JP4809620B2 - Method for producing polymer - Google Patents
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Description
本発明は、高分子量かつ分子量分布の狭いポリマーの製造方法に関する。 The present invention relates to a method for producing a polymer having a high molecular weight and a narrow molecular weight distribution.
塩化ビニル系樹脂用の加工助剤・改質剤等の添加剤、液晶スペーサ、滑り性付与剤、トナー等にはポリマー微粒子が用いられ、そのようなポリマー微粒子としては、高分子量かつ分子量分布の狭い微粒子が要求されている。
特に、塩化ビニル系樹脂は各種物理的および化学的性質に優れているために広く用いられているが、加工温度が熱分解温度に近く許容成形加工領域が狭いばかりでなく、ゲル化速度が遅い等の種々の加工上の問題を有している。また、発泡成形も好適な用途であり、例えば、合成木材等を指向した建材部材として発泡成形体の製造が試みられている。
しかしながら、塩化ビニル系樹脂からそのまま発泡体を製造する場合には、塩化ビニル系樹脂の通常の成形加工温度下では伸び特性、溶融強度が不足するため、不均質な発泡セル構造しか与えず、また任意の高発泡倍率とすることができず、満足な発泡成形体を得ることは困難であった。さらに、前述したように、塩化ビニル系樹脂は許容成形加工領域が狭いため、成形加工条件の変更だけによって満足な発泡成形体を得ることも困難であった。
このような塩化ビニル系樹脂を外観性を損なうことなく高発泡させる為に、主に溶融強度の付与を目的として、高分子量かつ分子量分布の狭いポリマー微粒子、特にアクリル系樹脂からなる微粒子を添加する手法が種々検討されている。
しかし、高分子量のポリマー微粒子を得るためには乳化重合法が挙げられるが、単純にビニル系単量体を乳化重合で重合した場合、その重合発熱により、重合温度が上がり、平均分子量は高いものが得られても、その分子量分布が広くなってしまう（例えば、特許文献１）。また、重合発熱をコントロールするために、単量体の一部、または全量を滴下する方法が挙げられるが、その滴下時間や滴下温度をコントロールしなければ分子量分布が広くなったり、充分な高分子量のポリマー微粒子が得られない（例えば、特許文献２）。
In particular, vinyl chloride resins are widely used because they are excellent in various physical and chemical properties, but the processing temperature is close to the thermal decomposition temperature and the allowable molding processing area is narrow, and the gelation rate is slow. Etc. have various processing problems. Foam molding is also a suitable application. For example, attempts have been made to produce a foam molded body as a building material member oriented toward synthetic wood or the like.
However, in the case of producing a foam as it is from a vinyl chloride resin, the stretch characteristics and melt strength are insufficient at the normal molding processing temperature of the vinyl chloride resin, which gives only a non-uniform foam cell structure. It was impossible to obtain an arbitrary high expansion ratio, and it was difficult to obtain a satisfactory foamed molded article. Furthermore, as described above, since the vinyl chloride resin has a narrow allowable molding process area, it is difficult to obtain a satisfactory foamed molded article only by changing the molding process conditions.
In order to make such a vinyl chloride resin highly foamed without impairing the appearance, polymer fine particles having a high molecular weight and a narrow molecular weight distribution, particularly fine particles made of an acrylic resin, are added mainly for the purpose of imparting melt strength. Various methods have been studied.
However, in order to obtain high molecular weight polymer fine particles, an emulsion polymerization method can be mentioned. However, when a vinyl monomer is simply polymerized by emulsion polymerization, the polymerization temperature rises due to the polymerization heat generation, and the average molecular weight is high. Is obtained, the molecular weight distribution becomes wide (for example, Patent Document 1). In addition, in order to control the polymerization exotherm, a method of dropping a part or all of the monomer can be mentioned. However, if the dropping time and dropping temperature are not controlled, the molecular weight distribution becomes wide or the sufficient high molecular weight. Polymer fine particles cannot be obtained (for example, Patent Document 2).
