JPS6289703A - Production of chlorinated vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain the titled high-purity resin industrially advantageously, by polymerizing a vinyl chloride monomer in the absence of an emulsifying agent by the use of a water-soluble persulfate as a polymerization initiator, adding a slightly water-soluble inorganic phosphate in the middle of the polymerization and chlorinating the prepared resin. CONSTITUTION:Polymerization of a vinyl chloride monomer or a mixture of it and another monomer (e.g., ethylene, vinyl acetate, etc.,) copolymerizable with the monomer is started in an aqueous medium (e.g., solution of potassium persulfate in water, etc.,) by the use of a water-soluble persulfate (e.g., potassium persulfate, ammonium persulfate, etc.,) in the absence of an emulsifying agent. In the middle of the polymerization, preferably at a period of 5-50wt% polymerization conversion ratio, a slightly water-soluble inorganic phosphate (e.g., Ca phosphate, Al phosphate, Mg phosphate, etc.,) is added to the polymerization system and the prepared vinyl chloride resin is chlorinated. EFFECT:The aimed resin having a low impurity content free from a dispersant film on the surface of particles is produced in a state to readily remove heat and in a small amount of deposit scale on a polymerizer.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は塩素化塩化ビニル系樹脂の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing chlorinated vinyl chloride resin.

さらに詳しくは、塩素化塩化ビニル系樹脂を製造するに
あたり、その前工程となる塩化ビニル系樹脂の製造を特
定の重合法で行ない、そののち常法に従うて塩素化して
塩素化塩化ビニル系樹脂を製造する方法に関する。More specifically, in producing chlorinated vinyl chloride resin, the pre-process of producing vinyl chloride resin is carried out using a specific polymerization method, and then chlorinated according to a conventional method to produce chlorinated vinyl chloride resin. Relating to a method of manufacturing.

［従来の技術・発明が解決しようとする問題点］塩化ビ
ニル系樹脂（以下、ＰｖＣという）の軟化温度を向上さ
せるという性質を有している塩素化塩化ビニル系樹脂（
以下、ｃｐｖｃという）は、ＰｖＣを後塩素化して製造
されている。[Prior art/problems to be solved by the invention] Chlorinated vinyl chloride resin (hereinafter referred to as PvC) has the property of improving the softening temperature of vinyl chloride resin (hereinafter referred to as PvC).
(hereinafter referred to as cpvc) is produced by post-chlorinating PvC.

ｃｐｖｃの原料樹脂としてのＰｖＣは、通常、部分鹸化
ポリビニルアルコール、メチルセルロース、ヒドロキシ
プロピルメチルセルロースなどの懸濁安定剤およびラウ
ロイルパーオキサイド、ジー２−エチルヘキシルパーオ
キシネオデカノエート、ｔ−ブチルパーオキシネオデカ
ノエート、α、α　−アゾビス−２，４−ジメチルバレ
ロニトリルなどの油溶性重合開始剤を使用した懸濁重合
法で重合されるのが一般的である。しかるに該懸濁重合
法でえられたＰｖＣは、通常、粒子表面が分散剤皮膜で
覆われているためにゲル化性、可塑剤吸収性などの点に
おいて、乳化重合法によるＰｖＣに劣ることは知られて
いる。PvC as a raw material resin for CPVC usually contains suspension stabilizers such as partially saponified polyvinyl alcohol, methyl cellulose, and hydroxypropyl methyl cellulose, and lauroyl peroxide, di-2-ethylhexyl peroxy neodecanoate, and t-butyl peroxy neodecanoate. Polymerization is generally carried out by a suspension polymerization method using an oil-soluble polymerization initiator such as noate, α, α-azobis-2,4-dimethylvaleronitrile. However, PvC obtained by the suspension polymerization method is usually inferior to PvC obtained by the emulsion polymerization method in terms of gelability, plasticizer absorption, etc. because the particle surface is usually covered with a dispersant film. Are known.

前記懸濁重合法でえられたＰｖＣを用いてｃｐｖｃを製
造すると、ゲル化性や初期着色性などの劣るＣＰＶＣＬ
かえられない。When CPVC is produced using PvC obtained by the suspension polymerization method, CPVCL has poor gelling properties and initial coloring properties.
I can't go back.

一方、乳化重合法でえられたＰＶＣは、基本粒子が極め
て小さく、ゲル化性、可塑剤吸収性が良く、加工性の点
では懸濁重合法によるＰＶＣより優れているが、塩析操
作を必要とし、塩析によりえられた重合物は微細で嵩比
重が小さく、また不純物の混入も大きく、熱安定性など
がわるいという欠点がある。On the other hand, PVC obtained by emulsion polymerization has extremely small basic particles, has good gelling properties and plasticizer absorption, and is superior to PVC obtained by suspension polymerization in terms of processability. The polymer obtained by salting out is fine and has a low bulk density, contains a large amount of impurities, and has poor thermal stability.

