾淵化學社製，商品名「M511」）8重量份、滑 劑（二井化學社製，商品名「Hiwax2203A」）1重量份及滑劑 (理研維他命社製，商品名「SL800」）〇·5重量份，攪拌混合 後衣付CPVC組成物。將所得CPVC組成物供至播壓機（長田 23 200823241 製作所社製，商品名「SLM-50」），並以擠壓樹脂溫度205 °C、旋槳（screw)轉數19.5rpm進行擠壓成形，製作出外徑 A 20mm、厚3mm之管狀成形體。 (實施例2) 5 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度1000之PVC50重量份，攪拌 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 φ 氧，同時升溫至l〇〇°C。該氯化步驟中未照射紫外線。 其次，將氣供至反應容器中使氯分壓成為〇.4MPa，一 10邊以每1小時1重量份(320ppm/小時）添加0.2重量％過氧化 氫一邊進行氯化反應，反應進行至經氯化之氯乙烯樹脂的 氯含量達62重量％為止。 接著，在經氯化之氯乙烯樹脂的氯含量達到62重量 %(離目標還差5重量％)時，使〇·2重量％過氧化氫之添加量 15減少至每1小時0·1重量份(200Ppm/小時），使平均氯消耗速 • 度調整為0.012kg/pvc-Kg · 5min再進行氯化，並在達到64 重1%(離目標還差3重量％)時，使〇·2重量％過氧化氫之添 ' 加量減少至每1小時15〇PPm/小時，使平均氯消耗速度調整 • 為0.008kg/PVC-Kg · 5min後進行氯化，而製得氯含量67·3 20重量％之氯化氯乙烯樹脂。 使用所得之氯化氯乙烯樹月旨，與實施例i相同地製得管 狀成形體。 (實施例3) 於内谷積300公升之玻璃襯裡製反應容器中供給離子 24 200823241 父換水200重量份與平均聚合度1〇〇(^ρν(：5〇重量份，授拌 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 氧，同時升溫至10CTC。該氯化步驟中未照射紫外線。 其次，將氯供至反應容器中使氯分壓成為04MPa，一 5邊以每1小時1重量份(320PPm/小時）添加〇·2重量％過氧化 氫邊進行氯化反應，反應進行至經氯化之氯乙烯樹脂的 氣含里達66重量％為止。 接著，在經氯化之氯乙烯樹脂的氯含量達到66重量 %(離目標還差5重量％)時，使〇·2重量％過氡化氫之添加量 10減少至每1小時200Ppm/小時，使平均氯消耗速度調整為 0.016kg/PVC-Kg · 5min再進行氯化，並在達到68重量％⑽ 目標還差3重量％)時，使〇.2重量％過氧化氫之添加量減少至 每1小時150ppm/小時，使平均氯消耗速度調整為 0.012kg/PVC-Kg · 5min後進行氯化，而製得氯含量7〇 7重 15量％之氯化氯乙烯樹脂。 CPVC成龙體之製作 於1〇〇重量份所得CPVC中添加有機錫安定劑（三共有 機合成社製，商品名r〇NZ_100F」）2〇重量份、衝擊改質 劑（鍾淵化學社製，商品名「M511」）8重量份、滑劑（三井 20化學社製，商品名「Hiwax2203A」）1·5重量份及滑劑（理研 維他命社製，商品名rSL8〇〇」）1·〇重量份，攪拌混合後製 得CPVC組成物。將所得CPVC組成物供至擠壓機(長田製作 所社製，商品名「SLM-50」），並以擠壓樹脂溫度205Χ：、 旋槳轉數19.5rpm進行擠壓成形，製作出外徑2〇nim、厚3mm 25 200823241 之管狀成形體。 (實施例4) 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度1〇〇〇ipVC5〇重量份，攪拌 5使PVC均勻分散至離子交換水中，減壓除去反應容器中之 氧，同時升溫至litre。該氣化步驟中未照射紫外線。 其-人，將氯供至反應容器中使氯分壓成為〇 4MPa，一For example, the stone enamel and the polyene ene are not particularly limited, and two or more kinds may be used in combination. On the 1st, brown coal and soil were reduced. These may be used alone, and the processing aid is not particularly limited, and examples thereof include, for example, a weight average of: 100,000 to 2 million of two guar acid ketone methyl acetophenone ketone ketone vinegar, etc. Acrylic processing aid. The acrylic auxiliaries are not particularly limited, and examples thereof include methyl propyl acetonate methyl propyl methacrylate copolymer and 2-ethylhexyl propyl acetonate methyl methacrylate methyl vinegar. Methyl acetonate butyl hydrazine # These may be used singly or in combination of two or more. 5 (4) The modified shelling agent is not particularly limited, and examples thereof include methyl methacrylate-butadiene-ethylene copolymer _s), chlorinated polyethylene and acrylic rubber. The heat-resistant sputum-removing agent is not particularly limited, and examples thereof include α-methyl phenylethylamide and N-phenylmaleamide-based resin. The antioxidant is not particularly limited, and examples thereof include antioxidants. The feed line absorbent is not particularly limited, and examples thereof include ultraviolet absorbers such as Salicylic S (tetra), benzophenone, benzotriazole, and cyanoacrylate. The light stabilizer is not particularly limited, and examples thereof include a light stabilizer such as a hindered amine system. 21 200823241 The filler is not particularly limited, and examples thereof include pigments such as calcium carbonate and talc, and examples thereof include an azo system, a phthalocyaniiie system, a threne system, and a lake. It is a base pigment such as a dye; an inorganic pigment such as an oxide system, a molybdenum chromate system, a sulfide compound, a 6th alkoxide system or a ferrite 5 phthalocyanine system. In order to improve the workability at the time of molding, a plasticizer may be added to the molded body, but the heat resistance of the molded body may be lowered, and it is not preferable to use it in a large amount. The plasticizer is not particularly limited, and examples thereof include dibutyl phthalate, di-2-ethylhexyl