JP2009040981A - Method for evaluating powder characteristics of polyvinyl chloride - Google Patents
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本発明は、ポリ塩化ビニルの粉体特性を評価する方法に関する。詳しくは、塩化ビニルモノマー（ＶＣＭ）を懸濁重合して得られるポリ塩化ビニル（ＰＶＣ）の粉体特性を評価する方法に関する。 The present invention relates to a method for evaluating the powder characteristics of polyvinyl chloride. Specifically, the present invention relates to a method for evaluating the powder characteristics of polyvinyl chloride (PVC) obtained by suspension polymerization of vinyl chloride monomer (VCM).
ポリ塩化ビニル（ＰＶＣ）は、機械的物性や化学的物性に優れた樹脂であり、安価であるため、物性と経済性のバランスがとれた樹脂として汎用されている。ポリ塩化ビニルは、塩化ビニルモノマー（ＶＣＭ）を懸濁重合することで得ることができる。 Polyvinyl chloride (PVC) is a resin excellent in mechanical properties and chemical properties, and is inexpensive, and thus is widely used as a resin having a balance between physical properties and economy. Polyvinyl chloride can be obtained by suspension polymerization of vinyl chloride monomer (VCM).
具体的には、塩化ビニルモノマーを水性媒体中で、重合開始剤や分散剤の存在下で懸濁重合を行う。懸濁重合後、粉状〜微粒子状態のポリ塩化ビニルを得ることができるが、ポリ塩化ビニルの微細構造は重合条件によって変化する。従って、使用用途に適した物性であるポリ塩化ビニルを得るためには、重合反応を適切に制御する必要がある。 Specifically, suspension polymerization is performed in a water medium with a vinyl chloride monomer in the presence of a polymerization initiator or a dispersant. After suspension polymerization, polyvinyl chloride in a powdery to fine particle state can be obtained, but the microstructure of polyvinyl chloride varies depending on the polymerization conditions. Therefore, in order to obtain polyvinyl chloride having physical properties suitable for the intended use, it is necessary to appropriately control the polymerization reaction.
ポリ塩化ビニルの粉体特性に関しては、例えば、懸濁重合時における重合液の撹拌動力や分散剤の界面活性能等の影響を受ける。これに関して、特許文献１には、所定の大型重合器を用い、重合開始剤として１０時間半減期温度が３４〜５０℃の一種または二種以上のパーエステル開始剤を重合に使用する全開始剤の５０重量％以上使用し、且つ重合器の内容液１ｍ３当たりの正味撹拌動力を１．０〜３．０ｋＷ／ｍ３の範囲に制御して、重合時間を６時間以内の範囲として重合完結させる技術等が開示されている。 The powder characteristics of polyvinyl chloride are affected by, for example, the stirring power of the polymerization solution during suspension polymerization and the surface activity of the dispersant. In this regard, Patent Document 1 discloses a total initiator that uses a predetermined large polymerization vessel and uses one or more perester initiators having a 10-hour half-life temperature of 34 to 50 ° C. as a polymerization initiator for polymerization. The polymerization is completed within a period of 6 hours or less by controlling the net stirring power per 1 m 3 of the content liquid of the polymerization vessel in the range of 1.0 to 3.0 kW / m 3. The technique etc. to be made are disclosed.
また、塩化ビニルモノマーの懸濁重合に関しては、重合器のスケールアップと数平均粒子径との関係について多くの研究が行われており、例えば非特許文献１には、重合液の撹拌動力や界面活性能との相関式が下記一般式で表されている。 As for suspension polymerization of vinyl chloride monomer, many studies have been conducted on the relationship between the scale-up of the polymerization vessel and the number average particle diameter. For example, Non-Patent Document 1 describes the stirring power and interface of the polymerization solution. The correlation formula with the activity ability is represented by the following general formula.
式中、ｄｐは平均粒子径、ｋは定数、σは表面張力、Nは回転数、ｄは撹拌翼長、ηｓｐは比粘度、Ｐ／Ｖは単位容積あたりの所要動力を表している。 In the formula, d p is the average particle diameter, k is a constant, σ is the surface tension, N is the rotational speed, d is the stirring blade length, η sp is the specific viscosity, and P / V is the required power per unit volume. .