前記乳化重合法でえられたＰｖＣを用いてＣＰＶＣを製
造すると、ＰｖＣの不純物の混入による熱安定性などが
わるい、嵩比重か低いなどの問題がＣＰＶＣにものこる
上、ＰＶＣをうる際の塩析操作によるコストアップなど
がそのままＣＰＶＣのコストなどにも影響する。When CPVC is manufactured using PvC obtained by the emulsion polymerization method, problems such as poor thermal stability and low bulk specific gravity due to the contamination of PvC impurities arise in CPVC. The cost increase due to analysis operations directly affects the cost of CPVC.

したがって、懸濁重合法および乳化重合法の長所を兼ね
備えたＰｖＣｌすなわち不純物合釘Ｍ−が少なく、乳化
重合物のような基本粒子か凝集体をなし、懸濁重合法に
よるばあいのごとき粒子状の外観をＨし、該粒子状物の
表面には分散剤皮膜が存在せず、かつ塩析操作などを行
なわなくてもえられるＰｖＣを原料樹脂としたｃｐｖｃ
は、懸濁重合法や乳化重合法によるＰｖＣを原料樹脂と
したｃｐｖｃとは異なる優れた特徴をａし、しかも低コ
ストで製造しうると考えられる。Therefore, PvCl, which combines the advantages of the suspension polymerization method and the emulsion polymerization method, has less impurity dowel M-, and forms basic particles or aggregates like emulsion polymers, and particles like the suspension polymerization method. CPVC which has a H appearance, has no dispersant film on the surface of the particulate matter, and uses PvC as a raw material resin, which can be obtained without salting out operations etc.
It is thought that it has excellent characteristics different from CPVC, which uses PvC as a raw material resin by suspension polymerization or emulsion polymerization, and can be manufactured at low cost.

このような特徴を有するｃｐｖｃの原料樹脂の重合方法
として、特公昭４５−３０８３３号公報に乳化剤の不存
在下、水性媒体中、該媒体に可溶性の重合開始剤の存在
下で一次粒子（基本粒子）の凝集体よりなる球状ＰＶＣ
をうる方法（以下、ソープフリー（ｓｏａｐ−１’ｒｃ
ｃ）乳化重合法という）が開示されている。しかし、該
方法では基本粒子が凝集して球状粒子が生成する際に重
合系が不安定となり、除熱が困難であること、付着スケ
ール量が非常に多いことなどの欠点がある。As a method for polymerizing raw material resin for CPVC having such characteristics, Japanese Patent Publication No. 45-30833 discloses that primary particles (basic particles) are polymerized in an aqueous medium in the absence of an emulsifier in the presence of a polymerization initiator soluble in the medium. ) Spherical PVC consisting of aggregates of
How to get soap-free (soap-1'rc)
c) Emulsion polymerization method) is disclosed. However, this method has drawbacks such as the polymerization system becomes unstable when the basic particles aggregate to form spherical particles, heat removal is difficult, and the amount of attached scale is extremely large.

本発明はソープフリー乳化重合法の上記問題点、すなわ
ちソープフリー乳化重合法によるＰｖＣを用いたｃｐｖ
ｃの問題点を解決するためになされたものである。The present invention solves the above-mentioned problems of the soap-free emulsion polymerization method, that is, cpv using PvC by the soap-free emulsion polymerization method.
This was done to solve the problem of c.

［問題点を解決するための手段］ 本発明者らは重合系内の状態を透視しうる耐圧ガラス製
重合機を用いてソープフリー乳化重合法について鋭意研
究を重ねた結果、基本粒子が凝集し、重合系が不安定化
する前に水難溶性無機リン酸塩を添加すると、重合系の
流動状態を維持しながら球状粒子を生成させることがで
き、付着スケール量を減少させうることを見出した。[Means for Solving the Problems] The present inventors have conducted intensive research on the soap-free emulsion polymerization method using a pressure-resistant glass polymerization machine that allows the state inside the polymerization system to be seen through, and have found that the basic particles are agglomerated. discovered that by adding a poorly water-soluble inorganic phosphate before the polymerization system becomes unstable, it is possible to generate spherical particles while maintaining the fluidity of the polymerization system, and the amount of attached scale can be reduced.

本発明は前記知見に基づきなされたものであり、塩化ビ
ニル単量体またはこれと共重合しつる他の単量体との混
合物を水性媒体中で、水溶性過硫酸塩を重合開始剤とし
て乳化剤不存在下で重合を開始し、重合途中で水難溶性
無機リン酸塩を添加【７てえられる塩化ビニル系樹脂を
後塩素化することを特徴とする塩素化塩化ビニル系樹脂
の製造方法に関する。The present invention has been made based on the above findings, and consists of adding a vinyl chloride monomer or a mixture of vinyl chloride monomers and other monomers copolymerized with the vinyl chloride monomer to an emulsifying agent using a water-soluble persulfate as a polymerization initiator in an aqueous medium. This invention relates to a method for producing a chlorinated vinyl chloride resin, characterized in that polymerization is started in the absence of the vinyl chloride resin, and a poorly water-soluble inorganic phosphate is added during the polymerization.

