JP2005048024A - Scale deposition preventive agent for polymerization reactor - Google Patents
Scale deposition preventive agent for polymerization reactor Download PDFInfo
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- JP2005048024A JP2005048024A JP2003204781A JP2003204781A JP2005048024A JP 2005048024 A JP2005048024 A JP 2005048024A JP 2003204781 A JP2003204781 A JP 2003204781A JP 2003204781 A JP2003204781 A JP 2003204781A JP 2005048024 A JP2005048024 A JP 2005048024A
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- Prior art keywords
- polymerization reactor
- scale adhesion
- polymerization
- compound
- weight
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- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- PZHNNJXWQYFUTD-UHFFFAOYSA-N phosphorus triiodide Chemical compound IP(I)I PZHNNJXWQYFUTD-UHFFFAOYSA-N 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CONVKSGEGAVTMB-RKJRWTFHSA-M potassium (2R)-2-[(1R)-1,2-dihydroxyethyl]-4-hydroxy-5-oxo-2H-furan-3-olate Chemical compound [K+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] CONVKSGEGAVTMB-RKJRWTFHSA-M 0.000 description 1
- 235000019275 potassium ascorbate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- CONVKSGEGAVTMB-RXSVEWSESA-M potassium-L-ascorbate Chemical compound [K+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] CONVKSGEGAVTMB-RXSVEWSESA-M 0.000 description 1
- 235000019153 potassium-L-ascorbate Nutrition 0.000 description 1
- 239000011725 potassium-L-ascorbate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
- 239000011755 sodium-L-ascorbate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、各種ポリマーの重合反応器に塗布され、該重合反応器へのポリマーの付着を防止する重合反応器用スケール付着防止剤に関する。
【０００２】
【従来の技術】
各種ポリマーを重合する場合において、その重合に使用される重合反応器の内面には、重合物等がスケールとして強固に付着することが知られている。このようなスケールの付着は、重合体の収率を低下させたり、該重合反応器の冷却能力を低下させるといった問題を生じる。
【０００３】
従来、このようなスケールの付着を防止するために、例えば、塩化ビニルの懸濁重合においては、ナフトールとアルデヒド化合物等の極性有機化合物からなるスケール付着防止剤を重合反応器の内面に塗布し、スケールの付着を防止する方法が提案されている（特許文献１参照）。
しかしながら、該スケール付着防止剤は濃紺色や黒褐色のものであるため、重合反応器内面から剥離して重合体に混入すれば、製品となる重合体の着色やフィッシュアイの原因となり、製品の品質低下を招く場合がある。
【０００４】
重合反応器からの剥離を防止するスケール付着防止剤としては、２，３−ジヒドロキシナフタリンの２量体化合物とホルムアルデヒドとを縮合させて得られる分子量５００〜１００万の縮合化合物のアルカリ性溶液を含有してなるスケール付着防止剤も開示されている（特許文献２参照）。しかし、くり返し重合反応に使用される重合反応器内面に塗布されるスケール付着防止剤について、内面からの剥離を完全に無くすことは不可能である。
【０００５】
そこで従来、スケール付着防止剤による着色を改善すべく、ナフトールとアルデヒド化合物にヒドロ亜硫酸塩を添加することにより、該スケール付着防止剤を透明な状態とする方法が提案されている（特許文献３参照）。
【０００６】
【特許文献１】
特公平１−３１５２３号公報
【特許文献２】
特開平１０−２１８９０４号公報
【特許文献３】
特表平１１−５０５５５８号公報
【０００７】
