JPH11263808A - Preparation of chlorinated vinyl chloride-based resin - Google Patents
Preparation of chlorinated vinyl chloride-based resinInfo
- Publication number
- JPH11263808A JPH11263808A JP6882498A JP6882498A JPH11263808A JP H11263808 A JPH11263808 A JP H11263808A JP 6882498 A JP6882498 A JP 6882498A JP 6882498 A JP6882498 A JP 6882498A JP H11263808 A JPH11263808 A JP H11263808A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chlorination
- temperature
- chlorination reaction
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩素化塩化ビニル
系樹脂の製造方法に関する。[0001] The present invention relates to a method for producing a chlorinated vinyl chloride resin.
【０００２】[0002]
【従来の技術】塩化ビニル系樹脂（以下、ＰＶＣとい
う）は、機械的強度、耐候性、耐薬品性に優れた材料と
して、多くの分野に用いられている。しかしながら、耐
熱性に劣るため、ＰＶＣ樹脂を塩素化することにより耐
熱性を向上させた塩素化塩化ビニル系樹脂（以下、ＣＰ
ＶＣという）が開発されている。2. Description of the Related Art Vinyl chloride resin (hereinafter, referred to as PVC) is used in many fields as a material having excellent mechanical strength, weather resistance and chemical resistance. However, since the heat resistance is poor, a chlorinated vinyl chloride resin (hereinafter, referred to as CP) in which the heat resistance is improved by chlorinating a PVC resin.
VC).
【０００３】ＰＶＣは、熱変形温度が低く使用可能な上
限温度が６０〜７０℃付近であるため、熱水に対して使
用できないのに対し、ＣＰＶＣは熱変形温度がＰＶＣよ
りも２０〜４０℃も高いため、熱水に対しても使用可能
であり、例えば、耐熱パイプ、耐熱継手、耐熱バルブ等
に好適に使用されている。[0003] PVC has a low heat distortion temperature and the maximum usable temperature is around 60 to 70 ° C, so that it cannot be used for hot water, whereas CPVC has a heat deformation temperature of 20 to 40 ° C than PVC. Therefore, it can be used for hot water, and is suitably used for heat-resistant pipes, heat-resistant joints, heat-resistant valves, and the like.
【０００４】しかしながら、ＣＰＶＣは熱変形温度が高
いため、成形加工性時にゲル化させるには高温と強い剪
断力とを必要とし、成形加工時に分解して着色しやすい
という傾向があった。従って、ＣＰＶＣは成形加工幅が
狭く、不充分なゲル化状態で製品化されることが多く、
素材のもつ性能を充分発揮できているとはいえなかっ
た。また、これらゲル化性能向上の要求に加えて、より
高い耐熱性も要求されるようになっている。However, since CPVC has a high heat deformation temperature, a high temperature and a strong shearing force are required for gelling at the time of molding processability, and it tends to be decomposed and colored during molding. Therefore, CPVC is often produced in a narrow molding process width and in an insufficiently gelled state,
The performance of the material was not fully demonstrated. Further, in addition to the demand for improving the gelation performance, higher heat resistance is also required.
【０００５】このような問題点を解決するため、例え
ば、特開昭４９−６０８０号公報には、イオン性乳化
剤、水溶性金属塩及び水溶性高分子分散剤からなる懸濁
安定剤を使用し、約１μｍの基本粒子からなる凝集体で
構成されたＰＶＣを塩素化する方法が開示されている
（樹脂粒子の改良提案）。しかしながら、この方法で
は、成形加工時のゲル化性能は向上しているもののまだ
充分ではなく、また、重合の際に多量のスケールが発生
し、これが重合槽の壁面に付着して除熱効果を阻害する
ため、そのスケール除去作業を必要とするという問題点
があった。In order to solve such problems, for example, Japanese Patent Application Laid-Open No. 49-6080 discloses a method of using a suspension stabilizer comprising an ionic emulsifier, a water-soluble metal salt and a water-soluble polymer dispersant. Discloses a method of chlorinating PVC composed of aggregates composed of basic particles of about 1 μm (improvement of resin particles). However, in this method, the gelling performance at the time of molding has been improved, but it is not yet sufficient, and a large amount of scale is generated at the time of polymerization, which adheres to the wall surface of the polymerization tank to reduce the heat removal effect. There is a problem that the scale removal operation is required for the inhibition.
【０００６】また、例えば、特開平５−１３２６０２号
公報には、ＣＰＶＣとＰＶＣとを特定の粘度範囲内にな
るようにブレンドし、高耐熱性を得る方法が開示されて
いる。しかしながら、この方法では、ビカット値で３〜
４℃程度の耐熱性の向上と、溶融粘度の改善による若干
のゲル化性能の向上が期待できる程度で、我々が目指し
ているような高い耐熱性とゲル化性能とを充分に達成す
るものではなかった。[0006] For example, Japanese Patent Application Laid-Open No. 5-132602 discloses a method of blending CPVC and PVC so as to be within a specific viscosity range to obtain high heat resistance. However, in this method, the Vicat value is 3 to
An improvement in heat resistance of about 4 ° C and a slight improvement in gelation performance due to an improvement in melt viscosity can be expected, and those that sufficiently achieve the high heat resistance and gelation performance that we are aiming for cannot be achieved. Did not.
【０００７】一方、塩素化反応時に塩素を樹脂粒子内部
に均一に拡散させた後に塩素化反応を行う方法は均一に
塩素化する方法として従来より知られているが、例え
ば、特公昭４５−６０３２号公報には、塩素を樹脂粒子
内に均一に拡散させるために、クロロホルム等の塩素含
有溶媒で樹脂を膨潤処理することを提案している。しか
しながら、反応系でのクロロホルム、四塩化炭素等の塩
素系溶媒の使用は、その添加効果である塩素源の円滑な
浸透については認められるものの、反応後に溶媒を除去
する工程が煩雑であり、又大幅な耐熱性向上の目的は達
せられないものであった。On the other hand, a method in which chlorine is uniformly diffused into resin particles during the chlorination reaction and then the chlorination reaction is conventionally known as a method of uniformly chlorinating, for example, Japanese Patent Publication No. 45-6032 In order to uniformly diffuse chlorine in resin particles, Japanese Patent Application Laid-Open No. H11-163873 proposes swelling the resin with a chlorine-containing solvent such as chloroform. However, the use of a chlorinated solvent such as chloroform or carbon tetrachloride in the reaction system, although the effect of the addition of the chlorine source is observed to be smooth, the step of removing the solvent after the reaction is complicated, and The purpose of greatly improving heat resistance has not been achieved.
【０００８】又、特表昭５７−５０１１８４号公報、及
び特表昭５７−５０２２１８号公報では、いずれも液体
塩素を膨潤剤として使用する提案であり、膨潤溶媒自身
が同時に塩素化のための塩素源でもある点で、塩素化反
応プロセス上、優れた方法である。しかしながら、特表
昭５７−５０１１８４号公報の提案は、予め少量の液体
塩素でＰＶＣを膨潤させた後、固体離散の粉体状態で反
応を進めているが、塩素化反応の樹脂粒子位置によるバ
ラツキが大きく、好ましい耐熱性が得られないという問
題点があった。特表昭５７−５０２２１８号公報では、
液体塩素を溶媒としてＰＶＣの５〜３０倍という大量に
使用し、膨潤時の温度は−５０〜＋５０℃という範囲で
あり、塩素化反応の好ましい範囲は−３０〜＋２５℃と
している。この方法の問題点は、液化塩素をＰＶＣの懸
濁媒体として使用しているが、液化状態を保つ為に低温
下で膨潤と反応を継続する必要があり、光照射による反
応開始後のラジカル転移反応が遅く、又バラツキが大き
いことである。従って、好ましい高い耐熱性も得られ
ず、又大過剰の液体塩素を回収再生するプロセスも煩雑
であり、工程コストが嵩むという問題点もあった。Further, Japanese Patent Publication No. 57-501184 and Japanese Patent Publication No. 57-502218 each propose the use of liquid chlorine as a swelling agent, and the swelling solvent itself contains chlorine for chlorination at the same time. It is an excellent method in the chlorination reaction process because it is also a source. However, in the proposal of Japanese Patent Publication No. 57-501184, after the PVC is swollen with a small amount of liquid chlorine in advance, the reaction is advanced in the form of a discrete solid powder. However, there was a problem that favorable heat resistance could not be obtained. In Japanese Patent Publication No. 57-502218,
Liquid chlorine is used as a solvent in a large amount of 5 to 30 times that of PVC, the temperature at the time of swelling is in the range of -50 to + 50 ° C, and the preferable range of the chlorination reaction is -30 to + 25 ° C. The problem with this method is that liquefied chlorine is used as a suspending medium for PVC, but it is necessary to continue swelling and reaction at low temperature in order to maintain a liquefied state, and radical transfer after the start of reaction by light irradiation. The reaction is slow and the variation is large. Therefore, a preferable high heat resistance cannot be obtained, and a process of recovering and regenerating a large excess of liquid chlorine is complicated, resulting in an increase in process cost.
【０００９】更に、例えば、特開平６−１２８３２０号
公報では、ＰＶＣの塩素化方法として、２段階の工程に
よる塩素化方法（２段階後塩素化法）が開示されてい
る。この方法は、塩素含有率を７０〜７５重量％と高く
することにより、高い耐熱性をもつＣＰＶＣを得ようと
するものである（高塩素化方法による改良提案）。しか
しながら、この方法では、塩素含有率に応じて高耐熱性
を期待することはできるものの、高塩素化により予測さ
れるゲル化性能の悪化を食い止めるための手段が示され
ていないため、高耐熱性とゲル化性能とを実用レベルで
達成するものではなかった。Further, for example, JP-A-6-128320 discloses a chlorination method for PVC by a two-step process (a two-step chlorination method). This method aims to obtain CPVC having high heat resistance by increasing the chlorine content to 70 to 75% by weight (improvement proposal by high chlorination method). However, in this method, although high heat resistance can be expected according to the chlorine content, there is no means to prevent the deterioration of gelation performance predicted by high chlorination, so that high heat resistance is not exhibited. And gelation performance were not achieved on a practical level.
【００１０】更に、例えば、特公昭３９−１４８２０号
公報では、結晶性の塩化ビニル系樹脂を塩素化し、その
結晶性を利用して高耐熱性（高熱変形性）を保持しつ
つ、成形性を向上させる方法が開示されている。しかし
ながら、塩化ビニル系樹脂の結晶性の利用だけでは本発
明の目的にあるような高い耐熱性とゲル化性は得られな
い。[0010] Further, for example, Japanese Patent Publication No. 39-14820 discloses a method of chlorinating a crystalline vinyl chloride resin and utilizing the crystallinity to maintain high heat resistance (high heat deformability) and improve moldability. A method for improving is disclosed. However, high heat resistance and gelling property as in the object of the present invention cannot be obtained only by utilizing the crystallinity of the vinyl chloride resin.
【００１１】更に、例えば、特表昭５７−５０１２８５
号公報では、塩素化反応開始前に、塩化ビニル系樹脂、
水媒体、及び塩素源の存在下で攪拌混合して充分な懸濁
状態にした後に、塩素化反応を実施する方法が開示され
ている。ここでは、反応前の充分な拡散を目的としてい
る。耐熱性の向上は認められるが、ゲル化性の向上は認
められなかった。Further, for example, Japanese Patent Application Laid-Open No. 57-501285
In the gazette, before starting the chlorination reaction, vinyl chloride resin,
A method of performing a chlorination reaction after stirring and mixing in the presence of an aqueous medium and a chlorine source to form a sufficient suspension is disclosed. Here, the purpose is to sufficiently diffuse before the reaction. An improvement in heat resistance was observed, but no improvement in gelation was observed.
【００１２】このように、従来の技術では、塩素化に際
して、塩素の拡散速度と塩素化分布状態に着目した塩素
化温度条件と、塩化ビニル系樹脂のガラス転移温度及び
微細粒子構造からの検討がなされていないため、最適な
塩素化分布状態が得られず、従って耐熱性と加工性に優
れたＣＰＶＣが得られていないのである。As described above, in the prior art, in the chlorination, the chlorination temperature condition focusing on the diffusion rate of chlorine and the chlorination distribution state, and the glass transition temperature and the fine particle structure of the vinyl chloride resin are examined. As a result, an optimal chlorination distribution state cannot be obtained, and thus a CPVC having excellent heat resistance and processability cannot be obtained.
【００１３】又、従来の技術では、塩素化反応後の冷却
による結晶化作用に着目した技術も開示されておらず、
耐熱性と加工性に優れたＣＰＶＣが得られていないので
ある。Further, the prior art does not disclose a technique that focuses on the crystallization action by cooling after the chlorination reaction.
CPVC excellent in heat resistance and workability has not been obtained.
【００１４】更に、従来の技術では、塩素化反応前の懸
濁状態に着目し、且つ、過冷却状態下で懸濁塩素化反応
に着目した技術は開示されておらず、耐熱性と加工性に
優れたＣＰＶＣが得られていないのである。Further, the prior art does not disclose a technique focusing on the suspension state before the chlorination reaction and focusing on the suspension chlorination reaction under the supercooled state. No excellent CPVC has been obtained.
【００１５】[0015]
【発明が解決しようとする課題】本発明は、上記に鑑
み、塩素化に際して、最適な塩素化分布状態を達成する
塩素化反応条件と、その塩素化反応に適した粒子構造を
提示し、また、塩素化反応前の懸濁状態に着目し、且
つ、過冷却状態下で懸濁塩素化反応に着目し、更に塩素
化反応後の結晶化作用に着目した塩素化反応条件を提示
し、その結果として、ゲル化性能と耐熱性に優れたＣＰ
ＶＣの製造方法を提供することを目的とする。In view of the above, the present invention provides chlorination reaction conditions for achieving an optimum chlorination distribution state during chlorination, and a particle structure suitable for the chlorination reaction. Focusing on the suspension state before the chlorination reaction, and focusing on the suspension chlorination reaction under supercooled state, and further presenting the chlorination reaction conditions focusing on the crystallization action after the chlorination reaction, As a result, CP with excellent gelation performance and heat resistance
An object of the present invention is to provide a method for manufacturing a VC.
