JPS5812893B2 - Polymerization method of vinyl chloride - Google Patents

Description

【発明の詳細な説明】 本発明は、塩化ビニルの改良された単独又は共重合方法
に関し、更に詳しくは、重合に際して、重合槽内壁及び
重合操作中にモノマーが接触する装置部分へのポリマー
付着防止方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for homopolymerization or copolymerization of vinyl chloride, and more particularly, to a method for preventing polymer adhesion to the inner wall of a polymerization tank and parts of equipment that come into contact with monomers during polymerization. Regarding the method.

塩化ビニルを単独で、またはこれと共重合しうるモノマ
ーと共に重合（以下単に重合と略称）するに際し、重合
槽内壁、還流冷却器、攪拌翼、邪魔板および各種付属配
管接続部等、重合操作中に千ノマーが接触する装置部分
にポリマーが付着するため重合槽の冷却能力が減少した
り、あるいは一旦付着した後剥離したポリマーが塩化ビ
ニルのヰ独重合体にまたは共重合体（以下製品と略称）
中に混入して製品の品質を低下させるなどの問題が生じ
る。When vinyl chloride is polymerized alone or together with a monomer that can be copolymerized with vinyl chloride (hereinafter simply referred to as polymerization), the inner walls of the polymerization tank, reflux condenser, stirring blades, baffle plates, and various attached piping connections, etc., are damaged during the polymerization operation. The cooling capacity of the polymerization tank may be reduced because the polymer adheres to the parts of the equipment that come in contact with the polymer, or the polymer that peels off after adhering may turn into a vinyl chloride homopolymer or copolymer (hereinafter referred to as the product). )
This causes problems such as contamination in the product and deterioration of product quality.

従って重合終了後毎回重合槽内を清掃した後再び重合す
るのが通例であるが、そのためには多犬の労力と時間を
必要とし重合槽の稼動率の低下や製品コストの増加をも
たらしている。Therefore, it is customary to clean the inside of the polymerization tank after each polymerization and then perform polymerization again, but this requires the labor and time of many people, resulting in a decrease in the operating rate of the polymerization tank and an increase in product costs. .

従来からこのような重合槽内壁へのポリマー付着防止に
関して多くの方法が提案されているが、それらの方法は
ポリマー付着防止に効果はあっても、たとえば重合速度
を遅くしたり製品の諸物性を悪化させるなど種々の欠点
があり、いずれも工業的に用いる方法としては満足でき
るものではなかった。Many methods have been proposed to prevent polymer adhesion to the inner wall of the polymerization tank, but although these methods are effective in preventing polymer adhesion, they may slow down the polymerization rate or affect the physical properties of the product. There are various drawbacks such as deterioration, and none of these methods are satisfactory for industrial use.

重合速度や製品の諸物性に悪影響を与えない方法も提供
されているが、か匁る方法はポリマー付着防止の効果が
大きくない欠点がある。Methods have been proposed that do not adversely affect the polymerization rate or the physical properties of the product, but the boiling method has the disadvantage that it is not very effective in preventing polymer adhesion.

たとえば、特開昭５０−８７号は、一成分としてアルデ
ヒドを有する反応混合物から形成される極性基を含有す
る架橋した重合体物質の不溶性層が沈着している内壁面
を有する反応容器中で塩化ビニルの重合を行う方法を開
示している。For example, JP-A-50-87 discloses chlorination in a reaction vessel having an inner wall on which is deposited an insoluble layer of a crosslinked polymeric material containing polar groups formed from a reaction mixture having an aldehyde as one component. A method for carrying out the polymerization of vinyl is disclosed.

この方法によるならば、壁面に沈着した重合体物質は架
橋一すなわち三次元化しているので、塩化ビニルの重合
反応液に溶出して行きにくく、たしかに重合速度が遅く
なるようなことはない。According to this method, since the polymer substance deposited on the wall surface is crosslinked, that is, three-dimensional, it is difficult to be eluted into the vinyl chloride polymerization reaction solution, and the polymerization rate does not become slow.

重合体物質を塗布することにより、ポリマー付着を防止
する方法は、その重合体物質がラジカル捕捉剤として働
くか、あるいは親水性であるために壁面が撥油性を示し
塩化ビニルモノマーをよせつけないかのような理由で効
果を発揮するものと考えられる。The method of preventing polymer adhesion by applying a polymer substance is that the polymer substance acts as a radical scavenger or that the wall surface is oil repellent due to its hydrophilic properties and does not attract vinyl chloride monomer. It is thought that it is effective for the following reasons.

ところが、特開昭５０−８７号記載の方法のように、架
橋した重合体物質を用いると、そのような効果が小さく
なる。However, when a crosslinked polymer material is used as in the method described in JP-A-50-87, such effects are reduced.

たとえば一例として、出発原料としてフェノールとホル
ムアルデヒドを用いた架橋縮合物はフェノール樹脂とし
て知られているが、この樹脂は親水性を示さず、またラ
ジカル捕捉効果も有していないため、ポリマー付着防止
に有効ではない。For example, a cross-linked condensate using phenol and formaldehyde as starting materials is known as a phenolic resin, but this resin does not exhibit hydrophilicity and does not have a radical scavenging effect, so it is difficult to prevent polymer adhesion. Not valid.

本発明の目的は、塩化ビニルの重合に際して、上記のよ
うな悪影響を及ぼさないで、かつ充分にポリマー付着を
防止する実用的な重合方法を提供することである。An object of the present invention is to provide a practical polymerization method that does not cause the above-mentioned adverse effects and sufficiently prevents polymer adhesion during the polymerization of vinyl chloride.

本発明者らは研究を重ねた結果、塩化ビニルを重合する
に際し、重合槽内壁やそのほか重合操作中にモノマーが
接触する重合装置、重合付属機器の部分に、あらかじめ
ある種の薬物を塗布しておけばポリマーの付着が大巾に
減少し、かつ少量付着したポリマーも水洗等によって容
易に除去でき、しかも重合反応を遅くしたり製品の諸物
性を悪化させるなどの悪影響がないことを見い出し、本
発明に到達した。As a result of repeated research, the present inventors have found that when polymerizing vinyl chloride, a certain type of drug is applied in advance to the inner walls of the polymerization tank and other parts of the polymerization equipment and polymerization accessory equipment that come into contact with the monomer during the polymerization operation. They discovered that polymer adhesion can be greatly reduced if the polymer is left in place, and that even a small amount of adhering polymer can be easily removed by washing with water, and that there are no negative effects such as slowing down the polymerization reaction or deteriorating the physical properties of the product. invention has been achieved.

