JP2008031265A - Method for preparing chlorinated vinyl chloride resin - Google Patents
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- JP2008031265A JP2008031265A JP2006205373A JP2006205373A JP2008031265A JP 2008031265 A JP2008031265 A JP 2008031265A JP 2006205373 A JP2006205373 A JP 2006205373A JP 2006205373 A JP2006205373 A JP 2006205373A JP 2008031265 A JP2008031265 A JP 2008031265A
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- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000005660 chlorination reaction Methods 0.000 abstract description 32
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052753 mercury Inorganic materials 0.000 abstract description 19
- 230000035484 reaction time Effects 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 5
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 238000004040 coloring Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- -1 ethylene, propylene, vinyl Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、塩素化塩化ビニル系樹脂の製造方法に関する。さらに詳しくは、初期着色を抑制し、熱安定性を低下させることなく、生産性を大幅に向上できる塩素化塩化ビニル系樹脂の製造方法を提供するものである。 The present invention relates to a method for producing a chlorinated vinyl chloride resin. More specifically, the present invention provides a method for producing a chlorinated vinyl chloride resin capable of suppressing the initial coloring and greatly improving the productivity without deteriorating the thermal stability.
塩素化塩化ビニル系樹脂は、塩素化によって塩化ビニル系樹脂の耐熱温度を向上させるという性能を有しており、耐熱パイプ、耐熱工業板、耐熱フィルム・シートなど巾広い分野で使用されている。 Chlorinated vinyl chloride resins have the ability to improve the heat resistance temperature of vinyl chloride resins by chlorination, and are used in a wide range of fields such as heat resistant pipes, heat resistant industrial plates, heat resistant films and sheets.
該樹脂は、塩化ビニル系樹脂粒子を水性媒体中に懸濁させ、該懸濁液に塩素を供給しつつ、塩素化して製造される。塩素化の際、塩素ラジカルを生成させるために、水銀灯による紫外線照射（光塩素化法）、熱による励起（熱塩素化法）、触媒による励起（触媒塩素化法）あるいはこれらの方法の組合せなどが一般的に実施されている。 The resin is produced by suspending vinyl chloride resin particles in an aqueous medium and chlorinating the suspension while supplying chlorine. In order to generate chlorine radicals during chlorination, ultraviolet irradiation with a mercury lamp (photochlorination method), excitation with heat (thermal chlorination method), excitation with catalyst (catalytic chlorination method), or a combination of these methods, etc. Is generally implemented.
従来より、光塩素化法による該樹脂の生産性を向上させて製造コストを低下させる種々の試みがなされてきている。代表的な生産性向上方法としては、１）塩素化反応中の反応温度を上げて、反応時間を短縮して生産性を向上させる方法、２）仕込樹脂濃度をアップして生産性を向上させる方法、３）塩素化反応時の圧力を上昇させる方法、４）塩素化反応中の紫外線光量を増加させて生産性を向上させる方法、などが提案されている。 Conventionally, various attempts have been made to improve the productivity of the resin by the photochlorination method and to reduce the manufacturing cost. Typical productivity improvement methods are: 1) A method of increasing the reaction temperature during the chlorination reaction to shorten the reaction time and improving the productivity. 2) Increasing the concentration of the charged resin to improve the productivity. There have been proposed a method, 3) a method of increasing the pressure during the chlorination reaction, and 4) a method of increasing productivity by increasing the amount of ultraviolet light during the chlorination reaction.