【００１６】[0016]
【課題を解決するための手段】請求項１記載の発明（以
下、本発明１という）は、塩化ビニル系樹脂を塩素化し
てなる塩素化塩化ビニル系樹脂の製造方法であって、塩
素化反応において、塩素含有率６０〜７０重量％の範囲
で、塩素化反応温度〔Ｔ℃〕と逐次塩素化されてなる塩
素化塩化ビニル系樹脂の塩素含有率〔Ｐ重量％〕との関
係が、式１を満たした条件で、塩素化反応を行うことを
特徴とする。式１ 〔５．８Ｐ−２８７〕≦〔Ｔ〕≦
〔５．８Ｐ−２６２〕The invention according to claim 1 (hereinafter referred to as the present invention 1) is a method for producing a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin. In the range of 60 to 70% by weight of chlorine content, the relationship between the chlorination reaction temperature [T ° C.] and the chlorine content [P% by weight] of the chlorinated vinyl chloride resin obtained by successive chlorination is expressed by the following equation. The chlorination reaction is carried out under conditions satisfying 1. Formula 1 [5.8P-287] ≦ [T] ≦
[5.8P-262]
【００１７】請求項２記載の発明（以下、本発明２とい
う）は、請求項１記載の塩素化塩化ビニル系樹脂の製造
方法において、毎分０．３〜３℃の昇温速度で塩素化反
応を行うことを特徴とする。According to a second aspect of the present invention, there is provided a method for producing a chlorinated vinyl chloride resin according to the first aspect, wherein the chlorination is performed at a rate of 0.3 to 3 ° C. per minute. Performing a reaction.
【００１８】請求項３記載の発明（以下、本発明３とい
う）は、塩化ビニル系樹脂を塩素化してなる塩素化塩化
ビニル系樹脂の製造方法であって、塩素化反応におい
て、１１０〜１４０℃で塩素化反応後、６０〜７０℃に
達する迄、毎分０．２〜３℃で冷却することを特徴とす
る。The invention according to claim 3 (hereinafter referred to as invention 3) is a method for producing a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin. After the chlorination reaction, cooling is performed at a rate of 0.2 to 3 ° C. per minute until the temperature reaches 60 to 70 ° C.
【００１９】請求項４記載の発明（以下、本発明４とい
う）は、塩化ビニル系樹脂を塩素化してなる塩素化塩化
ビニル系樹脂の製造方法であって、塩素化反応におい
て、１１０〜１４０℃〔第一反応温度〕で塩素化反応
後、毎分０．５〜３℃で冷却した後、第一反応温度より
３０〜５０℃低い温度〔第二反応温度〕でさらに塩素化
反応を継続し、第一反応温度での反応完了時点より塩素
含有率を３〜８重量％高くなるまで塩素化反応を行うこ
とを特徴とする。The invention according to claim 4 (hereinafter referred to as invention 4) is a method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, wherein the chlorination reaction is performed at 110 to 140 ° C. After the chlorination reaction at the [first reaction temperature], after cooling at 0.5 to 3 ° C. per minute, the chlorination reaction is further continued at a temperature 30 to 50 ° C. lower than the first reaction temperature [second reaction temperature]. The chlorination reaction is carried out until the chlorine content becomes 3 to 8% by weight higher than the completion of the reaction at the first reaction temperature.
【００２０】請求項５記載の発明（以下、本発明５とい
う）は、塩化ビニル系樹脂を塩素化してなる塩素化塩化
ビニル系樹脂の製造方法であって、塩化ビニル系樹脂の
水懸濁液を１１０〜１４０℃に加熱した後、毎分３〜１
５℃で冷却して６０〜９０℃となし、気体塩素又は液体
塩素の存在下で、光塩素化又は熱塩素化により、塩素化
反応を行うことを特徴とする。An invention according to claim 5 (hereinafter referred to as Invention 5) is a method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, wherein the aqueous suspension of the vinyl chloride resin is provided. After heating to 110 to 140 ° C.,
The chlorination reaction is carried out by cooling at 5 ° C. to 60 to 90 ° C. and performing photochlorination or hot chlorination in the presence of gaseous chlorine or liquid chlorine.
【００２１】請求項６記載の発明（以下、本発明６とい
う）は、請求項１〜５記載の塩化ビニル系樹脂が、ＢＥ
Ｔ比表面積値１．３〜８ｍ2 ／ｇであり、ＥＳＣＡ分析
（電子分光化学分析）による粒子表面分析において、炭
素元素と塩素元素との１Ｓ結合エネルギー値（ｅＶ）に
おけるピーク比（塩素元素ピーク×２／炭素元素ピー
ク）が０．６を超えるものであることを特徴とする。The invention according to claim 6 (hereinafter referred to as invention 6) is characterized in that the vinyl chloride resin according to claims 1 to 5 is BE
The T specific surface area value is 1.3 to 8 m 2 / g, and in the particle surface analysis by ESCA analysis (electron spectrochemical analysis), the peak ratio (the chlorine element peak) at the 1S binding energy value (eV) between the carbon element and the chlorine element × 2 / carbon element peak) exceeds 0.6.
【００２２】以下に本発明を詳述する。上記ＰＶＣと
は、塩化ビニル単量体（以下、ＶＣＭという）単独、又
は、ＶＣＭ及びＶＣＭと共重合可能な他の単量体の混合
物を公知の方法で重合してなる樹脂である。上記ＶＣＭ
と共重合可能な他の単量体としては特に限定されず、例
えば、酢酸ビニル等のアルキルビニルエステル類；エチ
レン、プロピレン等のα−モノオレフィン類；塩化ビニ
リデン；スチレン等が挙げられる。これらは単独で用い
られてもよく、２種以上が併用されてもよい。Hereinafter, the present invention will be described in detail. The PVC is a resin obtained by polymerizing a vinyl chloride monomer (hereinafter, referred to as VCM) alone or a mixture of VCM and another monomer copolymerizable with VCM by a known method. The above VCM
The other monomer copolymerizable with is not particularly limited, and includes, for example, alkyl vinyl esters such as vinyl acetate; α-monoolefins such as ethylene and propylene; vinylidene chloride; styrene and the like. These may be used alone or in combination of two or more.
【００２３】上記ＰＶＣの平均重合度は特に限定され
ず、通常用いられる４００〜３，０００のものが使用で
きる。The average degree of polymerization of the above PVC is not particularly limited, and those commonly used in the range of 400 to 3,000 can be used.
【００２４】本発明で用いられるＰＶＣは、表面特性及
びスキン層構造については特に限定されず、懸濁重合、
塊状重合、又は、乳化重合等一般に知られる方法によっ
て製造されたものが使用できる。The PVC used in the present invention is not particularly limited in terms of surface properties and skin layer structure.
Those produced by a generally known method such as bulk polymerization or emulsion polymerization can be used.
【００２５】しかしながら、本発明で用いられるＰＶＣ
は、塩素化反応に供されるものであるから、その樹脂粒
子の表面特性やスキン構造については、好ましい範囲が
提示できる。即ち、本発明で用いられるＰＶＣのＢＥＴ
比表面積値は、１．３〜８ｍ 2 ／ｇが好ましく、１．５
〜５ｍ2 ／ｇがより好ましい。比表面積値が１．３ｍ 2
／ｇ未満であると、ＰＶＣ粒子内部に０．１μｍ以下の
微細孔が少なくなるため、塩素化が均一になされなくな
り、熱安定性が向上しなくなる恐れがある。また、比表
面積値が８ｍ2 ／ｇを超えると、塩素化前のＰＶＣ粒子
自体の熱安定性が低下するため、得られるＣＰＶＣの加
工性が悪くなる恐れがある。However, the PVC used in the present invention
Is used for the chlorination reaction.
Regarding the surface characteristics and skin structure of the
Can be presented. That is, the BET of the PVC used in the present invention.
Specific surface area value is 1.3-8m Two/ G is preferred, and 1.5
~ 5mTwo/ G is more preferred. Specific surface area value is 1.3m Two
/ G is less than 0.1 μm inside the PVC particles.
Chlorination is not uniform due to fewer micropores
Heat stability may not be improved. Also, ratio table
Area value is 8mTwo/ G, PVC particles before chlorination
Since the thermal stability of itself decreases, the added CPVC
The workability may deteriorate.
【００２６】上記ＰＶＣは、ＥＳＣＡ分析（電子分光化
学分析）による粒子表面分析において、炭素元素と塩素
元素との１Ｓ結合エネルギー値（ｅＶ）におけるピーク
比（塩素元素ピーク×２／炭素元素ピーク）が、小さく
なるとＰＶＣ粒子表面に分散剤等の添加剤が吸着してい
ると考えられるため、後工程での塩素化速度が遅くなる
だけでなく、ＣＰＶＣの成形加工性が損なわれる恐れが
ある。従って、上記ＰＶＣの１Ｓ結合エネルギー値（ｅ
Ｖ）におけるピーク比は、０．６を超えるものが好まし
く、０．７を超えるものがより好ましい。The above PVC has a peak ratio (chlorine element peak × 2 / carbon element peak) at 1S binding energy value (eV) of carbon element and chlorine element in particle surface analysis by ESCA analysis (electron spectrochemical analysis). When the particle size becomes smaller, it is considered that an additive such as a dispersant is adsorbed on the surface of the PVC particles, so that not only the chlorination rate in the subsequent step is reduced, but also the processability of CPVC may be impaired. Therefore, the 1S binding energy value (e
The peak ratio in V) is preferably higher than 0.6, and more preferably higher than 0.7.
【００２７】上記ピーク比が０．６を超えるＰＶＣの中
には、ＰＶＣ粒子表面の表皮（以下、スキンという）面
積が少なく、粒子内部の微細構造（１次粒子）が露出し
ている粒子（スキンレスＰＶＣという）が存在する。同
じエネルギー比である場合は、スキンレスＰＶＣを用い
ることが好ましい。Among the PVC having a peak ratio exceeding 0.6, particles having a small skin (hereinafter referred to as skin) area on the surface of the PVC particles and exposing a fine structure (primary particles) inside the particles ( Skinless PVC). If the energy ratio is the same, it is preferable to use skinless PVC.
【００２８】上記ＰＶＣの化学的構造の原子存在比は、
塩素原子：炭素原子＝１：２であり（末端構造、分岐を
考慮しない時）、上記１Ｓ結合エネルギー値（ｅＶ）に
おけるピーク比（塩素元素ピーク×２／炭素元素ピー
ク）は０〜１の値となる。ピーク比が０の場合は、ＰＶ
Ｃ粒子表面がＰＶＣ以外で、かつ、塩素を含まない他の
物質により覆われていることを意味し、ピーク比が１の
場合は、ＰＶＣ粒子表面が、完全に塩化ビニル成分のみ
で覆われていることを意味する。The atomic abundance in the chemical structure of PVC is as follows:
Chlorine atom: carbon atom = 1: 2 (when the terminal structure and branching are not considered), and the peak ratio (chlorine element peak × 2 / carbon element peak) in the above 1S binding energy value (eV) is 0 to 1. Becomes If the peak ratio is 0, PV
It means that the surface of the C particles is covered with other substances other than PVC and does not contain chlorine. When the peak ratio is 1, the surface of the PVC particles is completely covered with only the vinyl chloride component. Means that
【００２９】上記に示したＢＥＴ比表面積値及び１Ｓ結
合エネルギー値（ｅＶ）におけるピーク比を有するＰＶ
Ｃは、例えば、分散剤として高ケン化度（６０〜９０モ
ル％）若しくは低ケン化度（２０〜６０モル％）又はそ
の両方のポリ酢酸ビニル、高級脂肪酸エステル類等を、
乳化剤としてアニオン系乳化剤、ノニオン系乳化剤等を
添加して水懸濁重合することにより得ることができる。The PV having the peak ratio at the BET specific surface area value and the 1S binding energy value (eV) shown above.
C is, for example, a high saponification degree (60 to 90 mol%) or a low saponification degree (20 to 60 mol%) or both of polyvinyl acetate and higher fatty acid esters as a dispersant;
It can be obtained by adding an anionic emulsifier, a nonionic emulsifier, or the like as an emulsifier and performing water suspension polymerization.
【００３０】本発明で上記ＰＶＣを重合する際に用いる
ことができる重合器（耐圧オートクレーブ）の形状及び
構造としては特に限定されず、従来よりＰＶＣの重合に
使用されているもの等を用いることができる。また、攪
拌翼としては特に限定されず、例えば、ファウドラー
翼、パドル翼、タービン翼、ファンタービン翼、ブルマ
ージン翼等の汎用的に用いられているもの等が挙げられ
るが、特にファウドラー翼が好適に用いられ、邪魔板
（バッフル）との組み合わせも特に制限されない。The shape and structure of the polymerization vessel (pressure-resistant autoclave) that can be used in the polymerization of the PVC in the present invention are not particularly limited, and those that have been conventionally used for polymerization of PVC may be used. it can. In addition, the stirring blade is not particularly limited, and includes, for example, those generally used such as a Faudler blade, a paddle blade, a turbine blade, a fan turbine blade, and a bull margin blade, and the like is particularly preferable. And the combination with a baffle is not particularly limited.
【００３１】本発明１の塩素化反応は、塩素含有率６０
〜７０重量％の範囲で、塩素化反応温度〔Ｔ℃〕と逐次
塩素化されてなるＣＰＶＣの塩素含有率〔Ｐ重量％〕と
の関係が、式１を満たした条件で、塩素化反応を進める
ＣＰＶＣの製造方法であって、式１は、〔５．８Ｐ−２
８７〕≦〔Ｔ〕≦〔５．８Ｐ−２６２〕で表される。The chlorination reaction of the present invention 1 has a chlorine content of 60%.
When the relationship between the chlorination reaction temperature [T ° C.] and the chlorine content [P weight%] of the sequentially chlorinated CPVC satisfies the expression 1 in the range of 70% by weight, the chlorination reaction is carried out. This is a method of manufacturing a CPVC to be advanced.
87] ≦ [T] ≦ [5.8P-262].