phthalate, diethylhexyl adipate, and the like. Further, in order to improve the workability, a thermoplastic elastomer may be added to the molded body. The thermoplastic elastomer is not particularly limited, and examples thereof include acrylonitrile, butadiene copolymer (NBR), ethylene/vinyl acetate copolymer (EVA), and ethylene vinyl acetate-carbon monoxide copolymer (evac®). Vinyl chloride-based vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, etc., vinyl chloride 15-based thermoplastic elastomer, ethylene-based thermoplastic elastomer, ladder-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer Body, polyester-based thermoplastic elastomer, polyamine-based thermoplastic elastomer, and the like. These heat-plastic elastic bodies may be used singly or in combination of two or more. The method of mixing the additive in the CPVC is not particularly limited, and the examples are as follows: 20 thermal blending and cold blending. The examples of the CPVC, the molded article and the method for producing cpvc of the present invention are described in T, but the present invention is not limited to the following examples. (Example 1) ° Covering system of capping i-gas acetylene resin 22 200823241 In a glass lining reaction vessel having an internal volume of 300 liters, 200 parts by weight of ion-exchange water and 50 parts by weight of PVC having an average degree of polymerization of 1000 are supplied, and stirred to make PVC The solution was uniformly dispersed in ion-exchanged water, and the oxygen in the reaction vessel was removed under reduced pressure while raising the temperature to 90 °C. 5 The ultraviolet light is not irradiated in this chlorination step. In the same manner, the gas is supplied to the reaction vessel to have a chlorine partial pressure of 0.4 MPa, and a chlorination reaction is carried out by adding 〇2% by weight of hydrogen peroxide k per 1 hour by weight (320 Ppm/hour), and the reaction proceeds to the reaction. The vaporized vinyl chloride resin has a chlorine content of 62% by weight. 10 Next, when the chlorine content of the chlorinated vinyl chloride resin reaches 62% by weight (a difference of 5% by weight from the target), the amount of 〇·2% by weight of hydrogen peroxide is reduced to 0.1 part by weight per hour ( 200ppm / hour), the average chlorine consumption rate is adjusted to 0.012kg / PVC-Kg · 5min and then chlorination, and when the material weight % (3% by weight from the target), 〇 · 2% by weight peroxidation The amount of hydrogen added 15 was reduced to 15 〇 PPm/hr per hour, and the average chlorine consumption rate was adjusted to 0.008 kg/PVC-Kg · 5 min, followed by chlorination to obtain chlorine chloride having a chlorine content of 66 9 wt%. Vinyl resin. In the gpvc molded article, 1.5 parts by weight of an organic tin disulfide (manufactured by the Organic Co., Ltd., trade name "ONZ-100F") was added to 100 parts by weight of the obtained chlorinated vinyl chloride resin, and the impact modifier was changed. 8 parts by weight, a lubricant (manufactured by Mitsui Chemicals, Ltd., trade name "Hiwax 2203A"), 1 part by weight, and a lubricant (manufactured by Riken Vitamin Co., Ltd., trade name "SL800") 〇·5 weight The mixture was stirred and mixed to pay the CPVC composition. The obtained CPVC composition was supplied to a weaving machine (manufactured by Nagata 23 200823241, manufactured under the trade name "SLM-50"), and extruded at a resin temperature of 205 ° C and a screw revolution of 19.5 rpm. A tubular molded body having an outer diameter of A 20 mm and a thickness of 3 mm was produced. (Example 2) 5 200 parts by weight of ion-exchanged water and 50 parts by weight of PVC having an average degree of polymerization of 1000 were supplied to a glass lining reaction vessel having an internal volume of 300 liters, stirred to uniformly disperse PVC into ion-exchanged water, and the reaction vessel