このように従来の技術では高分子量かつ分子量分布の狭いポリマー微粒子を効率よく生産するのは困難であった。
本発明は前記課題を解決するためになされたもので、高分子量かつ分子量分布の狭いポリマーを効率よく製造することを目的とする。
As described above, it has been difficult to efficiently produce polymer fine particles having a high molecular weight and a narrow molecular weight distribution by the conventional technique.
The present invention has been made to solve the above-described problems, and an object thereof is to efficiently produce a polymer having a high molecular weight and a narrow molecular weight distribution.
本発明者らは、上記の課題を解決すべく鋭意検討した結果、ビニル系単量体を重合するにあたり、特定の重合条件、すなわち、単量体の滴下速度をＷ[mol/s]、熱分解性重合開始剤の初期濃度をＩ0[mol/m3]、熱分解性重合開始剤の濃度をＩ[mol/m3]、熱分解性重合開始剤の分解速度定数をｋ[1/s]、媒体の体積をＶ[m3]、滴下時間をｔm[s]とした場合に、重合中、下記式１を満たし、かつ、重合中のＷ／２ｋＩＶの最大値と最小値の比が１.５以下の条件を満たして全単量体を滴下重合することで高分子量かつ分子量分布の狭いポリマーを効率よく製造できることを見出し、本発明に到達した。
式１：３×１０４<Ｗｔm/（２Ｉ0（1−exp(−ｋｔm)）Ｖ）<１.５×１０５
As a result of intensive studies to solve the above problems, the present inventors have determined that when polymerizing a vinyl monomer, the specific polymerization conditions, that is, the dropping rate of the monomer is W [mol / s], heat The initial concentration of the decomposable polymerization initiator is I 0 [mol / m 3 ], the concentration of the heat decomposable polymerization initiator is I [mol / m 3 ], and the decomposition rate constant of the heat decomposable polymerization initiator is k [1 / s], the volume of the medium is V [m 3 ], and the dropping time is t m [s], the following formula 1 is satisfied during the polymerization, and the maximum and minimum values of W / 2 kIV during the polymerization are The inventors have found that a polymer having a high molecular weight and a narrow molecular weight distribution can be efficiently produced by dropping polymerization of all monomers under the condition that the ratio is 1.5 or less, and the present invention has been achieved.
Formula 1: 3 × 10 4 <Wt m / (2I 0 (1−exp (−kt m )) V) <1.5 × 10 5
本発明によるポリマーは、高分子量かつ分子量分布の狭いものであるので、塩化ビニル系樹脂用の加工助剤・改質剤、液晶スペーサ、滑り性付与剤、トナー等として有用である。 Since the polymer according to the present invention has a high molecular weight and a narrow molecular weight distribution, it is useful as a processing aid / modifier for a vinyl chloride resin, a liquid crystal spacer, a slipperiness imparting agent, a toner and the like.