【発明が解決しようとする課題】
しかしながら、ヒドロ亜硫酸塩を添加してなるスケール付着防止剤は、重合反応器内面へ塗布する際にヒドロ亜硫酸塩がイオウ臭を発生させ、作業環境を悪化させるという問題が指摘されている。
そこで本発明は、重合反応器から剥離して重合体中へ混入した場合であっても、重合体の着色やフィッシュアイの発生を抑制し、しかも重合反応器への塗布時においても作業環境を悪化させることのない重合反応器用スケール付着防止剤を提供することを課題とする。
【０００８】
【課題を解決するための手段】
前記課題を解決すべく、本発明者が鋭意研究したところ、ナフトール化合物とアルデヒド類とを縮合させて得られる分子量５００〜１０万の縮合生成物にアスコルビン酸化合物を加えて得たスケール付着防止剤は、該スケール付着防止剤が重合反応器から剥離して重合体中に混入した場合であっても、重合体（即ち、ポリマー製品）の着色等を防止し得るものであることを見出した。
即ち、本発明は、ナフトール化合物とアルデヒド類とが縮合した重量平均分子量５００〜１０万の縮合生成物と、アスコルビン酸化合物とを含有してなることを特徴とする重合反応器用スケール付着防止剤を提供する。
本発明の重合反応器用スケール付着防止剤を使用すれば、重合体の着色やフィッシュアイの発生を効果的に抑制でき、しかも重合反応器への塗布作業において有害ガスを発生させず作業環境を悪化させる虞もない。
【０００９】
このように、アスコルビン酸化合物がスケール付着防止剤による着色等を防止し得るのは、該アスコルビン酸化合物の強い還元作用によるものと考えられる。
【００１０】
また、本発明は、前記ナフトール化合物１００重量部に対し、前記アスコルビン酸化合物が１〜１００重量部配合されてなる重合反応器用スケール付着防止剤を提供する。
斯かる配合割合でアスコルビン酸化合物を添加することにより、重合体の着色やフィッシュアイの発生をより一層効果的に防止し得るものとなる。
【００１１】
また、本発明は、１−ナフトールとホルムアルデヒドとがモル比１．０：０．５〜１．０：１．５で水溶液中に１〜４０重量％の濃度で混合され、さらに窒素雰囲気下、ｐＨ１１〜１３のアルカリ中で縮合させて得られた縮合生成物と、アスコルビン酸化合物とを含有してなることを特徴とする重合反応器用スケール付着防止剤を提供する。
【００１２】
さらに、本発明の重合反応器用スケール付着防止剤は、好ましくは水溶性高分子化合物を含有するものである。
【００１３】
水溶性高分子化合物が含有されていることにより、該スケール付着防止剤の重合反応器への付着作用を高め、重合体への混入を低減して重合体の着色やフィッシュアイの発生をより効果的に防止し得るスケール付着防止剤となる。また、スケール付着防止効果の改善をより一層高めることができる。
【００１４】
【発明の実施の形態】
本発明の重合反応器用スケール付着防止剤は、ナフトール化合物とアルデヒド類とを縮合させて得られる分子量５００〜１０万の縮合生成物と、アスコルビン酸化合物とを含有することを特徴とするものである。
【００１５】
本発明において、アスコルビン酸化合物としては、Ｌ−アスコルビン酸（ビタミンＣ）の他、Ｌ−アスコルビン酸ナトリウム、Ｌ−アスコルビン酸カリウム等のＬ−アスコルビン酸の塩、或いは、イソアスコルビン酸（エリソルビン酸）、イソアスコルビン酸ナトリウム（エリソルビン酸ナトリウム）、イソアスコルビン酸カリウム（エリソルビン酸カリウム）などのＬ−アスコルビン酸の異性体およびその塩を使用することができる。これらは、１種単独、又は２種以上の混合物として使用することができる。
中でも、安価であるという点で、特にイソアスコルビン酸ナトリウム（エリソルビン酸ナトリウム）が好ましい。
【００１６】
また、該アスコルビン酸化合物の添加により重合体の着色やフィッシュアイの発生を効果的に防止するには、ナフトール化合物１００重量部に対し、前記アスコルビン酸化合物の配合量を１〜１００重量部とすることが好ましく、さらに、１０〜５０重量部とすることがより好ましい。
【００１７】
本発明において、ナフトール化合物としては、１−ナフトール、２−ナフトール、１，３−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、６−ヒドロキシ−２−ナフトエ酸、１−ヒドロキシ−２−ナフトエ酸、２−ヒドロキシ−１−ナフトエ酸、１−ヒドロキシ−８−ナフトエ酸などを使用できる。これらは、１種単独、又は２種以上の混合物として使用することができる。
【００１８】
また、アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、フルフラールなどを使用することができる。これらは１種単独、又は２種以上の混合物として使用することができる。
【００１９】
特に、前記ナフトール化合物として１−ナフトールを用い、前記アルデヒド類としてホルムアルデヒドを用い、これら１−ナフトールとホルムアルデヒドとを１．０：０．５〜１．０：１．５のモル比で縮合させて得られる縮合生成物と、前記アスコルビン酸化合物との混合によって得られたスケール付着防止剤は、重合反応器内面への付着強度が高く、繰り返し重合反応に使用しても剥離しにくいものとなり、重合体の着色やフィッシュアイの発生を極めて有効に防止することができる。
【００２０】
また、本発明においては、縮合生成物として重量平均分子量が５００〜１０万のものを使用するが、中でも、水洗浄による除去性に優れるという観点から、特に分子量５００〜５０００のものがより好ましい。
【００２１】