しかし、ポリ塩化ビニルの粉体特性を評価するには、実際に塩化ビニルモノマーを用いて重合を行ってポリ塩化ビニルを得なければならない。そして、塩化ビニルモノマーは、揮発性（常圧時の沸点：−１３℃）であるため取り扱いが困難であり、発がん性の疑いが高い物質（ＩＡＲＣ発がん性グループ１）でもある。このように、塩化ビニルモノマーの重合は保安や安全性の問題を抱えている。 However, in order to evaluate the powder characteristics of polyvinyl chloride, it is necessary to actually perform polymerization using a vinyl chloride monomer to obtain polyvinyl chloride. The vinyl chloride monomer is volatile (boiling point at normal pressure: −13 ° C.) and therefore difficult to handle, and is also a substance (IARC carcinogenic group 1) that is highly suspected to be carcinogenic. Thus, the polymerization of vinyl chloride monomer has security and safety problems.
そこで、本発明は、簡便でありながら安全性に優れたポリ塩化ビニルの粉体特性を評価する方法を提供することを主目的とする。 Accordingly, the main object of the present invention is to provide a method for evaluating the powder characteristics of polyvinyl chloride which is simple and excellent in safety.
本願発明者らは、塩化ビニルモノマーの代替モノマーを用いることに着想を得た。さらに、ポリ塩化ビニルの粉体特性として数平均粒子径と可塑剤吸収量に着目した。これらの着想から鋭意研究を重ねた結果、本発明を完成させた。
まず、本発明は、懸濁重合により得られるポリ塩化ビニルの粉体特性を評価する方法であって、代替モノマーとして２，３−ジクロロ−１，３−ブタジエンを用いて、水性媒体と重合開始剤と分散剤と析出助剤との存在下で、重合液単位体積あたりの撹拌動力の条件を変えて懸濁重合を行い、得られた重合体の数平均粒子径及び／又は可塑剤吸収量を測定することで、懸濁重合における撹拌動力に対するポリ塩化ビニルの粉体特性を評価する方法を提供する。
代替モノマーとして２，３−ジクロロ−１，３−ブタジエンを用い、この重合体の数平均粒子径及び／又は可塑剤吸収量を測定する。これにより、塩化ビニルモノマーの懸濁重合を行う場合の撹拌動力に対し、どのような粉体特性を有するポリ塩化ビニルが得られるのか評価できる。更に、２，３−ジクロロ−１，３−ブタジエンは水との沸点差が小さく、水性媒体中での懸濁重合を行う際の取り扱いも容易である。
次に、本発明は、前記分散剤が、重合度１０００〜３０００、けん化度７５〜９０％のポリビニルアルコールであるポリ塩化ビニルの粉体特性を評価する方法を提供する。分散剤としてこのようなポリビニルアルコールを用いることで、ポリ塩化ビニルの粉体特性をより正確に評価できる。
そして、本発明は、前記析出助剤が飽和脂肪族炭化水素であるポリ塩化ビニルの粉体特性を評価する方法を提供する。更に、前記析出助剤はｎ−ヘプタンであることが好ましい。
The inventors have come up with the idea of using an alternative monomer for the vinyl chloride monomer. Furthermore, attention was paid to the number average particle size and the plasticizer absorption as powder characteristics of polyvinyl chloride. As a result of intensive research from these ideas, the present invention was completed.
First, the present invention is a method for evaluating the powder characteristics of polyvinyl chloride obtained by suspension polymerization, using 2,3-dichloro-1,3-butadiene as an alternative monomer and starting polymerization with an aqueous medium. Suspension polymerization in the presence of an agent, a dispersant, and a precipitation aid, changing the conditions of stirring power per unit volume of the polymerization solution, and the number average particle diameter and / or plasticizer absorption of the resulting polymer Is measured to provide a method for evaluating the powder characteristics of polyvinyl chloride with respect to stirring power in suspension polymerization.
2,3-dichloro-1,3-butadiene is used as an alternative monomer, and the number average particle size and / or plasticizer absorption of this polymer is measured. Thereby, it can be evaluated what kind of polyvinyl chloride is obtained with respect to the stirring power when suspension polymerization of the vinyl chloride monomer is performed. Furthermore, 2,3-dichloro-1,3-butadiene has a small boiling point difference from water and is easy to handle when performing suspension polymerization in an aqueous medium.
Next, the present invention provides a method for evaluating the powder characteristics of polyvinyl chloride in which the dispersant is polyvinyl alcohol having a polymerization degree of 1000 to 3000 and a saponification degree of 75 to 90%. By using such polyvinyl alcohol as a dispersant, the powder characteristics of polyvinyl chloride can be more accurately evaluated.