［実施例］ 本発明に用いる塩化ビニル単量体と共重合しうる他の単
量体としては、たとえばエチレン、プロピレンなどのオ
レフィ、ン頌、酢酸ビニル、ステアリン酸ビニルなどの
ビニルエステル類、アクリル酸メチル、メタクリル酸メ
チルなとのアクリル酸エステル類、マレイン酸またはフ
マル酸などの酸のエステル類や無水物類、アクリロニト
リルなどのニトリル化合物類、塩化ビニリデンのごとき
ビニリデン化合物類なとかあげられる。[Example] Examples of other monomers that can be copolymerized with the vinyl chloride monomer used in the present invention include olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, and acrylics. Examples include acrylic acid esters such as methyl acid and methyl methacrylate, esters and anhydrides of acids such as maleic acid or fumaric acid, nitrile compounds such as acrylonitrile, and vinylidene compounds such as vinylidene chloride.

本発明においては塩化ビニル単量体またはこれと共重合
しうる他の単量体との混合物を水性媒体中で重合する際
に、乳化剤不存在下で水溶性過硫酸塩を重合開始剤とし
て重合が開始せしめられる。In the present invention, when vinyl chloride monomer or a mixture with other monomers copolymerizable with vinyl chloride monomer is polymerized in an aqueous medium, a water-soluble persulfate is used as a polymerization initiator in the absence of an emulsifier. is started.

前記水性媒体中とは、水に、重合開始剤である、たとえ
ば過硫酸カリウム、過硫酸アンモニウムなどの水溶性過
硫酸塩を加え、さらに要すればトリクロロエチレン、プ
ロピオンアルデヒド、ｎ−ペンタン、２−メルカプトエ
タノールなどの分子量調節剤、亜硫酸ナトリウム、亜硫
酸水素ナトリウムなどの還元剤などを加えた水性液のこ
とである。In the aqueous medium, a polymerization initiator such as a water-soluble persulfate such as potassium persulfate or ammonium persulfate is added to water, and if necessary, trichlorethylene, propionaldehyde, n-pentane, or 2-mercaptoethanol is added. It is an aqueous liquid to which molecular weight regulators such as sodium sulfite and reducing agents such as sodium sulfite and sodium bisulfite are added.

前記重合反応に使用される水溶性過硫酸塩、分子量調節
剤、還元剤などは最ＩＪに一括して水に添加してもよい
が、重合反応中、分割して添加してもよい。The water-soluble persulfate, molecular weight regulator, reducing agent, etc. used in the polymerization reaction may be added all at once to the water, or may be added in portions during the polymerization reaction.

前記水溶性過硫酸塩などの水に対する添加量は、生産性
、品質に対する影響などの点から最終的に単量体に対し
て水溶性過硫酸塩のばおいて通常０．０１〜１．０％（
重量９６、以下同様）、好ましくは０．０５〜０．２％
、分子は調節剤のばおいて通常０〜１０％、好ましくは
０〜５％、還元剤のばおいて通常θ〜０．５％、好まし
くは０．０１−０．１％である。The amount of the water-soluble persulfate added to water is usually 0.01 to 1.0 in terms of the final amount of water-soluble persulfate relative to the monomer, from the viewpoint of productivity, quality, etc. %(
weight 96, the same applies hereinafter), preferably 0.05 to 0.2%
In the case of regulators, the molecular weight is usually 0 to 10%, preferably 0 to 5%, and in the case of reducing agents, it is usually θ to 0.5%, preferably 0.01 to 0.1%.

塩化ビニル単量体またはこれと共重合しうる他の単量体
との混合物の水との比率は、生産性、ｍ合機での除熱な
どの点から最終的に水／単量体−１ｌｌ〜５／１が好ま
しく、ｌ／Ｌ〜３／ｌがさらに好ましい。なお塩化ビニ
ル単量体とこれと共重合しうる他の単量体との混合物を
用いるばあいの組成としては、全混合物中に塩化ビニル
単量体が７０％以上含まれていることが品質などの点か
ら好ましく、８５％以上であることがさらに好ましい。The ratio of vinyl chloride monomer or a mixture with other monomers copolymerizable with vinyl chloride monomer to water is determined from the viewpoint of productivity, heat removal in the mixer, etc. 1 liter to 5/1 is preferable, and 1/L to 3/L is more preferable. In addition, when using a mixture of vinyl chloride monomer and other monomers that can be copolymerized with it, the composition must contain 70% or more of vinyl chloride monomer in the entire mixture for quality reasons. It is preferable from this point of view, and more preferably 85% or more.