＜媒体中での重合＞
本発明は、熱分解性重合開始剤の存在下、ビニル系単量体を媒体に滴下して重合するポリマーの製造方法に適用される。
ここで、ビニル系単量体を滴下する媒体は水を主要な成分とするものである。
即ち、本発明を適用する重合法としては、乳化重合、ソープフリー重合が挙げられる。好ましくは乳化重合である。
乳化重合法を適用する場合に用いることのできる乳化剤としては、特に限定されるものではなく各種のものが使用でき、例えば、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルリン酸エステル塩、ジアルキルスルホコハク酸塩等のアニオン性界面活性剤、またポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン酸脂肪エステル、グリセリン脂肪酸エステル等のノニオン性界面活性剤、さらにはアルキルアミン塩等カチオン性界面活性剤を使用することができる。また、これらの乳化剤は単独でまたは併用して使用することができる。また、使用乳化剤の種類により重合系のｐＨがアルカリ側になるときは、メタクリル酸アルキルエステルの加水分解を防止するために適当なｐＨ調節剤を使用することもできる。ｐＨ調節剤としては、ホウ酸−塩化カリウム−水酸化カリウム、リン酸二水素カリウム−リン酸水素二ナトリウム、ホウ酸−塩化カリウム−炭酸カリウム、クエン酸−クエン酸水素カリウム、リン酸二水素カリウム−ホウ砂、リン酸水素二ナトリウム−クエン酸等を使用することができる。
＜ビニル系単量体＞
ビニル系単量体としては、例えば、メタクリル酸メチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ペンチル、アクリル酸エチル、アクリル酸−ｎ−ブチル、アクリル酸−２−エチルヘキシル、アクリル酸ベンジル、アクリル酸フェニルのようなアクリル酸エステル；スチレン、α−メチルスチレン、ビニルトルエンのような芳香族ビニル化合物；アクリロニトリル、メタクレロニトリルのようなシアン化ビニル化合物；酢酸ビニルのようなビニルエステル；無水マレイン酸のような酸無水物等が挙げられるが、本発明はこれらの具体例のみに限定されるものではない。特にメタクリル酸メチル、メタクリル酸ブチル、アクリル酸−ｎ−ブチルが好適に用いられる。これらは、目的に応じて１種あるいは２種以上組み合わせて用いることができる。
＜熱分解性重合開始剤＞
本発明において使用する熱分解性重合開始剤には、水溶性、油溶性両方の熱分解性重合開始剤が使用できる。例として通常の過硫酸塩等の無機開始剤が挙げられる。さらにｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、過酸化ベンゾイル、過酸化ラウロイル等の有機過酸化物、アゾ化合物等を用いることもできるが、本発明はこれら具体例のみに限定されるものではない。
<Polymerization in medium>
The present invention is applied to a method for producing a polymer in which a vinyl monomer is dropped into a medium and polymerized in the presence of a thermally decomposable polymerization initiator.
Here, the medium in which the vinyl monomer is dripped contains water as a main component.
That is, examples of the polymerization method to which the present invention is applied include emulsion polymerization and soap-free polymerization. Emulsion polymerization is preferred.
The emulsifier that can be used when applying the emulsion polymerization method is not particularly limited, and various types of emulsifiers can be used. For example, fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonate salts, alkyl phosphate ester salts , Anionic surfactants such as dialkylsulfosuccinates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, and cationic amines such as alkylamine salts Surfactants can be used. These emulsifiers can be used alone or in combination. In addition, when the pH of the polymerization system is on the alkali side depending on the type of emulsifier used, an appropriate pH adjuster can be used to prevent hydrolysis of the alkyl methacrylate. Examples of pH regulators include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, potassium dihydrogen phosphate -Borax, disodium hydrogen phosphate-citric acid and the like can be used.
<Vinyl monomer>
Examples of the vinyl monomer include methyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, benzyl acrylate, and acrylic acid. Acrylic esters such as phenyl; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; maleic anhydride Examples of such acid anhydrides may be mentioned, but the present invention is not limited to these specific examples. In particular, methyl methacrylate, butyl methacrylate, and acrylic acid-n-butyl are preferably used. These can be used alone or in combination of two or more according to the purpose.
<Pyrolytic polymerization initiator>
As the thermal decomposable polymerization initiator used in the present invention, both water-soluble and oil-soluble thermal decomposable polymerization initiators can be used. Examples include inorganic initiators such as ordinary persulfate. Furthermore, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, and azo compounds can be used, but the present invention is not limited to these specific examples. Absent.
＜滴下して重合＞
重合釜に、必要な水、乳化剤、熱分解性重合開始剤等を仕込み、単量体は全量滴下する。重合カレットを防止するため、重合の後半に状態に応じて乳化剤を追加滴下してよい。
<Drip and polymerize>
In a polymerization kettle, necessary water, an emulsifier, a thermally decomposable polymerization initiator and the like are charged, and the entire amount of monomer is dropped. In order to prevent polymerization cullet, an emulsifier may be added dropwise depending on the state in the latter half of the polymerization.