was removed under reduced pressure. In the middle of φ oxygen, the temperature is raised to l〇〇 °C. No ultraviolet rays were irradiated in this chlorination step. Next, the gas is supplied to the reaction vessel to have a chlorine partial pressure of 〇.4 MPa, and a chlorination reaction is carried out while adding 0.2% by weight of hydrogen peroxide per 1 hour by weight (320 ppm/hour) per 10 hours, and the reaction proceeds to the reaction. The chlorinated vinyl chloride resin has a chlorine content of 62% by weight. Next, when the chlorine content of the chlorinated vinyl chloride resin reaches 62% by weight (a difference of 5% by weight from the target), the amount of addition of 15% by weight of hydrogen peroxide is reduced to 0.1 weight per hour. Serving (200Ppm/hour), adjusting the average chlorine consumption rate to 0.012kg/pvc-Kg · 5min and then chlorinating, and when it reaches 64% 1% (3% by weight from the target), make 〇· The addition of 2% by weight of hydrogen peroxide is reduced to 15 〇 PPm/hour per hour, so that the average chlorine consumption rate is adjusted. • It is 0.008 kg/PVC-Kg. After 5 minutes, chlorination is carried out to obtain a chlorine content of 67. 3 20% by weight of chlorinated vinyl chloride resin. A tubular molded body was obtained in the same manner as in Example i using the obtained chlorinated vinyl chloride tree. (Example 3) Ion ions were supplied in a 300 liter glass lining reaction vessel in the inner grain pool. 200823241 Parent water exchange 200 parts by weight and average polymerization degree 1 〇〇 (^ρν(: 5 〇 by weight, mixing to uniformly disperse PVC) In the ion-exchanged water, the oxygen in the reaction vessel is removed under reduced pressure, and the temperature is raised to 10 CTC. The chlorination step is not irradiated with ultraviolet rays. Next, chlorine is supplied to the reaction vessel to make the chlorine partial pressure to be 04 MPa, one for five sides per 1 The chlorination reaction is carried out by adding 〇·2% by weight of hydrogen peroxide per hour in an amount of 1 part by weight (320 ppm/hour), and the reaction proceeds until the gas content of the chlorinated vinyl chloride resin reaches 66% by weight. When the chlorine content of the vinyl chloride resin reaches 66% by weight (a difference of 5% by weight from the target), the addition amount 10 of 〇·2% by weight of hydrogen peroxide is reduced to 200 Ppm/hour per hour to make the average chlorine consumption rate. Adjusted to 0.016 kg / PVC-Kg · 5min and then chlorinated, and reached 68% by weight (10) target difference of 3% by weight), the amount of 〇. 2% by weight of hydrogen peroxide was reduced to 150ppm per hour / In hours, the average chlorine consumption rate is adjusted to 0.012kg/PVC-Kg. After 5 minutes, chlorination was carried out to obtain a chlorinated vinyl chloride resin having a chlorine content of 7〇7 and 15% by weight. Preparation of CPVC into a dragon body Adding an organic tin stabilizer to the obtained CPVC in 1 part by weight (Sangong Organic Synthesis Co., Ltd. , , 〇 〇 〇 Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi 1·5 parts by weight and a slip agent (trade name: rSL8〇〇, manufactured by Riken Vitamin Co., Ltd.) 1·〇 by weight, stirred and mixed to obtain a CPVC composition. The obtained CPVC composition is supplied to an extruder (Nagata Manufacturing Co., Ltd.) The product name was "SLM-50", and extrusion molding was carried out at a temperature of 205 rpm: a propeller rotation speed of 19.5 rpm to prepare a tubular molded body having an outer diameter of 2 〇 nim and a thickness of 3 mm 25 200823241. 4) 200 parts by weight of ion-exchanged water and an average degree of polymerization of 1 〇〇〇 ipVC 5 〇 parts by weight in a glass lining reaction vessel having an internal volume of 300 liters, and stirring 5 to uniformly disperse PVC into ion-exchanged water, and removing the reaction vessel under reduced pressure Oxygen in the middle while warming up to litre. In the gasification step, no ultraviolet rays are irradiated. In the case of human, chlorine is supplied to the reaction vessel to make the partial pressure of chlorine into 〇 4 MPa, one