１）の塩素化反応温度を上げる方法では、原料の塩化ビニル系樹脂または反応中の塩素化塩化ビニル系樹脂の軟化温度をこえる温度まで塩素化反応温度を上げることにより、大幅に塩素化反応速度が上昇し、塩素化反応時間の大幅な短縮により生産性が向上する。しかしながら、反応温度を該樹脂の軟化温度をこえる温度にすることで樹脂の劣化がおこり、加工時の初期着色を抑制することができず、熱安定性が大幅に悪化する。
２）の仕込樹脂濃度をアップする方法では、反応時間は伸びるが、１バッチ当たりの塩素化塩化ビニル系樹脂の生産量がそれを相殺する以上に大きくなり、生産性は向上する。しかしながら、樹脂濃度が高くなるにつれて、樹脂の塩素化の度合いが不均一になり、加工時の初期着色を抑制することができず、熱安定性が徐々に低下する。さらに、仕込樹脂濃度を３５重量％以上にすると、攪拌によっても樹脂が水性媒体中に均一に懸濁せず、塩素化反応を均一に行なうことができないのみならず、生産した塩素化塩化ビニル系樹脂の加工時の初期着色を抑制することができず、熱安定性が大幅に低下する。したがって、工業的には、仕込量と反応速度のバランスがとれる２０〜３５重量％の仕込樹脂濃度に抑制することにより、最適バランス点で生産されている。
３）の塩素化反応時の圧力を上げる方法では、塩素化反応時の圧力を上げることにより、塩素化反応時間が若干短縮され、初期着色を抑制することができ、熱安定性の向上が認められる。しかしながら、光塩素化法では、水銀灯の破損の危険性が増すにもかかわらず、塩素化反応時の圧力上昇による反応時間短縮効果はそれほど大きなものでない。
４）の紫外線光量を増加させる方法についていくつかの提案がなされている。たとえば、塩化ビニル系樹脂懸濁液を１ガロン当たり１０ワット程度の紫外光照射により塩素化する方法が開示されている（特許文献１）。光塩素化法においては、前記紫外線光量は、一般的な光量であり、反応時間は８時間程度となる。しかしながら、紫外線光量を増加すると、初期着色を抑制することができず、熱安定性の悪化が著しく、生産性の向上が望まれているにもかかわらず、紫外線光量増加による反応時間短縮は実施されていない。
また、品質と生産性のバランスを向上させる目的で、塩化ビニル系樹脂１ｋｇあたり１．６モルに達するまでは、反応速度が塩化ビニル系樹脂１ｋｇあたり０．７５〜０．２５モル／時間の範囲内にあるように紫外線の照射光量を調節することが提案されている（特許文献２）。これにより、確かに熱安定性などの品質は向上するものの、反応時間が１０〜１２時間と長くなり、極めて生産性を落とす結果となっている。
更に、塩化ビニル系樹脂１ｋｇあたりの紫外線光量を２０〜６０ワットに調節して照射することが提案されている（特許文献３）。この場合、攪拌数を一定で実施しており、紫外線光量の設定、攪拌数の設定しだいでは、反応速度が増加し、反応熱量が、除熱能力を上回り、内温が大きく上昇し、内温の制御を困難にさせ、品質低下を起こす結果となる。
In the method 1) of increasing the chlorination reaction temperature, the chlorination reaction rate is greatly increased by raising the chlorination reaction temperature to a temperature exceeding the softening temperature of the raw material vinyl chloride resin or the chlorinated vinyl chloride resin during the reaction. As a result, the productivity is improved by greatly shortening the chlorination reaction time. However, when the reaction temperature is set to a temperature exceeding the softening temperature of the resin, the resin deteriorates, the initial coloring during processing cannot be suppressed, and the thermal stability is greatly deteriorated.
In the method 2) in which the concentration of the charged resin is increased, the reaction time is extended, but the production amount of the chlorinated vinyl chloride resin per batch becomes larger than the offset, and the productivity is improved. However, as the resin concentration increases, the degree of chlorination of the resin becomes non-uniform, initial coloration during processing cannot be suppressed, and thermal stability gradually decreases. Furthermore, when the concentration of the charged resin is 35% by weight or more, the resin is not uniformly suspended in the aqueous medium even by stirring, and the chlorination reaction cannot be performed uniformly. The initial coloring during the processing of the resin cannot be suppressed, and the thermal stability is greatly reduced. Therefore, industrially, it is produced at an optimal balance point by suppressing the charged resin concentration to 20 to 35% by weight, which can balance the charged amount and the reaction rate.
In the method 3) of increasing the pressure during the chlorination reaction, by increasing the pressure during the chlorination reaction, the chlorination reaction time is slightly shortened, initial coloration can be suppressed, and an improvement in thermal stability is recognized. It is done. However, in the photochlorination method, although the risk of damage to the mercury lamp increases, the reaction time shortening effect due to the pressure increase during the chlorination reaction is not so great.
Several proposals have been made on the method 4) of increasing the amount of ultraviolet light. For example, a method of chlorinating a vinyl chloride resin suspension by irradiation with ultraviolet light of about 10 watts per gallon is disclosed (Patent Document 1). In the photochlorination method, the ultraviolet light amount is a general light amount, and the reaction time is about 8 hours. However, when the amount of ultraviolet light is increased, the initial coloring cannot be suppressed, the thermal stability is significantly deteriorated, and the reaction time is shortened by the increase of the amount of ultraviolet light even though improvement in productivity is desired. Not.