【００３２】尚、塩素含有率６０〜７０重量％の範囲
で、塩素化反応温度〔Ｔ℃〕と逐次塩素化されてなるＣ
ＰＶＣの塩素含有率〔Ｐ重量％〕との関係を規定する理
由は、この範囲の塩素化反応過程が耐熱性とゲル化性に
強い影響を与えるという我々の知見によるものである。
従って、塩素含有率６０〜７０重量％の範囲外での昇温
操作は品質に悪影響を与え、６０重量％未満で、毎分
０．３℃以上の昇温操作は、初期の塩素化分布状態が著
しく不均一になるため好ましくなく、７０重量％を超え
てからの毎分０．３℃以上の昇温操作は、１，１型塩素
付加が増加することによると推定され、それにより耐熱
性を損ねるので好ましくない。即ち、本発明１では、昇
温操作とは、毎分０．３℃以上の温度変化を示す。In a chlorine content range of 60 to 70% by weight, the chlorination reaction temperature [T.degree.
The reason for defining the relationship with the chlorine content (P wt%) of PVC is based on our knowledge that the chlorination reaction process in this range strongly affects heat resistance and gelling property.
Therefore, the temperature raising operation at a chlorine content outside the range of 60 to 70% by weight adversely affects the quality, and the temperature raising operation at less than 60% by weight and 0.3 ° C./min or more is performed in the initial chlorination distribution state. It is not preferable because the temperature becomes extremely non-uniform, and it is presumed that the temperature increasing operation at 0.3 ° C./min or more after exceeding 70% by weight is due to an increase in the addition of 1,1-type chlorine. It is not preferable because it impairs. That is, in the present invention 1, the temperature raising operation indicates a temperature change of 0.3 ° C. or more per minute.
【００３３】塩素化反応温度〔Ｔ℃〕は式１の範囲に限
定され、〔５．８Ｐ−２８２〕≦〔Ｔ〕≦〔５．８Ｐ−
２６７〕が好ましい。〔Ｔ℃〕が〔５．８Ｐ−２８７〕
未満では、塩素化反応速度が遅く、塩素拡散速度に比べ
て反応速度が遅すぎるため、塩素化分布が著しく不均一
になり、高耐熱性が得られず、ゲル化性も良くない。
〔Ｔ℃〕が〔５．８Ｐ−２６２〕を超えると、ＰＶＣの
ガラス転移温度よりは低いが、転移温度に接近しすぎる
ため、塩素化反応時にブロックし易い。The chlorination reaction temperature [T ° C.] is limited to the range of the formula 1, and [5.8P-282] ≦ [T] ≦ [5.8P-
267] is preferred. [T ° C] is [5.8P-287]
If it is less than 1, the chlorination reaction rate is slow, and the reaction rate is too slow as compared with the chlorine diffusion rate, so that the chlorination distribution becomes extremely non-uniform, high heat resistance cannot be obtained, and the gelling property is poor.
When [T ° C] exceeds [5.8P-262], it is lower than the glass transition temperature of PVC, but is too close to the transition temperature, so that it is easily blocked during the chlorination reaction.
【００３４】塩素含有率に対応して塩素化反応温度を限
定する技術的理由は、塩素化反応の進行によりＣＰＶＣ
のガラス転移温度が上昇するが、このガラス転移温度よ
り約２０〜４０℃低い温度領域で、塩素化反応を進める
ことが、高耐熱性を得るための最適な塩素化分布を実現
する一つの有力な方法であるということである。塩素含
有率を高くすれば、ガラス転移温度は高くなるが、両者
の関係は、公知の文献で知られている。例えば、「ポリ
塩化ビニル樹脂−その基礎と応用」（社団法人 近畿化
学協会ビニル部会編、日刊工業新聞社、１９８８年発
行）１７５頁に記載されている。こららの知見と、樹脂
粒子内の塩素化分布と耐熱性、ゲル化性との関係に着目
し、鋭意検討の末、本発明に至ったのである。The technical reason for limiting the chlorination reaction temperature in accordance with the chlorine content is that the progress of the chlorination reaction causes
Although the glass transition temperature rises, promoting the chlorination reaction in a temperature range of about 20 to 40 ° C. lower than this glass transition temperature is one of the most effective ways to realize the optimal chlorination distribution for obtaining high heat resistance. It is an effective method. As the chlorine content increases, the glass transition temperature increases, but the relationship between the two is known in the known literature. For example, it is described on page 175 of "Polyvinyl Chloride Resin-Basics and Applications" (edited by Kinki Chemical Association Vinyl Subcommittee, published by Nikkan Kogyo Shimbun, 1988). Focusing on these findings and the relationship between the chlorination distribution in the resin particles and the heat resistance and gelling properties, the present inventors have made intensive studies and arrived at the present invention.
【００３５】本発明１及び２の好ましい態様としては、
塩素化反応温度の昇温速度が、塩素含有率６０〜７０重
量％の範囲において、毎分０．３〜３℃の範囲でＰＶＣ
を塩素化するのが好ましく、毎分０．５〜２℃の範囲が
より好ましい。昇温速度が毎分０．３℃未満では、塩素
化反応の制御が困難であり、耐熱性の向上が乏しく、毎
分３℃を超えると、塩素化分布が著しく不均一になり、
高耐熱性が得られず、ゲル化性の向上も乏しい。The preferred embodiments of the present inventions 1 and 2 include:
When the rate of temperature increase of the chlorination reaction temperature is in the range of 0.3 to 3 ° C./min.
Is preferably chlorinated, more preferably in the range of 0.5 to 2 ° C. per minute. If the rate of temperature rise is less than 0.3 ° C. per minute, it is difficult to control the chlorination reaction, and the heat resistance is poorly improved. If it exceeds 3 ° C. per minute, the chlorination distribution becomes extremely uneven,
High heat resistance cannot be obtained, and improvement in gelling properties is poor.
【００３６】塩素化反応時の塩素含有率と昇温速度を制
御するに際し、塩素化反応触媒としては限定されない
が、例えば、過酸化水素（水）、又は１０時間半減期温
度が６０〜１３０℃の範囲の油溶性開始剤から選択でき
る。過酸化水素（水）は、水溶性のパーオキサイド化合
物として、上記反応温度の範囲でラジカル生成が円滑に
進行する。同様に、１０時間半減期温度が６０〜１３０
℃の範囲の油溶性開始剤も上記反応温度の範囲でラジカ
ル生成が円滑に進行する。In controlling the chlorine content and the rate of temperature increase during the chlorination reaction, the chlorination reaction catalyst is not limited. For example, hydrogen peroxide (water) or a 10-hour half-life temperature of 60 to 130 ° C. Can be selected from the range of oil-soluble initiators. Hydrogen peroxide (water) is a water-soluble peroxide compound, and radical generation proceeds smoothly within the above reaction temperature range. Similarly, the 10-hour half-life temperature is 60-130.
Radical generation proceeds smoothly even in the oil-soluble initiator in the range of the above-mentioned reaction temperature.
【００３７】塩素化反応触媒として、更に好ましい例
は、過酸化水素（水）である。塩素化に際して、分子量
が小さいため、ＰＶＣ粒子内の細部に行き渡り、塩素化
反応を促進させるので、塩素化が樹脂粒子内で円滑に進
むために、高耐熱性の樹脂が得られる。又、ラジカル生
成物の分解物が、着色の原因を引き起こす恐れもない。A more preferred example of the chlorination reaction catalyst is hydrogen peroxide (water). At the time of chlorination, since the molecular weight is small, it spreads over the details in the PVC particles and promotes the chlorination reaction. Therefore, the chlorination proceeds smoothly in the resin particles, so that a resin having high heat resistance can be obtained. Further, there is no danger that a decomposition product of the radical product causes a cause of coloring.
【００３８】上記１０時間半減期温度が６０〜１３０℃
の範囲の油溶性開始剤としては、有機パーオキサイド化
合物、アゾ系化合物の中から選択される。The above 10-hour half-life temperature is 60 to 130 ° C.
Is selected from organic peroxide compounds and azo compounds.
【００３９】上記１０時間半減期温度が６０〜１３０℃
の有機パーオキサイド化合物の例としては、メチルエチ
ルケトンパーオキサイド（１０時間半減期温度＝１０５
℃、以下同じ）、メチルイソブチルケトンパーオキサイ
ド（１０５℃）、シクロヘキサノンパーオキサイド（９
０℃）、メチルシクロヘキサノンパーオキサイド（９６
℃）、等のケトンパーオキサイド化合物；The above 10-hour half-life temperature is 60 to 130 ° C.
Examples of the organic peroxide compound are methyl ethyl ketone peroxide (10 hour half-life temperature = 105
° C, the same applies hereinafter), methyl isobutyl ketone peroxide (105 ° C), cyclohexanone peroxide (9
0 ° C.), methylcyclohexanone peroxide (96
° C), etc .;
【００４０】ラウロイルパーオキサイド（６１℃）、ビ
ス−３，５，５−トリメチルヘキサノイルパーオキサイ
ド（６０℃）、アセチルパーオキサイド（６９℃）、ベ
ンゾイルパーオキサイド（７２℃）、ｐ−クロロベンゾ
イルパーオキサイド（７５℃）等のジアシルパーオキサ
イド化合物；Lauroyl peroxide (61 ° C.), bis-3,5,5-trimethylhexanoyl peroxide (60 ° C.), acetyl peroxide (69 ° C.), benzoyl peroxide (72 ° C.), p-chlorobenzoyl peroxide Diacyl peroxide compounds such as oxide (75 ° C.);
【００４１】ジクミルパーオキサイド（１１７℃）、
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキセン（１１８℃）、１，３−ビス（ｔ−ブチル
パーオキシ−イソプロピル）ベンゼン（１２１℃）、ｔ
−ブチルクミルパーオキサイド（１２１℃）、ジ−ｔ−
ブチルパーオキサイド（１２６℃）等のジアルキルパー
オキサイド化合物；Dicumyl peroxide (117 ° C.)
2,5-dimethyl-2,5-di (t-butylperoxy) hexene (118 ° C.), 1,3-bis (t-butylperoxy-isopropyl) benzene (121 ° C.), t
-Butylcumyl peroxide (121 ° C.), di-t-
Dialkyl peroxide compounds such as butyl peroxide (126 ° C.);
【００４２】１，１−ジ−ｔ−ブチルパーオキシ−３，
３，５−トリメチルシクロヘキサン（９５℃）、１，１
−ジ−ｔ−ブチルパーオキシシクロヘキサン（９７
℃）、２，２−ジ−ｔ−ブチルパーオキシブタン（１０
２℃）、４，４−ジ−ｔ−ブチルパーオキシ−ｎ−ブチ
ルバレレート（１１０℃）等のパーオキシケタール化合
物；1,1-di-t-butylperoxy-3,
3,5-trimethylcyclohexane (95 ° C.), 1,1
-Di-t-butylperoxycyclohexane (97
° C), 2,2-di-t-butylperoxybutane (10
Peroxy ketal compounds such as 2,4-di-t-butylperoxy-n-butylvalerate (110 ° C.);
【００４３】ｔ−ブチルパーオキシ−２−エチルヘキサ
ノエート（７４℃）、ｔ−ブチルパーオキシ−イソブチ
レート（７８℃）、ジ−ｔ−ブチルパーオキシ−ヘキサ
ハイドロテレフタレート（８３℃）、ｔ−ブチルパーオ
キシ−アゼレート（９９℃）、ｔ−ブチルパーオキシ−
３，５，５−トリメチルヘキサノエート（１００℃）、
ｔ−ブチルパーオキシ−アセテート（１０３℃）、ｔ−
ブチルパーオキシ−ベンゾエート（１０５℃）等のアル
キルパーエステル化合物：T-butyl peroxy-2-ethylhexanoate (74 ° C.), t-butyl peroxy-isobutyrate (78 ° C.), di-t-butyl peroxy-hexahydroterephthalate (83 ° C.), t-butyl Butyl peroxy-azelate (99 ° C.), t-butyl peroxy-
3,5,5-trimethylhexanoate (100 ° C),
t-butyl peroxy-acetate (103 ° C.), t-
Alkyl perester compounds such as butyl peroxy-benzoate (105 ° C.):
【００４４】ｔ−ブチルパーオキシ−イソプロピルカー
ボネート（９７℃）等のパーカーボネート化合物などが
挙げられる。A percarbonate compound such as t-butyl peroxy-isopropyl carbonate (97 ° C.) is exemplified.
【００４５】又、上記１０時間半減期温度が６０〜１３
０℃のアゾ系化合物としては、例えば、２，２’−アゾ
ビス（２−メチルプロピオニトリル）（６５℃）、２，
２’−アゾビス（２−メチルブチロニトリル）（６７
℃）、１，１’−アゾビス（シクロヘキサン−１−カル
ボニトリル）（８８℃）、２−フェニルアゾ−４−メト
キシ−２，４−ジメチルバレロニトリル（１２２℃）等
のアゾニトリル化合物；２，２’−アゾビス（２，４，
４−トリメチルペンタン）（１１０℃）等のアルキルア
ゾ化合物などが挙げられる。The above 10 hour half-life temperature is 60 to 13
Examples of the azo compound at 0 ° C. include, for example, 2,2′-azobis (2-methylpropionitrile) (65 ° C.),
2'-azobis (2-methylbutyronitrile) (67
C), 1,1'-azobis (cyclohexane-1-carbonitrile) (88C), azonitrile compounds such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile (122C); 2,2 ' -Azobis (2, 4,
Alkylazo compounds such as 4-trimethylpentane) (110 ° C.).
【００４６】本発明３の塩素化反応は、ＰＶＣを塩素化
してなるＣＰＶＣの製造方法であって、塩素化反応にお
いて、１１０〜１４０℃で塩素化反応後、６０〜７０℃
に達するまで、毎分０．２〜３℃で冷却するＣＰＶＣの
製造方法である。The chlorination reaction of the present invention 3 is a method for producing CPVC by chlorinating PVC. In the chlorination reaction, the chlorination reaction is carried out at 110 to 140 ° C., then at 60 to 70 ° C.
Until the temperature reaches 0.2 to 3 ° C. per minute.