邊以每i小時i重量份(320ppm/小時)添加0 2重量％過氧化 氮-邊進行氯化反應，反應進行至經氯化之氯乙稀樹脂的 10 氯含量達66重量％為止。 按者，在經氯化之 ^邱树脂的氯含量達到66重量 稱目標還差5重量辦，使㈣量％過氧化氫之添加量 減少至私小時(U重量份_ppm/小時），使平均氯消耗速 度調整為0.016kg/PVC-Kg · 5min再推七> 15 20 行延仃鼠化，並在達到68 重量％(離目標還差3重量％)時，佶 I旦4I — 士 ·重量％過氧化氫之添 加ΐ減少至母14、時150ppm/小時，你 1更平均氯消耗速度調整 為 0.010kg/PVC-Kg · 5min後進行蠢几 ^ ^ ^ 虱化，而製得氯含量70.9 重量％之氯化氯乙烯樹脂。 與貫施例3相同地製得管 使用所得之氯化氯乙烯樹月|， 狀成形體。 (比較例1) 於内部設有光照射設備且内容 製反應容器中供給離子交換㈣之玻璃襯裡 1000之PVC5G重量份，攪拌使pVc 4與平均聚合度 ^勻分散至離子交換水 26 200823241 中’減壓除去反應容器中之氧，同時升溫至6〇°c。 其次，將氯供至反應容器中使氣分壓成為(X〇5MPa，並 以30kwh之強度照射水銀燈，進行氣化反應，反應進行至經 ， 氣化之氣乙炸樹脂的氣含置達67 · 3重量％為止。 5 使用所得之氯化氣乙烯樹脂，與實施例1相同地製得管 „ 狀成形體。 (實施例5) • i化氣乙烯樹脂之調製 於内部設有光照射設備且内容積3〇〇公升之玻璃襯裡 10製反應容器中供給離子交換水200重量份與平均聚合度800 之PVC50重量份，攪拌使PVC均勻分散至離子交換水中， 減壓除去反應容器中之氧，同時升溫至6〇°c。 其次，將氯供至反應容器中使氯分壓成為〇.〇5MPa，並 以30kwh之強度照射水銀燈，進行氯化反應，反應進行至經 15 氯化之氯乙烯樹脂的氯含量達70.0重量％為止。 φ 使用所得之氯化氯乙烯樹脂，與實施例3相同地製得管 狀成形體。 - 測定前述實施例1〜5及比較例1所得之氯化氯乙烯樹脂The chlorination reaction was carried out while adding 0.2% by weight of nitrogen peroxide per i part by weight (320 ppm/hour), and the reaction was carried out until the chlorine content of the chlorinated vinyl chloride resin was 66% by weight. According to the chlorinated resin, the chlorine content reaches 66 weight, and the target is still 5 weights, so that the amount of (four) amount of hydrogen peroxide is reduced to the private hour (U parts by weight _ppm/hour). The average chlorine consumption rate is adjusted to 0.016kg/PVC-Kg · 5min and then pushes seven > 15 20 lines of squirrels, and when it reaches 68% by weight (3% by weight from the target), 佶I Dan 4I - 士·When the weight % hydrogen peroxide is added, the amount is reduced to the mother 14, 150ppm / hour, and your average chlorine consumption rate is adjusted to 0.010kg / PVC-Kg · 5min after the stupid ^ ^ ^ 虱, and the chlorine A chlorinated vinyl chloride resin having a content of 70.9% by weight. The obtained chlorinated vinyl chloride tree was used in the same manner as in Example 3, and the shaped body was obtained. (Comparative Example 1) A 5 5 parts by weight of a glass lining 1000 of an ion exchange (4) was supplied to a content-made reaction vessel, and the mixture was stirred so that the pVc 4 and the average degree of polymerization were uniformly dispersed in the ion-exchanged water 26 200823241. The oxygen in the reaction vessel was removed under reduced pressure while raising the temperature to 6 °C. Next, chlorine is supplied to the reaction vessel to make the partial pressure of the gas (X〇5 MPa, and the mercury lamp is irradiated with an intensity of 30 kwh to carry out a gasification reaction, and the reaction proceeds to the passage, and the gas content of the gas-burning resin is 67. 3 parts by weight. 5 Using the obtained chlorinated vinyl resin, a tube-shaped formed body was obtained in the same manner as in Example 1. (Example 5) • i-gas ethylene resin was prepared and light-irradiating equipment was provided therein. And 200 parts by weight of ion-exchanged water and 50 parts by weight of PVC having an average polymerization degree of 800 are supplied to a glass lining 10 reaction vessel having an internal volume of 3 liters, stirred to uniformly disperse PVC into ion-exchanged water, and the oxygen in the reaction vessel is removed under reduced pressure. At the same time, the temperature is raised to 6 ° C. Next, chlorine is supplied to the reaction vessel to make the partial pressure of chlorine into 〇.〇5 MPa, and the mercury lamp is irradiated with an intensity of 30 kwh to carry out a chlorination reaction, and the reaction proceeds to 15 chlorinated chlorine. The chlorine content of the vinyl resin was up to 70.0% by weight. φ A tubular molded body was obtained in the same manner as in Example 3 using the obtained chlorinated vinyl chloride resin. - The chlorine chloride obtained in the above Examples 1 to 5 and Comparative Example 1 was measured. Vinyl tree fat