In order to improve the balance between quality and productivity, the reaction rate is in the range of 0.75 to 0.25 mol / hour per kg of vinyl chloride resin until reaching 1.6 mol per kg of vinyl chloride resin. It has been proposed to adjust the irradiation light quantity of ultraviolet rays so as to be within (Patent Document 2). As a result, the quality such as thermal stability is improved, but the reaction time is as long as 10 to 12 hours, resulting in a very low productivity.
Furthermore, it has been proposed that the amount of ultraviolet light per kg of vinyl chloride resin is adjusted to 20 to 60 watts for irradiation (Patent Document 3). In this case, the number of agitation is constant, and depending on the setting of the amount of UV light and the number of agitation, the reaction rate increases, the amount of reaction heat exceeds the heat removal capacity, the internal temperature rises significantly, and the internal temperature As a result, it is difficult to control the quality of the product and the quality is degraded.
前述したように、１）塩素化反応中の反応温度、２）仕込樹脂濃度をアップして生産性を向上させる方法、３）塩素化反応時の圧力を上昇させる方法、４）塩素化反応中の紫外線光量を増加させて生産性を向上させる方法の提案がされているが、初期着色を抑制することができず、熱安定性などの品質が大きく低下するため、品質を確保するためにある程度生産性を犠牲にして製造されており、このバランスを向上させることが工業的には大きな課題となっている。
すなわち、本発明は、塩化ビニル系樹脂を水性懸濁下で、塩素化して塩素化塩化ビニル系樹脂を製造するにあたり、加工時の初期着色を抑制し、塩素化反応時間を大幅に短縮して生産性を向上する塩素化塩化ビニル系樹脂の製造方法を提供するものである。 That is, in the present invention, when producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin in an aqueous suspension, initial coloring during processing is suppressed, and the chlorination reaction time is greatly shortened. The present invention provides a method for producing a chlorinated vinyl chloride resin that improves productivity.
本発明は、水性懸濁液中で、紫外線の照射下で、塩化ビニル系樹脂を塩素化する塩素化塩化ビニル系樹脂の製造方法において、攪拌翼径ｄと反応容器槽径Ｄの比であるｄ／Ｄが０．３以上０．９以下となる攪拌翼で水性懸濁液を攪拌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（請求項１）に関する、
本発明は、攪拌翼が幅流型であることを特徴とする請求項１記載の塩素化塩化ビニル系樹脂の製造方法（請求項２）に関する、ものである。
The present invention relates to a ratio of a stirring blade diameter d to a reaction vessel tank diameter D in a method for producing a chlorinated vinyl chloride resin in which a vinyl chloride resin is chlorinated under ultraviolet irradiation in an aqueous suspension. Regarding the method for producing a chlorinated vinyl chloride resin, wherein the aqueous suspension is stirred with a stirring blade having a d / D of 0.3 or more and 0.9 or less,
The present invention relates to a method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the stirring blade is of a wide flow type (claim 2).
本発明は、塩素化塩化ビニル系樹脂の反応時間を短縮するものである。 The present invention shortens the reaction time of a chlorinated vinyl chloride resin.
本発明において、原料として使用する塩化ビニル系樹脂とは、塩化ビニルの単独重合体、または塩化ビニルと他の共重合可能な単量体（たとえば、エチレン、プロピレン、酢酸ビニル、塩化アリル、アリルグリシジルエーテル、アクリル酸エステル、ビニルエーテルなど）との共重合体を示す。 In the present invention, the vinyl chloride resin used as a raw material is a homopolymer of vinyl chloride or other copolymerizable monomer (for example, ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl). And ethers, acrylic acid esters, vinyl ethers and the like).
該塩化ビニル系樹脂は、部分ケン化ポリ酢酸ビニル、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分散剤およびラウロイルパーオキサイド、ジ−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て懸濁重合で重合される。 The vinyl chloride resin includes a partially saponified polyvinyl acetate, a dispersant such as methylcellulose, hydroxypropylmethylcellulose, and lauroyl peroxide, di-2-ethylhexylperoxyneodecanoate, t-butylperoxyneodecanoate, Polymerization is carried out by suspension polymerization using an oil-soluble polymerization initiator such as α, α'-azobis-2,4-dimethylvaleronitrile.