【００４７】本発明３の塩素化反応温度は１１０〜１４
０℃が好ましく、１２０〜１３５℃がより好ましい。１
１０℃未満では、ＣＰＶＣの徐冷による結晶化効果が充
分に発揮できず、耐熱性が充分に向上しない。１４０℃
を超えると、塩素化の際に樹脂粒子内への塩素の溶解量
が著しく減少し、塩素化反応速度が減じるし、分子内で
の塩素化が不均一反応し易く、生成樹脂に着色が生じる
ので好ましくない。The chlorination reaction temperature of the present invention 3 is 110 to 14
0 ° C is preferable, and 120 to 135 ° C is more preferable. 1
If the temperature is lower than 10 ° C., the crystallization effect due to the slow cooling of the CPVC cannot be sufficiently exhibited, and the heat resistance cannot be sufficiently improved. 140 ° C
When it exceeds, the amount of chlorine dissolved in the resin particles during chlorination is significantly reduced, the chlorination reaction rate is reduced, and chlorination in the molecule is liable to undergo a heterogeneous reaction, and the resulting resin is colored. It is not preferable.
【００４８】上記のようにして、塩素化反応により、Ｃ
ＰＶＣが必要な耐熱性レベルの塩素含有率に達したこと
を発生塩酸の滴定等により確認後、反応器内の塩素ガス
を窒素ガス等の不活性ガスで置換した後、６０〜７０℃
に達する迄、冷却速度として毎分０．２〜３℃が好まし
い。冷却速度が毎分０．２℃未満では、ゲル化性が阻害
される他、塩素化工程時間が長くなり生産性が低下す
る。冷却速度が毎分３℃を超えると、徐冷によるＣＰＶ
Ｃの結晶化効果が充分に発揮せず、耐熱性の向上に乏し
い。As described above, by the chlorination reaction, C
After confirming that the PVC has reached the chlorine content of the required heat resistance level by titration of generated hydrochloric acid or the like, the chlorine gas in the reactor is replaced with an inert gas such as nitrogen gas, and then 60 to 70 ° C.
, A cooling rate of 0.2 to 3 ° C per minute is preferred. If the cooling rate is less than 0.2 ° C. per minute, the gelling property will be impaired, and the chlorination step will take a long time to lower the productivity. When the cooling rate exceeds 3 ° C / min, CPV by slow cooling
The crystallization effect of C is not sufficiently exhibited, and the improvement in heat resistance is poor.
【００４９】また、徐冷操作の温度範囲は６０〜７０℃
に限定され、６０℃より低いと、徐冷時間長くなるが、
耐熱性の向上が殆ど望めず好ましくなく、７０℃より高
いと、徐冷による結晶化効果が充分に発揮せず、耐熱性
が充分に向上しない。尚、これらの徐冷による結晶化作
用は、ＣＰＶＣの成形加工工程の熱履歴を経ても保持し
ており、耐熱性の向上に有効に作用する。The temperature range of the slow cooling operation is 60 to 70 ° C.
If the temperature is lower than 60 ° C., the annealing time will be longer,
When the temperature is higher than 70 ° C., the crystallization effect by slow cooling is not sufficiently exhibited, and the heat resistance is not sufficiently improved. Incidentally, the crystallization action by these slow cooling is maintained even after passing through the heat history of the forming process of CPVC, and effectively acts to improve the heat resistance.
【００５０】塩素化反応時の、塩素化反応触媒としては
限定されないが、例えば、本発明１及び２と同様に、過
酸化水素（水）、又は１０時間半減期温度が８０〜１３
０℃の範囲の油溶性開始剤から選択できる。過酸化水素
（水）は、水溶性のパーオキサイド化合物として、上記
反応温度の範囲でラジカル生成が円滑に進行する。同様
に、１０時間半減期温度が８０〜１３０℃の範囲の油溶
性開始剤も上記反応温度の範囲でラジカル生成が円滑に
進行する。The chlorination reaction catalyst at the time of the chlorination reaction is not limited. For example, hydrogen peroxide (water) or a 10-hour half-life temperature of 80-13
It can be selected from oil-soluble initiators in the range of 0 ° C. Hydrogen peroxide (water) is a water-soluble peroxide compound, and radical generation proceeds smoothly within the above reaction temperature range. Similarly, in the case of an oil-soluble initiator having a 10-hour half-life temperature in the range of 80 to 130 ° C, radical generation proceeds smoothly within the above-mentioned reaction temperature range.
【００５１】塩素化反応触媒として、更に好ましい例
は、本発明１及び２と同様な理由により過酸化水素
（水）である。A more preferred example of the chlorination reaction catalyst is hydrogen peroxide (water) for the same reason as in the present inventions 1 and 2.
【００５２】上記１０時間半減期温度が８０〜１３０℃
の範囲の油溶性開始剤としては、有機パーオキサイド化
合物、アゾ系化合物の中から選択される。The 10-hour half-life temperature is 80 to 130 ° C.
Is selected from organic peroxide compounds and azo compounds.
【００５３】上記１０時間半減期温度が８０〜１３０℃
の有機パーオキサイド化合物の例としては、本発明１及
び２で例示された中で１０時間半減期温度が８０〜１３
０℃ものが同様に用いられる。The above-mentioned 10-hour half-life temperature is 80 to 130 ° C.
Examples of the organic peroxide compound of the present invention include those exemplified in the present invention 1 and 2 having a 10-hour half-life temperature of 80 to 13;
A 0 ° C. is used as well.
【００５４】本発明４の塩素化反応は、ＰＶＣを塩素化
してなるＣＰＶＣの製造方法であって、塩素化反応にお
いて、１１０〜１４０℃〔第１反応温度〕で塩素化反応
後、毎分０．５〜３℃で冷却した後、第１反応温度より
３０〜５０℃低い温度〔第２反応温度〕で更に塩素化反
応を継続し、第１反応終了時点より塩素含有率を３〜８
重量％高くなるまで塩素化反応を行うＣＰＶＣの製造方
法である。The chlorination reaction of the present invention 4 is a method for producing CPVC by chlorinating PVC. In the chlorination reaction, after the chlorination reaction at 110 to 140 ° C. [first reaction temperature], the chlorination reaction is carried out at a rate of 0 minutes per minute. After cooling at 0.5 to 3 ° C, the chlorination reaction is further continued at a temperature 30 to 50 ° C lower than the first reaction temperature (second reaction temperature), and the chlorine content is reduced to 3 to 8 from the end of the first reaction.
This is a method for producing CPVC in which a chlorination reaction is carried out until the weight percentage increases.
【００５５】本発明４の塩素化反応温度は２段階で行わ
れるが、塩素化第１反応の反応温度は１１０〜１４０℃
が好ましく、１２０〜１３５℃がより好ましい。１１０
℃未満では、ＣＰＶＣの徐冷による結晶化効果が充分に
発揮できず、耐熱性が充分に向上しない。１４０℃を超
えると、塩素化の際に樹脂粒子内への塩素の溶解量が著
しく減少し、塩素化反応速度が減じるし、分子内での塩
素化が不均一反応し易く、生成樹脂に着色が生じるので
好ましくない。The chlorination reaction temperature of the present invention 4 is performed in two stages, but the reaction temperature of the first chlorination reaction is 110 to 140 ° C.
Is preferable, and 120 to 135 ° C. is more preferable. 110
If the temperature is lower than ℃, the crystallization effect due to the slow cooling of the CPVC cannot be sufficiently exhibited, and the heat resistance cannot be sufficiently improved. If the temperature exceeds 140 ° C, the amount of chlorine dissolved in the resin particles during chlorination decreases significantly, the chlorination reaction rate decreases, and the chlorination in the molecule tends to undergo a heterogeneous reaction, and the resulting resin is colored. Is not preferred.
【００５６】塩素化第２反応温度は、第１反応温度より
３０〜５０℃低い温度〔第２反応温度〕で更に塩素化反
応を行うことが好ましく、２５〜４０℃低い温度がより
好ましい。第１反応温度より３０℃未満の低い温度で
は、第一反応温度と第二反応温度との温度差が小さすぎ
て、その冷却時のＣＰＶＣの分子構造の秩序化が充分で
なく、耐熱性が充分に向上しない。第１反応温度より５
０℃を超えて低い温度では、分子構造の秩序化が進行し
すぎて、ゲル化性の向上が阻害される。The chlorination second reaction temperature is preferably 30 to 50 ° C. lower than the first reaction temperature (second reaction temperature), and more preferably 25 to 40 ° C. lower. At a temperature lower than the first reaction temperature by less than 30 ° C., the temperature difference between the first reaction temperature and the second reaction temperature is too small, so that the molecular structure of CPVC upon cooling is not sufficiently ordered, and the heat resistance is poor. Does not improve enough. 5 from the first reaction temperature
If the temperature is lower than 0 ° C., the ordering of the molecular structure proceeds excessively, and the improvement of the gelling property is hindered.
【００５７】第一反応温度から第二反応温度間の冷却速
度は、毎分０．５〜３℃が好ましく、０．７〜２℃がよ
り好ましい。冷却速度が毎分０．５℃未満では、分子構
造の秩序化が進行しすぎて、ゲル化性の向上が阻害され
る。冷却速度が毎分３℃を超えると、分子構造の秩序化
が充分でなく、耐熱性が充分に向上しない。The cooling rate between the first reaction temperature and the second reaction temperature is preferably 0.5 to 3 ° C. per minute, more preferably 0.7 to 2 ° C. If the cooling rate is less than 0.5 ° C. per minute, the ordering of the molecular structure proceeds too much, and the improvement of the gelling property is hindered. If the cooling rate exceeds 3 ° C. per minute, the ordering of the molecular structure is not sufficient, and the heat resistance is not sufficiently improved.
【００５８】第二反応温度における塩素化は、塩素含有
率として３〜８重量％高くなるまでの塩素化するのが好
ましく、４〜７重量％がより好ましい。塩素含有率が３
重量％未満では、第二反応温度において、分子構造が秩
序化した部分以外の所での塩素化の進行程度が低く、塩
素化分布による熱変形温度の向上が乏しい。塩素含有率
が８重量％を超えると、分子構造が秩序化した部分も塩
素化されるため、同様に熱変形温度の向上が乏しい。The chlorination at the second reaction temperature is preferably performed until the chlorine content increases by 3 to 8% by weight, more preferably 4 to 7% by weight. Chlorine content is 3
When the amount is less than% by weight, at the second reaction temperature, the degree of progress of chlorination other than the portion where the molecular structure is ordered is low, and the improvement of the heat distortion temperature due to the chlorination distribution is poor. If the chlorine content exceeds 8% by weight, the portion where the molecular structure is ordered is also chlorinated, so that the heat deformation temperature is similarly poorly improved.
【００５９】上記塩素化反応においては、第一塩素化反
応、第二塩素化反応共に塩素化反応触媒は、特に限定さ
れず、例えば、本発明１及び２と同様に、過酸化水素
（水）、又は１０時間半減期温度が６０〜１３０℃の範
囲の油溶性開始剤が好ましく、７０〜１２０℃の範囲が
より好ましい。過酸化水素（水）は、水溶性のパーオキ
サイド化合物として、上記反応温度の範囲でラジカル生
成が円滑に進行する。同様に、１０時間半減期温度が６
０〜１３０℃の範囲の油溶性開始剤も上記反応温度の範
囲でラジカル生成が円滑に進行する。In the chlorination reaction, the chlorination reaction catalyst is not particularly limited for both the first chlorination reaction and the second chlorination reaction. For example, as in the present inventions 1 and 2, hydrogen peroxide (water) is used. Alternatively, an oil-soluble initiator having a 10-hour half-life temperature in the range of 60 to 130 ° C is preferable, and the range of 70 to 120 ° C is more preferable. Hydrogen peroxide (water) is a water-soluble peroxide compound, and radical generation proceeds smoothly within the above reaction temperature range. Similarly, a 10-hour half-life temperature of 6
Radical generation proceeds smoothly in the oil-soluble initiator in the range of 0 to 130 ° C. in the above reaction temperature range.
【００６０】塩素化反応温度に対して、油溶性開始剤の
１０時間半減期温度は−３０〜＋１０℃の範囲になるよ
うに、油溶性開始剤を選定するのが好ましい。It is preferable to select the oil-soluble initiator so that the 10-hour half-life temperature of the oil-soluble initiator is in the range of -30 to + 10 ° C. with respect to the chlorination reaction temperature.
【００６１】塩素化反応触媒として、更に好ましい例
は、本発明１及び２と同様な理由により過酸化水素
（水）である。A more preferred example of the chlorination reaction catalyst is hydrogen peroxide (water) for the same reason as in the present inventions 1 and 2.
【００６２】上記１０時間半減期温度が６０〜１３０℃
の範囲の油溶性開始剤としては、本発明１及び２と同様
に有機パーオキサイド化合物、アゾ系化合物の中から選
択される。The 10-hour half-life temperature is 60 to 130 ° C.
Is selected from organic peroxide compounds and azo compounds as in the case of the present inventions 1 and 2.
【００６３】本発明５の塩素化反応は、ＰＶＣを塩素化
してなるＣＰＶＣの製造方法であって、ＰＶＣの水懸濁
液を１１０〜１４０℃に加熱した後、毎分３〜１５℃で
冷却して６０〜９０℃となし、気体塩素又は液体塩素の
存在下で、光塩素化又は熱塩素化により、塩素化反応を
行うＣＰＶＣの製造方法である。The chlorination reaction of the present invention 5 is a method for producing CPVC by chlorinating PVC, in which a water suspension of PVC is heated to 110 to 140 ° C. and then cooled at 3 to 15 ° C. per minute. This is a method for producing CPVC in which a chlorination reaction is carried out by photochlorination or hot chlorination in the presence of gaseous chlorine or liquid chlorine.
【００６４】上記の様に、ＰＶＣの水懸濁液を１１０〜
１４０℃の範囲に加熱することに限定され、１１５〜１
３５℃が好ましい。１１０℃未満では、後の冷却による
過冷却状態が充分でないため、塩素化反応時に塩素化分
布の均一性が損なわれ、耐熱性が向上しない。１４０℃
を超えると、ＰＶＣの水懸濁液攪拌時に樹脂粒子同士が
合着し、後の塩素化反応時に塩素化拡散が円滑に進行せ
ず、耐熱性が向上しない。As described above, the aqueous suspension of PVC was prepared for
Limited to heating in the range of 140 ° C .;
35 ° C. is preferred. If the temperature is lower than 110 ° C., since the supercooling state by the subsequent cooling is not sufficient, the uniformity of the chlorination distribution is impaired during the chlorination reaction, and the heat resistance is not improved. 140 ° C
When it exceeds, the resin particles coalesce during stirring of the aqueous suspension of PVC, and the chlorination diffusion does not proceed smoothly during the subsequent chlorination reaction, and the heat resistance does not improve.