本発明は、塩化ビニルを単独で、またはこれと共重合し
うるモノマーと共に、水性媒体中に於てまたは塊状にて
重合するに際し、重合槽内壁および重合操作中にモノマ
ーが接触する装置部分に、あらかじめフェノールとアル
デヒドとの初期縮合物を塗布することを特徴とする塩化
ビニルの単独又は共重合方法である。In the present invention, when vinyl chloride is polymerized alone or together with a monomer that can be copolymerized with vinyl chloride in an aqueous medium or in bulk, This is a method for monopolymerizing or copolymerizing vinyl chloride, which is characterized by applying an initial condensate of phenol and aldehyde in advance.

本発明では塗布薬物としてフェノールとアルデヒドとの
初期縮合物が使用されるが、こゝで本発明にいうフェノ
ールとは石炭酸、クレゾール、エチルフェノール等の一
価フェノール、レゾルシン、ハイドロキノン等の多価フ
ェノール、ビスフェノールＡ等のビスフェノール又はこ
れらの核置換体を意味する。In the present invention, an initial condensate of phenol and aldehyde is used as a topical drug, and phenol in the present invention refers to monohydric phenols such as carbolic acid, cresol, and ethylphenol, and polyhydric phenols such as resorcinol and hydroquinone. , refers to bisphenols such as bisphenol A, or their nuclear substituted products.

また本発明にいうアルデヒドとはＣＨＯ基を有する有機
化合物をいい、例としてはホルムアルデヒド、アセトア
ルデヒド、フルフラールなどをあげることができる。Furthermore, the aldehyde referred to in the present invention refers to an organic compound having a CHO group, and examples thereof include formaldehyde, acetaldehyde, and furfural.

本発明の方法においては、工業的に安価で容易に入手す
ることができる石炭酸とホルムアルデヒド（又はパラホ
ルムアルデヒド）を主体とする縮合物を使用するのが便
利である。In the method of the present invention, it is convenient to use a condensate mainly consisting of carbolic acid and formaldehyde (or paraformaldehyde), which is industrially inexpensive and easily available.

フェノールとアルデヒドとの縮合反応の反応条件、操作
については一般のフェノール・ホルムアルデヒド縮合物
の製法に準じた条件が適用される。Regarding reaction conditions and operations for the condensation reaction of phenol and aldehyde, conditions similar to those for the production of general phenol-formaldehyde condensates are applied.

特にフェノールとホルムアルデヒドとの縮合反応では、
一般に、初期縮合物として、酸性触媒ではノボラツクを
与え、塩基性触媒ではレンールを与える。Especially in the condensation reaction between phenol and formaldehyde,
Generally, acidic catalysts give novolaks and basic catalysts give renol as the initial condensate.

本発明においては、重合槽内壁等に塗布すべきフェノー
ルとアルデヒドとの初期縮合物は、水溶液の形で取り扱
うのが操作の上で便利なので、縮合物を水溶液の形でう
ろことができるレゾール型のフェノール・ホルムアルデ
ヒド縮合物を使用するのが有利である。In the present invention, since it is convenient for operation to handle the initial condensate of phenol and aldehyde to be applied to the inner wall of the polymerization tank in the form of an aqueous solution, a resol type is used in which the condensate can be disseminated in the form of an aqueous solution. It is advantageous to use a phenol-formaldehyde condensate of

この場合、フェノールに対してホルムアルデヒドを過剰
に使用し、かつ塩基性触媒として苛性ソーダ、苛性カリ
、アンモニア、アミン類等が用いられる。In this case, formaldehyde is used in excess of phenol, and caustic soda, caustic potash, ammonia, amines, etc. are used as the basic catalyst.

本発明を実施するにあたり、フェノール・ホルムアルデ
ヒド縮合物は水溶液の形で塗布するのが便利であるが、
有機溶媒に溶解して塗布することもできるので、上記縮
合物を溶解し得る溶媒と共に用いることは差支えない。In carrying out the present invention, it is convenient to apply the phenol-formaldehyde condensate in the form of an aqueous solution;
Since it can be applied by dissolving it in an organic solvent, there is no problem in using the above condensate together with a solvent in which it can be dissolved.

また縮合物がアルカリ水溶液の形で得られるレゾール型
フェノール・ホルムアルデヒド縮合物ヲ用いる場合は、
必要に応じ縮合物を濃縮または水もしくはアルカリ水で
希釈して塗布に供する。In addition, when using a resol type phenol formaldehyde condensate obtained in the form of an alkaline aqueous solution,
If necessary, the condensate is concentrated or diluted with water or alkaline water before application.

ノボラツク型フェノール・ホルムアルデヒド縮合物の場
合は、縮合物をアルカリ水もしくはメタノール等の有機
溶媒に溶解して使用することができる。In the case of a novolak-type phenol-formaldehyde condensate, the condensate can be used by dissolving it in alkaline water or an organic solvent such as methanol.

塗布液の調製に際し、さらに変性剤により変性したのち
使用する場合も本発明の実施態様の一つである。It is also an embodiment of the present invention to use the coating solution after further modifying it with a modifier when preparing the coating solution.

変性剤を縮合物に加えて加熱することにより変性が行な
われる。Modification is carried out by adding a modifier to the condensate and heating it.

レゾール型縮合物の場合は、オルト位、メタ位又はパラ
位がアルキル置換されているアルキルフェノール類、レ
ゾルシン、ハイドロキノン、ビスフェノールＡなどの二
価フェノール類などが変性剤として使用され、一方ノボ
ラツク型縮合物の場合はアルデヒド、ヘキサメチレンテ
トラミンなどが変性剤として使用される。In the case of resol-type condensates, alkylphenols substituted with alkyl at the ortho-, meta-, or para-positions, dihydric phenols such as resorcinol, hydroquinone, and bisphenol A are used as modifiers, while novolak-type condensates In this case, aldehyde, hexamethylenetetramine, etc. are used as a denaturing agent.

本発明において塗布に供するレゾール型フェノール・ホ
ルムアルデヒド縮合物は、１０重量％苛性ソーダ水溶液
と相溶するものであることが望ましい。The resol-type phenol-formaldehyde condensate used for coating in the present invention is preferably one that is compatible with a 10% by weight aqueous caustic soda solution.

こ〜にいう相溶とは該縮合物と１０重量％苛性ソーダ水
溶液とを混合した場合、その混合割合如何にか匁わらず
該混合物は均一な一つの相を形成することを意味する。Compatibility here means that when the condensate and a 10% by weight aqueous caustic soda solution are mixed, the mixture forms one uniform phase, regardless of the mixing ratio.

１０重量％苛性ソーダ水溶液と相溶する縮合物の平均的
な分子の大きさは、かなり広範囲にわたるものであるが
、その中でも１〜２０核体のものが特に好ましく、５〜
１０核体のものが最も望ましい。The average molecular size of condensates that are compatible with a 10% by weight aqueous caustic soda solution ranges over a fairly wide range, but those with 1 to 20 nuclei are particularly preferred, and those with 5 to 20 nuclei are particularly preferred.
The one with 10 nuclei is most desirable.

こゝにいう核体数は縮合物１分子中に含まれるベンセン
核の数を意味する。The number of nuclei here means the number of benzene nuclei contained in one molecule of the condensate.