本発明の塩素化塩化ビニル系樹脂は、水性懸濁下において塩素を供給しつつ、紫外線照射の下、懸濁液中の上記塩化ビニル系樹脂を塩素化することによって得られる。塩素化塩化ビニル系樹脂とは、塩化ビニル系樹脂を塩素化したものである。 The chlorinated vinyl chloride resin of the present invention can be obtained by chlorinating the vinyl chloride resin in the suspension under ultraviolet irradiation while supplying chlorine in an aqueous suspension. The chlorinated vinyl chloride resin is a chlorinated vinyl chloride resin.
ここで、水性懸濁液の濃度は、１０〜４０重量％とすることが好ましく、２０〜３５重量部とすることが更に好ましい。１０〜４０重量％の範囲であれば生産性、水性懸濁液の粘度安定性、及び撹拌時の均一混合性の観点から、好ましい。２０〜３５重量％の範囲であれば、生産性と撹拌の均一混合の観点から更に好ましい。 Here, the concentration of the aqueous suspension is preferably 10 to 40% by weight, and more preferably 20 to 35 parts by weight. The range of 10 to 40% by weight is preferable from the viewpoints of productivity, viscosity stability of the aqueous suspension, and uniform mixing during stirring. If it is the range of 20 to 35 weight%, it is still more preferable from a viewpoint of uniform mixing of productivity and stirring.
ここでいう水性懸濁液とは、塩化ビニル系樹脂と水との混合液をさしている。 The aqueous suspension here refers to a mixed liquid of vinyl chloride resin and water.
塩素化塩化ビニル系樹脂の製造での塩素供給方法は、反応開始前に初期一括で塩素を仕込む方法、断続的に塩素を供給する方法、連続で供給する方法、等があり、水性懸濁液中に、塩素を供給できる方法であれば、いずれの方法を用いてもかまわない。 Chlorine supply methods used in the manufacture of chlorinated vinyl chloride resins include initial batches of chlorine before starting the reaction, intermittent chlorine supply methods, and continuous supply methods. Any method may be used as long as it can supply chlorine.
紫外線を発生する水銀灯とはガラス管内の水銀蒸気中のアーク放電により発生する光放射を利用した光源であり、点灯中の水銀圧力が１〜１０ｋＰａ程度の低圧水銀灯や点灯中の水銀圧力が１００〜１０００ｋＰａ程度の高圧水銀灯、あるいは点灯中の水銀圧力が１０００ｋＰａを超える超高圧水銀灯などがあるが、紫外線放射があればどの水銀灯をもちいてもかまわない。 A mercury lamp that generates ultraviolet rays is a light source that utilizes light radiation generated by arc discharge in mercury vapor in a glass tube, and a low-pressure mercury lamp with a mercury pressure of about 1 to 10 kPa or a mercury pressure of 100 to 100 There are a high-pressure mercury lamp of about 1000 kPa, or an ultra-high pressure mercury lamp whose mercury pressure during lighting exceeds 1000 kPa, but any mercury lamp can be used as long as it has ultraviolet radiation.
水性懸濁液に供給する塩素は、気体状であっても液体状であっても良いが、取扱いの容易さの観点から、気体状の塩素ガスを水性媒体の下部より供給する方法が好ましい。 The chlorine supplied to the aqueous suspension may be gaseous or liquid, but from the viewpoint of ease of handling, a method of supplying gaseous chlorine gas from the lower part of the aqueous medium is preferable.
塩素化反応時の最高反応温度は９０℃以下が好ましい。最高反応温度が、９０℃以下であれば、塩化ビニル系樹脂の劣化抑制や得られる製品の着色抑制を行うことができる。尚、反応最高温度は、８８℃以下とすることがより好ましく、８６℃以下とすることが更に好ましい。 The maximum reaction temperature during the chlorination reaction is preferably 90 ° C. or lower. If the maximum reaction temperature is 90 ° C. or lower, it is possible to suppress the deterioration of the vinyl chloride resin and the coloring of the resulting product. The maximum reaction temperature is more preferably 88 ° C. or less, and still more preferably 86 ° C. or less.