【００６５】上記冷却速度は、毎分３〜１５℃に限定さ
れ、４〜１２℃が好ましい。毎分３℃未満であると、過
冷却状態を形成できず、即ち、結晶化が進行し易いた
め、塩素化分布の均一性が損なわれ、耐熱性が向上しな
い。毎分１５℃を超えると、反応器内で部分的に冷却速
度が異なるため、その後の塩素化時に塩素化分布が生じ
やすくなり、耐熱性が向上しない。又、高速に冷却する
ために、大型の冷凍機と熱交換機を必要とし好ましくな
い。The cooling rate is limited to 3 to 15 ° C. per minute, preferably 4 to 12 ° C. If the temperature is less than 3 ° C. per minute, a supercooled state cannot be formed, that is, crystallization easily proceeds, so that the uniformity of the chlorination distribution is impaired and the heat resistance is not improved. If the temperature exceeds 15 ° C. per minute, the cooling rate is partially different in the reactor, so that chlorination distribution is likely to occur during the subsequent chlorination, and the heat resistance is not improved. In addition, a large-sized refrigerator and a heat exchanger are required for high-speed cooling, which is not preferable.
【００６６】反応器内容物の冷却温度、及び塩素化反応
温度は、６０〜９０℃に限定され、６５〜８５℃が好ま
しい。６０℃未満では、塩素の拡散速度が遅くなりすぎ
るため、塩素化分布が生じやすくなり、耐熱性の向上が
望めない。９０℃を超えると、過冷却効果が小さく、塩
素の均一性も良くないので、耐熱性が向上しない。The cooling temperature of the reactor contents and the chlorination reaction temperature are limited to 60 to 90 ° C., preferably 65 to 85 ° C. If the temperature is lower than 60 ° C., the diffusion rate of chlorine becomes too slow, so that chlorination distribution is apt to occur, and improvement in heat resistance cannot be expected. If it exceeds 90 ° C., the supercooling effect is small and the uniformity of chlorine is not good, so that the heat resistance is not improved.
【００６７】上記塩素化反応においては、塩素化反応触
媒は、特に限定されず、例えば、本発明１及び２と同様
に、過酸化水素（水）、又は１０時間半減期温度が３０
〜１００℃の範囲の油溶性開始剤が好ましく、４０〜９
５℃の範囲がより好ましい。過酸化水素（水）は、水溶
性のパーオキサイド化合物として、上記反応温度の範囲
でラジカル生成が円滑に進行する。同様に、１０時間半
減期温度が３０〜１００℃の範囲の油溶性開始剤も上記
反応温度の範囲でラジカル生成が円滑に進行する。In the above chlorination reaction, the chlorination reaction catalyst is not particularly limited. For example, as in the case of the first and second inventions, hydrogen peroxide (water) or a 10-hour half-life temperature of 30
Oil soluble initiators in the range of -100 ° C to 40 ° C are preferred.
A range of 5 ° C. is more preferred. Hydrogen peroxide (water) is a water-soluble peroxide compound, and radical generation proceeds smoothly within the above reaction temperature range. Similarly, in the case of an oil-soluble initiator having a 10-hour half-life temperature in the range of 30 to 100 ° C, radical generation proceeds smoothly within the above-mentioned reaction temperature range.
【００６８】塩素化反応温度に対して、油溶性開始剤の
１０時間半減期温度は−３０〜＋１０℃の範囲になるよ
うに、油溶性開始剤を選定するのが好ましい。It is preferable to select the oil-soluble initiator so that the 10-hour half-life temperature of the oil-soluble initiator is in the range of -30 to + 10 ° C. with respect to the chlorination reaction temperature.
【００６９】塩素化反応触媒として、更に好ましい例
は、本発明１及び２と同様な理由により過酸化水素
（水）である。A more preferred example of the chlorination reaction catalyst is hydrogen peroxide (water) for the same reason as in the present inventions 1 and 2.
【００７０】上記１０時間半減期温度が３０〜１００℃
の範囲の油溶性開始剤としては、本発明１及び２と同様
に有機パーオキサイド化合物、アゾ系化合物の中から選
択される。The above 10-hour half-life temperature is 30 to 100 ° C.
Is selected from organic peroxide compounds and azo compounds as in the case of the present inventions 1 and 2.
【００７１】上記１０時間半減期温度が３０〜１００℃
の有機パーオキサイド化合物の例としては、本発明１及
び２で例示された中で１０時間半減期温度が８０〜１３
０℃ものの内、６０〜１００℃のものが同様に用いられ
る他、以下の３０℃以上６０℃未満のものが挙げられ
る。The above 10-hour half-life temperature is 30 to 100 ° C.
Examples of the organic peroxide compound of the present invention include those exemplified in the present invention 1 and 2 having a 10-hour half-life temperature of 80 to 13;
Of those at 0 ° C., those having a temperature of 60 to 100 ° C. are similarly used, and those having the following 30 ° C. or more and less than 60 ° C. are also exemplified.
【００７２】上記１０時間半減期温度が３０℃以上６０
℃未満の有機パーオキサイド化合物の例としては、イソ
ブチリルパーオキサイド（１０時間半減期温度＝３３
℃、以下同じ）２，４−ジクロロベンゾイルパーオキサ
イド（５４℃）、ｏ−メチルベンゾイルパーオキサイド
（５７℃）等のジアシルパーオキサイド化合物；The above 10-hour half-life temperature is 30 ° C. or higher and 60
As an example of an organic peroxide compound having a temperature of less than 10 ° C., isobutyryl peroxide (10-hour half-life temperature = 33
Diacyl peroxide compounds such as 2,4-dichlorobenzoyl peroxide (54 ° C.) and o-methylbenzoyl peroxide (57 ° C.);
【００７３】アセチルシクロヘキサンスルホニルシル
（３７℃）、２，４，４−トリメチルペンチルパーオキ
シフェノキシアセテート（３８℃）、α−クミルパーオ
キシネオデカノエート（３８℃）、４−トリメチルペン
チル−２−パーオキシ−２−ネオデカノエート（４１
℃）、α−クミルパーオキシネオヘキサノエート（４１
℃）、ｔ−ヘキシルパーオキシネオデカノエート（４５
℃）、ｔ−ブチルパーオキシネオデカノエート（４７
℃）、ｔ−ヘキシルパーオキシネオヘキサノエート（４
９℃）、ｔ−ヘキシルパーオキシピバレート（５３
℃）、ｔ−ブチルパーオキシピバレート（５６℃）等の
パーエステル化合物；Acetylcyclohexanesulfonylsyl (37 ° C.), 2,4,4-trimethylpentylperoxyphenoxyacetate (38 ° C.), α-cumylperoxy neodecanoate (38 ° C.), 4-trimethylpentyl-2-yl Peroxy-2-neodecanoate (41
° C), α-cumylperoxyneohexanoate (41
C), t-hexylperoxy neodecanoate (45
° C), t-butyl peroxy neodecanoate (47
° C), t-hexylperoxyneohexanoate (4
9 ° C.), t-hexyl peroxypivalate (53
C), perester compounds such as t-butyl peroxypivalate (56C);
【００７４】ジアリルパーオキシジカーボネート（３９
℃）、ジ−ｎ−プロピルパーオキシジカーボネート（４
１℃）、ジミリスチルパーオキシジカーボネート（４１
℃）、ジ（２−エトキシエチル）パーオキシジカーボネ
ート（４３℃）、ジ（３−メトキシブチル）パーオキシ
ジカーボネート（４３℃）、ジ（メトキシイソプロピ
ル）パーオキシジカーボネート（４４℃）、ジ（２−エ
トキシヘキシル）パーオキシジカーボネート（４４
℃）、ビス（４−ｔ−ブチルシクロヘキシル）パーオキ
シジカーボネート（４４℃）、ジイソプロピルパーオキ
シジカーボネート（４５℃）、ジ（ｓｅｃ−ブチル）パ
ーオキシジカーボネート（４５℃）、ジ（３−メチル−
３−メトキシブチル）パーオキシジカーボネート（４７
℃）等のパーカーボネート化合物；The diallyl peroxydicarbonate (39
° C), di-n-propylperoxydicarbonate (4
1 ° C.), dimyristyl peroxydicarbonate (41
° C), di (2-ethoxyethyl) peroxydicarbonate (43 ° C), di (3-methoxybutyl) peroxydicarbonate (43 ° C), di (methoxyisopropyl) peroxydicarbonate (44 ° C), (2-ethoxyhexyl) peroxydicarbonate (44
° C), bis (4-t-butylcyclohexyl) peroxydicarbonate (44 ° C), diisopropylperoxydicarbonate (45 ° C), di (sec-butyl) peroxydicarbonate (45 ° C), di (3- Methyl-
3-methoxybutyl) peroxydicarbonate (47
C) and the like;
【００７５】また、上記１０時間半減期温度が３０℃以
上６０℃未満のアゾ系化合物の例としては、例えば、
α，α’−アゾビス（４−メトキシ−２，４−ジメチル
バレロニトリル）（３０℃）、α，α’−アゾビス（２
−シクロプロピルプロピオニトリル）（４２℃）、α，
α’−アゾビス（２，４−ジメチルバレロニトリル）
（５１℃）等のアゾニトリル化合物が挙げられる。Examples of the azo compound having a 10-hour half-life temperature of 30 ° C. or more and less than 60 ° C. include, for example,
α, α′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (30 ° C.), α, α′-azobis (2
-Cyclopropylpropionitrile) (42 ° C.), α,
α'-azobis (2,4-dimethylvaleronitrile)
(51 ° C.).
【００７６】本発明の塩素化反応触媒の添加量は、ＰＶ
Ｃ１００重量部に対して、０．０００５〜０．２重量部
の範囲が好ましい。The amount of the chlorination reaction catalyst of the present invention is PV
The range of 0.0005 to 0.2 part by weight is preferably based on 100 parts by weight of C.
【００７７】本発明に使用する塩素化反応器の材質は、
グラスライニングが施されたステンレス製反応器の他、
チタン製反応器等、一般に使用されるものが適用でき
る。The material of the chlorination reactor used in the present invention is as follows.
In addition to a stainless steel reactor with glass lining,
A commonly used one such as a titanium reactor can be applied.
【００７８】本発明における塩素化反応に供する塩素源
は、液体塩素又は気体塩素が好ましい。本発明では、液
体塩素を導入することが工程上からも効率的である。
為、又、塩素化反応の進行に伴う塩素の補給について
は、液体塩素の他、気体塩素を適宜吹き込むこともでき
る。The chlorine source used for the chlorination reaction in the present invention is preferably liquid chlorine or gaseous chlorine. In the present invention, the introduction of liquid chlorine is efficient from the viewpoint of the process.
Therefore, as for the replenishment of chlorine accompanying the progress of the chlorination reaction, gaseous chlorine can be appropriately blown in addition to liquid chlorine.
【００７９】本発明では、塩素化はＰＶＣを水性媒体に
より懸濁状態になした状態で、液体塩素又は気体塩素を
導入することにより、塩素源を塩素化反応器内に導入す
るが、液体塩素を導入することが工程上からも効率的で
ある。反応途中の圧力調製の為、又、塩素化反応の進行
に伴う塩素の補給については、液体塩素の他、気体塩素
を適宜吹き込むこともできる。In the present invention, chlorination is carried out by introducing liquid chlorine or gaseous chlorine in a state where PVC is suspended in an aqueous medium to introduce a chlorine source into the chlorination reactor. Is efficient from the viewpoint of the process. For adjusting the pressure during the reaction and for replenishing chlorine with the progress of the chlorination reaction, gaseous chlorine can be blown in as appropriate in addition to liquid chlorine.
【００８０】上記ＰＶＣを懸濁状態に調製する方法とし
ては、ＰＶＣを重合の後、乾燥させたものを再度、水性
媒体で懸濁化してもよく、あるいは、重合系中より、塩
酸等、塩素化反応に好ましくない物質を除去した懸濁液
を使用しても良い。反応器内に仕込む水性媒体の量は、
特に制限はないが、一般にＰＶＣの重量１に対して２〜
１０倍（重量）量を仕込む。As a method for preparing the above-mentioned PVC in a suspended state, the PVC may be polymerized and then dried and then re-suspended in an aqueous medium. A suspension from which substances unfavorable for the chemical reaction have been removed may be used. The amount of aqueous medium charged into the reactor is
Although not particularly limited, generally 2 to 2 per weight of PVC.
Charge 10 times (weight).
【００８１】上記懸濁した状態で塩素化する場合は、例
えば、反応生成物に光を照射して光反応的に塩素化を促
進する方法、熱により樹脂の結合や塩素を励起させて塩
素化を促進する方法等により行うことができる。光エネ
ルギーにより塩素化する場合に用いられる光源としては
特に限定されず、例えば、紫外光線；水銀灯、アーク
灯、白熱電球、蛍光灯、カーボンアーク灯等の可視光線
等が挙げられ、特に、紫外光線が効果的である。熱エネ
ルギーにより塩素化する場合の加熱方法としては特に限
定されず、例えば、反応器壁からの外部ジャケット方式
の他、内部ジャケット方式、スチーム吹き込み方式等が
挙げられ、通常は、外部ジャケット方式又は内部ジャケ
ット方式が効果的である。In the case of chlorination in the suspended state, for example, a method of irradiating a reaction product with light to accelerate chlorination in a photoreactive manner, or exchanging heat with resin to excite the chlorination and chlorination. Can be carried out by a method that promotes The light source used in the case of chlorination by light energy is not particularly limited, and includes, for example, ultraviolet light; visible light such as a mercury lamp, arc lamp, incandescent lamp, fluorescent lamp, and carbon arc lamp; Is effective. The heating method in the case of chlorination by heat energy is not particularly limited, and examples thereof include an outer jacket method from the reactor wall, an inner jacket method, a steam blowing method, and the like. The jacket method is effective.