本発明のフェノールとアルデヒドとの初期縮合物を塩化
ビニルの重合槽内壁等へ塗布すれば何故ポリマー付着を
防止することができるのか明らかでないが、おそらくこ
の初期縮合物が有しているＯＨ基もしくはＣＨ２０Ｈ基
が親水基として働き、重合槽等のモノマーと接触する部
分の壁面を親水性にするためではないかと考えることが
できる。It is not clear why polymer adhesion can be prevented by applying the initial condensate of phenol and aldehyde of the present invention to the inner wall of a vinyl chloride polymerization tank, but it is probably due to the OH groups that this initial condensate has or It can be considered that this is because the CH20H group acts as a hydrophilic group and makes the wall surface of the portion of the polymerization tank that comes into contact with the monomer hydrophilic.

事実、未処理の重合槽等の壁面は通常かなりの撥水性を
示すのに対し、本発明の処理を施した壁面は水面に対し
ての濡れがひじようによくなり撥油性を示すことが観察
される。In fact, it has been observed that while untreated walls such as polymerization tanks usually exhibit considerable water repellency, walls treated with the present invention have an elbow-like wettability with the water surface and exhibit oil repellency. be done.

従って重合反応中にモノマーが壁面へ接近することが妨
げられてポリマー付着の防止に効果があると考えること
ができる。Therefore, it can be considered that the monomer is prevented from approaching the wall surface during the polymerization reaction, which is effective in preventing polymer adhesion.

一方、フェノール・ホルムアルデヒドの縮合反応を高度
に行ない縮合物が架橋した場合には、親水性を消失して
ポリマー付着防止の効果は現われない。On the other hand, if the condensation reaction of phenol/formaldehyde is carried out to a high degree and the condensate is crosslinked, the hydrophilicity is lost and the effect of preventing polymer adhesion is not exhibited.

本発明を実施するにあたり、フェノール・アルデヒド初
期縮合物及びさらに要すれば変性剤を加えた混合物の液
を重合槽内壁等へ塗布するのであるが、その固形分濃度
は０．０５〜１５重量％の範囲で用いるのが作業上好都
合である。In carrying out the present invention, a liquid mixture of the phenol-aldehyde initial condensate and, if necessary, a modifier added thereto, is applied to the inner wall of the polymerization tank, etc., and the solid content concentration thereof is 0.05 to 15% by weight. It is convenient for work to use it within the range of .

こゝで固形分とは縮合物を意味し、具体的には試料を１
３５℃のエアバスに入れ、１時間乾燥後の不揮発成分の
量を測定することによって固形分を表わす。Here, solid content means condensate, and specifically, the sample is
The solid content is expressed by placing in an air bath at 35° C. and measuring the amount of non-volatile components after drying for 1 hour.

本発明で塗布とは、作業の態様ではなく結果としてフェ
ノール・アルデヒド初期縮合物を器壁に存在させること
を意味し、塗布の方法は特に限定を要しないが、通常は
刷毛塗りあるいはスプレー等の方法で行うことができ、
その塗布量も特に限定を要しないが通常は固形分として
０．００５〜１０ｇ／ｍ２とするのが好ましい。In the present invention, application refers to the presence of a phenol-aldehyde initial condensate on the vessel wall as a result, not the mode of operation, and the method of application is not particularly limited, but it is usually applied by brushing or spraying. It can be done in a way,
The coating amount is also not particularly limited, but it is usually preferably 0.005 to 10 g/m2 in terms of solid content.

本発明を実施するにあたって、特にフェノール・ホルム
アルデヒド初期縮合物を用いる場合には、縮合物を塗布
後、水で塗布面を洗滌するのが好ましい。In carrying out the present invention, especially when using a phenol-formaldehyde initial condensate, it is preferable to wash the coated surface with water after applying the condensate.

この操作によりたとえ必要以上に塗布された塗布液も洗
い流されるし、また一般にフェノール・ホルムアルデヒ
ド縮合物は中性の水には溶解しないので重合槽等の壁面
への縮合物の固着を促進する。By this operation, even if the coating solution is applied in excess of the amount required, it is washed away, and since phenol-formaldehyde condensates generally do not dissolve in neutral water, it promotes the adhesion of the condensates to the walls of the polymerization tank or the like.

さらに有利なことは、過剰のフェノール・ホルムアルデ
ヒド縮合物が除去されるため、塩化ビニルの重合反応を
遅くしたりあるいはえられる製品の諸物性を悪くしたり
する悪影響が回避される。A further advantage is that the excess phenol-formaldehyde condensate is removed, thereby avoiding the negative effects of slowing down the vinyl chloride polymerization reaction or deteriorating the physical properties of the resulting product.

尚、水の代りに塩酸、硝酸、りん酸、炭酸等の無機酸、
あるいは蟻酸、酢酸、フイチン酸等の有機酸でＰＨ６以
下に調節した酸性水で塗布面を洗滌してもよい。In addition, instead of water, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, etc.
Alternatively, the coated surface may be washed with acidic water whose pH has been adjusted to 6 or less with an organic acid such as formic acid, acetic acid, or phytic acid.

塗布は、毎パッチ重合開始前に行なってもよく、また塗
布後数パッチ以上簡単な水洗のみで継続して重合を行う
こともできる。Coating may be carried out before starting polymerization for each patch, or polymerization may be continued for several patches or more after coating by simply washing with water.

また本発明が適用できる重合は、塩化ビニルの単独重合
のみならず、塩化ビニルと共重合しうるモノマー、たと
えば、エチレン、プロピレン等のオレフイン、酢酸ビニ
ル、スチレン等のビニル系モノマー、アクリルニトリル
、アクリル酸エステル等のアクリル系モノマー、マレイ
ン酸、マレイン酸エステル、フマル酸、フマル酸エステ
ル等のジカルボン酸系モノマー等との共重合に有効に適
用できる。Polymerization to which the present invention can be applied includes not only homopolymerization of vinyl chloride, but also monomers copolymerizable with vinyl chloride, such as olefins such as ethylene and propylene, vinyl monomers such as vinyl acetate and styrene, acrylonitrile, and acrylic monomers. It can be effectively applied to copolymerization with acrylic monomers such as acid esters, dicarboxylic acid monomers such as maleic acid, maleic esters, fumaric acid, and fumaric esters.

これらの共重合すべきモノマーは、塩化ビニルに対して
２０重量％を越えない範囲で使用することができる。These monomers to be copolymerized can be used in an amount not exceeding 20% by weight based on vinyl chloride.

さらに本発明が適用できる重合形式は、上記モノマーの
水性懸濁重合、水性乳化重合及び、上記モノマーのみで
重合媒体を含まないいわゆる塊状重合にも各々の通常の
重合条件下で有効に適用できる。Furthermore, the polymerization format to which the present invention can be applied can be effectively applied to aqueous suspension polymerization of the above monomers, aqueous emulsion polymerization of the above monomers, and so-called bulk polymerization containing only the above monomers without a polymerization medium under each usual polymerization condition.