尚、本発明において、縮合生成物の重量平均分子量は、ＧＰＣ法を採用し、ポリスチレンに換算した値である。具体的には、ＧＰＣ本体として島津製作所製、Ｃ−Ｒ４Ａを使用し、カラム温度４０℃、ポンプ流量０．８ｍＬ／分に設定するとともに、検出器として島津製作所製、ＵＶ（ＳＰＤ−６Ａ、λ＝２５４ｎｍ）検出器を用い、データ処理は、あらかじめ分子量が既知のポリスチレンの検量線（分子量４００以上での検量）を用いて、ポリスチレン換算分子量として分子量を得るものとする。
使用カラム：東ソー社製、Ｇ４０００ＨＸＬ・１本、Ｇ３０００ＨＸＬ・１本、Ｇ２０００ＨＸＬ・１本、Ｇ１０００ＨＸＬ・２本
移動相：テトラヒドロフラン（ＴＨＦ）
注入量：２０μＬ
サンプル濃度：０．０２％（ｗ／ｗ）
【００２２】
また、本発明の重合反応器用スケール付着防止剤は、他の成分として、水溶性高分子化合物を添加することが好ましい。水溶性高分子化合物を添加することにより、スケール付着防止剤の重合反応器内壁への付着強度をより一層高めることができ、重合体への混入による着色やフィッシュアイの発生をより効果的に防止することができる。さらに、水溶性高分子化合物を添加すれば、該スケール付着防止剤塗布面の親水性が高くなるため、スケール付着防止効果をより一層高めることもできる。
【００２３】
斯かる水溶性高分子化合物としては、具体的には、ポリビニルアルコール、部分ケン化ポリビニルアルコール、ポリビニルピロリドン、ヒドロキシエチルセルロース、ペクチン、カルボキシメチルセルロース、ポリアクリル酸およびその塩、ポリスチレンスルホン酸およびその塩、ゼラチン、カゼイン、ポリオキシアルキレングリコール、ポリメチルビニルエーテル、ポリメタクリル酸およびその塩、アクリル酸−メタクリル酸共重合体およびその塩、アルキルビニルエーテル−マレイン酸共重合体およびその塩、酢酸ビニル−マレイン酸共重合体およびその塩、スチレン−マレイン酸共重合体およびその塩、ジイソブチレン−マレイン酸共重合体およびその塩、マレイン化ポリブテン、マレイン化ポリブタジエン、ポリアクリルアミド、ポリエチレンイミン、メチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、メチルヒドロキシプロピルセルロース、可溶性デンプン、カルボキシメチルデンプン、ジアルデヒドデンプン、コーンスターチ、アルギン酸ナトリウム、デキストラン、コラーゲン、キサンタンガム、ラムザンガム、アルギン酸、キトサンなどが挙げられる。これらは、１種単独で使用することができ、２種以上の混合物として使用することもできる。
特に、重合体がポリ塩化ビニルである場合には、その重合の原料でもあるポリビニルアルコールや部分ケン化ポリビニルアルコールを使用することが好ましい。
【００２４】
本発明に係る重合反応器用スケール付着防止剤の製造方法としては、ナフトール化合物とアルデヒド類とアスコルビン酸化合物とを混合し、所定の温度に加熱してナフトール化合物とアルデヒド類とを縮合重合させる方法を好適に採用することができる。該重合反応は、窒素雰囲気下において、ｐＨ１１〜１３のアルカリ溶液中で行うことが好ましい。また、該重合反応は、ナフトール化合物とアルデヒド類との合計が１〜４０重量％となるような水溶液中で行うことが好ましい。
【００２５】
本発明に係る重合反応器用スケール付着防止剤は、塩化ビニル、塩化ビニリデン、スチレン、アクリロニトリル、ブタジエン、アクリル酸、酢酸ビニル、エチレン、プロピレン、アクリルアミド、アクリル酸エステル、イソプレン、クロロプレンなどの各種ポリマー原料を重合させるための重合プロセスに用いる重合反応器の内面に塗布して使用することができる。
また、本発明に係る重合反応器用スケール付着防止剤は、前記単量体を単独又は２種以上組み合わせて用いられる懸濁重合法、ミクロ懸濁重合法、乳化重合法などに適用できる。
特に、塩化ビニル単独の重合体や、塩化ビニルと他の重合体とが共重合した塩化ビニル系共重合体といった塩化ビニル系重合体を懸濁重合により製造する際に用いる重合反応器に使用した場合、特にその効果が顕著となる。
【００２６】
本発明に係る重合反応器用スケール付着防止剤は、さらに、必要に応じて各種の還元剤を配合することもできる。そのような還元剤の例としては、ナトリウム、リチウムなどのアルカリ金属、マグネシウム、カルシウム、アルミニウム、亜鉛などの金属およびそのアマルガム、硫化鉄（ＩＩ）、塩化スズ（ＩＩ）、三塩化チタン（ＩＩＩ）などの金属塩類、一酸化炭素、二酸化イオウ、チオ硫酸ナトリウム、チオ亜硫酸ナトリウム、亜硫酸ナトリウム、亜硫酸カリウム、重亜硫酸ナトリウム、ハイドロサルファイトナトリウム、ロンガリット、硫化ナトリウム、ポリ硫化ナトリウム、硫化アンモニウム、三塩化リン、三ヨウ化リン、トリメチルホスフィン、トリフェニルホスフィン、トリメチルホスフィット、次亜リン酸ナトリウム、ヒドラジン、ジボラン、エタン−１，２−ジアミノボラン、ジメチルアミン−ボラン、ピリジンボランなどが挙げられる。
【００２７】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２８】
（実施例１）
滴下漏斗、還流冷却器、温度計および攪拌機を備えた５Ｌのセパラブルフラスコに、イオン交換水１Ｌ、１−ナフトール１８０ｇ、および触媒として水酸化ナトリウム３８ｇを仕込み、次いでオイルバスにて７０℃に加温し、窒素気流下で３７％ホルムアルデヒド水溶液１０２ｇを徐々に滴下した。滴下終了後、１２％イソアスコルビン酸ナトリウム水溶液４００ｇを配合し、６０℃に冷却し、３時間反応させた。次に、９８℃に昇温し、１．５時間反応させた後、反応混合物に水を加えて固形分を５％に調整し、淡褐色のスケール付着防止剤を得た。
上述のＧＰＣ法によって該スケール付着防止剤の分子量を測定したところ、重量平均分子量が１０００であった。