- 的氯含量、UV吸光度及脫HC1時間，並進行分子結構解析， 20 以測定-CC12-、-CHC1-及-CH2-之莫耳比及4分子以上之VC 單位的莫耳比率，結果示於表1。 前述測定方法如下所示。 (1)氣含量之測定 以JIS K 7229為準進行測定。 27 200823241 (2)分手結構解析 以 R. A. Komoroski，R. G· Parker，J. Ρ· Shocker， — Macromolecules，1985, 18, 1257-1265 所記載之NMR測定方 ^ 法為準進行測定。 5 NMR测定條件係如下所示。 裝置：FT-NMRJEOLJNM-AL-300 測定核：13C(質子完全解耦合) ^ 脈衝幅度：90° PD · 2.4sec 10 溶劑：鄰二氯苯：重氫化苯(C5D5)=3 : 1 試劑濃度：約20%- Chlorine content, UV absorbance and de-HC1 time, and molecular structure analysis, 20 to determine the molar ratio of -CC12-, -CHC1- and -CH2- and the molar ratio of VC units of 4 or more molecules, the results show In Table 1. The above measurement method is as follows. (1) Measurement of gas content The measurement was carried out in accordance with JIS K 7229. 27 200823241 (2) Analysis of the breakup structure The measurement was carried out in accordance with the NMR measurement method described in R. A. Komoroski, R. G. Parker, J. Shock Shocker, Macromolecules, 1985, 18, 1257-1265. 5 NMR measurement conditions are as follows. Apparatus: FT-NMRJEOLJNM-AL-300 Determination of core: 13C (proton completely decoupled) ^ Pulse amplitude: 90° PD · 2.4 sec 10 Solvent: o-dichlorobenzene: heavy hydrogenated benzene (C5D5) = 3 : 1 Reagent concentration: About 20%
溫度：110°C 基準物質：令苯之中央信號為128ppm。 累計次數：110°C 15 (3)uy吸光度之測定（216nm) ^ 以下述條件測定216nm波長中之UV吸光度。Temperature: 110 ° C Reference material: The central signal of benzene is 128 ppm. Cumulative number: 110 ° C 15 (3) Measurement of uy absorbance (216 nm) ^ The UV absorbance at a wavelength of 216 nm was measured under the following conditions.
裝置：自記分光光度計曰立製作所U-3500 溶劑：THF 濃度·試劑20mg/THF25ml......800ppm(實施例1、2及比較例1) 20 試劑 l〇mg/THF25ml......400ppm(實施例 3 〜5) ⑷脫HC1時間 將所得氯化氯乙烯樹脂lg放入試管，使用油浴以19〇 C加熱’將產生之HC1氣體回收並溶解於i〇〇mi之離子交換 水’測定pH值。從pH值算出氯化氯乙浠樹脂每1〇〇萬§產生 28 200823241 幾g的HC1，再從該值算出到達7000ppm之時間。 (5)熱安定性評估 ^ 將所得管狀成形體切成2cmx3cm，並於200°C之傳動爐 - (gear_oven)中裝入預定片數，每10分鐘取出，計測黑化時間。 表1 實施例 比較例 1 1 2 3丨 4 ! 5 1 氣化氣乙烯樹脂 虱含夏(重量％) 66,9 ] 67.3 | 70.7 I 1 70.9 1 | ταοΠ Γ^73~ 分子結構 ----- -CClr(莫耳 6.1 5.8 16.6 15.0 12.5 5.6 -CHC1-(莫耳 ％) 58.6 60.2 47.7 56.3 52.8 57.6 •CHr(莫耳％) 35.3 34.0 35.7 27.8 34.7 36.8 4分子以上之VC單位 (莫耳％) 26.8 26.4 15.7 10.7 22.2 33.2 UV吸光度(216nm) 0.7 0.6 5.7 7.4 8.3 13 脫氯時間 80 78 152 181 72 32 敢初氣消耗速度變更時 間點的PVC氯含量 (重量％) 62 62 66 66 最初氧消耗速度變更時 間點的氣消耗速度(1) 0.012 0.012 0.016 0.016 "^2次氯消耗速度變更 時間點的PVC含氯量 (重量％) 64 64 68 68 第2次氯消耗速度^變更 時間點的氯消耗速度(2) 0.008 0.008 0.012 0.010 成形體 --- 熱安定性 | 丨 100 | | 110 | 「80 | 1 8〇Π Lto~1 f~70~ (實施例6) 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度10〇〇之pVC5〇重量份，檀摔 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 10 氧，同時升溫至100°c。該氯化步驟中未照射紫外線。 其次，將氯供至反應容器中使氯分壓成為0.4MPa，以 29 200823241 3卿_):時添加〇·2重量％過氧化氫使氯化反應開始，反應 進行至經氯化之氯乙稀樹脂的氯含量達62重量％為止。 接著，在經氯化之PVC氯含量達到62重量％(離目標還 差5重夏％)時，使〇·2重量％過氧化氫之添加量減少至 5 200ppm/小’使氯消耗速度調整為〇 〇l2kg/pvc_Kg · 5論 再進行氯化，並在氯含量達到64重量％(離目標還差3重量 %)時，使0·2重量％過氧化氫之添加量減少至每〗小時 150ppm(/小時），使氯消耗速度調整為〇 〇〇8kg/pvC Kg · 5min後進行氣化，氯化計6小時後，製得氯含量π重量％之 10 CPVC。 (實施例7) 於内容積300公升之玻璃襯裡製反應容器中供給離子 父換水200重量份與平均聚合度1000之PVC50重量份，授拌 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 15氧，同時升溫至100°c。此外，該氯化步驟中未照射紫外線。 其次’將氯供至反應容器中使氯分壓成為〇.4MPa，以 320ppm/小時添加〇·2重量％過氧化氫使氯化反應開始 ，反應 進行至經氯化之PVC的氯含量達66重量％為止。 接著，在經氣化之PVC氣含量達到66重量％(離目標還 差5重里％)時’使〇·2重量％過氧化氫之添加量減少至 3〇〇PPm/小時，並將氣消耗速度調整為0 016kg/PVC-Kg · 5mm再進行氯化，並在氯含量達到68重量％(離目標還差3 重里％)時’使q·2重量％過氧化氫之添加量減少至2〇〇ppm/ 小時’使氯消耗速度調整為0.012kg/PVC-Kg · 5min後進行 30 200823241 氯化，氯化計9.0小時後，製得氣含量71重量％2CPVC。 (比較例2) 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度1000之pVC5〇重量份，攪拌 5 使均勻分散至離子交換水中，減壓除去反應容器中之 氧’同時升溫至l〇(TC。此外，該氯化步驟中未照射紫外線。 其次，將氯供至反應容器中使氯分壓成為0.4MPa，以 320ppm/小時添加〇·2重量％過氧化氫使氯化反應開始，反應 進行至經氯化之PVC的氯含量達60重量％為止。 1〇 在經氯化之氯乙烯樹脂的氯含量達到60重量％(離目標 還差7重量％)時，使0.2重量％過氧化氫之添加量減少至 150PPm/小時，使氯消耗速度調整為0.005kg/PVC-Kg· 5min 再進行氯化，氯化8小時而製得氯含量67重量％2CPVC。 (比較例3) 15 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度1〇〇〇之pvC5〇重量份，攪拌 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 氧’同時升溫至l〇(TC。此外，該氯化步驟中未照射紫外線。 其次’將氯供至反應容器中使氯分壓成為〇.4MPa，以 20 3 20Ppm/小時添加〇·2重量％過氧化氫使氯化反應開始，反應 進行至經氯化之氯乙烯樹脂的氯含量達60重量％為止。 接著’在經氯化之PVC的氯含量達到60重量％(離目標 還差11重量％)時，使〇·2重量％過氧化氫之添加量調整至可 使氯消耗速度為0.012kg/PVC-Kg · 5min再進行氣化，氯化 31 200823241 5.8小時而製得氯含量67重量％之匸？乂0 (比較例4) 於内容積300公升之玻璃襯裡製反應容器中供給離子 交換水200重量份與平均聚合度1000之PVC50重量份，攪拌 5 使PVC均勻分散至離子交換水中，減壓除去反應容器中之 氧，同時升溫至100°C。此外，該氯化步驟中未照射紫外線。 其次，將氣供至反應容器中使氯分壓成為0.4MPa，以 3 20ppm/小時添加〇·2重量％過氧化氫使氯化反應開始，反應 進行至經氣化之氯乙烯樹脂的氣含量達60重量％為止。 10 接著，在經氯化之PVC的氯含量達到60重量％(離目標 還差11重量％)時，使0.2重量％過氧化氫之添加量減少至 150ppm/小時，並使氯消耗速度調整為〇.005kg/pvC-Kg · 5min再進行氣化，氯化18小時而製得氯含量71重量％之 CPVC 〇 15 使所得CPVC100重量份、有機錫系安定劑（三共有機合 成社製，商品名「ONZ-100F」）1·5重量份、MBS系衝擊改 質劑(鍾淵化學社製，商品名「M511」）8重量份、丙烯酸系 加工助劑（三菱嫘縈社製，商品名「美塔本連ρ_55〇」）1重量 份及硬脂酸系滑劑(理研維他命社製，商品名rSL8〇〇」）〇·5 20重1份所構成之樹脂組成物藉195°C的輥子而捲附於輥子 後，進行3分鐘之輥混合攪拌。再使用所得輥片實施係一種 靜態熱安定性試驗之熱老化試驗(2〇〇。(：，每10><14〇分），測 定至黑化為止的時間（分）。 將所得CPVC lg放至i〇mi之玻璃製試管，於氮氣流下 32 200823241 於190°C之油浴中加熱，使CVC產生之鹽酸在水中被捕捉， 再測定該水的pH值，藉此測定所發生的鹽酸量到達 5000ppm之時間。 茲將各實施例與比較例的氣化條件、黑化時間及脫鹽 5 酸時間示於表2。 實施例 比較例 6 7 2 3 4 CPVC之氯含量(重量％) 67 71 67 67 71 PVC之平均聚合度 1000 1000 1000 1000 1000 反應溫度°〇 100 100 100 100 100 反應時間(小時） 6 9 8 5.8 18 最初氯消耗速度變更時間點的 PVC氯含量(重量％) 62 66 60 60 60 最初氣消耗速度變更時間點的 氯消耗速度(1) 0.012 0.016 0.005 0Ό12 0.005 第2次氣消耗速度變更時間點的 PVC含氯量(重量％) 64 68 — — — 第2次氯消耗速度變更時間點的 氯消耗速度(2) , 0.008 0.012 0.005 0.012 0.005 黑化時蘭(分) 60 80 60 40 80 脫氯時間(分） 42 64 41 33 58Apparatus: Self-recording spectrophotometer 曰立制作所 U-3500 Solvent: THF concentration·reagent 20 mg/THF 25 ml...800 ppm (Examples 1, 2 and Comparative Example 1) 20 Reagent l〇mg/THF 25 ml.... .. 400 ppm (Examples 3 to 5) (4) Time for deHC1 The chlorinated vinyl chloride resin lg was placed in a test tube, and heated at 19 ° C using an oil bath to recover and dissolve the generated HC1 gas in the ion of i〇〇mi. Exchange water' to determine the pH. From the pH value, the chlorinated chlorinated ruthenium resin was produced every 10,000 s. 28 200823241 A few g of HC1, and the time to reach 7000 ppm was calculated from this value. (5) Thermal stability evaluation ^ The obtained tubular molded body was cut into 2 cm x 3 cm, and a predetermined number of sheets were placed in a 200 ° C drive furnace - (gear_oven), taken out every 10 minutes, and the blackening time was measured. Table 1 Example Comparative Example 1 1 2 3丨4 ! 5 1 Gasification gas Vinyl resin 虱 Summer (% by weight) 66,9 ] 67.3 | 70.7 I 1 70.9 1 | ταοΠ Γ^73~ Molecular structure---- - -CClr (mole 6.1 5.8 16.6 15.0 12.5 5.6 -CHC1-(mole%) 58.6 60.2 47.7 56.3 52.8 57.6 •CHr (mole%) 35.3 34.0 35.7 27.8 34.7 36.8 VC units of 4 or more molecules (% by mole) 26.8 26.4 15.7 10.7 22.2 33.2 UV absorbance (216nm) 0.7 0.6 5.7 7.4 8.3 13 Dechlorination time 80 78 152 181 72 32 PVC chlorine content (% by weight) at the time of change of initial gas consumption rate 62 62 66 66 Initial oxygen consumption rate Gas consumption rate at the time of change (1) 0.012 0.012 0.016 0.016 "^2 Chlorine content of PVC at the time of change of chlorine consumption rate (% by weight) 64 64 68 68 Second chlorine consumption rate ^Change time point of chlorine Consumption speed (2) 0.008 0.008 0.012 0.010 Formed body --- Thermal stability | 丨100 | | 110 | "80 | 1 8〇Π Lto~1 f~70~ (Example 6) In the inner volume of 300 liters of glass 200 parts by weight of ion-exchanged water and pVC5〇 having an average polymerization degree of 10 中 in a lining reaction vessel In parts by weight, the sandalwood disperses the PVC uniformly into the ion-exchanged water, and removes 10 oxygen in the reaction vessel under reduced pressure while raising the temperature to 100 ° C. The chlorination step is not irradiated with ultraviolet rays. Second, chlorine is supplied to the reaction vessel. The partial pressure of chlorine is 0.4 MPa, and the temperature of the