本発明の方法によれば、ポリマー付着防止の効果が従来
方法より格段に大きくなり、しかも重合速度が遅くなっ
たりあるいは製品の諸物性が悪くなったりするような悪
影響はない。According to the method of the present invention, the effect of preventing polymer adhesion is much greater than that of conventional methods, and there are no adverse effects such as slowing down the polymerization rate or deteriorating various physical properties of the product.

以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.

フェノール・アルデヒド縮合物の製造例１：還流冷却器
付三ツ口フラスコに石炭酸９４ｇ（１モル）、４８重量
％ホルマリン１００ｇ（ホルムアルデヒド１．６モル）
、苛性ソーダ２ｇ（０．０５モル）を装入し、８５℃ま
で２０分間で攪拌下昇温した。Production example 1 of phenol-aldehyde condensate: 94 g (1 mol) of carbolic acid and 100 g of 48% by weight formalin (1.6 mol of formaldehyde) in a three-necked flask with a reflux condenser.
, 2 g (0.05 mol) of caustic soda was charged, and the temperature was raised to 85° C. over 20 minutes with stirring.

さらにこの温度で３．５時間反応させ、然る後同じ温度
で減圧下固形分濃度が７５重量％になるまで濃縮した。The reaction was further carried out at this temperature for 3.5 hours, and then concentrated at the same temperature under reduced pressure until the solid content became 75% by weight.

このようにしてえられたレゾールは、ＡＳＴＭＤ２１９
６に記載された方法に準拠して６ ０ ｒｐｍでＮｏ４
のスピンドルを用いて２５℃の粘度を測定したところ、
２５００センチポイズを示した。The resol obtained in this way meets ASTM D219
No. 4 at 60 rpm according to the method described in 6.
When the viscosity at 25°C was measured using a spindle of
It showed 2500 centipoise.

このレゾール５０ｇにレゾルシン（レゾルシノール）４
ｇを加え、９５℃まで３０分間で攪拌下昇温し、さらに
この温度に１０分間保ち、然る後縮合物を２重量％の苛
性ソーダ水に溶解して固形分濃度が５重量％になるよう
に調節した。50g of this resol and 4 resorcinol
g was added, the temperature was raised to 95°C under stirring for 30 minutes, the temperature was kept at this temperature for another 10 minutes, and then the condensate was dissolved in 2% by weight of caustic soda water so that the solid content concentration was 5% by weight. It was adjusted to

実施例 １ 上記製造例のようにして調製された塗布液を、内容積７
ｍ３のステンレス製重合槽の内壁に噴霧器でスプレーし
、さらに塩酸でＰＨ４に調節した水で壁面を洗滌した。Example 1 The coating liquid prepared as in the above production example was coated with an internal volume of 7
The mixture was sprayed onto the inner wall of a 3 m3 stainless steel polymerization tank using a sprayer, and the wall surface was further washed with water adjusted to pH 4 with hydrochloric acid.

このような処置をした後、脱イオン水３０００ｋｇ、ヒ
ーブチルパーオキシピパレート０． ６ ｋｇ、鹸化度
８０モル％の部分鹸化ポリビニルアルコール２ｋｇを装
入し、内部の空気を真空ポンプで排除した。After such treatment, 3000 kg of deionized water and 0.0 kg of hebutyl peroxypiparate were added. 6 kg of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol% was charged, and the air inside was removed using a vacuum pump.

然る後塩化ビニル２０００ｋｇを装入し、５７℃で圧力
が５ｋｇ／ｃｍ２に達するまで反応を続けた。Thereafter, 2000 kg of vinyl chloride was charged, and the reaction was continued at 57°C until the pressure reached 5 kg/cm2.

反応終了後未反応モノマーを回収し、ポリマースラリー
を排出後重合槽内壁に付着したポリマーの重量を調べた
。After the reaction was completed, unreacted monomers were collected, and after the polymer slurry was discharged, the weight of the polymer attached to the inner wall of the polymerization tank was determined.

ポリマースラリーは脱水後乾燥し製品として取得し、第
１表に注記した方法により諸物性を測定した。The polymer slurry was dehydrated and dried to obtain a product, and its physical properties were measured by the methods noted in Table 1.

第１表に示した如く、本発明の方法によれば、ポリマー
付着量が顕著に少なく、また付着したポリマーも簡単な
水洗で容易に洗い流すことができた。As shown in Table 1, according to the method of the present invention, the amount of polymer adhesion was significantly small, and the adhering polymer could be easily washed away with simple water washing.

えられた製品の物性もすぐれている。比較例 １ 上記レゾール塗布液の塗布をまったく行わなかった以外
は実施例１と同様にした例であるが、第１表に示したと
同じように内壁へのポリマー付着量はきわめて多い。The physical properties of the resulting product are also excellent. Comparative Example 1 This is an example similar to Example 1 except that the resol coating liquid was not applied at all, but as shown in Table 1, the amount of polymer adhering to the inner wall was extremely large.

フェノール・アルデヒド縮合物の製造例２：還流冷却器
付三ツ口フラスコに石炭酸１１２８ｇ（１２モル）、４
０重量％ホルマリン１２０３ｇ（１９．２モル）、４０
重量％苛性ソーダ水溶液６ ０ｇ（ ０．６モル）を装
入し、８５℃まで２０分間で攪拌下昇温した。Production example 2 of phenol-aldehyde condensate: In a three-neck flask with a reflux condenser, 1128 g (12 mol) of carbolic acid, 4
0% by weight formalin 1203g (19.2mol), 40
60 g (0.6 mol) of a wt % aqueous solution of caustic soda was charged, and the temperature was raised to 85° C. for 20 minutes with stirring.

さらにこの温度で１時間反応させ、前記の方法に基づき
６ ０ｒｐｍで扁１のスピンドルを用いて粘度を測定し
たところ、８０℃で１０センチポイズであった。The reaction was further allowed to proceed at this temperature for 1 hour, and the viscosity was measured at 60 rpm using a flat 1 spindle according to the method described above, and found to be 10 centipoise at 80°C.

この縮合物の固形分濃度は７４重量％であった。The solid content concentration of this condensate was 74% by weight.

この縮合物をＧ２と名付けた。This condensate was named G2.

フェノール・アルテヒド縮合物の製造例３〜６： 還流冷却器付玉ソロフラスコに製造例２でえられた縮合
物Ｇ２をｉｏｏｏｙ装入し、これにレゾルシン（レゾル
シノール）１ ００Ｐを加え、８５℃まで２０分間で攪
拌下昇温し、さらにこの温度に保ちなから縮合反応を続
けた。Production Examples 3 to 6 of phenol-altehyde condensates: Charge the condensate G2 obtained in Production Example 2 to a solo flask with a reflux condenser, add 100P of resorcinol, and heat to 85°C. The temperature was raised under stirring for 20 minutes, and the condensation reaction was continued while maintaining this temperature.