And this invention provides the method of evaluating the powder characteristic of the polyvinyl chloride whose said precipitation adjuvant is a saturated aliphatic hydrocarbon. Further, the precipitation aid is preferably n-heptane.
本発明によれば、簡便でありながら安全性に優れたポリ塩化ビニルの粉体特性を評価する方法とすることができる。 According to the present invention, it is possible to provide a method for evaluating the powder characteristics of polyvinyl chloride which is simple and excellent in safety.
以下、本発明についてより詳細に説明する。以下は本発明の例示であり、これにより本発明の範囲が狭く解釈されることはない。 Hereinafter, the present invention will be described in more detail. The following are examples of the present invention, and the scope of the present invention is not interpreted narrowly.
図１は、本発明に係るポリ塩化ビニルの粉体特性を評価する方法を説明するための概念図である。本発明は、２，３−ジクロロ−１，３−ブタジエン（ＤＣ）を用いて懸濁重合を行う。これにより得られた重合体を評価することにより、塩化ビニルモノマーを懸濁重合させて得られるポリ塩化ビニルの重合液単位体積あたりの撹拌動力に対する粉体特性を評価するものである。 FIG. 1 is a conceptual diagram for explaining a method for evaluating the powder characteristics of polyvinyl chloride according to the present invention. In the present invention, suspension polymerization is performed using 2,3-dichloro-1,3-butadiene (DC). By evaluating the polymer thus obtained, the powder characteristics with respect to the stirring power per unit volume of the polymerization liquid of polyvinyl chloride obtained by suspension polymerization of the vinyl chloride monomer are evaluated.
２，３−ジクロロ−１，３−ブタジエンは、塩化ビニルモノマーの代替モノマーとして懸濁重合に用いる。水性媒体中で、重合開始剤と分散剤と析出助剤の存在下で、２，３−ジクロロ−１，３−ブタジエンを懸濁重合させて重合体を得る。得られた重合体の数平均粒子径及び／又は可塑剤吸収量を測定することで、同様の製造条件で塩化ビニルモノマーを懸濁重合させて得られるポリ塩化ビニルの粉体特性を評価する（図１参照）。代替モノマーである２，３−ジクロロ−１，３−ブタジエンは水との沸点差が小さいため、重合時の取り扱い性も容易である。 2,3-dichloro-1,3-butadiene is used in suspension polymerization as an alternative monomer to the vinyl chloride monomer. In an aqueous medium, 2,3-dichloro-1,3-butadiene is subjected to suspension polymerization in the presence of a polymerization initiator, a dispersant, and a precipitation aid to obtain a polymer. By measuring the number average particle size and / or plasticizer absorption of the obtained polymer, the powder characteristics of polyvinyl chloride obtained by suspension polymerization of a vinyl chloride monomer under the same production conditions are evaluated ( (See FIG. 1). Since the alternative monomer 2,3-dichloro-1,3-butadiene has a small difference in boiling point from water, it is easy to handle during polymerization.
水性媒体は、塩化ビニルモノマーの懸濁重合において通常使用されるものを用いることができ、特に限定するものではなく、例えば、イオン交換水、蒸留水、限外ろ過や逆浸透膜等で処理した水を用いることができる。但し、水性媒体中には、単量体の重合を阻害する物質を含まないことが好ましい。 As the aqueous medium, those usually used in the suspension polymerization of vinyl chloride monomer can be used, and are not particularly limited. For example, the aqueous medium is treated with ion exchange water, distilled water, ultrafiltration, reverse osmosis membrane, or the like. Water can be used. However, it is preferable that the aqueous medium does not contain a substance that inhibits polymerization of the monomer.
重合開始剤は、塩化ビニルモノマーの重合開始剤で通常使用されるものを用いることができ、特に限定するものではないが、例えば、ジイソプロピルパーオキシジカーボネ−ト、ジエトキシエチルパーオキシジカーボネ−ト等のパーオキシカーボネート類、ラウロイルパーオキサイド等のパーオキサイド類、アゾビス−２，４−ジメチルバレロニトリル等のアゾ化合物を使用することができる。これらの重合開始剤は単独で使用しても２種以上を併用してもよい。また、その使用量も特に限定されず、従来公知の範囲で使用できる。 As the polymerization initiator, those usually used for the polymerization initiator of vinyl chloride monomer can be used, and are not particularly limited, and examples thereof include diisopropyl peroxydicarbonate, diethoxyethyl peroxydicarbonate. Peroxycarbonates such as neat, peroxides such as lauroyl peroxide, and azo compounds such as azobis-2,4-dimethylvaleronitrile can be used. These polymerization initiators may be used alone or in combination of two or more. Moreover, the usage-amount is not specifically limited, It can use in a conventionally well-known range.