本発明は使用する単量体全量を滴下して重合するものであり、その滴下速度が、その重合温度における熱分解性重合開始剤の分解速度に対して、ある一定の範囲で重合を行う。即ち、単量体の滴下速度をＷ[mol/s]、熱分解性重合開始剤の初期濃度をＩ0[mol/m3]、熱分解性重合開始剤の濃度をＩ[mol/m3]、熱分解性重合開始剤の分解速度定数をｋ[1/s]、媒体の体積をＶ[m3]、滴下時間をｔm[s]とした場合に、重合中、下記条件１、条件２を満たす。
この条件を満たして重合を行うことにより、高分子量かつ、分子量分布が狭いポリマーを得ることが可能となる。
具体的には、質量平均分子量が２００万から１０００万、質量平均分子量Ｍｗ／数平均分子量ＭＮとの比Ｍｗ／ＭＮが２.２以下のポリマーを効率よく重合することが可能になりうる。
尚、ビニル系単量体を滴下する媒体は水を主要な成分とするので、実際には、媒体の体積Ｖは実質的には水の体積を意味することになる。
＜条件１＞
３×１０４<Ｗｔm/（２Ｉ0（1−exp(−ｋｔm)）Ｖ）<１.５×１０５
Ｗｔm/（２Ｉ0（1−exp(−ｋｔm)）Ｖ）が３×１０４以下であると、充分に分子量が高くならない。逆に、Ｗｔm/（２Ｉ0（1−exp(−ｋｔm)）Ｖ）が１.５×１０５以上であると、溶存酸素や単量体に含まれている重合禁止剤の影響を大きく受けてしまい、安定した重合ができない恐れがある。
＜条件２＞
Ｗ／２ｋＩＶの最大値と最小値の比が１.５以下
これは、滴下時間、滴下温度をコントロールすることで成される。比は、好ましくは１.３以下、さらに好ましくは１.１以下である。重合中のＷ／２ｋＩＶの最大値と最小値の比が１.５を超えてしまうと、分子量分布が広くなる恐れがある。また、重合中のＷ／２ｋＩＶの最大値と最小値の比を１.５以下にコントロールするために、滴下途中に熱分解性重合開始剤を追加してもよい。
また、Ｗ／２ｋＩＶの範囲として、上限としては１.５×１０５以下が好ましい。より好ましくは１.２×１０５以下、さらに好ましくは１×１０５以下、さらに好ましくは８×１０４以下である。また下限としては３×１０４以上が好ましい。より好ましくは４×１０４以上、さらに好ましくは５×１０４以上、さらに好ましくは６×１０４以上である。
In the present invention, polymerization is carried out by dropping the entire amount of the monomer used, and polymerization is carried out within a certain range with respect to the decomposition rate of the thermally decomposable polymerization initiator at the polymerization temperature. That is, the monomer dropping rate is W [mol / s], the initial concentration of the thermal decomposable polymerization initiator is I 0 [mol / m 3 ], and the concentration of the thermal decomposable polymerization initiator is I [mol / m 3]. ], The decomposition rate constant of the thermally decomposable polymerization initiator is k [1 / s], the volume of the medium is V [m 3 ], and the dropping time is t m [s]. Condition 2 is satisfied.
By performing the polymerization while satisfying this condition, it is possible to obtain a polymer having a high molecular weight and a narrow molecular weight distribution.
Specifically, it may be possible to efficiently polymerize a polymer having a mass average molecular weight of 2 million to 10 million and a ratio Mw / MN of 2.2 or less with respect to the mass average molecular weight Mw / number average molecular weight MN.
In addition, since the medium in which the vinyl monomer is dropped has water as a main component, the volume V of the medium actually means the volume of water.
<Condition 1>
3 × 10 4 <Wt m / (2I 0 (1−exp (−kt m )) V) <1.5 × 10 5
When Wt m / (2I 0 (1−exp (−kt m )) V) is 3 × 10 4 or less, the molecular weight is not sufficiently increased. Conversely, if Wt m / (2I 0 (1−exp (−kt m )) V) is 1.5 × 10 5 or more, the influence of the polymerization inhibitor contained in the dissolved oxygen or monomer There is a risk that stable polymerization will not be possible.