乳化剤不存在下で重合が進行するメカニズムについては
種々の説が提案されているが、水溶性過流酸塩が分解し
て生成した硫酸根ラジカル（・８０４−　）にモノマー
（Ｍ）が反応し、硫酸根を末端に有するオリゴマー（Ｍ
Ｍ−−ＭＳＯ４−）が乳化剤的機能をはだすものと考え
られる。したかって重合開始剤分解物を末端に白°する
オリゴマーが乳化剤的機能をはたさないときには、重合
が全く進行しないか、重合速度が非常に小さいものとな
るため、乳化剤不存在下で本発明に用いる重合開始剤と
して、水溶性過硫酸塩を用いることが必須である。Various theories have been proposed regarding the mechanism by which polymerization proceeds in the absence of an emulsifier, but one theory is that the monomer (M) reacts with the sulfate radical (・804-) generated by the decomposition of a water-soluble persulfate. , an oligomer with a sulfate group at the end (M
M--MSO4-) is thought to function as an emulsifier. Therefore, if the oligomer containing the decomposed product of the polymerization initiator does not function as an emulsifier, the polymerization will not proceed at all or the polymerization rate will be very low. It is essential to use a water-soluble persulfate as a polymerization initiator.

本発明においては重合途中で水難溶性無機リン酸塩が添
加される。In the present invention, a poorly water-soluble inorganic phosphate is added during polymerization.

前記水難溶性１！！（機リン酸塩としては、たとえばリ
ン酸のカルシウム塩、ストロンチウム塩、バリウム塩、
マグネシウム塩、アルミニウム塩、鉛塩などがあげられ
、これらのうちではリン酸カルシウムが重合安定性、品
質、コストなどの点から好ましい。Said poorly water soluble 1! ! (For example, phosphates include calcium salts, strontium salts, barium salts of phosphoric acid,
Examples include magnesium salts, aluminum salts, lead salts, etc. Among these, calcium phosphate is preferred from the viewpoint of polymerization stability, quality, cost, etc.

前記水難溶は無機リン酸塩の使用量にはとくに限定はな
いが、塩化ビニル単量体またはその混合物１００部（重
量部、以下同様）に対し０．０１〜１部使用するのが重
合安定性、品質なとの点から好ましく、０．０５〜０．
５部であるのがさらに好ましい。Although there is no particular limitation on the amount of the inorganic phosphate used as the poorly water-soluble salt, it is preferable to use 0.01 to 1 part per 100 parts (by weight, hereinafter the same) of the vinyl chloride monomer or mixture thereof to ensure polymerization stability. It is preferable from the point of view of performance and quality, and is 0.05 to 0.
More preferably, it is 5 parts.

水難溶性無機リン酸塩の添加は重合初期のラテックス状
のものが不安化する前に添加することが好ましく、重合
条件により異なるが、一般に重合転化率で５〜５０％、
さらには１０〜３０％の範囲である。該無機リン酸塩の
添加は１回だけに限られるものではなく、要すれば２回
以上でもよいが、最初の添加は上記重合転化率の範囲で
行なうことが好ましい。重合初期のラテックス状のもの
に凝集がおこり、不安定化したのちに該無機リン酸塩を
添加しても本発明の効果は少なく、逆に無機リン酸塩を
仕込時に添加すると基本粒子の凝集状態に影響をおよぼ
し、えられる球状粒子の粒子内空隙（ポロシティ−）が
小さくなる傾向が生ずる。It is preferable to add the poorly water-soluble inorganic phosphate before the latex becomes unstable at the initial stage of polymerization, and generally the polymerization conversion rate is 5 to 50%, although it varies depending on the polymerization conditions.
Furthermore, it is in the range of 10 to 30%. The addition of the inorganic phosphate salt is not limited to one time, and may be added two or more times if necessary, but the first addition is preferably carried out within the above-mentioned polymerization conversion range. Even if the inorganic phosphate is added after the latex-like material agglomerates and becomes unstable in the early stage of polymerization, the effect of the present invention will be small; conversely, if the inorganic phosphate is added at the time of preparation, the basic particles will agglomerate. This affects the state of the particles, and the porosity of the resulting spherical particles tends to become smaller.

水難溶性リン酸塩の添加と同時またはそののちであれば
界面活性剤、懸濁安定剤、Ｉ）１１調整剤などを添加し
てもよい。A surfactant, suspension stabilizer, I)11 regulator, etc. may be added at the same time as or after the addition of the poorly water-soluble phosphate.

本発明における重合反応の温度範囲は通常４０〜７５℃
であるが、とくに限定されるものではない。The temperature range of the polymerization reaction in the present invention is usually 40 to 75°C.
However, it is not particularly limited.

以上説明したような本発明に用いる方法によりＰｖＣを
製造すると、粒子表面の分散剤皮膜がなく、基本粒子の
凝集体からなる球状粒子を、重合器内の付着スケール量
を少なく、除熱が容易な状態で重合することができる。When PvC is produced by the method used in the present invention as explained above, there is no dispersant film on the particle surface, and the spherical particles are made of aggregates of basic particles. It can be polymerized under the following conditions.