分散剤は、塩化ビニルモノマーの懸濁重合で通常使用されるものを用いることができ、特に限定するものではないが、例えば、ポリビニルアルコール（ＰＶＡ）、ゼラチン、水溶性セルロース等を使用することができる。より好適には、重合度１０００〜３０００、けん化度７５〜９０％のポリビニルアルコールを用いることが望ましい（ＪＩＳ Ｋ ６７２６に準拠）。これらの分散剤は単独で使用しても２種類以上を併用してもよい。また、その使用量も特に限定されず、従来公知の範囲で使用できる。 As the dispersant, those commonly used in suspension polymerization of vinyl chloride monomers can be used, and are not particularly limited. For example, polyvinyl alcohol (PVA), gelatin, water-soluble cellulose and the like can be used. it can. More preferably, it is desirable to use polyvinyl alcohol having a polymerization degree of 1000 to 3000 and a saponification degree of 75 to 90% (based on JIS K 6726). These dispersants may be used alone or in combination of two or more. Moreover, the usage-amount is not specifically limited, It can use in a conventionally well-known range.
析出助剤は、塩化ビニルモノマーの懸濁重合で通常使用されるものを用いることができ、特に限定するものではないが、好適には、ｎ−ヘプタン、ｎ−オクタン、ｎ−ノナン等の飽和脂肪族炭化水素を用いることが好ましい。これらの中でも、ｎ−ヘプタンは、水との沸点差が小さく重合時の取り扱いが容易であるためより好適である。 As the precipitation aid, those usually used in the suspension polymerization of vinyl chloride monomer can be used, and are not particularly limited, but preferably saturated such as n-heptane, n-octane, and n-nonane. It is preferable to use an aliphatic hydrocarbon. Among these, n-heptane is more preferable because it has a small boiling point difference with water and is easy to handle during polymerization.
懸濁重合の重合温度は特に限定するものではないが、４０℃〜７０℃の範囲で行うと重合が好適に行われるため好ましい。懸濁重合の重合時間は特に限定するものではないが、２〜４時間の範囲で行うと重合が好適に行われるため好ましい。 The polymerization temperature of the suspension polymerization is not particularly limited, but it is preferable to perform the polymerization in the range of 40 ° C to 70 ° C because the polymerization is suitably performed. The polymerization time for suspension polymerization is not particularly limited, but it is preferable to perform the polymerization in the range of 2 to 4 hours because the polymerization is suitably performed.
重合装置は、撹拌動力を任意に制御できる撹拌装置を備えた反応装置であればよく、その種類や構造等については限定されず、従来公知の槽状反応器等を使用することができる。 The polymerization apparatus only needs to be a reaction apparatus provided with a stirrer capable of arbitrarily controlling the stirring power, and the type and structure thereof are not limited, and a conventionally known tank reactor or the like can be used.
重合装置の撹拌動力を制御する方法としては、例えば、「橋本健治編、工業反応装置、初版、株式会社培風館、昭和５９年、２０１頁〜２２８頁」等を参酌できる。種々の形状の重合装置についての撹拌系のレイノルズ数Ｒｅと動力数Ｎｐの関係を表す実験式や線図を利用してもよい。あるいは、実際に動力を計測することにより動力数Ｎｐを求めて、翼回転数を変更することで任意に撹拌動力を調整してもよい。 As a method for controlling the stirring power of the polymerization apparatus, for example, “Kenji Hashimoto, Industrial Reaction Equipment, First Edition, Baifukan Co., Ltd., 1984, pages 201 to 228” can be referred to. Empirical formulas and diagrams representing the relationship between the Reynolds number Re and the power number Np of the stirring system for various shapes of the polymerization apparatus may be used. Alternatively, the stirring power may be arbitrarily adjusted by obtaining the power number Np by actually measuring the power and changing the blade rotation speed.