<Condition 2>
The ratio of the maximum value and the minimum value of W / 2 kIV is 1.5 or less. This is achieved by controlling the dropping time and dropping temperature. The ratio is preferably 1.3 or less, more preferably 1.1 or less. If the ratio between the maximum value and the minimum value of W / 2 kIV during polymerization exceeds 1.5, the molecular weight distribution may be widened. Further, in order to control the ratio of the maximum value and the minimum value of W / 2 kIV during polymerization to 1.5 or less, a thermally decomposable polymerization initiator may be added during the dropping.
Further, the upper limit of the range of W / 2 kIV is preferably 1.5 × 10 5 or less. More preferably, it is 1.2 × 10 5 or less, further preferably 1 × 10 5 or less, and further preferably 8 × 10 4 or less. The lower limit is preferably 3 × 10 4 or more. More preferably 4 × 10 4 or more, further preferably 5 × 10 4 or more, and further preferably 6 × 10 4 or more.
＜重合開始温度＞
重合開始温度ｔ（℃）と熱分解性重合開始剤の１０時間半減期温度τ（℃）とが次式を満たすことが望ましい。
τ−２０＜ｔ＜τ＋１０
さらに、τ−１０＜ｔ＜τを満たすことがより望ましい。
尚、熱分解性重合開始剤の１０時間半減期温度τとは、１０時間で熱分解性重合開始剤濃度が半分になる温度を意味する。
ｔ≦τ−２０では、熱分解性重合開始剤が充分に分解されず、重合がうまく進行しないことが懸念される。またｔ≧τ＋１０では、熱分解性重合開始剤の分解速度が速くなり、重合初期では比較的低分子量成分が、重合後期では比較的高分子量成分が重合され、分子量分布が狭いポリマー微粒子を得ることが困難になる。
<Polymerization start temperature>
It is desirable that the polymerization start temperature t (° C.) and the 10-hour half-life temperature τ (° C.) of the thermally decomposable polymerization initiator satisfy the following formula.
τ−20 <t <τ + 10
Furthermore, it is more desirable to satisfy τ−10 <t <τ.
The 10-hour half-life temperature τ of the thermally decomposable polymerization initiator means a temperature at which the concentration of the thermally decomposable polymerization initiator becomes half in 10 hours.
When t ≦ τ−20, there is a concern that the thermally decomposable polymerization initiator is not sufficiently decomposed and the polymerization does not proceed well. In addition, when t ≧ τ + 10, the decomposition rate of the thermally decomposable polymerization initiator is increased, and relatively low molecular weight components are polymerized in the early stage of polymerization, and relatively high molecular weight components are polymerized in the late stage of polymerization, thereby obtaining polymer fine particles having a narrow molecular weight distribution. Becomes difficult.
本発明において滴下重合中は重合温度を一定に保つことが望ましい。望ましくは重合開始温度ｔ±3℃、さらに望ましくはｔ±1℃以内で制御することが望ましい。
また、本発明において滴下する単量体に含まれる酸素濃度は10mg/L以下が望ましく、さらに好ましくは5mg/L以下、さらに好ましくは1mg/L以下が望ましい。
In the present invention, it is desirable to keep the polymerization temperature constant during the dropping polymerization. Desirably, the polymerization start temperature is controlled within t ± 3 ° C., more preferably within t ± 1 ° C.
In the present invention, the oxygen concentration contained in the dropped monomer is preferably 10 mg / L or less, more preferably 5 mg / L or less, and further preferably 1 mg / L or less.
上記製造されたポリマーは、その重合工程後に、例えば、噴霧乾燥する粒子化工程を経ることにより、粒子とすることができ、高分子量かつ分子量分布の狭いポリマー粒子を得ることができる。 The polymer produced as described above can be converted into particles by, for example, a spray-drying particle forming step after the polymerization step, and polymer particles having a high molecular weight and a narrow molecular weight distribution can be obtained.