このようにして、前記の方法に基づく粘度（ ６ ０
ｒｐｍでＡ３もしくはＮｏ４のスピンドル使用）が８０
℃において５００センチポイズ、１０００センチポイズ
、２０００センチポイズ、５０００センチポイズのラッ
プサンプルを各５０１採取し、それぞれＧ３、Ｇ４、Ｇ
５、Ｇ６と名付けた。In this way, the viscosity (60
rpm using A3 or No.4 spindle) is 80
501 lap samples each of 500 centipoise, 1000 centipoise, 2000 centipoise, and 5000 centipoise were collected at ℃, and G3, G4, and G
5. Named G6.

尚、これらの縮合物の固形分濃度は７６重量％であった
。The solid content concentration of these condensates was 76% by weight.

フェノール・アルデヒド縮合物の製造例７〜８：還流冷
却器付玉ソロフラスコに製造例２でえられた縮合物Ｇ２
を１００７装入した。Production Examples 7 to 8 of phenol/aldehyde condensate: Condensate G2 obtained in Production Example 2 in a ball solo flask with a reflux condenser
1007 were charged.

これに製造例７ではハイドロキノンを、製造例８ではビ
スフェノールＡをそれぞれ１０ｇ加え、８５℃まで２０
分間で攪拌下昇温し、さらにこの温度に保ちながら前記
の方法に基づく粘度（ ６ ０ ｒｐｎでＮｏ３スピン
ドル）が８０℃において１０００センチポイズになるま
で縮合反応を続けた。To this was added 10 g of hydroquinone in Production Example 7 and 10 g of bisphenol A in Production Example 8, and the mixture was heated to 85°C.
The temperature was raised with stirring for 1 minute, and the condensation reaction was continued while maintaining this temperature until the viscosity based on the above method (No. 3 spindle at 60 rpm) reached 1000 centipoise at 80°C.

これら縮合物の固形分濃度は７６重量％であり、それぞ
れＧ７、Ｇ８と名付けた。The solid content concentration of these condensates was 76% by weight, and they were named G7 and G8, respectively.

実施例２〜８ 製造例２〜８のようにしてられた縮合物を２重量％の苛
性ソーダ水に溶解して濃度が５重量％になるよう調節し
て塗布液を調製した。Examples 2 to 8 Coating solutions were prepared by dissolving the condensates prepared in Production Examples 2 to 8 in 2% by weight caustic soda water and adjusting the concentration to 5% by weight.

これら塗布液を、内容積７ｍ２のステンレス製重合槽の
内壁に噴霧器でスプレーし、さらに水で壁面を洗滌した
。These coating solutions were sprayed onto the inner wall of a stainless steel polymerization tank having an internal volume of 7 m 2 using a sprayer, and the wall surface was further washed with water.

このような処置をした後、脱イオン水３０００ｋｇ、２
・２’−アゾビス−２・４−ジメチルバレロニトリル０
．５ｋｇ、鹸化度８０モル％の部分鹸化ポリビニルアル
コール１ｋｇ、ヒドロキシプ口ピルメチルセルロース１
ｋｇを装入し、内部の空気を真空ポンプで除去した。After such treatment, 3000 kg of deionized water, 2
・2'-azobis-2,4-dimethylvaleronitrile 0
．． 5 kg, 1 kg of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol%, 1 kg of hydroxypropyl methylcellulose
kg was charged, and the air inside was removed using a vacuum pump.

然る後塩化ビニル２０００ｋｇを装入し、５７℃で圧力
が５ ｋｇ／ｃｍ２に達するまで反応を続けた。Thereafter, 2000 kg of vinyl chloride was charged, and the reaction was continued at 57°C until the pressure reached 5 kg/cm2.

反応終了後未反応モノマーを回収し、ポリマースラリー
を排出後重合槽内に付着したポリマーの重量を調べた。After the reaction was completed, unreacted monomers were collected, and after the polymer slurry was discharged, the weight of the polymer adhering to the inside of the polymerization tank was determined.

第２表に示した如く、本発明の方法によれば、ポリマー
付着量が顕著に少く、また付着したポリマーも簡単な水
洗で容易に洗い流すことができた。As shown in Table 2, according to the method of the present invention, the amount of polymer adhesion was significantly reduced, and the adhering polymer could be easily washed away with simple water washing.

比較例 ２ １ 上記レゾール塗布液の塗布をまったく行わなかった
以外は実施例２と同様にした例であるが、第２表に示し
たように内壁へのポリマー付着はきわめて多い。Comparative Example 2 1 This is an example similar to Example 2 except that the above resol coating liquid was not applied at all, but as shown in Table 2, there was an extremely large amount of polymer adhesion to the inner wall.

実施例 ９ （乳化重合の例） フェノール・ホルムアルテヒド縮合物の製造例４でえら
れた縮合物Ｇ４を２重量％の苛性ソーダ水に溶解して濃
度が５重量％になるよう調節して塗布液を調製した。Example 9 (Example of emulsion polymerization) Condensate G4 obtained in Production Example 4 of phenol-formaltehyde condensate was dissolved in 2% by weight of caustic soda water, adjusted to a concentration of 5% by weight, and applied. A liquid was prepared.

この塗布液を内容積１０００１のグラスライニング重合
槽の内壁に０．５ｇ／ｍ２の割合で噴霧器でスプレーし
、さらに水で壁面を洗滌した。This coating liquid was sprayed onto the inner wall of a glass-lined polymerization tank having an internal volume of 10,001 cm at a rate of 0.5 g/m2 using a sprayer, and the wall surface was further washed with water.

このような処理なした後、脱イオン水３００ｋｇ、ソデ
イウム・ラウリルサフエート２ｋｇ、セチルアルコール
４ｋｇを装入し、５５℃に加熱して５０ｒｐｍのゆるや
かな攪拌速度で１０分間攪拌して乳化剤分散液を調節し
た。After this treatment, 300 kg of deionized water, 2 kg of sodium lauryl sulfate, and 4 kg of cetyl alcohol were charged, heated to 55°C, and stirred at a gentle stirring speed of 50 rpm for 10 minutes to form an emulsifier dispersion. Adjusted.

然る後この乳化剤分散液を３５℃まで冷却し、２・２−
アゾビスー２・４−ジメチルバレロニトリル０．１２ｋ
ｇを添加し、内部の空気を真空ポンプで排除した。Thereafter, this emulsifier dispersion was cooled to 35°C, and 2.2-
Azobis-2,4-dimethylvaleronitrile 0.12k
g and the internal air was removed with a vacuum pump.