反応最低温度は、水性懸濁液が攪拌機によって、容易に流動することが好ましく、０℃を超えることが好ましい。反応時間を短縮する上で、３０℃以上が好ましく、５０℃以上が更に好ましい。 The minimum reaction temperature is preferably such that the aqueous suspension flows easily with a stirrer, and preferably exceeds 0 ° C. In order to shorten the reaction time, 30 ° C. or higher is preferable, and 50 ° C. or higher is more preferable.
具体的な温度制御方法としては、塩素化反応は発熱反応であり、反応途中に内温が上昇するため、内温を制御するために、公知の冷却用ジャケットを装備した反応器等を利用することができ、除熱量と発熱量のバランスをとりながら、反応温度をコントロールする。又、冷却ジャケットによる除熱量以上の発熱が発生した場合は、攪拌数を減少することによって、塩化ビニル樹脂の水銀灯への衝突頻度を低くなり、反応速度を遅くし、発熱を抑制することも可能である。 As a specific temperature control method, the chlorination reaction is an exothermic reaction, and the internal temperature rises during the reaction. Therefore, in order to control the internal temperature, a reactor equipped with a known cooling jacket is used. It is possible to control the reaction temperature while balancing the heat removal amount and the heat generation amount. In addition, if heat generation exceeds the amount of heat removed by the cooling jacket, by reducing the number of stirring, the frequency of collision of the vinyl chloride resin with the mercury lamp can be reduced, the reaction rate can be reduced, and heat generation can be suppressed. It is.
水性懸濁液の攪拌に使用する攪拌翼は、回転によって発生する吐出流方向に形成される反応器内の液のフローパターンから、プロペラ翼等に代表される軸流型と、パドル翼、タービン翼等に代表される幅流型に大別され、双方の形状に限定するものではないが、塩化ビニル樹脂粒子が水銀灯照射表面との接触頻度を効率よくさせるには、羽根板の回転の遠心作用で翼の半径方向の流れを発生させる幅流型の攪拌翼が好ましい。更には、攪拌翼から吐出された塩化ビニル樹脂粒子が、水銀灯の照射面に衝突するような位置に、攪拌翼と水銀灯を設置することが好ましい。 The stirring blade used for stirring the aqueous suspension is composed of an axial flow type represented by a propeller blade, a paddle blade, and a turbine from the flow pattern of the liquid in the reactor formed in the discharge flow direction generated by rotation. Although it is broadly classified into a wide flow type typified by wings and the like, it is not limited to both shapes. However, in order to make the frequency of contact of the vinyl chloride resin particles with the mercury lamp irradiation surface efficient, centrifugal rotation of the blades is performed. A wide-flow type stirring blade that generates a radial flow of the blade by the action is preferable. Furthermore, it is preferable to install the stirring blade and the mercury lamp at a position where the vinyl chloride resin particles discharged from the stirring blade collide with the irradiation surface of the mercury lamp.
攪拌翼は、攪拌翼径ｄと反応容器槽径Ｄの比であるｄ／Ｄ比が０．３以上０．９以下となる攪拌翼を用いる。尚、攪拌翼の先端部分が、水銀灯表面、バッフル等に接触しないような範囲であれば、ｄ／Ｄ比は高いことが好ましい。従い、使用する反応容器の形状に合わせて、攪拌翼のｄ／Ｄを最大になるように選定することが望ましい。 As the stirring blade, a stirring blade having a d / D ratio of 0.3 or more and 0.9 or less, which is a ratio of the stirring blade diameter d and the reaction vessel tank diameter D, is used. In addition, it is preferable that d / D ratio is high if the front-end | tip part of a stirring blade is a range which does not contact a mercury lamp surface, a baffle, etc. Therefore, it is desirable to select the stirrer blade so that the d / D is maximized according to the shape of the reaction vessel to be used.
攪拌翼のｄ／Ｄ比が０．３以上０．９以下の範囲にあれば、攪拌翼から吐出された塩化ビニル樹脂粒子が、水銀灯との衝突頻度、反応速度が良好であり、高い生産性を得ることができるために好ましい。 If the d / D ratio of the stirring blade is in the range of 0.3 or more and 0.9 or less, the vinyl chloride resin particles discharged from the stirring blade have good collision frequency and reaction speed with the mercury lamp, and high productivity. Is preferable.