上述したポリマーないしポリマー粒子は、目的に応じて、例えば、種々の樹脂と共に使用される。特に、塩化ビニル系樹脂用の加工助剤・改質剤等の添加剤等に好適に利用される。
配合方法、割合等は、適宜、周知の方法を適用できる。
本発明で得られるポリマー微粒子は、高分子量かつ分子量分布が狭いので、例えば、樹脂用の添加剤、液晶スペーサ、滑り性付与剤、トナー等として優れており、特に、塩化ビニル系樹脂に添加することで、その成形加工性、発泡成形を顕著に向上できる。
The polymer or polymer particle described above is used together with various resins, for example, depending on the purpose. In particular, it is suitably used for additives such as processing aids and modifiers for vinyl chloride resins.
A known method can be appropriately applied as a blending method, a ratio, and the like.
The polymer fine particles obtained in the present invention have a high molecular weight and a narrow molecular weight distribution, so that they are excellent, for example, as additives for resins, liquid crystal spacers, slipperiness imparting agents, toners, and the like, and particularly added to vinyl chloride resins. Thereby, the moldability and foam molding can be remarkably improved.
以下、実施例および比較例により本発明を更に詳しく説明するが、本発明はその要旨を超えない限り、以下の例に制限されるものではない。
なお、以下の例中で、「部」とあるのは「質量部」を示す。
また、全ての試薬は、特に断りがない限り、市販の良好品を使用した。
数平均分子量、質量平均分子量、および分子量分布については、次に示すGPC分析装置および方法で測定した。システム：SHIMAZU社製GPCシステム、カラム：ＳＨＯＤＥＸ ＧＰＣ Ｋ−８０７Ｌ 移動相：クロロホルム。数平均分子量などはポリエチレン換算で求めた。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited to the following examples, unless the summary is exceeded.
In the following examples, “part” means “part by mass”.
All reagents used were commercially good products unless otherwise specified.
The number average molecular weight, mass average molecular weight, and molecular weight distribution were measured by the following GPC analyzer and method. System: GPC system manufactured by SHIMAZU, column: SHODEX GPC K-807L Mobile phase: chloroform. The number average molecular weight was determined in terms of polyethylene.
［実施例１］
蒸留水１１８部、ラウリル硫酸ナトリウム１部、炭酸ナトリウム０.１部を、攪拌翼、熱電対、窒素導入口を備えた反応容器に仕込み、攪拌しながら、窒素気流を通ずることによって反応容器内の雰囲気の窒素置換を行った。その後、系内を６０℃に昇温して内部の液温が６０℃になった時点で、過硫酸カリウム０.０１２部と蒸留水４部からなる混合液を加え、窒素置換を充分行ったメチルメタクリレート８０部、ブチルメタクリレート２０部を６時間かけて等量滴下し、ラジカル重合を開始せしめた。
尚、過硫酸カリウムの１０時間半減期温度（τ）は６７℃である。
滴下終了後、２時間保持して重合を完結して共重合体粒子分散液を得た。この液を噴霧乾燥し、粉体を得た（Ａ−１）。
この共重合体粒子の質量平均分子量は３８０万、数平均分子量は１８０万だった。Ｗｔm/２Ｉ0（1−exp(−ｋｔm)）Ｖ＝７.７×１０４、Ｗ／２ｋＩＶの最大値と最小値の比１.１５
粉体（Ａ−１）５部を塩化ビニル系樹脂（平均重合度１０５０）１００部、ジオクチルフタレート８０部、ステアリン酸カルシウム０.５部、ステアリン酸亜鉛０.２部、エポキシ化大豆油３.０部、発泡剤（分解型）３.０部、顔料０.１部と共にヘンシエルミキサにて混合して軟質塩化ビニル系樹脂組成物を得た（Ｂ−１）。
[Example 1]
Charge 118 parts of distilled water, 1 part of sodium lauryl sulfate, and 0.1 part of sodium carbonate into a reaction vessel equipped with a stirring blade, a thermocouple, and a nitrogen inlet, and pass through a nitrogen stream while stirring. The atmosphere was purged with nitrogen. Thereafter, when the temperature inside the system was raised to 60 ° C. and the internal liquid temperature reached 60 ° C., a mixed solution consisting of 0.012 part of potassium persulfate and 4 parts of distilled water was added, and nitrogen substitution was sufficiently performed. Equivalent amounts of 80 parts of methyl methacrylate and 20 parts of butyl methacrylate were dropped over 6 hours to initiate radical polymerization.