さらに乳化重合法によるばあいのように、塩析操作を必
要としないので工程が短かく、不純物の混入も少なく、
熱安定性も良好なＰｖＣかえられる。Furthermore, unlike the emulsion polymerization method, there is no need for salting out, so the process is short and there is less contamination of impurities.
PvC also has good thermal stability.

本発明に用いる方法によれば、通常、粒子径１〜８＋ｎ
ｍ程度のＰｖＣの球状粒子かえられるが、一旦これを水
性媒体から分離したのち、後塩素化反応によりｃｐｖｃ
が製造される。According to the method used in the present invention, the particle size is usually 1 to 8+n.
Spherical particles of PvC with a size of about
is manufactured.

後塩素化反応前に球状粒子を粉砕してもしなくてもよい
が、塩素化反応の均一性を高め、塩素化反応速度を大き
くし、ｃｐｖｃの初期着色性、熱安定性などの品質を向
上させるという面からすると粉砕する方が好ましい。It is not necessary to crush the spherical particles before the post-chlorination reaction, but it improves the uniformity of the chlorination reaction, increases the chlorination reaction rate, and improves the initial coloring property, thermal stability, and other qualities of CPVC. From the viewpoint of improving the quality of the material, pulverization is preferable.

球状粒子を粉砕するばあいには、たとえばハンマーミル
、インペラープレカー、ボールミル、チューブミルなど
の粉砕機を用いる通常の固体の粉砕に利用される方法で
粉砕すればよい。When pulverizing spherical particles, it may be pulverized by a method commonly used for pulverizing solids using a pulverizer such as a hammer mill, impeller pulverizer, ball mill, or tube mill.

後塩素化反応としては、水性懸濁法、（−ｊ′機溶媒懸
濁法、溶液法、気相法などの方法か知られており、いず
れの方法も採用しうる。これらのうちでは水性懸濁法が
、重合時に添加した水難溶性無機リン酸塩が後塩素化反
応時の強酸性条件下で水性媒体中に溶出し、重合体中に
ほとんど残存しなくなり、ＣＰＶＣの品質面（とくに透
明性）からみて好ましい。As the post-chlorination reaction, there are known methods such as an aqueous suspension method, a (-j' solvent suspension method, a solution method, and a gas phase method. Any of these methods can be adopted. In the suspension method, the poorly water-soluble inorganic phosphate added during polymerization is eluted into the aqueous medium under strongly acidic conditions during the post-chlorination reaction, and almost no longer remains in the polymer. preferred in terms of gender).

つぎに本発明の方法を実施例および比較例に基づいて説
明するが、本発明はこれらに限定されるものではない。Next, the method of the present invention will be explained based on Examples and Comparative Examples, but the present invention is not limited thereto.

なお、以下の物性評価は下記の方法に従って行なった。In addition, the following physical property evaluation was performed according to the following method.

（粒度分布） ふるい振盪法によった。(particle size distribution) The sieve-shaking method was used.

（ｈ゛、り比重） 月Ｓ　Ｋ　６７２１によった。(h゛、ri specific gravity) According to the month SK 6721.

（ポロシティ−） 米国ＡＭＩＮＣＯ社製の水銀圧入式ポロシメーター（５
−７１１８型）を用いて、絶対圧１１−１０１１ｐｓｉ
（口ｉ１０．１７〜１５．９μＩｍ）の間に樹脂１００
ｇ当りに圧入される水銀の容量をΔ−１定してポロシテ
ィ−を求めた。(Porosity) Mercury intrusion porosimeter (5
-7118 model) at an absolute pressure of 11-1011 psi.
(mouth i10.17-15.9 μIm)
The porosity was determined by fixing the volume of mercury injected per gram by Δ-1.

（ゲル化時間） ＣＰＶＣ１００部、カネエ−スＢ−２２（鐘淵化学工業
■製）７部、スズ系安定剤（日東化成■製のＴＶＳ−８
８３１）　２部、ステアリン酸（日本油脂■製）２部を
ホモジナイザーにて５分間攪拌（１０１００００ｒｐ　
して作製したコンパウンド５４ｇをブラベンダー社製プ
ラストグラフ試験機に入れ、ローターの回転数３Ｏｒｐ
ｍ　、チャンバ一温度１８０’Ｃの条件下に投入してか
ら最高トルクに達するまでの時間を７１ｐ１定した。(Gelification time) 100 parts of CPVC, 7 parts of Kane Ace B-22 (manufactured by Kanebuchi Chemical Industry Ltd.), tin-based stabilizer (TVS-8 manufactured by Nitto Kasei Ltd.)
831) 2 parts and 2 parts of stearic acid (manufactured by NOF ■) were stirred for 5 minutes using a homogenizer (1010000 rpm).
54 g of the compound prepared by
m, and the time from when it was introduced to reaching the maximum torque under the condition of a chamber temperature of 180'C was determined to be 71p1.