【００２９】
（実施例２）
１２％イソアスコルビン酸ナトリウム水溶液を５５０ｇ混合する点を除き、他は実施例１と同様にしてスケール付着防止剤を得た。また、同様にして分子量を測定したところ、重量平均分子量が１５００であった。
【００３０】
（実施例３）
１２％イソアスコルビン酸ナトリウム水溶液の代わりに２０％Ｌ−アスコルビン酸ナトリウム水溶液を２４０ｇ配合する点を除き、他は実施例１と同様にしてスケール付着防止剤を得た。また、同様にして分子量を測定したところ、重量平均分子量が１０００であった。
【００３１】
（実施例４）
滴下漏斗、還流冷却器、温度計および攪拌機を備えた５Ｌのセパラブルフラスコに、イオン交換水１Ｌ、１−ナフトール１８０ｇ、および触媒として水酸化ナトリウム３８ｇを仕込み、次いでオイルバスにて７０℃に加温し、窒素気流下で３７％ホルムアルデヒド水溶液１０２ｇを徐々に滴下した。滴下終了後、１２％イソアスコルビン酸ナトリウム水溶液４００ｇを配合し、６０℃に冷却し、３時間反応させた。次に、９８℃に昇温し、１．５時間反応させた後、反応混合物に水とポリビニルアルコール（けん化度＝９８ｍｏｌ％以上、重合度＝１７００）を加えて固形分のうち０．５％がポリビニルアルコールになるように、固形分を５．５％に調整し、淡褐色のスケール付着防止剤を得た。
上述のＧＰＣ法によって該スケール付着防止剤の分子量を測定したところ、重量平均分子量が１０００であった。
【００３２】
（実施例５）
滴下漏斗、還流冷却器、温度計および攪拌機を備えた５Ｌのセパラブルフラスコに、イオン交換水１Ｌ、１−ナフトール１８０ｇ、および触媒として水酸化ナトリウム３８ｇを仕込み、次いでオイルバスにて７０℃に加温し、窒素気流下で３７％ホルムアルデヒド水溶液１０２ｇを徐々に滴下した。滴下終了後、１２％イソアスコルビン酸ナトリウム水溶液３８０ｇを配合し、次いで１２％ハイドロサルファイトナトリウム水溶液２０ｇを配合し、６０℃に冷却し、３時間反応させた。次に、９８℃に昇温し、１．５時間反応させた後、反応混合物に水とポリビニルアルコール（けん化度＝９８ｍｏｌ％以上、重合度＝１７００）を加えて固形分のうち０．５％がポリビニルアルコールになるように、固形分を５．５％に調整し、淡黄色のスケール付着防止剤を得た。
上述のＧＰＣ法によって該スケール付着防止剤の分子量を測定したところ、重量平均分子量が１０００であった。
【００３３】
（比較例１）
１２％イソアスコルビン酸ナトリウム水溶液を混合しない点を除き、他は実施例１と同様にしてスケール付着防止剤を得た。また、同様にして分子量を測定したところ、重量平均分子量が７００であった。
【００３４】
（比較例２）
１２％イソアスコルビン酸ナトリウム水溶液の代わりに１２％ハイドロサルファイトナトリウム水溶液４００ｇを混合する点を除き、他は実施例１と同様にしてスケール付着防止剤を得た。また、同様にして分子量を測定したところ、重量平均分子量が１０００であった。
【００３５】
（性能試験）
内容量１０００Ｌの攪拌機付きステンレス製重合反応器の内壁に、上述のようにして作製した重合反応器用スケール付着防止剤を噴霧塗布し、次いで重合反応器内を十分水洗いした。
その後、該重合反応器中に水４００ｋｇ、塩化ビニル２００ｋｇ、部分ケン化ポリビニルアルコール２５０ｇ、ヒドロキシプロピルメチルセルロース２５ｇ、及び３，５，５−トリメチルヘキサノイルパーオキサイド７０ｇを仕込み、攪拌しながら６０℃で６時間重合した。重合終了後、生成した重合体スラリーを排出し、脱モノマー工程によってモノマーを除去し、脱水後得られたポリマーを乾燥させることにより、ＰＶＣレジンを得た。
さらに、該重合反応器を洗浄し、同様にして第２回目の重合を行った。以後、同様にして合計１０回の重合を行い、最後（即ち１０回目）に得られた製品および使用後の重合反応器について、以下の測定を行った。
【００３６】
（スケール付着量の測定）
重合反応器内壁の所定個所１×１ｍの区域に付着したポリマーをへらで掻き落とし、天秤で計量することにより、スケールの付着量を測定した。
【００３７】
（フィッシュアイの測定）
得られたＰＶＣレジン１００重量部に対して、ジオクチルフタレート５０重量部と三塩基性硫酸鉛２重量部とを混合し、１５０℃で５分間ロールミルを用いて混練し、厚み０．２ｍｍのシートを作製して、その１０×１０ｃｍの領域中に存在するフィッシュアイの個数を目視により調べた。
【００３８】
（着色異物の測定）
得られたＰＶＣレジン１００重量部に対して、ジオクチルフタレート２０重量部と三塩基性硫酸鉛２重量部とを混合し、１４×１４ｃｍの正方形で厚み３ｃｍの型枠に入れ、次いで１８０℃の温度で３５ｋｇ／ｃｍ２の圧力で加圧成形することにより、シートを作製し、着色異物の個数を目視により調べた。
【００３９】
測定結果を表１に示す。
【表１】
【発明の効果】
以上のように、本発明に係る重合反応器用スケール付着防止剤は、塗布時に臭気を発生させて作業環境を悪化させることなく、また、重合体の着色やフィッシュアイの発生による品質低下を効果的に防止し得るものとなる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an anti-scale adhesion agent for a polymerization reactor that is applied to a polymerization reactor of various polymers and prevents the adhesion of the polymer to the polymerization reactor.