The 10-hour half-life temperature (τ) of potassium persulfate is 67 ° C.
After completion of dropping, the mixture was held for 2 hours to complete the polymerization to obtain a copolymer particle dispersion. This liquid was spray-dried to obtain a powder (A-1).
The copolymer particles had a mass average molecular weight of 3,800,000 and a number average molecular weight of 1,800,000. Wt m / 2I 0 (1−exp (−kt m )) V = 7.7 × 10 4 , ratio of maximum value and minimum value of W / 2 kIV 1.15
5 parts of powder (A-1) 100 parts of vinyl chloride resin (average polymerization degree 1050), 80 parts of dioctyl phthalate, 0.5 part of calcium stearate, 0.2 part of zinc stearate, epoxidized soybean oil 3.0 A soft vinyl chloride resin composition was obtained by mixing with a Henschel mixer together with 3.0 parts of a foaming agent (decomposition type) and 0.1 part of a pigment (B-1).
［実施例２］
蒸留水３３２部、ラウリル硫酸ナトリウム０.６部、炭酸ナトリウム０.１部を、攪拌翼、熱電対、窒素導入口を備えた反応容器に仕込み、攪拌しながら、窒素気流を通ずることによって反応容器内の雰囲気の窒素置換を行った。その後、系内を６５℃に昇温して内部の液温が６５℃になった時点で、過硫酸カリウム０.０１２部と蒸留水４部からなる混合液を加え、窒素置換を充分行ったメチルメタクリレート８０部、ブチルメタクリレート２０部を１６０分かけて等量滴下し、ラジカル重合を開始せしめた。
滴下終了後、２時間保持して重合を完結し共重合体粒子分散液を得た。この液を噴霧乾燥し、粉体を得た（Ａ−２）。
この共重合体粒子の質量平均分子量は３６０万、数平均分子量は１７０万だった。Ｗｔm/２Ｉ0（1−exp(−ｋｔm)）Ｖ＝８.４×１０４、Ｗ／２ｋＩＶの最大値と最小値の比１.１４
実施例１と同様の配合を行い、軟質塩化ビニル系樹脂組成物を得た（Ｂ−２）。
[Example 2]
Charge 332 parts of distilled water, 0.6 part of sodium lauryl sulfate, and 0.1 part of sodium carbonate into a reaction vessel equipped with a stirring blade, a thermocouple, and a nitrogen inlet, and pass through a nitrogen stream while stirring. The atmosphere was replaced with nitrogen. Thereafter, when the temperature in the system was raised to 65 ° C. and the internal liquid temperature reached 65 ° C., a mixed solution consisting of 0.012 parts of potassium persulfate and 4 parts of distilled water was added, and nitrogen substitution was sufficiently performed. Equivalent amounts of 80 parts of methyl methacrylate and 20 parts of butyl methacrylate were dropped over 160 minutes to initiate radical polymerization.
After completion of dropping, the mixture was held for 2 hours to complete the polymerization to obtain a copolymer particle dispersion. This liquid was spray-dried to obtain a powder (A-2).
The copolymer particles had a mass average molecular weight of 3.6 million and a number average molecular weight of 1.7 million. Wt m / 2I 0 (1−exp (−kt m )) V = 8.4 × 10 4 , ratio of the maximum value and the minimum value of W / 2 kIV 1.14
The same blending as in Example 1 was performed to obtain a soft vinyl chloride resin composition (B-2).