次に塩化ビニル２００ｋｇを装入し５０℃にて５０ｒｐ
ｍの攪拌速度で重合槽内の圧力が４ｋｇ／ｃｍ２になる
まで重合したところ重合槽内には凝集生成物がほとんど
ない、かつ安定な塩化ビニルポリマーラテックスかえら
れた。Next, 200 kg of vinyl chloride was charged and 50 rp at 50°C.
When the polymerization was carried out at a stirring speed of 500 m until the pressure in the polymerization tank reached 4 kg/cm2, a stable vinyl chloride polymer latex with almost no agglomerated products in the polymerization tank was obtained.

未反応モノマーを回収後ラテックスを排出し重合槽内壁
の状態を調べたところ、ポリマー付着は実質的に皆無で
あった。After collecting unreacted monomers, the latex was discharged and the condition of the inner wall of the polymerization tank was examined, and it was found that there was virtually no polymer adhesion.

比較例 ３ 実施例９において、フェノール・ホルムアルデヒド樹脂
の塗布を行わなかった以外はすべて実施例９と同じよう
にして塩化ビニルの重合を行ない、重合後の重合槽内壁
の状態を調べたところ、内壁全面に多量の膜状ポリマー
の付着が認められた。Comparative Example 3 Vinyl chloride was polymerized in the same manner as in Example 9 except that the phenol-formaldehyde resin was not applied. When the condition of the inner wall of the polymerization tank after polymerization was examined, it was found that the inner wall A large amount of film-like polymer was observed to adhere to the entire surface.

実施例 １０ （塊状重合の例） 重合装置として内容積４ｌのステンレス製たて型重合槽
と内容積６ｌのステンレス製横型重合槽を組合せたもの
を使用した。Example 10 (Example of bulk polymerization) A combination of a stainless steel vertical polymerization tank with an internal volume of 4 liters and a stainless steel horizontal polymerization tank with an internal volume of 6 liters was used as a polymerization apparatus.

これら重合槽の内壁およびその他塩化ビニルが接触する
部分に、実施例９で使用した塗布液を０． ２ｇ／ｍ２
の割合で質霧器でスプレーし、さらに水で壁面を洗滌し
た。The coating liquid used in Example 9 was applied to the inner walls of the polymerization tank and other parts that come into contact with vinyl chloride at 0.000. 2g/m2
The wall surface was then washed with water.

このような処置をした後、真空ポンプを用いて内部の空
気を排除し、第１段の４１たて型重合槽に塩化ビニル１
５００ｇ、２・２’−アゾビス−２・４一ジメチルバレ
ロニトリル０．３２を装入し、温度６０℃で１時間重合
を行なった後、内容物を第２段の６１の横型重合槽に移
送した。After taking these steps, remove the air inside using a vacuum pump, and add 1 liter of vinyl chloride to the first stage 41 vertical polymerization tank.
After charging 500 g and 0.32 of 2,2'-azobis-2,4-dimethylvaleronitrile and carrying out polymerization at a temperature of 60°C for 1 hour, the contents were transferred to the second stage, No. 61 horizontal polymerization tank. did.

移送後５７℃で圧力が６． −５ ｋｇ／ｃｒｔｆに達
するまで反応を続けた。After transfer, the pressure was 6.5℃ at 57℃. The reaction was continued until -5 kg/crtf was reached.

未反応モノマーを回収後内容物を排出し、重合槽内壁の
状態を調べたところ、ごく少量のポリマー付着が認めら
れるのみであった。After collecting the unreacted monomers, the contents were discharged and the condition of the inner wall of the polymerization tank was examined, and only a small amount of polymer adhesion was observed.

付着しているポリマーはひじように脆弱で、２ｋｇ／ｃ
ｒｔｆの弱い水圧の水で容易に除去することができ、除
去したポリマーを乾燥後重量測定したところ、第１段重
合槽のものは４グ、第２段重合槽のものは５０グであっ
た。The attached polymer is as fragile as an elbow and weighs 2kg/c.
It can be easily removed with water under low RTF water pressure, and when the weight of the removed polymer was measured after drying, it was 4 g in the first stage polymerization tank and 50 g in the second stage polymerization tank. .

比較例 ４ 実施例１０において、フェノール・アルデヒド縮合物の
塗布な行わなかった以外はすべて実施例１０と同じよう
にして塩化ビニルの重合を行ない、重合後の重合槽内壁
の状態を調べたところ、多量のポリマー付着が認められ
た。Comparative Example 4 Vinyl chloride was polymerized in the same manner as in Example 10 except that the phenol-aldehyde condensate was not applied, and the condition of the inner wall of the polymerization tank after polymerization was examined. A large amount of polymer adhesion was observed.

付着しているポリマーはひじように強固で、１５ｋｇ／
ｃｍ２の水圧の水でも除去することができなかった。The attached polymer is as strong as an elbow and weighs 15 kg/
It could not be removed even with water at a pressure of cm2.

機械的に除去したポリマーの乾燥重量は、第１段重合槽
のものは１０２、第２段重合槽のものは４８０２であっ
た。The dry weight of the mechanically removed polymer was 102 in the first stage polymerization tank and 4802 in the second stage polymerization tank.

フェノール・アルデヒド縮合物の製造例９二還流冷却器
付反応機に石炭酸１ ８．８ｋｙ（ ２０ ０モル）、
メタクレゾール５．４ｋｇ（５０モル）、４８重量％ホ
ルマリン２ ５．０ｋｇ（ ４ ０ ０モル）、４０％
苛性ソーダ水］．．２ ５ｋｇ（ １ ２．５モル）を
装入し、８５℃で反応を行なった。Production example 9 of phenol-aldehyde condensate In a reactor equipped with two reflux condensers, 18.8 ky (200 mol) of carbolic acid was added.
Metacresol 5.4 kg (50 mol), 48% by weight Formalin 25.0 kg (400 mol), 40%
Caustic soda water]. ．． 25 kg (12.5 mol) was charged, and the reaction was carried out at 85°C.

このようにして、すでに記述した方法に基づく粘度（６
０ｒｐｎでＮｏ３スピンドル使用）が８０℃において５
００センチポイズになるまで縮合反応を続け、この縮合
物を０９と名付けた。In this way, the viscosity (6
0 rpm using No. 3 spindle) is 5 at 80°C.
The condensation reaction was continued until it reached 00 centipoise, and this condensate was named 09.

このＧ９の固形分濃度は７５重量％であった。The solid content concentration of this G9 was 75% by weight.

実施例 １１ （還流冷却器使用の例） 上記のようにしてえられた縮合物Ｇ９を２重量％苛性ソ
ーダ水に溶解して濃度が２重量％になるよう調節して塗
布液を調製した。Example 11 (Example of using a reflux condenser) Condensate G9 obtained as described above was dissolved in 2% by weight caustic soda water and the concentration was adjusted to 2% by weight to prepare a coating liquid.