（初期着色性） ｃｐｖｃ　ｔｏｏ部、カネｘ　−ス１３−２２　１０部
、スズ系安定剤（日東化成■製のＴＶＳ−８８３１）　
２部、滑剤ＶＰＩ＋−４（ヘキスト社製）０．７部、ス
テアリン酸（日本油脂■製）１部を混合したのち、１８
５℃×３分間混練して厚さｌｌｌ１ｆｆｌのロールシー
トを作製し、該ロールシートから厚さ５１ＩＩＩｌのプ
レス阪（プレス条件１９０℃×１０分）を作り、その初
期着色性を評価した。(Initial coloration) CPVC too part, Kanex-S 13-22 10 parts, tin stabilizer (TVS-8831 manufactured by Nitto Kasei ■)
After mixing 2 parts of lubricant VPI+-4 (manufactured by Hoechst), 0.7 parts of stearic acid (manufactured by NOF ■), 18
A rolled sheet having a thickness of lll1ffl was prepared by kneading at 5°C for 3 minutes, and a pressed plate having a thickness of 51IIIl (press condition: 190°C for 10 minutes) was made from the rolled sheet, and its initial colorability was evaluated.

（熱安定性） 初期６色性評価のために作製したのと同様のロールシー
トを作製し、１９５℃のギヤーオーブン内に入れて１５
分毎にシートを取出し、黒化するまでの時間を測定した
。(Thermal stability) A roll sheet similar to that prepared for the initial six-color evaluation was prepared and placed in a gear oven at 195°C for 15 minutes.
The sheets were taken out every minute and the time until blackening was measured.

実施例１ 内容積１．７ｍ　’の重合機に水２００部、過硫酸カリ
ウム０．０８５部、亜硫酸ナトリウム０．０３４部を仕
込み、内部の空気を真空ポンプで排除したのち塩化ビニ
ル単量体１００部（４４０ｋｇ）を装入し、所定の攪拌
条件下で６４℃まで昇温しで重合させた。Example 1 200 parts of water, 0.085 parts of potassium persulfate, and 0.034 parts of sodium sulfite were charged into a polymerization machine with an internal volume of 1.7 m', and after removing the air inside with a vacuum pump, 100 parts of vinyl chloride monomer was charged. (440 kg) was charged, and the temperature was raised to 64° C. under predetermined stirring conditions to polymerize.

重合転化率１５％到達時にリン酸カルシウム０．１部を
添加し、内圧が定常圧より　２．５ｋｇ／ｃｎｆ低下し
たとき未反応単量体を回収した（重合時＋＋ａ　６時間
５分）。重合転化率は８５％、重合時のジャケット最低
温度は４　Ｂ　’Ｃであり、缶内付着スケール量はウェ
ット状態て０，１％（対佳込モノマー量）と少なかった
。えられたＰｖＣは、平均粒子Ｉ子が５１６０μｍで粒
子径の非常にシャープな球状粒子であり、走査型電子顕
微鏡により観察した結果、その球状粒子は基本粒子（粒
子径的０．１〜２μｆｆ１）の凝集体であり、通常の懸
濁重合法によるＰｖＣで観察される分散剤皮膜は認めら
れなかった。When the polymerization conversion rate reached 15%, 0.1 part of calcium phosphate was added, and when the internal pressure decreased by 2.5 kg/cnf from the steady pressure, unreacted monomers were recovered (during polymerization ++a 6 hours 5 minutes). The polymerization conversion rate was 85%, the minimum jacket temperature during polymerization was 4 B'C, and the amount of scale deposited inside the can was as small as 0.1% (based on the amount of monomer added) in a wet state. The obtained PvC is a spherical particle with an average particle size of 5160 μm and a very sharp particle diameter, and as a result of observation with a scanning electron microscope, the spherical particle is a basic particle (particle diameter 0.1 to 2 μff1). The dispersant film observed in PvC produced by ordinary suspension polymerization was not observed.

この球状粒子を粉砕機により平均粒子径が２５０μｍの
粒子に粉砕した。ついで粉砕してえられたＰＶＣパウダ
ー９００ｇと水５１００ｇとを内容積８ｇの攪拌機付反
応器に仕込み、充分攪拌して懸濁液とし、反応器内にチ
ッ素ガスを吹込んで反応器内の空気をチッ素で置換した
。The spherical particles were pulverized into particles having an average particle diameter of 250 μm using a pulverizer. Next, 900 g of PVC powder obtained by pulverization and 5,100 g of water were charged into a reactor with an internal volume of 8 g equipped with a stirrer, stirred thoroughly to form a suspension, and nitrogen gas was blown into the reactor to remove the air inside the reactor. was replaced with nitrogen.