[0002]
[Prior art]
When polymerizing various polymers, it is known that a polymer or the like is firmly attached as a scale to the inner surface of a polymerization reactor used for the polymerization. Such scale adhesion causes problems such as lowering the yield of the polymer and lowering the cooling capacity of the polymerization reactor.
[0003]
Conventionally, in order to prevent such scale adhesion, for example, in suspension polymerization of vinyl chloride, a scale adhesion inhibitor composed of a polar organic compound such as naphthol and an aldehyde compound is applied to the inner surface of the polymerization reactor, A method for preventing adhesion of scale has been proposed (see Patent Document 1).
However, since the scale adhesion preventing agent is dark blue or blackish brown, if it is peeled off from the inner surface of the polymerization reactor and mixed into the polymer, it will cause coloring of the product polymer or fish eye, resulting in product quality. It may cause a decrease.
[0004]
The scale adhesion preventing agent for preventing peeling from the polymerization reactor contains an alkaline solution of a condensed compound having a molecular weight of 500 to 1,000,000 obtained by condensing a dimer compound of 2,3-dihydroxynaphthalene and formaldehyde. An anti-scale adhesion agent is also disclosed (see Patent Document 2). However, it is impossible to completely eliminate peeling from the inner surface of the scale adhesion preventing agent applied to the inner surface of the polymerization reactor used in the repeated polymerization reaction.
[0005]
Therefore, conventionally, a method has been proposed in which the scale adhesion inhibitor is made transparent by adding hydrosulfite to naphthol and an aldehyde compound in order to improve coloring due to the scale adhesion inhibitor (see Patent Document 3). ).
[0006]
[Patent Document 1]
Japanese Patent Publication No. 1-31523 [Patent Document 2]
JP-A-10-218904 [Patent Document 3]
Japanese National Patent Publication No. 11-505558
[Problems to be solved by the invention]
However, it has been pointed out that the scale adhesion preventing agent to which hydrosulfite is added has a problem that when it is applied to the inner surface of the polymerization reactor, the hydrosulfite generates a sulfur odor and deteriorates the working environment.
Therefore, the present invention suppresses the coloring of the polymer and the generation of fish eyes even when the polymer is peeled off from the polymerization reactor and mixed into the polymer, and the working environment is improved even when applied to the polymerization reactor. It is an object of the present invention to provide a scale deposition inhibitor for a polymerization reactor that does not deteriorate.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively researched and found that a scale adhesion inhibitor obtained by adding an ascorbic acid compound to a condensation product having a molecular weight of 500 to 100,000 obtained by condensing a naphthol compound and an aldehyde. Has found that even when the scale adhesion preventing agent is peeled off from the polymerization reactor and mixed into the polymer, coloring of the polymer (that is, polymer product) can be prevented.
That is, the present invention provides a scale deposition inhibitor for a polymerization reactor comprising a condensation product having a weight average molecular weight of 500 to 100,000 obtained by condensing a naphthol compound and an aldehyde, and an ascorbic acid compound. provide.
By using the scale adhesion preventing agent for the polymerization reactor of the present invention, the coloring of the polymer and the generation of fish eyes can be effectively suppressed, and the working environment is deteriorated without generating harmful gas in the coating operation to the polymerization reactor. There is no fear of making it happen.
[0009]
Thus, it is considered that the ascorbic acid compound can prevent coloring due to the scale adhesion inhibitor due to the strong reducing action of the ascorbic acid compound.
[0010]
Moreover, this invention provides the scale adhesion inhibitor for polymerization reactors by which 1-100 weight part of said ascorbic acid compounds are mix | blended with respect to 100 weight part of said naphthol compounds.
By adding the ascorbic acid compound at such a blending ratio, coloring of the polymer and generation of fish eyes can be more effectively prevented.
[0011]
In the present invention, 1-naphthol and formaldehyde are mixed in an aqueous solution at a molar ratio of 1.0: 0.5 to 1.0: 1.5 at a concentration of 1 to 40% by weight. There is provided a scale deposition inhibitor for a polymerization reactor comprising a condensation product obtained by condensation in an alkali having a pH of 11 to 13 and an ascorbic acid compound.
[0012]
Furthermore, the scale adhesion preventing agent for a polymerization reactor of the present invention preferably contains a water-soluble polymer compound.
[0013]
By containing a water-soluble polymer compound, the adhesion of the scale inhibitor to the polymerization reactor is enhanced, and mixing into the polymer is reduced, resulting in more effective coloring of the polymer and generation of fish eyes. It becomes a scale adhesion preventing agent that can be prevented automatically. Moreover, the improvement of the scale adhesion preventing effect can be further enhanced.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The scale adhesion preventive agent for a polymerization reactor according to the present invention comprises a condensation product having a molecular weight of 500 to 100,000 obtained by condensing a naphthol compound and an aldehyde, and an ascorbic acid compound. .