この塗布液を内容積７ｍ３のステンレス製重合槽の内壁
および重合付属装置である伝熱面積５ｍ′のステンレス
製還流冷却器の管内（塩化ビニルと接触する部分）に０
． ０ ５ｇ／ｍ２の割合で塗布した。This coating solution was applied to the inner wall of a stainless steel polymerization tank with an internal volume of 7 m3 and the tubes of a stainless steel reflux condenser with a heat transfer area of 5 m' (the part that comes into contact with vinyl chloride), which is an accessory device for polymerization.
．． It was applied at a rate of 0.5 g/m2.

このような処置をした後、脱イオン水３０００ｋｇ，２
・２′−アゾビス−２・４−ジメチルバレロニトリル０
． ６ ｋｇ、鹸化度７２モル％の部分鹸化ポリビニル
アルコール２ｋｇを装入し、内部の空気を真空ポンプで
排除した。After such treatment, 3000 kg of deionized water, 2
・2'-azobis-2,4-dimethylvaleronitrile 0
．． 6 kg of partially saponified polyvinyl alcohol with a degree of saponification of 72 mol% was charged, and the air inside was removed using a vacuum pump.

然る後塩化ビニル２ＯＯＯ ｋｇを装入し、５７℃で圧
力が５ ｋｇ／ｃｍ３に達するまで反応を続げた。Thereafter, 200 kg of vinyl chloride was charged, and the reaction was continued at 57°C until the pressure reached 5 kg/cm3.

この間、重合開始後１時間目から内圧降下がはじまるま
での期間反応熱の一部除去を還流冷却器を援用すること
により行なった。During this period, a part of the reaction heat was removed by using a reflux condenser from 1 hour after the start of polymerization until the internal pressure began to decrease.

反応終了後未反応モノマーを回収し、ポリマースラリー
を排出後重合槽内壁、還流冷却器管内、攪拌翼、攪拌軸
、バツフル等重合中塩化ビニルが接触する部分を簡単に
水洗するだけで、塗布液の塗布と重合バッチを合計３０
回くりかえした。After the reaction is complete, unreacted monomers are collected and the polymer slurry is discharged.The coating solution can be removed by simply washing with water the inner walls of the polymerization tank, the inside of the reflux condenser tube, stirring blades, stirring shafts, bubbles, and other parts that come in contact with vinyl chloride during polymerization. A total of 30 coating and polymerization batches
I repeated it.

この間重合槽および還流冷却器の冷却能力が低下するよ
うなことは認められず、また各壁面に付着ボリマーが蓄
積するようなこともなかった。During this period, no decrease in the cooling capacity of the polymerization tank or reflux condenser was observed, and no polymers adhered to the walls were accumulated.

フェノール・アルデヒド樹脂の製造例１０：還流冷却器
付三ツ口フラスコに、石炭酸９４ｇ（１モル）、４８重
量％ホルマリン１００ｇ（ホルムアルデヒド１．６モル
）、トリエチルアミン５．０５ｇ（０．０５モル）を装
入し、８５℃で反応を行なった。Production example 10 of phenol/aldehyde resin: A three-necked flask with a reflux condenser was charged with 94 g (1 mol) of carbolic acid, 100 g (1.6 mol) of 48% formalin by weight, and 5.05 g (0.05 mol) of triethylamine. The reaction was carried out at 85°C.

このようにして、すでに記述した方法に基づく粘度（６
０ｒｐｍでＮｏ１スピンドル使用）が８０℃において１
０センチポイズになるまで縮合反応を続け、縮合物をＧ
ＩＯと名付けた。In this way, the viscosity (6
1 spindle at 80°C)
Continue the condensation reaction until the temperature becomes 0 centipoise, and convert the condensate into G
It was named IO.

実施例 １２ （共重合の例） 上記のようにしてえられた縮合物ＧＩＯを２重量％の苛
性ソーダ水に溶解して濃度が２重量％になるよう調節し
て塗布液を調製した。Example 12 (Example of copolymerization) The condensate GIO obtained as described above was dissolved in 2% by weight of caustic soda water and the concentration was adjusted to 2% by weight to prepare a coating liquid.

この塗布液を内容積３００ｌのステンレス製重合槽の内
壁に０．５ｇ／ｍ２の割合で噴霧器でスプレーし、さら
に水で壁面を洗滌した。This coating solution was sprayed onto the inner wall of a stainless steel polymerization tank having an internal volume of 300 liters at a rate of 0.5 g/m2 using a sprayer, and the wall surface was further washed with water.

このような処置をした後、脱イオン水２００ｋｇ、ラウ
ロイルパーオキサイド０．０５ｋｇ、ヒドロキシグロピ
ルセルローズ０．１５ｋｇ、酢酸ビニル５ｋｇを装入し
内部の空気を真空ポンプで排除した。After such treatment, 200 kg of deionized water, 0.05 kg of lauroyl peroxide, 0.15 kg of hydroxyglopyl cellulose, and 5 kg of vinyl acetate were charged, and the air inside was removed using a vacuum pump.

然る後塩化ビニル９５ｋｇを装入し、６５℃で圧力が５
ｋｇ／ｃｍ２に達するまで反応を続けた。After that, 95 kg of vinyl chloride was charged and the pressure was increased to 5 at 65°C.
The reaction was continued until kg/cm2 was reached.

反応終了後未反応モノマーを回収し、ポリマースラリー
を排出後重合槽内壁に付着したポリマーを調べたところ
、２ ｋｇ／ｃｍ２の水圧の水で容易に除去できる付着
ポリマーが３０２存在したのみであった。After the reaction was completed, unreacted monomers were collected, and after discharging the polymer slurry, the polymer adhering to the inner wall of the polymerization tank was examined, and it was found that there were only 302 adhering polymers that could be easily removed with water at a pressure of 2 kg/cm2. .

比較例 ５ フェノール・アルデヒド縮合物の製造例６でえ、られた
縮合物Ｇ６を２％の苛性ソーダ水に溶解して濃度が５重
量％になるよう調節して塗布液を調製した。Comparative Example 5 The condensate G6 obtained in Production Example 6 of phenol-aldehyde condensate was dissolved in 2% caustic soda water and the concentration was adjusted to 5% by weight to prepare a coating solution.

この塗布液を、内容積７ｍ３のステンレス製重合槽の内
壁に０．５ｇ／ｍ２の割合で噴霧器でスプレー、８０℃
で３０分間加熱乾燥した。This coating solution was sprayed onto the inner wall of a stainless steel polymerization tank with an internal volume of 7 m3 at a rate of 0.5 g/m2 using a sprayer at 80°C.
It was heated and dried for 30 minutes.

このようにすることにより、縮合物は重合槽の内壁面上
で架橋反応を起し、塗布膜は１０重量％の苛性ソーダ水
溶液に溶解しないまでに硬化した。By doing so, the condensate caused a crosslinking reaction on the inner wall surface of the polymerization tank, and the coating film was cured to the point that it could not be dissolved in a 10% by weight aqueous solution of caustic soda.