そののちこの懸濁液に塩素ガスを導入し、反応系を塩素
で飽和させたのち、反応器を５０℃に昇温して塩素ガス
を過剰に供給しながら、高圧水銀灯の照射下でＰＶＣを
塩素化した。３．６時間後に生成物の塩素含有率が６４
％に達し、ここで高圧水銀灯照射と塩素の導入とを中止
し、チッ素ガスを通して反応器内の塩素をチッ素で置換
し、スラリー中のｃｐｖｃに対して塩酸ヒドロキシルア
ミンを　１．０％加えて攪拌しながら放置して、完全に
塩素を除去した。ついで濾過し、ｃｐｖｃを充分イオン
交換水で水洗したのち水酸化すトリウム水溶液を加えて
中和し、さらに水洗してから濾過・乾燥してｃｐｖｃを
えた。After that, chlorine gas was introduced into this suspension to saturate the reaction system with chlorine, and then the temperature of the reactor was raised to 50°C, and while supplying excess chlorine gas, PVC was heated under irradiation with a high-pressure mercury lamp. Chlorinated. After 3.6 hours, the chlorine content of the product was 64
%, the high-pressure mercury lamp irradiation and introduction of chlorine were stopped, nitrogen gas was passed to replace the chlorine in the reactor with nitrogen, and 1.0% of hydroxylamine hydrochloride was added to the CPVC in the slurry. The mixture was left to stand while stirring to completely remove chlorine. After filtration, the CPVC was sufficiently washed with ion-exchanged water, neutralized by adding a thorium hydroxide aqueous solution, further washed with water, filtered and dried to obtain CPVC.

えられたｃｐｖｃは第１表に示すようにゲル化性、初期
着色性、熱安定性共に優れたものであった。As shown in Table 1, the obtained CPVC had excellent gelling properties, initial coloring properties, and thermal stability.

実施例２ 実施例１で用いたリン酸カルシウムの添加漬を０．４部
にかえた他は実施例１と同様にして重合、後塩素化反応
を行ない、ＣＰＶＣをえた。Example 2 Polymerization and post-chlorination reaction were carried out in the same manner as in Example 1, except that the amount of calcium phosphate used in Example 1 was changed to 0.4 parts, and CPVC was obtained.

えられたＰＶＣは第１表に示すごとく、平均粒子径が３
８７０μｍで粒径分布のシャープな球状粒子で、重合時
のジャケット最低温度は４５℃と高く、付着スケール量
も少なかった。またえられたｃｐｖｃはゲル化性、初期
着色性、熱安定性共に良好なものであった。As shown in Table 1, the obtained PVC has an average particle diameter of 3.
They were spherical particles with a sharp particle size distribution of 870 μm, the minimum temperature of the jacket during polymerization was as high as 45° C., and the amount of attached scale was small. The obtained CPVC also had good gelation properties, initial coloring properties, and thermal stability.

比較例１ 実施例１で用いた過硫酸カリウムを０．０６５部、亜硫
酸ナトリウムを０．０２６部とし、リン酸カルシウムを
添加しない他は実施例１と同様にして（ｎ合、後塩素化
反応を行ない、ＣＰＶＣをえた。Comparative Example 1 The same procedure as in Example 1 was carried out except that the potassium persulfate used in Example 1 was changed to 0.065 parts, the sodium sulfite was changed to 0.026 parts, and calcium phosphate was not added (in the n-combination, a post-chlorination reaction was carried out). , obtained CPVC.

えられたＣＰＶＣは第１表に示すごとく、ゲル化性、初
期着色性、熱安定性共に優れたものであったが、ＰｖＣ
重合時におけるジャケット最低温度が２３℃と低く、ス
ケールアップに際して除熱が困難であり、缶内付着スケ
ール量は４　、５９６（対仕込モノマー量）と非常に多
かった。したがって、この方法で塩化ビニル単量体から
ｃｐｖｃを製造する際のスケールアップに問題のあるこ
とがわかる。As shown in Table 1, the obtained CPVC had excellent gelling properties, initial coloring properties, and thermal stability.
The minimum temperature of the jacket during polymerization was as low as 23°C, making it difficult to remove heat during scale-up, and the amount of scale adhering inside the can was extremely large at 4,596 (relative to the amount of monomer charged). Therefore, it can be seen that there is a problem in scaling up when producing CPVC from vinyl chloride monomer using this method.