[0015]
In the present invention, as an ascorbic acid compound, in addition to L-ascorbic acid (vitamin C), a salt of L-ascorbic acid such as sodium L-ascorbate and potassium L-ascorbate, or isoascorbic acid (erythorbic acid) Isomers of L-ascorbic acid such as sodium isoascorbate (sodium erythorbate) and potassium isoascorbate (potassium erythorbate) and salts thereof can be used. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, sodium isoascorbate (sodium erythorbate) is particularly preferable because it is inexpensive.
[0016]
Moreover, in order to effectively prevent the coloring of the polymer and the generation of fish eyes by adding the ascorbic acid compound, the amount of the ascorbic acid compound is 1 to 100 parts by weight with respect to 100 parts by weight of the naphthol compound. More preferably, it is more preferably 10 to 50 parts by weight.
[0017]
In the present invention, as the naphthol compound, 1-naphthol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 6-hydroxy-2 -Naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-8-naphthoic acid and the like can be used. These can be used individually by 1 type or in mixture of 2 or more types.
[0018]
Moreover, as aldehydes, formaldehyde, acetaldehyde, benzaldehyde, furfural, etc. can be used. These can be used individually by 1 type or in mixture of 2 or more types.
[0019]
In particular, 1-naphthol is used as the naphthol compound, formaldehyde is used as the aldehyde, and the 1-naphthol and formaldehyde are condensed at a molar ratio of 1.0: 0.5 to 1.0: 1.5. The scale adhesion inhibitor obtained by mixing the resulting condensation product with the ascorbic acid compound has high adhesion strength to the inner surface of the polymerization reactor, and is difficult to peel off even when repeatedly used in the polymerization reaction. Coloring of coalescence and generation of fish eyes can be extremely effectively prevented.
[0020]
In the present invention, those having a weight average molecular weight of 500 to 100,000 are used as the condensation products, and among them, those having a molecular weight of 500 to 5000 are more preferable from the viewpoint of excellent removability by water washing.
[0021]
In the present invention, the weight average molecular weight of the condensation product is a value converted to polystyrene using the GPC method. Specifically, C-R4A manufactured by Shimadzu Corporation is used as the GPC body, the column temperature is set to 40 ° C., and the pump flow rate is set to 0.8 mL / min, and the detector is manufactured by Shimadzu Corporation UV (SPD-6A, λ = 254 nm) Using a detector, the data processing is to obtain a molecular weight as a polystyrene-equivalent molecular weight using a polystyrene calibration curve (a calibration with a molecular weight of 400 or more) having a known molecular weight in advance.
Column used: manufactured by Tosoh Corporation, G4000HXL · 1, G3000HXL · 1, G2000HXL · 1, G1000HXL · 2 Mobile phase: Tetrahydrofuran (THF)
Injection volume: 20 μL
Sample concentration: 0.02% (w / w)
[0022]
Moreover, it is preferable to add a water-soluble polymer compound as another component to the scale adhesion preventing agent for a polymerization reactor of the present invention. By adding a water-soluble polymer compound, the adhesion strength of the scale adhesion inhibitor to the inner wall of the polymerization reactor can be further increased, and coloring and fish eyes caused by mixing into the polymer can be more effectively prevented. can do. Furthermore, if a water-soluble polymer compound is added, the scale adhesion preventing effect can be further enhanced because the hydrophilicity of the surface to which the scale adhesion preventing agent is applied becomes high.
[0023]
Specific examples of such water-soluble polymer compounds include polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, pectin, carboxymethyl cellulose, polyacrylic acid and its salt, polystyrene sulfonic acid and its salt, gelatin Casein, polyoxyalkylene glycol, polymethyl vinyl ether, polymethacrylic acid and its salt, acrylic acid-methacrylic acid copolymer and its salt, alkyl vinyl ether-maleic acid copolymer and its salt, vinyl acetate-maleic acid copolymer Polymers and salts thereof, styrene-maleic acid copolymers and salts thereof, diisobutylene-maleic acid copolymers and salts thereof, maleated polybutene, maleated polybutadiene, polyacrylamide, Ethyleneimine, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, soluble starch, carboxymethyl starch, dialdehyde starch, corn starch, sodium alginate, dextran, collagen, xanthan gum, rhamsan, alginate, and chitosan and the like. These can be used alone or as a mixture of two or more.
In particular, when the polymer is polyvinyl chloride, it is preferable to use polyvinyl alcohol or partially saponified polyvinyl alcohol which is a raw material for the polymerization.
[0024]
As a method for producing a scale adhesion preventing agent for a polymerization reactor according to the present invention, a method of mixing a naphthol compound, an aldehyde and an ascorbic acid compound, heating the mixture to a predetermined temperature, and subjecting the naphthol compound and the aldehyde to condensation polymerization. It can be suitably employed. The polymerization reaction is preferably performed in an alkaline solution having a pH of 11 to 13 in a nitrogen atmosphere. Moreover, it is preferable to perform this polymerization reaction in aqueous solution that the sum total of a naphthol compound and aldehydes will be 1 to 40 weight%.
[0025]
The scale adhesion preventive agent for polymerization reactor according to the present invention comprises various polymer raw materials such as vinyl chloride, vinylidene chloride, styrene, acrylonitrile, butadiene, acrylic acid, vinyl acetate, ethylene, propylene, acrylamide, acrylate ester, isoprene, and chloroprene. It can apply | coat and use for the inner surface of the polymerization reactor used for the polymerization process for making it superpose | polymerize.