chlorinated vinyl chloride resin is 62% by weight. Then, when the chlorine content of the chlorinated PVC reaches 62% by weight (5% by weight from the target), the amount of 〇·2% by weight of hydrogen peroxide is reduced to 5 200 ppm/min. Adjusted to 〇〇l2kg/pvc_Kg · 5 on the chlorination, and when the chlorine content reaches 64% by weight (3% by weight from the target), the amount of 0.2% by weight of hydrogen peroxide is reduced to each After 150 ppm (/hour), the chlorine consumption rate was adjusted to 〇〇〇8 kg/pvC Kg · 5 minutes, and gasification was carried out. After 6 hours of chlorination, 10 CPVC having a chlorine content of π% by weight was obtained. (Example 7) In a glass lining reaction vessel having an internal volume of 300 liters, 200 parts by weight of ion-exchange water and 50 parts by weight of PVC having an average degree of polymerization of 1000 were supplied, and the PVC was uniformly dispersed in ion-exchanged water, and the reaction container was removed under reduced pressure. 15 of the oxygen, while heating to 100 ° c. Further, no ultraviolet rays are irradiated in the chlorination step. Secondly, 'chlorine is supplied to the reaction vessel to make the partial pressure of chlorine to 〇.4 MPa, and 〇·2% by weight of hydrogen peroxide is added at 320 ppm/hour to start the chlorination reaction, and the reaction proceeds until the chlorine content of the chlorinated PVC reaches 66. Up to % by weight. Then, when the gasified PVC gas content reaches 66% by weight (5% by weight from the target), the amount of 〇·2% by weight of hydrogen peroxide is reduced to 3〇〇PPm/hour, and the gas consumption is reduced. The speed is adjusted to 0 016kg/PVC-Kg · 5mm and then chlorinated, and when the chlorine content reaches 68% by weight (3% by weight from the target), the amount of q·2% by weight of hydrogen peroxide is reduced to 2 〇〇ppm/hour' adjusts the chlorine consumption rate to 0.012kg/PVC-Kg. After 5min, 30200823241 chlorination, after 9.0 hours of chlorination, a gas content of 71% by weight of 2CPVC is obtained. (Comparative Example 2) 200 parts by weight of ion-exchanged water and pVC 5 〇 parts by weight of an average degree of polymerization of 1000 were supplied to a glass lining reaction vessel having an internal volume of 300 liters, stirred for 5 to be uniformly dispersed in ion-exchanged water, and the reaction vessel was removed under reduced pressure. The oxygen in the middle is simultaneously heated to 1 〇 (TC. Further, the chlorination step is not irradiated with ultraviolet rays. Next, chlorine is supplied to the reaction vessel to make the partial pressure of chlorine 0.4 MPa, and 〇 2 wt% is added at 320 ppm/hour. Hydrogen peroxide starts the chlorination reaction, and the reaction proceeds until the chlorine content of the chlorinated PVC reaches 60% by weight. 1 The chlorine content of the chlorinated vinyl chloride resin reaches 60% by weight (7 weight difference from the target) %), the addition amount of 0.2% by weight of hydrogen peroxide was reduced to 150 ppm / hour, the chlorine consumption rate was adjusted to 0.005 kg / PVC - Kg · 5min, and then chlorination, chlorination for 8 hours to obtain a chlorine content of 67 weight (Comparative Example 3) 15 200 parts by weight of ion-exchanged water and 1 part by weight of pvC5 平均 of an average polymerization degree were supplied to a glass lining reaction vessel having an internal volume of 300 liters, and stirred to uniformly disperse PVC to ion exchange. Water, decompression The oxygen in the reaction vessel was simultaneously heated to 1 Torr (TC. In addition, the chlorination step was not irradiated with ultraviolet ray. Secondly, chlorine was supplied to the reaction vessel to make the chlorine partial pressure 〇.4 MPa to 20 3 20 Ppm/hour. The addition of 〇·2% by weight of hydrogen peroxide starts the chlorination reaction, and the reaction proceeds until the chlorine content of the chlorinated vinyl chloride resin reaches 60% by weight. Then the chlorine content of the chlorinated PVC reaches 60% by weight ( When the difference is 11% by weight from the target, the addition amount of 〇·2% by weight of hydrogen peroxide is adjusted so that the chlorine consumption rate can be 0.012 kg/PVC-Kg · 5 min and then gasification, chlorination 31 200823241 5.8 hours The chlorine content of 67% by weight was obtained. 