比較例２（懸濁重合法） 内容積１７ｍ　’の重合機にヒドロキシプロピルメチル
セルロース０．０６部を溶解した水２００部、重合開始
剤（ｔ−ブチルパーオキシネオデカノエート）　　０．
０１８部、３，５．５−）リメチルヘキサノイルバーオ
キサイド０．０２４部を仕込み、内部の空気を真空ポン
プで排除したのち塩化ビニル単量体１００部（４４０ｋ
ｇ）を装入し、所定の攪拌条件下で６４℃まで昇温しで
懸濁重合を開始させ、内圧が定常圧より　０．５ｋｇ／
ｃ−低下した時点で未反応単量体を回収した（重合時間
６時間）。重合転化率は７５％、重合時のジャケット最
低温度は４７℃、缶内付着スケール量はウェット状態で
０．０７％（対仕込モノマー量）であった。Comparative Example 2 (Suspension Polymerization Method) In a polymerization machine with an internal volume of 17 m', 200 parts of water in which 0.06 part of hydroxypropyl methylcellulose was dissolved, and a polymerization initiator (t-butyl peroxyneodecanoate) 0.
After charging 0.024 parts of 3,5.5-)limethylhexanoyl peroxide and removing the air inside with a vacuum pump, 100 parts of vinyl chloride monomer (440k
g) was charged, and the temperature was raised to 64°C under prescribed stirring conditions to start suspension polymerization, and the internal pressure was lower than the steady pressure by 0.5 kg/
c-Unreacted monomers were collected when the temperature decreased (polymerization time: 6 hours). The polymerization conversion rate was 75%, the minimum temperature of the jacket during polymerization was 47°C, and the amount of scale deposited inside the can was 0.07% (based on the amount of monomer charged) in a wet state.

えられたＰｖＣは平均粒子径１１０μｍであり、粒子表
面には特有の分散剤皮膜が認められた。The obtained PvC had an average particle diameter of 110 μm, and a unique dispersant film was observed on the particle surface.

このＰｖＣパウダーを粉砕せずに実施例１と同様にして
後塩素化反応を行ない、ＣＰＶＣをえた。This PvC powder was subjected to a post-chlorination reaction in the same manner as in Example 1 without being pulverized to obtain CPVC.

えられたｃｐｖｃは第１表に示すごとく、ゲル化性、初
期容色性共にわるかった。As shown in Table 1, the obtained CPVC had poor gelling properties and initial color properties.

［以下余白］ ［発明の効果］ 本発明に用いる方法によりＰｖＣを製造すると、粒子表
面に分散剤皮膜がなく、基本粒子の凝集体からなるＰＶ
Ｃ球状粒子を、組合器内への付着スケール量が少なく、
除熱が容易な状態でうろことかでき、乳化重合法による
ばあいのように塩析をする必要がないので不純物含量の
少ないＰＶＣかえられる。[Margins below] [Effects of the invention] When PvC is produced by the method used in the present invention, there is no dispersant film on the particle surface, and the PV is made of aggregates of basic particles.
C spherical particles have a small amount of scale adhering to the inside of the combination vessel,
It can be scaled with ease of heat removal, and there is no need for salting out as in the case of emulsion polymerization, so PVC with low impurity content can be used instead.

本発明の方法ではこのようなＰＶＣを後塩素化してＣＰ
ＶＣを製造するため、ゲル化性が良好で、川明ｊｒ１色
性が優れ、熱安定性の良好なＣＰＶＣを塩析を行なうこ
となく、大規模に製造しうるため、工業的価値はすこぶ
る大きいものである。In the method of the present invention, such PVC is post-chlorinated to form CP
To produce VC, CPVC, which has good gelling properties, excellent color properties, and good thermal stability, can be produced on a large scale without salting out, so it has great industrial value. It is something.

Claims (1)

【特許請求の範囲】 １　塩化ビニル単量体またはこれと共重合しうる他の単
量体との混合物を水性媒体中で、水溶性過硫酸塩を重合
開始剤として乳化剤不存在下で重合を開始し、重合途中
で水難溶性無機リン酸塩を添加してえられる塩化ビニル
系樹脂を後塩素化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。 ２　水溶性過硫酸塩が過硫酸カリウムまたは過硫酸アン
モニウムである特許請求の範囲第１項記載の製造方法。 ３　水難溶性無機リン酸塩がリン酸のカルシウム塩、ス
トロンチウム塩、バリウム塩、マグネシウム塩、アルミ
ニウム塩、鉛塩または亜鉛塩である特許請求の範囲第１
項記載の製造方法。 ４　水難溶性無機リン酸塩の添加時期が、重合転化率で
５〜５０重量％の範囲である特許請求の範囲第１項記載
の製造方法。[Claims] 1. Polymerization of a vinyl chloride monomer or a mixture with other monomers copolymerizable with it in an aqueous medium in the absence of an emulsifier using a water-soluble persulfate as a polymerization initiator. 1. A method for producing a chlorinated vinyl chloride resin, which comprises starting the polymerization and adding a poorly water-soluble inorganic phosphate during polymerization to post-chlorinate the obtained vinyl chloride resin. 2. The manufacturing method according to claim 1, wherein the water-soluble persulfate is potassium persulfate or ammonium persulfate. 3. Claim 1, wherein the poorly water-soluble inorganic phosphate is a calcium salt, strontium salt, barium salt, magnesium salt, aluminum salt, lead salt, or zinc salt of phosphoric acid.
Manufacturing method described in section. 4. The manufacturing method according to claim 1, wherein the slightly water-soluble inorganic phosphate is added at a time of 5 to 50% by weight in terms of polymerization conversion.