【００８２】上記塩素化の工程で、得られるＣＰＶＣの
塩素含有率は６０〜７２重量％となるように調製するの
が好ましく、６３〜７０重量％がより好ましい。塩素含
有率が６０重量５未満では、耐熱性に乏しく、７２重量
％を超えるとゲル化性能が悪化して、耐熱成形品を成形
するのに不利である。In the chlorination step, the CPVC obtained is preferably adjusted to have a chlorine content of 60 to 72% by weight, more preferably 63 to 70% by weight. If the chlorine content is less than 60% by weight, the heat resistance is poor, and if it exceeds 72% by weight, the gelling performance is deteriorated, which is disadvantageous for molding a heat-resistant molded product.
【００８３】上記反応器内のゲージ圧力は、特に限定さ
れないが、塩素圧力が高いほど塩素がＰＶＣ粒子の内部
に浸透し易いため、０．３〜２ＭＰａの範囲が好まし
い。The gauge pressure in the reactor is not particularly limited, but is preferably in the range of 0.3 to 2 MPa because the higher the chlorine pressure, the more easily chlorine penetrates into the PVC particles.
【００８４】[0084]
【発明の実施の形態】以下に実施例を掲げて本発明を更
に詳しく説明するが、本発明はこれら実施例のみに限定
されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００８５】（実施例１） 〔ＰＶＣの調製〕内容積１００リットルの重合器（耐圧
オートクレーブ）に脱イオン水５０ｋｇ、塩化ビニル単
量体に対して、平均ケン化度７２モル％及び重合度７０
０の部分ケン化ポリ酢酸ビニル４５０ｐｐｍ、ソルビタ
ンモノラウレート１，２００ｐｐｍ、ラウリン酸１，２
００ｐｐｍ、ポリアクリルアミド（２０℃、１ａｔｍで
０．１重量％水溶液のブルックフィールズ粘度が５１ｃ
ｐｓのもの）１５０ｐｐｍ並びにｔ−ブチルパーオキシ
ネオデカノエート５５０ｐｐｍを投入した。次いで、重
合器内を４５ｍｍＨｇまで脱気した後、塩化ビニル単量
体３３ｋｇを仕込み攪拌を開始した。重合器を５７℃に
昇温して重合を開始し、重合反応終了までこの温度を保
った。(Example 1) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water, an average saponification degree of 72 mol% and a polymerization degree of 70 with respect to a vinyl chloride monomer were used.
0 partially saponified polyvinyl acetate 450 ppm, sorbitan monolaurate 1,200 ppm, lauric acid 1,2
00 ppm, polyacrylamide (0.1% by weight aqueous solution at 20 ° C., 1 atm, Brookfield viscosity of 51 c
ps) and 150 ppm of t-butylperoxyneodecanoate. Next, after degassing the inside of the polymerization vessel to 45 mmHg, 33 kg of a vinyl chloride monomer was charged and stirring was started. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C., and this temperature was maintained until the polymerization reaction was completed.
【００８６】重合転化率が９０重量％になった時点で反
応を終了し、重合器内の未反応単量体を回収した後、重
合体をスラリー状で系外へ取り出し、脱水乾燥してＰＶ
Ｃを得た。得られたＰＶＣのＢＥＴ比表面積値は３．７
ｍ2 ／ｇであった。また、スキン層の存在程度を示すＥ
ＳＣＡ分析値は、０．８０であった。なお、ＢＥＴ比表
面積、及び、ＥＳＣＡ分析の測定は、下記方法により実
施した。When the polymerization conversion reached 90% by weight, the reaction was terminated. After the unreacted monomer in the polymerization vessel was recovered, the polymer was taken out of the system in the form of a slurry, dehydrated and dried to remove PVD.
C was obtained. The BET specific surface area of the obtained PVC was 3.7.
m 2 / g. In addition, E indicating the existence degree of the skin layer
The SCA analysis value was 0.80. The BET specific surface area and ESCA analysis were measured by the following methods.
【００８７】〔ＣＰＶＣの調製〕内容積２５０リットル
のチタン製耐圧反応器に脱イオン水６０ｋｇ〔対樹脂量
比＝２〕と上記で得たＰＶＣ３０ｋｇ〔これを１とす
る〕とを入れ、攪拌してＰＶＣを水中に分散させ、その
後反応器内に窒素ガスを吹き込み、器内を窒素ガスで置
換した。次に、反応器内に気体塩素を導入した後、反応
器を７０℃とし、塩素化反応触媒として、過酸化水素を
ＰＶＣ（重量対比）で２００ｐｐｍ一括投入し塩素化反
応を開始した。その後、塩素含有率が６０重量％に達し
た時点で昇温を開始し、塩素含有率が表１に示す時に、
反応温度がそれぞれ所定の温度になるように反応温度を
制御して反応を進めた。昇温速度は毎分１．１℃であっ
た。塩素化反応は熱エネルギーだけとして反応を継続
し、器内の塩酸濃度を測定して、塩素化反応の進行状況
を確認しながら塩素化反応を続け、生成したＣＰＶＣの
塩素含有率が７０．０重量％に達した時点で、塩素化反
応を終了させた。反応時間は８０分であった。[Preparation of CPVC] 60 kg of deionized water [resin ratio = 2] and 30 kg of PVC obtained above (referred to as 1) were placed in a 250 liter internal pressure resistant titanium reactor and stirred. Then, PVC was dispersed in water, and then nitrogen gas was blown into the reactor to replace the inside of the reactor with nitrogen gas. Next, after introducing gaseous chlorine into the reactor, the temperature of the reactor was set to 70 ° C., and as a chlorination reaction catalyst, 200 ppm of hydrogen peroxide was added in a lump in PVC (by weight) to start the chlorination reaction. Thereafter, when the chlorine content reached 60% by weight, the temperature was started. When the chlorine content was as shown in Table 1,
The reaction was proceeded by controlling the reaction temperature so that the reaction temperature became a predetermined temperature. The heating rate was 1.1 ° C./min. The chlorination reaction is continued only with heat energy, the chlorination reaction is continued while measuring the concentration of hydrochloric acid in the vessel and checking the progress of the chlorination reaction, and the chlorine content of the generated CPVC is 70.0%. When the weight percentage was reached, the chlorination reaction was terminated. The reaction time was 80 minutes.
【００８８】更に、器内に窒素ガスを吹き込んで未反応
塩素を除去し、得られた樹脂を水酸化ナトリウムで中和
した後、水で洗浄し脱水、乾燥して粉末状のＣＰＶＣを
得た。得られたＣＰＶＣの塩素含有率は、７０．０重量
％であった。Further, nitrogen gas was blown into the vessel to remove unreacted chlorine, and the obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. . The chlorine content of the obtained CPVC was 70.0% by weight.
【００８９】（実施例２）ＰＶＣの調製は、実施例１と
同様に実施した。ＣＰＶＣの調製は、表１に示す通り、
触媒としてメチルイソブチルケトンパーオキサイド（１
０時間半減期温度＝１０５℃）を使用し、添加量として
ＰＶＣ（重量対比）で３００ｐｐｍ、及び昇温速度を毎
分１．５℃とした条件以外は、実施例１と同様に実施し
た。但し、反応時間は５０分であった。Example 2 Preparation of PVC was carried out in the same manner as in Example 1. The preparation of CPVC is as shown in Table 1,
Methyl isobutyl ketone peroxide (1
(0 hour half-life temperature = 105 ° C.), and the same procedure as in Example 1 was carried out, except that the added amount was 300 ppm in terms of PVC (based on weight), and the heating rate was 1.5 ° C./min. However, the reaction time was 50 minutes.
【００９０】（実施例３）ＰＶＣの調製は、実施例１と
同様に実施した。ＣＰＶＣの調製は、表１に示す通り実
施した。反応は水銀ランプにより反応器内を紫外線で照
射して塩素化反応を行った。触媒の添加量はＰＶＣ（重
量対比）で５０ｐｐｍとし、塩素化反応温度、昇温速
度、昇温範囲を変更した以外は、実施例１と同様に実施
した。但し、反応時間は８５分であった。Example 3 Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 1. The reaction was performed by irradiating the inside of the reactor with ultraviolet rays using a mercury lamp to perform a chlorination reaction. The procedure was performed in the same manner as in Example 1 except that the amount of the catalyst added was 50 ppm in terms of PVC (based on weight), and the chlorination reaction temperature, the heating rate, and the heating range were changed. However, the reaction time was 85 minutes.
【００９１】（実施例４） 〔ＰＶＣの調製〕内容積１００リットルの重合器（耐圧
オートクレーブ）に脱イオン水５０ｋｇ、塩化ビニル単
量体に対して、平均ケン化度７６モル％及び重合度７０
０の部分ケン化ポリ酢酸ビニル７００ｐｐｍ、ポリオキ
シエチレンアルキルエーテル硫酸エステル塩１５０ｐｐ
ｍ並びにｔ−ブチルパーオキシネオデカノエート５００
ｐｐｍを投入した。次いで、重合器内を４５ｍｍＨｇま
で脱気した後、塩化ビニル単量体３３ｋｇを仕込み攪拌
を開始した。重合器を５７℃に昇温して重合を開始し、
重合反応終了までこの温度を保った。Example 4 [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water, an average saponification degree of 76 mol% and a polymerization degree of 70 with respect to a vinyl chloride monomer were used.
0, partially saponified polyvinyl acetate 700 ppm, polyoxyethylene alkyl ether sulfate 150 pp
m and t-butyl peroxy neodecanoate 500
ppm was input. Next, after degassing the inside of the polymerization vessel to 45 mmHg, 33 kg of a vinyl chloride monomer was charged and stirring was started. The polymerization was started by heating the polymerization vessel to 57 ° C,
This temperature was maintained until the end of the polymerization reaction.
【００９２】重合転化率が９０重量％になった時点で反
応を終了し、重合器内の未反応単量体を回収した後、重
合体をスラリー状で系外へ取り出し、脱水乾燥してＰＶ
Ｃを得た。得られたＰＶＣのＢＥＴ比表面積値は１．４
ｍ2 ／ｇであった。また、スキン層の存在程度を示すＥ
ＳＣＡ分析値は、０．６５であった。ＣＰＶＣの調製
は、表１に示す通り、実施例１と同様に実施した。When the polymerization conversion reached 90% by weight, the reaction was terminated. After the unreacted monomer in the polymerization vessel was recovered, the polymer was taken out of the system in the form of a slurry, dehydrated and dried, and dried.
C was obtained. The BET specific surface area value of the obtained PVC is 1.4.
m 2 / g. In addition, E indicating the existence degree of the skin layer
The SCA analysis value was 0.65. Preparation of CPVC was carried out in the same manner as in Example 1, as shown in Table 1.
【００９３】（実施例５） 〔ＰＶＣの調製〕内容積１００リットルの重合器（耐圧
オートクレーブ）に脱イオン水５０ｋｇ、塩化ビニル単
量体に対して、平均ケン化度７２モル％及び重合度７５
０の部分ケン化ポリ酢酸ビニル１，２００ｐｐｍ、ｔ−
ブチルパーオキシネオデカノエート５５０ｐｐｍを投入
した。次いで、重合器内を４５ｍｍＨｇまで脱気した
後、塩化ビニル単量体３３ｋｇを仕込み攪拌を開始し
た。重合器を５７℃に昇温して重合を開始し、重合反応
終了までこの温度を保った。(Example 5) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water, an average saponification degree of 72 mol% and a polymerization degree of 75 with respect to a vinyl chloride monomer were used.
1,200 ppm of partially saponified polyvinyl acetate of 0, t-
550 ppm of butyl peroxyneodecanoate were charged. Next, after degassing the inside of the polymerization vessel to 45 mmHg, 33 kg of a vinyl chloride monomer was charged and stirring was started. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C., and this temperature was maintained until the polymerization reaction was completed.
【００９４】重合転化率が９０重量％になった時点で反
応を終了し、重合器内の未反応単量体を回収した後、重
合体をスラリー状で系外へ取り出し、脱水乾燥してＰＶ
Ｃを得た。得られたＰＶＣのＢＥＴ比表面積値は０．７
ｍ2 ／ｇであった。また、スキン層の存在程度を示すＥ
ＳＣＡ分析値は、０．２であった。When the polymerization conversion reached 90% by weight, the reaction was terminated. After the unreacted monomer in the polymerization vessel was recovered, the polymer was taken out of the system in the form of a slurry, dehydrated and dried to remove PVD.
C was obtained. The BET specific surface area value of the obtained PVC is 0.7
m 2 / g. In addition, E indicating the existence degree of the skin layer
The SCA analysis value was 0.2.
【００９５】ＣＰＶＣの調製は、表１に示す通り、触媒
としてメチルイソブチルケトンパーオキサイド（１０時
間半減期温度＝１０５℃）を使用し、添加量としてＰＶ
Ｃ（重量対比）で６００ｐｐｍ、及び昇温速度を毎分
２．５℃とした条件以外は、実施例１と同様に実施し
た。但し、反応時間は４５分であった。As shown in Table 1, CPVC was prepared by using methyl isobutyl ketone peroxide (10-hour half-life temperature = 105 ° C.) as a catalyst and adding PV
Example 1 was carried out in the same manner as in Example 1, except that C (weight ratio) was 600 ppm, and the temperature was raised at a rate of 2.5 ° C./min. However, the reaction time was 45 minutes.
【００９６】（比較例１、２）ＰＶＣの調製は、実施例
１と同様に実施した。ＣＰＶＣの調製は、表２に示す通
り実施した。実施例１からの主たる変更点は塩素化反応
温度をそれぞれ７０℃と１１０℃の定温で実施したこと
である。(Comparative Examples 1 and 2) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 2. The main difference from Example 1 is that the chlorination reaction was carried out at a constant temperature of 70 ° C. and 110 ° C., respectively.
【００９７】（比較例３）ＰＶＣの調製は、実施例１と
同様に実施した。ＣＰＶＣの調製は、塩素化反応開始を
３０℃として、塩素含有率が５７重量％の時点から昇温
を開始し、最終反応温度を１５０℃とした以外は表２に
示す通り実施した。(Comparative Example 3) Preparation of PVC was carried out in the same manner as in Example 1. The preparation of CPVC was carried out as shown in Table 2 except that the start of the chlorination reaction was 30 ° C., the temperature was raised from the time when the chlorine content was 57% by weight, and the final reaction temperature was 150 ° C.
【００９８】（比較例４）ＰＶＣの調製は、実施例１と
同様に実施した。ＣＰＶＣの調製は、表２に示す通り実
施した。触媒量を増量し、昇温速度を速めて、塩素化速
度を速めた。(Comparative Example 4) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 2. The amount of catalyst was increased, the rate of temperature rise was increased, and the rate of chlorination was increased.