攪拌翼の攪拌速度は、攪拌機の性能で限定される。攪拌速度が高速であればあるほど、反応の進行を速くすることができる。攪拌機の電流値を定格電流値の８０〜９５％以内にし、攪拌機の最大限の性能で、水性懸濁液を安定的に攪拌することが好ましい。更には、攪拌翼のｄ／Ｄ比を大きくし、攪拌数の増加を組み合わせることで、反応時間を短縮させることができる。 The stirring speed of the stirring blade is limited by the performance of the stirrer. The higher the stirring speed, the faster the reaction can proceed. It is preferable to make the current value of the stirrer within 80 to 95% of the rated current value and to stir the aqueous suspension stably with the maximum performance of the stirrer. Furthermore, the reaction time can be shortened by increasing the d / D ratio of the stirring blade and combining the increase in the number of stirring.
ここで、攪拌翼径ｄとは攪拌翼径の長さを、反応容器槽径Ｄとは反応器の内径の長さをさしており、その長さは使用する反応器容量で決まる。 Here, the stirring blade diameter d refers to the length of the stirring blade diameter, and the reaction vessel tank diameter D refers to the length of the inner diameter of the reactor, and the length is determined by the reactor capacity to be used.
これらの塩素化反応終了後の水性懸濁液は、脱水後、塩化ビニル系樹脂のＴｇ以下の温度の温水を用い、樹脂中の塩酸を除去される。その後、脱水、乾燥工程を経て、塩素化塩化ビニル系樹脂が製造される。 The aqueous suspension after completion of these chlorination reactions is dehydrated, and the hydrochloric acid in the resin is removed using hot water having a temperature not higher than Tg of the vinyl chloride resin. Thereafter, a chlorinated vinyl chloride resin is produced through dehydration and drying processes.
以下に実施例および比較例をあげて本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。以下の実施例および比較例において説明する。なお、実施例および比較例における初期着色の測定は、８インチのロールにて１９５℃で３分間混練して得られたシートを２００℃で１０分間プレスして得られた厚さ３ｍｍの板の着色を目視にて判断した。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. The following examples and comparative examples will be described. In addition, the measurement of the initial coloring in the examples and the comparative examples was performed by measuring a sheet of 3 mm thickness obtained by pressing a sheet obtained by kneading at 195 ° C. for 3 minutes with an 8-inch roll at 200 ° C. for 10 minutes. The coloration was judged visually.
又、塩素化度とは、塩素化により塩素は塩化ビニルモノマー単位当たり１個付加するものとし、塩化ビニルモノマー単位の内に、付加した塩素原子量を表す指標であり、反応中に副生した塩酸を滴定することにより測定できる。例えば、塩素化度１００％とは、塩化ビニルモノマー単位当たりに、１個の塩素原子が付加していることを示す。 The degree of chlorination is an index representing the amount of added chlorine atoms in the vinyl chloride monomer unit, with one chlorine added per vinyl chloride monomer unit by chlorination, and hydrochloric acid produced as a by-product during the reaction. Can be measured by titrating. For example, a degree of chlorination of 100% indicates that one chlorine atom is added per vinyl chloride monomer unit.
反応中の樹脂温度は、水性懸濁液の液深中央部に、熱伝対を挿入した保護管を設置し、その指示値を読み取った。
（実施例１）
ｄ／Ｄ比が０．３の幅流型の攪拌翼をもった冷却ジャケットを装着した反応器に、３５ｋｇの純水と１５ｋｇの重合度１０００の塩化ビニル系樹脂（（株）カネカ製）を投入し、真空脱気および窒素置換を行なった。攪拌翼の回転数は６００ｒｐｍである。そののち塩素ガスを水性懸濁液の下部より吹き込み、１００ワットの高圧水銀ランプ２本（合計２００ワット）を照射して反応を開始した。反応開始時の温度は５０℃で、１時間後に８５℃になるように反応温度を直線的に上昇させた。１時間後からは８５℃の一定温度で塩素化反応をおこなった。塩素化度５２ｍｏｌ％に達したとき、水銀灯の照射を停止して塩素化反応を停止した。反応時間は３．３時間であった。反応中のジャケット最低温度は１５℃で、内温を制御した。窒素にて未反応塩素を追い出した後、残存塩酸を水洗にて除去し、乾燥して塩素化塩化ビニル系樹脂１７．５ｋｇを得た。 得られた塩素化塩化ビニル系樹脂１００重量部に対して、ＭＢＳ（（株）カネカ製のＢ３１）を１０重量部、スズ系安定剤２重量部、滑剤１．７部を配合し、８インチのロールにて１９５℃で３分間混練した。得られたシートを２００℃で１０分間プレスして、初期着色性を評価した。表１に評価結果を示す。
The resin temperature during the reaction was measured by installing a protective tube with a thermocouple in the middle of the depth of the aqueous suspension and reading the indicated value.