重合装置の撹拌動力Ｐ（Ｋｇ・ｍ／ｓ）は、式（２）で示される。この撹拌動力Ｐは、反応装置内の動力の損失分等を含まない、正味の撹拌動力である。なお、式（２）において、ｇｃは重力換算係数（ｋｇ・ｍ／Ｋｇ・ｓ２）を、ρは内容物の密度（ｋｇ／ｍ３）を、ｎは翼回転数（１／ｓ）を、ｄは翼スパン（ｍ）を、それぞれ示している。 The stirring power P (Kg · m / s) of the polymerization apparatus is represented by the formula (2). This agitation power P is a net agitation power that does not include power loss in the reactor. In Equation (2), g c is a gravity conversion coefficient (kg · m / Kg · s 2 ), ρ is a density of contents (kg / m 3 ), and n is a blade rotation speed (1 / s). D indicates the blade span (m).
液単位体積あたりの撹拌所要動力Ｐｖは、重合装置における撹拌強さや、混合の程度を示す目安となり、式（３）で示される。そして、式（２）の翼回転数ｎを変えることにより動力の調整を行うことができる。なお、下記式（３）において、Ｖは重合装置内の液量（ｍ３）を示している。この場合、撹拌所要動力Ｐｖは、重合液１ｍ３あたりの撹拌所要動力である。 The stirring required power Pv per unit volume of liquid is a standard indicating the stirring strength in the polymerization apparatus and the degree of mixing, and is expressed by the formula (3). The power can be adjusted by changing the blade rotational speed n in the equation (2). In the following formula (3), V indicates the amount of liquid (m 3 ) in the polymerization apparatus. In this case, the stirring required power Pv is the stirring required power per 1 m 3 of the polymerization liquid.
重合装置の撹拌翼としては、塩化ビニルモノマーの懸濁重合において汎用に使用されているものであればよく、その種類は限定されず、パドル翼、ファウドラー翼、タービン翼等を用いることができるが、好適にはパドル翼を用いることが望ましい。 The stirring blade of the polymerization apparatus may be any one that is generally used in the suspension polymerization of vinyl chloride monomer, and the type thereof is not limited, and a paddle blade, a fiddler blade, a turbine blade, or the like can be used. It is preferable to use a paddle blade.
重合装置のバッフルとしては、塩化ビニルモノマー懸濁重合において汎用に使用されているものであればよく、その種類は限定されないが、好適にはパイプバッフル（棒型）、フィンガー型バッフル等を用いることが望ましい。 The baffle of the polymerization apparatus is not particularly limited as long as it is commonly used in vinyl chloride monomer suspension polymerization, and a pipe baffle (bar type), a finger type baffle, or the like is preferably used. Is desirable.
得られた２，３−ジクロロ−１，３−ブタジエンの重合体の数平均粒子径の測定方法は限定されないが、例えば、レーザー光回折法や位相ドップラ法やローラータラップ式振動篩等により測定することができる。 The method for measuring the number average particle size of the obtained 2,3-dichloro-1,3-butadiene polymer is not limited, but is measured by, for example, a laser diffraction method, a phase Doppler method, a roller trap type vibrating sieve, or the like. be able to.
得られた２，３−ジクロロ−１，３−ブタジエンの重合体の可塑剤吸収量の測定方法は、例えば、ポリ塩化ビニルの可塑剤吸収量の評価法に準じ、ＪＩＳ Ｋ ７３８６に準拠して行うことができる。 The method for measuring the plasticizer absorption amount of the obtained 2,3-dichloro-1,3-butadiene polymer is, for example, in accordance with the evaluation method for the plasticizer absorption amount of polyvinyl chloride, in accordance with JIS K 7386. It can be carried out.
塩化ビニルモノマーを懸濁重合させる際の撹拌動力は、得られるポリ塩化ビニルの数平均粒子径や可塑剤吸収量に影響を与える。数平均粒子径や可塑剤吸収量は重合体の加工物性に関与する因子である。従って、代替モノマーとして２，３−ジクロロ−１，３−ブタジエンを用い、この重合体の粉体特性として数平均粒子径や可塑剤吸収量を測定することで、ポリ塩化ビニルの粉体特性を模擬することができる（図１参照）。 The stirring power at the time of suspension polymerization of the vinyl chloride monomer affects the number average particle diameter and plasticizer absorption of the obtained polyvinyl chloride. The number average particle size and the plasticizer absorption amount are factors related to the processed physical properties of the polymer. Therefore, by using 2,3-dichloro-1,3-butadiene as an alternative monomer and measuring the number average particle diameter and plasticizer absorption as the powder characteristics of this polymer, the powder characteristics of polyvinyl chloride can be improved. It can be simulated (see FIG. 1).