Moreover, the scale adhesion preventing agent for a polymerization reactor according to the present invention can be applied to a suspension polymerization method, a micro suspension polymerization method, an emulsion polymerization method or the like in which the monomers are used alone or in combination of two or more.
In particular, it was used in a polymerization reactor used when a vinyl chloride polymer such as a polymer of vinyl chloride alone or a vinyl chloride copolymer obtained by copolymerizing vinyl chloride and another polymer was produced by suspension polymerization. In this case, the effect is particularly remarkable.
[0026]
The scale adhesion preventing agent for a polymerization reactor according to the present invention may further contain various reducing agents as necessary. Examples of such reducing agents include alkali metals such as sodium and lithium, metals such as magnesium, calcium, aluminum and zinc and amalgams thereof, iron (II) sulfide, tin (II) chloride, titanium (III) chloride. Metal salts such as, carbon monoxide, sulfur dioxide, sodium thiosulfate, sodium thiosulfite, sodium sulfite, potassium sulfite, sodium bisulfite, hydrosulfite sodium, Rongalite, sodium sulfide, sodium polysulfide, ammonium sulfide, phosphorus trichloride , Phosphorus triiodide, trimethylphosphine, triphenylphosphine, trimethylphosphite, sodium hypophosphite, hydrazine, diborane, ethane-1,2-diaminoborane, dimethylamine-borane, pyridineborane, etc.
[0027]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples.
[0028]
(Example 1)
A 5 L separable flask equipped with a dropping funnel, reflux condenser, thermometer and stirrer was charged with 1 L of ion exchange water, 180 g of 1-naphthol, and 38 g of sodium hydroxide as a catalyst, and then heated to 70 ° C. in an oil bath. Warm, 102 g of 37% aqueous formaldehyde solution was gradually added dropwise under a nitrogen stream. After completion of the dropwise addition, 400 g of a 12% sodium isoascorbate aqueous solution was blended, cooled to 60 ° C., and reacted for 3 hours. Next, after heating up to 98 degreeC and making it react for 1.5 hours, water was added to the reaction mixture, solid content was adjusted to 5%, and the light brown scale adhesion preventing agent was obtained.
When the molecular weight of the scale adhesion inhibitor was measured by the GPC method described above, the weight average molecular weight was 1000.
[0029]
(Example 2)
A scale adhesion inhibitor was obtained in the same manner as in Example 1 except that 550 g of a 12% sodium isoascorbate aqueous solution was mixed. Moreover, when the molecular weight was measured similarly, the weight average molecular weight was 1500.
[0030]
(Example 3)
A scale adhesion inhibitor was obtained in the same manner as in Example 1 except that 240 g of 20% L-sodium ascorbate aqueous solution was blended in place of the 12% sodium isoascorbate aqueous solution. Moreover, when the molecular weight was measured similarly, the weight average molecular weight was 1000.
[0031]
(Example 4)
A 5 L separable flask equipped with a dropping funnel, reflux condenser, thermometer and stirrer was charged with 1 L of ion exchange water, 180 g of 1-naphthol, and 38 g of sodium hydroxide as a catalyst, and then heated to 70 ° C. in an oil bath. Warm, 102 g of 37% aqueous formaldehyde solution was gradually added dropwise under a nitrogen stream. After completion of the dropwise addition, 400 g of a 12% sodium isoascorbate aqueous solution was blended, cooled to 60 ° C., and reacted for 3 hours. Next, the temperature was raised to 98 ° C. and reacted for 1.5 hours. Then, water and polyvinyl alcohol (degree of saponification = 98 mol% or more, degree of polymerization = 1700) were added to the reaction mixture, and 0.5% of the solid content. The solid content was adjusted to 5.5% so as to become polyvinyl alcohol, and a light brown scale adhesion preventing agent was obtained.
When the molecular weight of the scale adhesion inhibitor was measured by the GPC method described above, the weight average molecular weight was 1000.
[0032]
(Example 5)
A 5 L separable flask equipped with a dropping funnel, reflux condenser, thermometer and stirrer was charged with 1 L of ion exchange water, 180 g of 1-naphthol, and 38 g of sodium hydroxide as a catalyst, and then heated to 70 ° C. in an oil bath. Warm, 102 g of 37% aqueous formaldehyde solution was gradually added dropwise under a nitrogen stream. After completion of dropping, 380 g of 12% aqueous sodium isoascorbate solution was blended, and then 20 g of 12% aqueous sodium hydrosulfite solution was blended, cooled to 60 ° C., and reacted for 3 hours. Next, the temperature was raised to 98 ° C. and reacted for 1.5 hours. Then, water and polyvinyl alcohol (degree of saponification = 98 mol% or more, degree of polymerization = 1700) were added to the reaction mixture, and 0.5% of the solid content. The solid content was adjusted to 5.5% so as to become polyvinyl alcohol to obtain a pale yellow scale adhesion preventive agent.
When the molecular weight of the scale adhesion inhibitor was measured by the GPC method described above, the weight average molecular weight was 1000.
[0033]
(Comparative Example 1)
A scale adhesion preventing agent was obtained in the same manner as in Example 1 except that 12% sodium isoascorbate aqueous solution was not mixed. Further, when the molecular weight was measured in the same manner, the weight average molecular weight was 700.