【００９９】（比較例５）ＰＶＣの調製は、実施例５と
同様に実施した。ＣＰＶＣの調製は、表２に示す通り実
施した。触媒を使用せず、昇温速度を毎分０．２℃で実
施した。(Comparative Example 5) Preparation of PVC was carried out in the same manner as in Example 5. Preparation of CPVC was performed as shown in Table 2. The temperature was raised at a rate of 0.2 ° C./min without using a catalyst.
【０１００】上記実施例１〜５、比較例１〜５で得られ
たＣＰＶＣにつき、下記の性能評価を行い、その結果を
表１、２に示した。The following performance evaluation was performed on the CPVC obtained in Examples 1 to 5 and Comparative Examples 1 to 5, and the results are shown in Tables 1 and 2.
【０１０１】[0101]
【表１】 [Table 1]
【０１０２】[0102]
【表２】 [Table 2]
【０１０３】尚、表１、２中塩素化反応触媒の物質名は
以下の通りである。 略号Ａ：メチルイソブチルケトンパーオキサイド。The names of the chlorination catalysts in Tables 1 and 2 are as follows. Abbreviation A: methyl isobutyl ketone peroxide.
【０１０４】（実施例６）ＰＶＣの調製は、実施例１と
同様に実施した。(Example 6) Preparation of PVC was carried out in the same manner as in Example 1.
【０１０５】〔ＣＰＶＣの調製〕内容積２５０リットル
のチタン製耐圧反応器に脱イオン水６０ｋｇ〔対樹脂量
比＝２〕と上記で得たＰＶＣ３０ｋｇ〔これを１とす
る〕とを入れ、攪拌してＰＶＣを水中に分散させ、その
後反応器内に窒素ガスを吹き込み、器内を窒素ガスで置
換した。次に、反応器内に気体塩素を導入した後、反応
器を１２０℃まで昇温した。その後塩素化反応触媒とし
て、過酸化水素をＰＶＣ（重量対比）で１００ｐｐｍ一
括投入し塩素化反応を開始した。塩素化反応は熱エネル
ギーだけとして反応を継続し、器内の塩酸濃度を測定し
て、塩素化反応の進行状況を確認しながら塩素化反応を
続け、生成したＣＰＶＣの塩素含有率が６９．０重量％
に達した時点で、器内に窒素ガスを吹き込んで未反応塩
素を除去した後、毎分１．０℃で６５℃になるまで冷却
した。[Preparation of CPVC] 60 kg of deionized water [resin ratio to resin = 2] and 30 kg of PVC obtained above (referred to as 1) were placed in a 250 liter titanium pressure-resistant reactor and stirred. Then, PVC was dispersed in water, and then nitrogen gas was blown into the reactor to replace the inside of the reactor with nitrogen gas. Next, after introducing gaseous chlorine into the reactor, the reactor was heated to 120 ° C. Thereafter, as a chlorination reaction catalyst, 100 ppm of hydrogen peroxide was added at a time by PVC (based on weight) to start a chlorination reaction. The chlorination reaction is continued by using only heat energy, the concentration of hydrochloric acid in the vessel is measured, and the chlorination reaction is continued while confirming the progress of the chlorination reaction. The chlorine content of the generated CPVC is 69.0. weight%
When the temperature reached, the nitrogen gas was blown into the vessel to remove unreacted chlorine, followed by cooling at 1.0 ° C per minute to 65 ° C.
【０１０６】得られた樹脂を水酸化ナトリウムで中和し
た後、水で洗浄し脱水、乾燥して粉末状のＣＰＶＣを得
た。得られたＣＰＶＣの塩素含有率は、６９．０重量％
であった。The obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC was 69.0% by weight.
Met.
【０１０７】（実施例７〜９）ＰＶＣの調製は、実施例
１と同様に実施した。ＣＰＶＣの調製は、表３に示す通
り実施した。(Examples 7 to 9) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 3.
【０１０８】（実施例１０）ＰＶＣの調製は、実施例４
と同様に実施した。ＣＰＶＣの調製は、表３に示す通り
実施した。Example 10 Preparation of PVC was performed according to Example 4.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 3.
【０１０９】（実施例１１）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、表３に示す通り
実施した。Example 11 Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 3.
【０１１０】（比較例６〜１０）ＰＶＣの調製は、実施
例１と同様に実施した。ＣＰＶＣの調製は、表４に示す
通り実施した。実施例６からの主たる変更点は比較例６
は、冷却速度を速くしたことである。比較例７は、冷却
速度を遅くしたことである。比較例８は、冷却終了時の
温度を８０℃としたことである。比較例９は、塩素化反
応温度を１００℃としたことである。比較例１０は、塩
素化反応温度を１５０℃としたことである。(Comparative Examples 6 to 10) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 4. The main change from Example 6 is Comparative Example 6.
Means that the cooling rate was increased. Comparative Example 7 is that the cooling rate was reduced. Comparative Example 8 is that the temperature at the end of cooling was 80 ° C. Comparative Example 9 is that the chlorination reaction temperature was 100 ° C. Comparative Example 10 is that the chlorination reaction temperature was 150 ° C.
【０１１１】（比較例１１）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、比較例６と同様
に実施した。(Comparative Example 11) Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed in the same manner as in Comparative Example 6.
【０１１２】上記実施例６〜１１、比較例６〜１１で得
られたＣＰＶＣにつき、下記の性能評価を行い、その結
果を表３、４に示した。The following performance evaluations were performed on the CPVC obtained in Examples 6 to 11 and Comparative Examples 6 to 11, and the results are shown in Tables 3 and 4.
【０１１３】[0113]
【表３】 [Table 3]
【０１１４】[0114]
【表４】 [Table 4]
【０１１５】尚、表３、４中塩素化反応触媒の物質名は
以下の通りである。 略号Ａ：メチルイソブチルケトンパーオキサイド、Ｂ：
ジ−ｔ−ブチルパーオキサイド。The names of the chlorination catalysts in Tables 3 and 4 are as follows. Abbreviations A: methyl isobutyl ketone peroxide, B:
Di-t-butyl peroxide.
【０１１６】（実施例１２）ＰＶＣの調製は、実施例１
と同様に実施した。(Example 12) Preparation of PVC was performed in the same manner as in Example 1.
Was performed in the same manner as described above.
【０１１７】〔ＣＰＶＣの調製〕内容積２５０リットル
のチタン製耐圧反応器に脱イオン水６０ｋｇ〔対樹脂量
比＝２〕と上記で得たＰＶＣ３０ｋｇ〔これを１とす
る〕とを入れ、攪拌してＰＶＣを水中に分散させ、その
後反応器内に窒素ガスを吹き込み、器内を窒素ガスで置
換した。次に、反応器内に気体塩素を導入した後、反応
器を１２０℃まで昇温した。その後塩素化反応触媒とし
て、過酸化水素をＰＶＣ（重量対比）で５０ｐｐｍ一括
投入し塩素化反応を開始した。塩素化反応は熱エネルギ
ーだけとして反応を継続し、器内の塩酸濃度を測定し
て、塩素化反応の進行状況を確認しながら塩素化反応を
続け、生成したＣＰＶＣの塩素含有率が６４．５重量％
に達した時点で、第一塩素化反応を終了させた。反応時
間は３０分であった。[Preparation of CPVC] 60 kg of deionized water [ratio to resin amount = 2] and 30 kg of PVC obtained above (referred to as 1) were placed in a 250 liter internal pressure resistant titanium reactor and stirred. Then, PVC was dispersed in water, and then nitrogen gas was blown into the reactor to replace the inside of the reactor with nitrogen gas. Next, after introducing gaseous chlorine into the reactor, the reactor was heated to 120 ° C. Thereafter, as a chlorination reaction catalyst, 50 ppm of hydrogen peroxide was added at a time by PVC (based on weight) to start the chlorination reaction. The chlorination reaction is continued by using only heat energy, the concentration of hydrochloric acid in the vessel is measured, and the chlorination reaction is continued while checking the progress of the chlorination reaction. The chlorine content of the generated CPVC is 64.5. weight%
, The first chlorination reaction was terminated. The reaction time was 30 minutes.
【０１１８】反応器をジャケット冷却にて、毎分１℃の
速度で８０℃まで冷却し、その温度に保持しつつ、過酸
化水素を２０ｐｐｍ追加し、第二塩素化反応を開始し
た。反応時間は５０分で、塩素含有率は５．５重量％上
昇し７０．０重量％となった。器内に窒素ガスを吹き込
んで未反応塩素を除去し、得られた樹脂を水酸化ナトリ
ウムで中和した後、水で洗浄し脱水、乾燥して粉末状の
ＣＰＶＣを得た。得られたＣＰＶＣの塩素含有率は、７
０．０重量％であった。The reactor was cooled to 80 ° C. at a rate of 1 ° C. per minute by jacket cooling, and while maintaining the temperature, 20 ppm of hydrogen peroxide was added to start the second chlorination reaction. The reaction time was 50 minutes, and the chlorine content increased by 5.5% by weight to 70.0% by weight. Unreacted chlorine was removed by blowing nitrogen gas into the vessel, and the obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC is 7
It was 0.0% by weight.
【０１１９】（実施例１３〜１５）ＰＶＣの調製は、実
施例１と同様に実施した。ＣＰＶＣの調製は、表５に示
す通り実施した。(Examples 13 to 15) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 5.
【０１２０】（実施例１６）ＰＶＣの調製は、実施例４
と同様に実施した。ＣＰＶＣの調製は、表５に示す通り
実施した。Example 16 Preparation of PVC was performed according to Example 4.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 5.
【０１２１】（実施例１７）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、表５に示す通り
実施した。(Example 17) Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 5.
【０１２２】（比較例１２〜１６）ＰＶＣの調製は、実
施例１と同様に実施した。ＣＰＶＣの調製は、表６、７
に示す通り実施した。(Comparative Examples 12 to 16) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC is described in Tables 6, 7
Was carried out as shown in FIG.
【０１２３】（比較例１７）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、表７に示す通り
実施した。(Comparative Example 17) Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 7.
【０１２４】（比較例１８）ＰＶＣの調製は、実施例１
と同様に実施した。ＣＰＶＣの調製は、表７に示す通
り、冷却工程を実施せず、一段塩素化反応で実施したこ
とである。(Comparative Example 18) Preparation of PVC was performed in the same manner as in Example 1.
Was performed in the same manner as described above. As shown in Table 7, the preparation of CPVC was performed in a single-stage chlorination reaction without performing a cooling step.
【０１２５】上記実施例１２〜１７、比較例１２〜１８
で得られたＣＰＶＣにつき、下記の性能評価を行い、そ
の結果を表５、６及び７に示した。Examples 12 to 17 and Comparative Examples 12 to 18
The following performance evaluations were performed on the CPVC obtained in Table 2, and the results are shown in Tables 5, 6, and 7.
【０１２６】[0126]
【表５】 [Table 5]
【０１２７】[0127]
【表６】 [Table 6]
【０１２８】[0128]
【表７】 [Table 7]
【０１２９】尚、表５、６及び７中塩素化反応触媒の物
質名は以下の通りである。 略号Ａ：メチルイソブチルケトンパーオキサイド、Ｂ：
ジ−ｔ−ブチルパーオキサイド、Ｃ：ベンゾイルパーオ
キサイド。The substance names of the chlorination catalysts in Tables 5, 6 and 7 are as follows. Abbreviations A: methyl isobutyl ketone peroxide, B:
Di-t-butyl peroxide, C: benzoyl peroxide.
【０１３０】（実施例１８）ＰＶＣの調製は、実施例１
と同様に実施した。Example 18 Preparation of PVC was performed according to Example 1.
Was performed in the same manner as described above.
【０１３１】〔ＣＰＶＣの調製〕内容積２５０リットル
のチタン製耐圧反応器に脱イオン水６０ｋｇ〔対樹脂量
比＝２〕と上記で得たＰＶＣ３０ｋｇ〔これを１とす
る〕とを入れ、攪拌してＰＶＣを水中に分散させ、その
後反応器内に窒素ガスを吹き込み、器内を窒素ガスで置
換した。攪拌しながら、反応器を１３０℃まで昇温し、
３０分間保持した後、毎分１０℃で冷却した。７０℃ま
で冷却した時点で、反応器内に気体塩素を導入した。そ
の後塩素化反応触媒として、過酸化水素をＰＶＣ（重量
対比）で１００ｐｐｍ一括投入し塩素化反応を開始し
た。塩素化反応は、水銀ランプにより紫外線照射を行
い、光エネルギーによる励起エネルギーでラジカル生成
を促進させた。器内の塩酸濃度を測定して、塩素化反応
の進行状況を確認しながら塩素化反応を続け、生成した
ＣＰＶＣの塩素含有率が６９．０重量％に達した時点
で、塩素化反応を終了させた。反応時間は１６０分であ
った。[Preparation of CPVC] 60 kg of deionized water [resin ratio to resin = 2] and 30 kg of PVC obtained above (referred to as 1) are placed in a 250 liter internal pressure resistant titanium reactor and stirred. Then, PVC was dispersed in water, and then nitrogen gas was blown into the reactor to replace the inside of the reactor with nitrogen gas. While stirring, heat the reactor to 130 ° C.
After holding for 30 minutes, it was cooled at 10 ° C. per minute. Upon cooling to 70 ° C., gaseous chlorine was introduced into the reactor. Thereafter, as a chlorination reaction catalyst, 100 ppm of hydrogen peroxide was added at a time by PVC (based on weight) to start a chlorination reaction. In the chlorination reaction, ultraviolet irradiation was performed by a mercury lamp, and radical generation was promoted by excitation energy by light energy. The chlorination reaction is continued while measuring the hydrochloric acid concentration in the vessel and checking the progress of the chlorination reaction, and the chlorination reaction is terminated when the chlorine content of the generated CPVC reaches 69.0% by weight. I let it. The reaction time was 160 minutes.
【０１３２】器内に窒素ガスを吹き込んで未反応塩素を
除去し、得られた樹脂を水酸化ナトリウムで中和した
後、水で洗浄し脱水、乾燥して粉末状のＣＰＶＣを得
た。得られたＣＰＶＣの塩素含有率は、６９．０重量％
であった。Unreacted chlorine was removed by blowing nitrogen gas into the vessel, and the obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC was 69.0% by weight.