以下の説明において特に断りのない限り、「％」は「質量基準」で示す。 In the following description, “%” is indicated by “mass basis” unless otherwise specified.
＜実施例１＞
撹拌翼として翼径５０ｍｍ、翼高２２ｍｍのパドル翼を装備した内径１００ｍｍのガラス製重合缶に、イオン交換水５８０ｇ、分散剤としてポリビニルアルコール「Ｗ−２０Ｎ」（電気化学工業社製、重合度＝２２１０、けん化度＝８０．０％）３．６ｇ、及び析出助剤としてｎ−ヘプタン３０ｇを仕込んだ。そして、窒素で１時間脱気後、重合開始剤として過酸化ラウロイル０．３ｇを２，３−ジクロロ−１，３−ブタジエン７０ｇに添加して、６０℃に昇温して重合を開始した。
撹拌所要動力Ｐｖ＝０．１ｋＷ／ｍ３とし、重合開始後３時間で重合を止めて、２，３−ジクロロ−１，３−ブタジエンの重合体を得た。
<Example 1>
A glass polymerization can with a diameter of 100 mm equipped with a paddle blade having a blade diameter of 50 mm and a blade height of 22 mm as a stirring blade, 580 g of ion-exchanged water, and polyvinyl alcohol “W-20N” (manufactured by Denki Kagaku Kogyo Co., Ltd., polymerization degree = 2210, saponification degree = 80.0%) 3.6 g, and 30 g of n-heptane as a precipitation aid were charged. Then, after deaeration with nitrogen for 1 hour, 0.3 g of lauroyl peroxide as a polymerization initiator was added to 70 g of 2,3-dichloro-1,3-butadiene, and the temperature was raised to 60 ° C. to initiate polymerization.
The power required for stirring was Pv = 0.1 kW / m 3, and the polymerization was stopped 3 hours after the start of polymerization to obtain a polymer of 2,3-dichloro-1,3-butadiene.
得られた重合体の数平均粒子径を、レーザー回折粒度分布計「ＳＡＬＤ３０００」（株式会社島津製作所製）を使用して測定した。
測定サンプルは、２，３−ジクロロ−１，３−ブタジエンの重合体とその固形分に対して９９％の水を含んだスラリー溶液を超音波により分散処理をした後、測定した。
The number average particle diameter of the obtained polymer was measured using a laser diffraction particle size distribution analyzer “SALD3000” (manufactured by Shimadzu Corporation).
The measurement sample was measured after ultrasonically dispersing a slurry solution containing 99% water with respect to a 2,3-dichloro-1,3-butadiene polymer and its solid content.
得られた２，３−ジクロロ−１，３−ブタジエンの重合体について、可塑剤吸収性を、ＪＩＳ Ｋ ７３８６に準じて、以下の手順、条件で測定した。まず、測定サンプル約２．０ｇを遠心管にとり、秤量した後、４ｃｍ３のフタル酸ジ−２−エチルヘキシルを添加して約１０分静置後、遠心分離機にセットして２４５００〜２９５００ｍ／ｓ２の加速度で６０分遠心分離を行い、樹脂に吸収された可塑剤の量を測定した。 About the obtained polymer of 2,3-dichloro-1,3-butadiene, the plasticizer absorbability was measured according to the following procedure and conditions according to JIS K7386. First, about 2.0 g of a measurement sample was taken in a centrifuge tube, weighed, 4 cm 3 of di-2-ethylhexyl phthalate was added, and the mixture was allowed to stand for about 10 minutes, and then set in a centrifuge to 24500-29500 m / s. Centrifugation was performed at an acceleration of 2 for 60 minutes, and the amount of plasticizer absorbed by the resin was measured.
＜実施例２＞
撹拌所要動力Ｐｖ＝０．３とした以外は実施例１と同様の操作を経て、２，３−ジクロロ−１，３−ブタジエンの重合体を製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Example 2>
A polymer of 2,3-dichloro-1,3-butadiene is produced through the same operation as in Example 1 except that the power required for stirring Pv = 0.3, and the number average particle diameter and the plasticizer absorption amount are set. It was measured.
＜実施例３＞
撹拌所要動力Ｐｖ＝０．０２とした以外は実施例１と同様の操作を経て、２，３−ジクロロ−１，３−ブタジエンの重合体を製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Example 3>
A polymer of 2,3-dichloro-1,3-butadiene is produced through the same operation as in Example 1 except that the required power for stirring Pv = 0.02, and the number average particle diameter and the plasticizer absorption amount are set. It was measured.