(Example 1)
A reactor equipped with a cooling jacket with a wide flow type stirring blade having a d / D ratio of 0.3 was charged with 35 kg of pure water and 15 kg of a vinyl chloride resin having a degree of polymerization of 1000 (manufactured by Kaneka Corporation). Then, vacuum degassing and nitrogen replacement were performed. The rotation speed of the stirring blade is 600 rpm. After that, chlorine gas was blown from the bottom of the aqueous suspension, and two 100-watt high-pressure mercury lamps (total 200 watts) were irradiated to initiate the reaction. The temperature at the start of the reaction was 50 ° C., and the reaction temperature was linearly increased so as to reach 85 ° C. after 1 hour. After 1 hour, the chlorination reaction was carried out at a constant temperature of 85 ° C. When the chlorination degree reached 52 mol%, the mercury lamp irradiation was stopped and the chlorination reaction was stopped. The reaction time was 3.3 hours. The minimum jacket temperature during the reaction was 15 ° C., and the internal temperature was controlled. After expelling unreacted chlorine with nitrogen, residual hydrochloric acid was removed by washing with water and dried to obtain 17.5 kg of a chlorinated vinyl chloride resin. To 100 parts by weight of the obtained chlorinated vinyl chloride resin, 10 parts by weight of MBS (B31 manufactured by Kaneka Corporation), 2 parts by weight of a tin stabilizer, and 1.7 parts of a lubricant are blended, and 8 inches. And kneaded at 195 ° C. for 3 minutes. The obtained sheet was pressed at 200 ° C. for 10 minutes to evaluate the initial colorability. Table 1 shows the evaluation results.
（実施例２）
ｄ／Ｄ比が０．４の幅流型の攪拌翼に変更した以外は、実施例１と同様の操作を実施した。反応時間は２．９時間であった。得られた塩素化塩化ビニル系樹脂を、実施例１と同様の方法で、配合、混練り、プレスし、評価した。表１に評価結果を示した。
(Example 2)
The same operation as in Example 1 was performed except that the width of the stirring blade was changed to a wide flow type stirring blade having a d / D ratio of 0.4. The reaction time was 2.9 hours. The obtained chlorinated vinyl chloride resin was blended, kneaded, pressed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
（実施例３）
ｄ／Ｄ比が０．５の幅流型の攪拌翼に変更した以外は、実施例１と同様の操作を実施した。反応時間は２．５時間であった。得られた塩素化塩化ビニル系樹脂を、実施例１と同様の方法で、配合、混練り、プレスし、評価した。表１に評価結果を示した。
(Example 3)
The same operation as in Example 1 was performed except that the width of the stirring blade was changed to a wide flow type stirring blade having a d / D ratio of 0.5. The reaction time was 2.5 hours. The obtained chlorinated vinyl chloride resin was blended, kneaded, pressed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
（比較例１）
攪拌翼を外し、攪拌軸のみとした以外は、実施例１と同様の操作を実施した。反応時間は６．５時間であった。得られた塩素化塩化ビニル系樹脂を、実施例１と同様の方法で、配合、混練り、プレスし、評価した。表１に評価結果を示した。
(Comparative Example 1)
The same operation as in Example 1 was performed except that the stirring blade was removed and only the stirring shaft was used. The reaction time was 6.5 hours. The obtained chlorinated vinyl chloride resin was blended, kneaded, pressed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
（比較例２）
ｄ／Ｄ比が０．２の幅流型の攪拌翼に変更した以外は、実施例１と同様の操作を実施した。反応時間は４．０時間であった。得られた塩素化塩化ビニル系樹脂を、実施例１と同様の方法で、配合、混練り、プレスし、評価した。表１に評価結果を示した。
(Comparative Example 2)
The same operation as in Example 1 was performed except that the width of the stirring blade was changed to a width flow type stirring blade having a d / D ratio of 0.2. The reaction time was 4.0 hours. The obtained chlorinated vinyl chloride resin was blended, kneaded, pressed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
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