硬化したフェノール・アルデヒド縮合物の塗布膜を有す
る壁面は水に対しての濡れがよくなく撥水性を示した。The wall surface coated with the cured phenol-aldehyde condensate did not wet well with water and exhibited water repellency.

このような処置をした後、脱イオン水３０００ｋｇ、２
・／〜アゾビス−２・４−ジメチルバレロニトリル０５
グ、鹸化度８０モル％の部分鹸化ポリビニルアルコール
ｌｋｇ、ヒドロキシプ口ピルメチルセルロース１ ｋｇ
を装入し、内部の空気を真空ポンプで除去した。After such treatment, 3000 kg of deionized water, 2
・/~Azobis-2,4-dimethylvaleronitrile 05
1 kg of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol%, 1 kg of hydroxypropylene methylcellulose
was charged, and the air inside was removed using a vacuum pump.

然る後塩化ビニル２０００ｋｇを装入し、５７℃で圧力
が５ ｋｇ／ｃｍ２に達するまで反応を続けた。Thereafter, 2000 kg of vinyl chloride was charged, and the reaction was continued at 57°C until the pressure reached 5 kg/cm2.

反応終了後未反応モノマーを回収し、ポリマースラリー
を排出後重合槽内壁の状態を調べたところ、内壁全面に
多量の膜状ポリマーの付着が認められた。After the reaction was completed, unreacted monomers were collected and the polymer slurry was discharged, and the condition of the inner wall of the polymerization tank was examined, and a large amount of film-like polymer was found to have adhered to the entire inner wall.

すなわち、本比較例により、フェノール・アルデヒドの
縮合反応を高度に行ない縮合物が架橋してしまうと、塗
布膜が撥水性を示してポリマー付着防止効果がなくなる
ことがわかる。That is, this comparative example shows that when the condensation reaction of phenol/aldehyde is carried out to a high degree and the condensate is crosslinked, the coating film exhibits water repellency and the effect of preventing polymer adhesion is lost.

比較例 ６ 還流冷却器付三ツ口フラスコにバラヒドロキシ安息香酸
６９ｇ（０．５モル）、水１００ｇ、３０重量％ホルマ
リン５０ｇ（ホルムアルデヒド０．５モル）、濃塩酸１
５ｇを装入し、還流下縮合物が沈澱してくるまで約１時
間反応させた。Comparative Example 6 In a three-necked flask with a reflux condenser, 69 g (0.5 mol) of rose hydroxybenzoic acid, 100 g of water, 50 g of 30% by weight formalin (0.5 mol of formaldehyde), and 1 mol of concentrated hydrochloric acid were added.
5 g of the reactor was charged, and the reaction was allowed to proceed for about 1 hour under reflux until the condensate precipitated.

然る後、約６０℃に冷却し、４０重量％の苛性ソーダ水
を縮合物が全部溶解するまで連続的に添加した。Thereafter, the mixture was cooled to about 60° C., and 40% by weight of caustic soda water was continuously added until all of the condensate was dissolved.

この溶液のＰＨは９．８であり、これをＡと名付けた。The pH of this solution was 9.8, and it was named A.

別に、バラヒドロキシ安息香酸６９Ｐ（０．５モル）と
３０重量％ホルマリン５０ｇ（ホルムアルデヒド０．５
モル）を混合し、ついで４０重量％の苛性ソーダ水をバ
ラヒドロキシ安息香酸が溶解するまで加えた。Separately, rose hydroxybenzoic acid 69P (0.5 mol) and 30 wt% formalin 50 g (formaldehyde 0.5
mol) was mixed and then 40% by weight aqueous caustic soda was added until the parahydroxybenzoic acid was dissolved.

この溶液のＰＨは９．８であり、これをＢと名付けた。The pH of this solution was 9.8, and it was named B.

ＡＫＢを加え、９５℃まで１５分間で昇温し、還流下２
０分間反応させた。Add AKB, raise the temperature to 95°C for 15 minutes, and reflux for 2 hours.
The reaction was allowed to proceed for 0 minutes.

生成した縮合物を希塩酸で沈澱させ、濾過、水洗、真空
乾燥した。The resulting condensate was precipitated with dilute hydrochloric acid, filtered, washed with water, and dried in vacuum.

このようにしてえられた縮合物を、エタノールに溶解し
て濃度が１０重量％になるように調節して塗布液を調製
した。The condensate thus obtained was dissolved in ethanol and the concentration was adjusted to 10% by weight to prepare a coating solution.

この塗布液を、内容積７ｍ３のステンレス製重合槽の内
壁に０．５ｇ／ｍの割合で噴霧器でスプレーし、８０℃
で３０分間加熱乾燥した。This coating liquid was sprayed with a sprayer at a rate of 0.5 g/m onto the inner wall of a stainless steel polymerization tank with an internal volume of 7 m3, and the temperature was 80°C.
It was heated and dried for 30 minutes.

このようにすることにより、縮合物は重合槽の内壁面上
で架橋反応を起し、塗布膜は１０重量％の苛性ソーダ水
溶液に溶解しないまでに硬化した。By doing so, the condensate caused a crosslinking reaction on the inner wall surface of the polymerization tank, and the coating film was cured to the point that it could not be dissolved in a 10% by weight aqueous solution of caustic soda.

硬化したバラヒドロキシ安息香酸・ホルムアルデヒド縮
合物の塗布膜を有する壁面は水に対しての濡れがよくな
く撥水性を示した。The wall surface coated with the cured rose hydroxybenzoic acid/formaldehyde condensate did not wet well with water and exhibited water repellency.

このような処置をした後、縮合物の塗布が異なるほかは
比較例５と同じ方法で塩化ビニルの重合を行ない、重合
槽内壁の状態を調べたところ、内壁全面に薄い膜状ボリ
マーの付着が認められた。After these treatments, vinyl chloride was polymerized in the same manner as in Comparative Example 5 except that the condensate was applied differently, and when the condition of the inner wall of the polymerization tank was examined, it was found that a thin film of polymer was adhered to the entire inner wall. Admitted.

Claims (1)

【特許請求の範囲】[Claims] １ 塩化ビニルを単独で、またはこれと共重合しうるモ
ノマーと共に、水性媒体中に於でまたは塊状にて重合す
るに際し、重合槽内壁および重合操作中にモノマーが接
触する装置部分に、あらかじめフェノールとアルデヒド
との初期縮合物若しくは該初期縮合物を変性剤で変性し
たものを塗布することを特徴とする塩化ビニルの単独又
は共重合方法。1. When vinyl chloride is polymerized alone or together with a monomer that can be copolymerized with vinyl chloride in an aqueous medium or in bulk, phenol is added to the inner wall of the polymerization tank and the parts of the equipment that come into contact with the monomer during the polymerization operation. A method for the homopolymerization or copolymerization of vinyl chloride, which comprises coating an initial condensate with an aldehyde or a modified initial condensate with a modifier.