[0034]
(Comparative Example 2)
A scale adhesion inhibitor was obtained in the same manner as in Example 1 except that 400 g of a 12% aqueous sodium hydrosulfite solution was mixed instead of the 12% aqueous sodium isoascorbate solution. Moreover, when the molecular weight was measured similarly, the weight average molecular weight was 1000.
[0035]
(performance test)
The polymerization reactor scale adhesion preventive agent produced as described above was sprayed onto the inner wall of a stainless steel polymerization reactor with an internal volume of 1000 L and equipped with a stirrer, and then the polymerization reactor was sufficiently washed with water.
Thereafter, 400 kg of water, 200 kg of vinyl chloride, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropylmethylcellulose, and 70 g of 3,5,5-trimethylhexanoyl peroxide were charged into the polymerization reactor, and the mixture was stirred at 60 ° C. for 6 hours. Polymerized for hours. After the polymerization was completed, the produced polymer slurry was discharged, the monomer was removed by a demonomer process, and the polymer obtained after dehydration was dried to obtain a PVC resin.
Further, the polymerization reactor was washed, and the second polymerization was performed in the same manner. Thereafter, a total of 10 polymerizations were carried out in the same manner, and the following measurements were performed on the product obtained at the end (that is, the 10th time) and the polymerization reactor after use.
[0036]
(Measurement of scale adhesion)
The amount of the scale adhered was measured by scraping the polymer adhering to a predetermined area of 1 × 1 m on the inner wall of the polymerization reactor with a spatula and measuring with a balance.
[0037]
(Fisheye measurement)
To 100 parts by weight of the obtained PVC resin, 50 parts by weight of dioctyl phthalate and 2 parts by weight of tribasic lead sulfate are mixed and kneaded using a roll mill at 150 ° C. for 5 minutes to form a sheet having a thickness of 0.2 mm. The number of fish eyes present in the 10 × 10 cm region was visually examined.
[0038]
(Measurement of colored foreign matter)
To 100 parts by weight of the obtained PVC resin, 20 parts by weight of dioctyl phthalate and 2 parts by weight of tribasic lead sulfate are mixed, placed in a 14 × 14 cm square and 3 cm thick mold, and then at a temperature of 180 ° C. The sheet was prepared by pressure molding at a pressure of 35 kg / cm 2 and the number of colored foreign matters was examined visually.
[0039]
The measurement results are shown in Table 1.
[Table 1]
【The invention's effect】
As described above, the scale adhesion preventive agent for the polymerization reactor according to the present invention does not deteriorate the working environment by generating odor during coating, and effectively reduces the quality due to the coloring of the polymer or the generation of fish eyes. It can be prevented.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003204781A JP2005048024A (en) | 2003-07-31 | 2003-07-31 | Scale deposition preventive agent for polymerization reactor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003204781A JP2005048024A (en) | 2003-07-31 | 2003-07-31 | Scale deposition preventive agent for polymerization reactor |
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| JP2005048024A true JP2005048024A (en) | 2005-02-24 |
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| JP2003204781A Withdrawn JP2005048024A (en) | 2003-07-31 | 2003-07-31 | Scale deposition preventive agent for polymerization reactor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9434844B2 (en) | 2011-10-12 | 2016-09-06 | Ineos Europe Ag | Additive, composition comprising it and use thereof |
| WO2018124241A1 (en) * | 2016-12-28 | 2018-07-05 | 株式会社クラレ | Polyvinyl alcohol composition and use thereof |
| JP2022013612A (en) * | 2020-06-29 | 2022-01-18 | 信越化学工業株式会社 | Additive condensate, manufacturing method and use thereof, polymerization reactor, as well as manufacturing method of polymer |
| JP2022013613A (en) * | 2020-06-29 | 2022-01-18 | 信越化学工業株式会社 | Manufacturing method of additive condensate |
-
2003
- 2003-07-31 JP JP2003204781A patent/JP2005048024A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9434844B2 (en) | 2011-10-12 | 2016-09-06 | Ineos Europe Ag | Additive, composition comprising it and use thereof |
| WO2018124241A1 (en) * | 2016-12-28 | 2018-07-05 | 株式会社クラレ | Polyvinyl alcohol composition and use thereof |
| CN110325585A (en) * | 2016-12-28 | 2019-10-11 | 株式会社可乐丽 | Polyvinyl alcohol compositions and its purposes |
| JPWO2018124241A1 (en) * | 2016-12-28 | 2019-10-31 | 株式会社クラレ | Polyvinyl alcohol composition and use thereof |
| US11208550B2 (en) | 2016-12-28 | 2021-12-28 | Kuraray Co., Ltd. | Polyvinyl alcohol composition and use thereof |
| JP2022013612A (en) * | 2020-06-29 | 2022-01-18 | 信越化学工業株式会社 | Additive condensate, manufacturing method and use thereof, polymerization reactor, as well as manufacturing method of polymer |
| JP2022013613A (en) * | 2020-06-29 | 2022-01-18 | 信越化学工業株式会社 | Manufacturing method of additive condensate |
| US11345651B2 (en) | 2020-06-29 | 2022-05-31 | Shin-Etsu Chemical Co., Ltd. | Addition condensation product, production method and use of same, polymerization vessel, and production method of polymer |
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