Met.
【０１３３】（実施例１９〜２１）ＰＶＣの調製は、実
施例１と同様に実施した。ＣＰＶＣの調製は、表８に示
す通り実施した。(Examples 19 to 21) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed as shown in Table 8.
【０１３４】（実施例２２）ＰＶＣの調製は、実施例４
と同様に実施した。ＣＰＶＣの調製は、表８に示す通り
実施した。Example 22 Preparation of PVC was performed according to Example 4.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 8.
【０１３５】（実施例２３）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、表８に示す通り
実施した。Example 23 Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 8.
【０１３６】（比較例１９〜２３）ＰＶＣの調製は、実
施例１と同様に実施した。ＣＰＶＣの調製は、表９、１
０に示す通り実施した。(Comparative Examples 19 to 23) Preparation of PVC was carried out in the same manner as in Example 1. The preparation of CPVC is described in Tables 9, 1
Performed as shown in FIG.
【０１３７】（比較例２４）ＰＶＣの調製は、実施例５
と同様に実施した。ＣＰＶＣの調製は、表１０に示す通
り実施した。(Comparative Example 24) Preparation of PVC was performed according to Example 5.
Was performed in the same manner as described above. Preparation of CPVC was performed as shown in Table 10.
【０１３８】（比較例２５）ＰＶＣの調製は、実施例１
と同様に実施した。ＣＰＶＣの調製は、表１０に示す通
り、冷却工程を実施せずに、塩素化反応を実施したこと
である。(Comparative Example 25) Preparation of PVC was performed in the same manner as in Example 1.
Was performed in the same manner as described above. As shown in Table 10, the preparation of CPVC was that the chlorination reaction was performed without performing the cooling step.
【０１３９】上記実施例１８〜２３、比較例１９〜２５
で得られたＣＰＶＣにつき、下記の性能評価を行い、そ
の結果を表８、９及び１０に示した。Examples 18 to 23 and Comparative Examples 19 to 25
The following performance evaluation was carried out on the CPVC obtained in Table 2, and the results are shown in Tables 8, 9 and 10.
【０１４０】[0140]
【表８】 [Table 8]
【０１４１】[0141]
【表９】 [Table 9]
【０１４２】[0142]
【表１０】 [Table 10]
【０１４３】尚、表８、９及び１０中塩素化反応触媒の
物質名は以下の通りである。略号Ｃ：ベンゾイルパーオ
キサイド、Ｄ：α−クミルパーオキシネオデカノエ ート。The substance names of the chlorination catalysts in Tables 8, 9 and 10 are as follows. Abbreviations C: benzoyl peroxide, D: α-cumylperoxy neodecanoate.
【０１４４】〔評価方法〕 （１）ＢＥＴ比表面積値の測定 試料管に測定サンプル約２ｇを投入し、前処理として７
０℃で３時間サンプルを真空脱気した後、サンプル重量
を正確に測定した。前処理の終了したサンプルを測定部
（４０℃恒温槽）に取り付けて測定を開始した。測定終
了後、吸着等温線の吸着側のデータからＢＥＴプロット
を行い、比表面積を算出した。なお、測定装置として比
表面測定装置「ＢＥＬＳＯＲＰ ２８ＳＡ」（日本ベル
社製）を使用し、測定ガスとして窒素ガスを使用した。[Evaluation method] (1) Measurement of BET specific surface area About 2 g of a measurement sample was put into a sample tube, and 7
After degassing the sample for 3 hours at 0 ° C., the sample weight was measured accurately. The sample after the pretreatment was attached to a measuring section (40 ° C. constant temperature bath) to start measurement. After the measurement, a BET plot was performed from the data on the adsorption side of the adsorption isotherm to calculate the specific surface area. Note that a specific surface measurement device “BELSORP 28SA” (manufactured by Bell Japan Co., Ltd.) was used as a measurement device, and nitrogen gas was used as a measurement gas.
【０１４５】（２）ＥＳＣＡ分析 ＰＶＣ粒子の表面をＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐ
ｅｃｔｒｏｓｃｏｐｙｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎ
ａｌｙｓｉｓ：電子分光化学分析）でスキャンし、Ｃ1S
（炭素）、Ｃｌ1S（塩素）、Ｏ1S（酸素）の各ピーク面
積より塩素量を基準に粒子表面の塩化ビニル樹脂成分を
定量分析した。 ・使用機器：日本電子社製「ＪＰＳ−９０ＦＸ」 ・使用条件：Ｘ線源（Ｍｇ Ｋα線）、１２ｋＶ−１５
ｍＡ ・スキャン速度：２００ｍｓ／０．１ｅＶ／ｓｃａｎ ・パスエネルギー：３０ｅＶ(2) ESCA Analysis The surface of the PVC particles was analyzed by ESCA (Electron Sp
electroscopyfor Chemical An
analysis (electron spectrochemical analysis) and C 1S
From the peak areas of (carbon), Cl 1S (chlorine), and O 1S (oxygen), the vinyl chloride resin component on the particle surface was quantitatively analyzed based on the amount of chlorine. -Equipment used: "JPS-90FX" manufactured by JEOL Ltd.-Usage conditions: X-ray source (Mg Kα ray), 12kV-15
mA Scan speed: 200 ms / 0.1 eV / scan Path energy: 30 eV
【０１４６】（３）加工性（ゲル化温度の測定） Ｈａａｋｅ社製プラストミル「レオコード９０」を使用
して、下記樹脂組成物５５ｇを、回転数４０ｒｐｍで、
温度を１５０℃から毎分５℃の昇温速度で上昇させなが
ら混練し混練トルクが最大になる時の温度を測定した。
なお、樹脂組成物としては、ＣＰＶＣ１００重量部に対
して、三塩基性硫酸鉛３重量部、二塩基性ステアリン酸
鉛１重量部及びＭＢＳ樹脂１０重量部からなるものを使
用した。(3) Processability (Measurement of Gelation Temperature) Using a Plastomill “Rheocord 90” manufactured by Haake, 55 g of the following resin composition was applied at a rotation speed of 40 rpm.
Kneading was performed while increasing the temperature from 150 ° C. at a rate of 5 ° C./min, and the temperature at which the kneading torque was maximized was measured.
The resin composition used was composed of 3 parts by weight of tribasic lead sulfate, 1 part by weight of dibasic lead stearate, and 10 parts by weight of MBS resin based on 100 parts by weight of CPVC.
【０１４７】（４）熱安定性試験 上記樹脂組成物を、８インチロール２本からなる混練機
に供給してロール表面温度２０５℃で混練し、混練物を
ロールに巻き付けてから３０秒毎に巻き付いたＣＰＶＣ
樹脂シートを切り返しながら、３分毎に少量のシートを
切り出して、シートの着色度を比較し、黒褐色に変わる
時間で熱安定性を判定した。(4) Thermal Stability Test The above resin composition was supplied to a kneader comprising two 8-inch rolls and kneaded at a roll surface temperature of 205 ° C., and the kneaded material was wound around a roll every 30 seconds. Wound CPVC
While turning over the resin sheet, a small amount of the sheet was cut out every three minutes, the degree of coloring of the sheet was compared, and the thermal stability was determined by the time when the sheet turned black-brown.
【０１４８】（５）ビカット軟化温度 上記熱安定性試験で作製した５ｍｍ厚のＣＰＶＣシート
を、１５ｍｍ角に切り出して測定用サンプルとし、Ｊ１
Ｓ Ｋ ７２０６（重り１．０ｋｇｆ）に準拠して測定
した。(5) Vicat softening temperature A 5 mm thick CPVC sheet prepared in the above thermal stability test was cut into 15 mm squares to prepare a sample for measurement.
It measured based on SK7206 (weight 1.0kgf).
【０１４９】[0149]
【発明の効果】本発明によって得られるＣＰＶＣは、上
述の樹脂構造からなるので、ゲル化性能及び耐熱性（熱
変形温度）に優れている。Since the CPVC obtained by the present invention has the above-mentioned resin structure, it has excellent gelation performance and heat resistance (heat deformation temperature).
Claims (6)
化塩化ビニル系樹脂の製造方法であって、塩素化反応に
おいて、塩素含有率６０〜７０重量％の範囲で、塩素化
反応温度〔Ｔ℃〕と逐次塩素化されてなる塩素化塩化ビ
ニル系樹脂の塩素含有率〔Ｐ重量％〕との関係が、式１
を満たした条件で、塩素化反応を行うことを特徴とする
塩素化塩化ビニル系樹脂の製造方法。 式１ 〔５．８Ｐ−２８７〕≦〔Ｔ〕≦〔５．８Ｐ−２６２〕 1. A method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, wherein the chlorination reaction is carried out at a chlorine content of 60 to 70% by weight and a chlorination reaction temperature [T ° C] and the chlorine content [P% by weight] of the chlorinated vinyl chloride resin obtained by successive chlorination is expressed by the following equation (1).
A method for producing a chlorinated vinyl chloride-based resin, wherein the chlorination reaction is performed under conditions satisfying the following conditions. Formula 1 [5.8P-287] ≦ [T] ≦ [5.8P-262]
応を行うことを特徴とする請求項１記載の塩素化塩化ビ
ニル系樹脂の製造方法。2. The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the chlorination reaction is carried out at a rate of 0.3 to 3 ° C. per minute.
化塩化ビニル系樹脂の製造方法であって、塩素化反応に
おいて、１１０〜１４０℃で塩素化反応後、６０〜７０
℃に達する迄、毎分０．２〜３℃で冷却することを特徴
とする塩素化塩化ビニル系樹脂の製造方法。3. A method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, wherein the chlorination reaction is carried out at 110 to 140 ° C., and then the chlorination reaction is carried out at 60 to 70 ° C.
A method for producing a chlorinated vinyl chloride-based resin, wherein the resin is cooled at a rate of 0.2 to 3 ° C. per minute until the temperature reaches the temperature.
化塩化ビニル系樹脂の製造方法であって、塩素化反応に
おいて、１１０〜１４０℃〔第一反応温度〕で塩素化反
応後、毎分０．５〜３℃で冷却した後、第一反応温度よ
り３０〜５０℃低い温度〔第二反応温度〕でさらに塩素
化反応を継続し、第一反応温度での反応完了時点より塩
素含有率を３〜８重量％高くなるまで塩素化反応を行う
ことを特徴とする塩素化塩化ビニル系樹脂の製造方法。4. A method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, wherein the chlorination reaction is carried out at 110 to 140 ° C. [first reaction temperature], and then every minute. After cooling at 0.5 to 3 ° C., the chlorination reaction is further continued at a temperature 30 to 50 ° C. lower than the first reaction temperature (second reaction temperature). Wherein the chlorination reaction is carried out until the amount of chlorinated vinyl chloride resin increases by 3 to 8% by weight.
化塩化ビニル系樹脂の製造方法であって、塩化ビニル系
樹脂の水懸濁液を１１０〜１４０℃に加熱した後、毎分
３〜１５℃で冷却して６０〜９０℃となし、気体塩素又
は液体塩素の存在下で、光塩素化又は熱塩素化により、
塩素化反応を行うことを特徴とする塩素化塩化ビニル系
樹脂の製造方法。5. A method for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin, comprising heating an aqueous suspension of the vinyl chloride resin to 110 to 140 ° C., Cool at 15 ° C. to 60-90 ° C., in the presence of gaseous chlorine or liquid chlorine, by photochlorination or hot chlorination,
A method for producing a chlorinated vinyl chloride resin, which comprises performing a chlorination reaction.
１．３〜８ｍ2 ／ｇであり、ＥＳＣＡ分析（電子分光化
学分析）による粒子表面分析において、炭素元素と塩素
元素との１Ｓ結合エネルギー値（ｅＶ）におけるピーク
比（塩素元素ピーク×２／炭素元素ピーク）が０．６を
超えるものであることを特徴とする請求項１〜５記載の
塩素化塩化ビニル系樹脂の製造方法。6. A vinyl chloride resin having a BET specific surface area value of 1.3 to 8 m 2 / g, and a 1S bond energy between a carbon element and a chlorine element in particle surface analysis by ESCA analysis (electron spectrochemical analysis). The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein a peak ratio (chlorine element peak × 2 / carbon element peak) at a value (eV) exceeds 0.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6882498A JPH11263808A (en) | 1998-03-18 | 1998-03-18 | Preparation of chlorinated vinyl chloride-based resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6882498A JPH11263808A (en) | 1998-03-18 | 1998-03-18 | Preparation of chlorinated vinyl chloride-based resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11263808A true JPH11263808A (en) | 1999-09-28 |
Family
ID=13384856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6882498A Pending JPH11263808A (en) | 1998-03-18 | 1998-03-18 | Preparation of chlorinated vinyl chloride-based resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11263808A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006328165A (en) * | 2005-05-25 | 2006-12-07 | Sekisui Chem Co Ltd | Method for producing chlorinated polyvinyl chloride-based resin |
| WO2013081133A1 (en) * | 2011-12-02 | 2013-06-06 | 徳山積水工業株式会社 | Method for producing chlorinated vinyl chloride-based resin |
-
1998
- 1998-03-18 JP JP6882498A patent/JPH11263808A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006328165A (en) * | 2005-05-25 | 2006-12-07 | Sekisui Chem Co Ltd | Method for producing chlorinated polyvinyl chloride-based resin |
| JP4728701B2 (en) * | 2005-05-25 | 2011-07-20 | 積水化学工業株式会社 | Method for producing chlorinated vinyl chloride resin |
| WO2013081133A1 (en) * | 2011-12-02 | 2013-06-06 | 徳山積水工業株式会社 | Method for producing chlorinated vinyl chloride-based resin |
| CN104011091A (en) * | 2011-12-02 | 2014-08-27 | 德山积水工业株式会社 | Method for producing chlorinated vinyl chloride-based resin |
| JPWO2013081133A1 (en) * | 2011-12-02 | 2015-04-27 | 徳山積水工業株式会社 | Method for producing chlorinated vinyl chloride resin |
| US9346901B2 (en) | 2011-12-02 | 2016-05-24 | Tokuyama Sekisui Co., ;Td. | Method for producing chlorinated vinyl chloride resin |
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