比较0 (Comparative Example 4) 200 parts by weight of ion-exchanged water and 50 parts by weight of PVC having an average degree of polymerization of 1000 were supplied to a glass lining reaction vessel having an internal volume of 300 liters, and stirring was carried out to make PVC The solution was uniformly dispersed in ion-exchanged water, and the oxygen in the reaction vessel was removed under reduced pressure while raising the temperature to 100° C. Further, the chlorination step was not irradiated with ultraviolet rays. Next, the gas was supplied to the reaction vessel to make the partial pressure of chlorine 0.4 MPa. , add 20· at 3 20ppm/hour· 2% by weight of hydrogen peroxide starts the chlorination reaction, and the reaction proceeds until the gas content of the vaporized vinyl chloride resin reaches 60% by weight. 10 Next, the chlorine content of the chlorinated PVC reaches 60% by weight (off-target When the difference was 11% by weight), the addition amount of 0.2% by weight of hydrogen peroxide was reduced to 150 ppm/hour, and the chlorine consumption rate was adjusted to 005.005 kg/pvC-Kg · 5 min, and then gasification was carried out, and chlorination was carried out for 18 hours. CPVC 〇15 having a chlorine content of 71% by weight, 100 parts by weight of the obtained CPVC, and an organotin-based stabilizer (trade name "ONZ-100F", manufactured by Sankyo Organic Co., Ltd.), 1.5 parts by weight, and an MBS-based impact modifier 8 parts by weight of an acrylic processing aid (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Meitabenlian ρ_55〇"), 1 part by weight, and a stearic acid-based lubricant, (manufactured by Kaneji Chemical Co., Ltd., trade name "M511") (The product name: rSL8〇〇, manufactured by Riken Vitamin Co., Ltd.) 〇·5 The resin composition composed of 20 parts by weight was wound on a roll by a roll of 195 ° C, and then subjected to roll mixing and stirring for 3 minutes. Further, using the obtained roll, a heat aging test (2: (1, per 10>< 14 〇) was performed for the static thermal stability test, and the time (minutes) until the blackening was measured. The test tube was placed in a glass tube of i〇mi, heated under a nitrogen stream at 32 200823241 in an oil bath at 190 ° C, and the hydrochloric acid produced by CVC was captured in water, and the pH of the water was measured to thereby determine the hydrochloric acid generated. The amount reached 5000 ppm. The gasification conditions, blackening time and desalting time of each of the examples and comparative examples are shown in Table 2. Example Comparative Example 6 Chlorine content (% by weight) of 7 2 3 4 CPVC 67 71 67 67 71 Average degree of polymerization of PVC 1000 1000 1000 1000 1000 Reaction temperature °〇100 100 100 100 100 Reaction time (hours) 6 9 8 5.8 18 PVC chlorine content (% by weight) at the time of initial chlorine consumption change time 62 66 60 60 60 Chlorine consumption rate at the time of initial gas consumption rate change (1) 0.012 0.016 0.005 0Ό12 0.005 PVC chlorine content (% by weight) at the time of the second gas consumption rate change 64 68 — — — 2nd chlorine consumption Chlorine at the time of speed change Consumption rate (2) 0.008 0.012 0.005 0.012 0.005 Blue blackening (minute) 6080604080 dechlorination time (minutes) 4264413358
C圖式簡單說明3 (無） 【主要元件符號說明】 (無） 33Simple description of C pattern 3 (none) [Explanation of main component symbols] (none) 33
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