＜実施例４＞
撹拌所要動力Ｐｖ＝０．０５とした以外は実施例１と同様の操作を経て、２，３−ジクロロ−１，３−ブタジエンの重合体を製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Example 4>
A polymer of 2,3-dichloro-1,3-butadiene was produced through the same operation as in Example 1 except that the required power for stirring Pv was set to 0.05, and the number average particle diameter and the plasticizer absorption amount were adjusted. It was measured.
＜実施例５＞
撹拌所要動力Ｐｖ＝０．１８とした以外は実施例１と同様の操作を経て、２，３−ジクロロ−１，３−ブタジエンの重合体を製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Example 5>
A polymer of 2,3-dichloro-1,3-butadiene is produced through the same operation as in Example 1 except that the required power for stirring Pv = 0.18, and the number average particle diameter and the plasticizer absorption amount are set. It was measured.
＜実施例６＞
撹拌所要動力Ｐｖ＝０．６６とした以外は実施例１と同様の操作を経て、２，３−ジクロロ−１，３−ブタジエンの重合体を製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Example 6>
A polymer of 2,3-dichloro-1,3-butadiene is produced through the same operation as in Example 1 except that the power required for stirring is Pv = 0.66, and the number average particle diameter and the plasticizer absorption amount are set. It was measured.
＜実験例１＞
撹拌翼として翼径１３８ｍｍ、翼高７２ｍｍのパドル翼を装備した内径２５０ｍｍのガラス製重合缶に、イオン交換水９１００ｇ、分散剤としてポリビニルアルコール「Ｗ−２０Ｎ」（電気化学工業社製）４ｇ、重合開始剤として過酸化ラウロイル２ｇを添加したものを仕込んで窒素で１時間脱気後、塩化ビニルモノマー３８００ｇを加えて５７．５℃に昇温して重合を開始した。撹拌所要動力Ｐｖ＝０．３ｋＷ／ｍ３とし、重合開始後３時間で重合を止めて、２，３−ジクロロ−１，３−ブタジエンの重合体を得た。
重合開始後４時間で重合を止め、得られたポリ塩化ビニルについて数平均粒子径及び可塑剤吸収量を実施例１と同様に測定した。
<Experimental example 1>
A glass polymerization can with an inner diameter of 250 mm equipped with a paddle blade with a blade diameter of 138 mm and a blade height of 72 mm as a stirring blade, 9100 g of ion-exchanged water, 4 g of polyvinyl alcohol “W-20N” (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a dispersant, and polymerization After adding 2 g of lauroyl peroxide as an initiator and degassing with nitrogen for 1 hour, 3800 g of vinyl chloride monomer was added and the temperature was raised to 57.5 ° C. to initiate polymerization. The power required for stirring was Pv = 0.3 kW / m 3, and the polymerization was stopped 3 hours after the start of polymerization to obtain a polymer of 2,3-dichloro-1,3-butadiene.
The polymerization was stopped 4 hours after the initiation of polymerization, and the number average particle size and plasticizer absorption amount of the obtained polyvinyl chloride were measured in the same manner as in Example 1.
＜実験例２＞
撹拌所要動力Ｐｖ＝０．６とした以外は実験例１と同様の操作を経てポリ塩化ビニルを製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Experimental example 2>
Polyvinyl chloride was produced through the same operation as in Experimental Example 1 except that the required power for stirring Pv was 0.6, and the number average particle diameter and the plasticizer absorption were measured.
＜実験例３＞
撹拌所要動力Ｐｖ＝１．２とした以外は実験例１と同様の操作を経てポリ塩化ビニルを製造し、数平均粒子径及び可塑剤吸収量を測定した。
<Experimental example 3>
Polyvinyl chloride was produced through the same operation as in Experimental Example 1 except that the required power for stirring Pv was 1.2, and the number average particle diameter and the plasticizer absorption were measured.
実施例１〜６および実験例１〜３の結果を表１に示す。 Table 1 shows the results of Examples 1 to 6 and Experimental Examples 1 to 3.
表１の結果に基づき、これらのデータをｄｐ＝Ｋ・（Ｐ／Ｖ）α、の形式で表記すると、数平均粒子径ｄｐと可塑剤吸収量Ｐａｄはそれぞれ下記式（４）で表すことができる。 Based on the results in Table 1, when these data are expressed in the form of d p = K · (P / V) α , the number average particle diameter d p and the plasticizer absorption amount Pad are expressed by the following formula (4), respectively. be able to.
そして、塩化ビニルモノマーを用いた場合は前述した式（１）等によってＰ／Ｖのべき数形で表すことができる。また、２，３−ジクロロ−１，３−ブタジエンを用いた場合も上記の式（４）によってＰ／Ｖのべき数形で表すことができる。 And when a vinyl chloride monomer is used, it can represent with the power form of P / V by Formula (1) etc. which were mentioned above. Also, when 2,3-dichloro-1,3-butadiene is used, it can be expressed in the power form of P / V by the above equation (4).
式（１）で用いられているＷ項は分散剤の物性を反映するので、使用する分散剤の種類や配合量等の実験処方を固定することにより、相関式をｄｐ＝Ｋ・（Ｐ／Ｖ）αの形式で表記することが可能となり、Ｐ／Ｖ、即ち懸濁重合時の撹拌動力に対する影響を評価できる。そして、本実施例によって、この関係式が可塑剤吸収量との間にも成立することが示唆されたので、本発明に係る方法は平均粒子径と可塑剤吸収量を正確に評価できる方法であることが示唆された。 Since the W term used in the formula (1) reflects the physical properties of the dispersant, the correlation formula is expressed as d p = K · (P by fixing the experimental formulation such as the type and blending amount of the dispersant used. / V) can be expressed in the form of α , and the influence on P / V, that is, the stirring power during suspension polymerization can be evaluated. And since this example suggested that this relational expression holds between the plasticizer absorption amount, the method according to the present invention is a method that can accurately evaluate the average particle diameter and the plasticizer absorption amount. It was suggested that there is.
ここで、撹拌所要動力Ｐｖに対する重合体の平均粒子径のグラフを図２に示す。撹拌所要動力Ｐｖに対する重合体の可塑剤吸収量のグラフを図３に示す。べき数式の傾きは単量体や濃度が異なるため完全には一致しないが、２，３−ジクロロ−１，３−ブタジエンを懸濁重合させた場合と、塩化ビニルモノマーを懸濁重合させた場合において、Ｐｖの相違に比例して数平均粒子径及び可塑剤吸収量が増減するという、ほぼ同一の評価結果が得られた。 Here, the graph of the average particle diameter of the polymer with respect to the stirring required power Pv is shown in FIG. A graph of the amount of plasticizer absorbed by the polymer versus the required power Pv for stirring is shown in FIG. The slope of the power formula does not match completely because the monomer and concentration are different, but the suspension polymerization of 2,3-dichloro-1,3-butadiene and the suspension polymerization of vinyl chloride monomer , Almost the same evaluation results were obtained that the number average particle diameter and the plasticizer absorption increased or decreased in proportion to the difference in Pv.
以上より、２，３−ジクロロ−１，３−ブタジエンを懸濁重合させて得られた重合体を評価することにより、塩化ビニルモノマーを懸濁重合させて得られるポリ塩化ビニルの、撹拌動力に対する粉体特性を簡便に評価できることが示された。 From the above, by evaluating the polymer obtained by suspension polymerization of 2,3-dichloro-1,3-butadiene, the polyvinyl chloride obtained by suspension polymerization of the vinyl chloride monomer can be used for the stirring power. It was shown that the powder characteristics can be easily evaluated.
Claims (4)
代替モノマーとして２，３−ジクロロ−１，３−ブタジエンを用いて、水性媒体と重合開始剤と分散剤と析出助剤との存在下で、重合液単位体積あたりの撹拌動力の条件を変えて懸濁重合を行い、得られた重合体の数平均粒子径及び／又は可塑剤吸収量を測定することで、懸濁重合における撹拌動力に対するポリ塩化ビニルの粉体特性を評価する方法。 A method for evaluating the powder characteristics of polyvinyl chloride obtained by suspension polymerization,
Using 2,3-dichloro-1,3-butadiene as an alternative monomer, in the presence of an aqueous medium, a polymerization initiator, a dispersant, and a precipitation aid, changing the conditions of stirring power per unit volume of the polymerization liquid A method of evaluating the powder characteristics of polyvinyl chloride with respect to stirring power in suspension polymerization by performing suspension polymerization and measuring the number average particle size and / or plasticizer absorption of the obtained polymer.
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| JP2013159690A (en) * | 2012-02-03 | 2013-08-19 | Denki Kagaku Kogyo Kk | Diene powder composition, method for producing the same, and diene rubber composition |
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