［比較例１］
メチルメタクリレート８０部、ブチルメタクリレート２０部、蒸留水１８１部、ラウリル硫酸ナトリウム１.３部、炭酸ナトリウム０.１部を、攪拌翼、熱電対、窒素導入口を備えた反応容器に仕込み、攪拌しながら、窒素気流を通ずることによって反応容器内の雰囲気の窒素置換を行った。その後、系内を５０℃に昇温して内部の液温が５０℃になった時点で、過硫酸カリウム０.１５部と蒸留水６部からなる混合液を加え、ラジカル重合を開始せしめた。
重合発熱終了後、２時間保持して重合を完結し共重合体粒子分散液を得た。この液を噴霧乾燥し、粉体を得た（Ａ−３）。
この共重合体粒子の質量平均分子量は３６０万、数平均分子量は１００万だった。
実施例１と同様の配合を行い、軟質塩化ビニル系樹脂組成物を得た（Ｂ−３）。
［比較例２］
蒸留水３２７部、ラウリル硫酸ナトリウム０.６部、炭酸ナトリウム０.１部を、攪拌翼、熱電対、窒素導入口を備えた反応容器に仕込み、攪拌しながら、窒素気流を通ずることによって反応容器内の雰囲気の窒素置換を行った。その後、系内を７０℃に昇温して内部の液温が７０℃になった時点で、過硫酸カリウム０.１部と蒸留水１０部からなる混合液を加え、窒素置換を充分行ったメチルメタクリレート８０部、ブチルメタクリレート２０部を９０分かけて等量滴下し、ラジカル重合を開始せしめた。
滴下終了後、２時間保持して重合を完結し共重合体粒子分散液を得た。この液を噴霧乾燥し、粉体を得た（Ａ−４）。
この共重合体粒子の質量平均分子量は９０万、数平均分子量は４２万だった。Ｗｔm/２Ｉ0（1−exp(−ｋｔm)）Ｖ＝８.９×１０３、Ｗ／２ｋＩＶの最大値と最小値の比１.１５
実施例１と同様の配合を行い、軟質塩化ビニル系樹脂組成物を得た（Ｂ−４）。
[Comparative Example 1]
80 parts of methyl methacrylate, 20 parts of butyl methacrylate, 181 parts of distilled water, 1.3 parts of sodium lauryl sulfate, and 0.1 part of sodium carbonate are charged into a reaction vessel equipped with a stirring blade, a thermocouple, and a nitrogen inlet and stirred. However, the atmosphere in the reaction vessel was replaced with nitrogen by passing through a nitrogen stream. Thereafter, when the temperature in the system was raised to 50 ° C. and the internal liquid temperature reached 50 ° C., a mixed solution consisting of 0.15 parts of potassium persulfate and 6 parts of distilled water was added to initiate radical polymerization. .
After completion of the polymerization exotherm, the polymerization was completed by holding for 2 hours to obtain a copolymer particle dispersion. This liquid was spray-dried to obtain a powder (A-3).
The copolymer particles had a mass average molecular weight of 3.6 million and a number average molecular weight of 1 million.
The same composition as in Example 1 was performed to obtain a soft vinyl chloride resin composition (B-3).
[Comparative Example 2]
327 parts of distilled water, 0.6 part of sodium lauryl sulfate and 0.1 part of sodium carbonate were charged into a reaction vessel equipped with a stirring blade, a thermocouple, and a nitrogen inlet, and the reaction vessel was passed through a nitrogen stream while stirring. The atmosphere was replaced with nitrogen. Thereafter, when the temperature in the system was raised to 70 ° C. and the internal liquid temperature reached 70 ° C., a mixed solution consisting of 0.1 part of potassium persulfate and 10 parts of distilled water was added, and nitrogen substitution was sufficiently performed. Equivalent amounts of 80 parts of methyl methacrylate and 20 parts of butyl methacrylate were dropped over 90 minutes to initiate radical polymerization.
After completion of dropping, the mixture was held for 2 hours to complete the polymerization to obtain a copolymer particle dispersion. This liquid was spray-dried to obtain a powder (A-4).
The copolymer particles had a mass average molecular weight of 900,000 and a number average molecular weight of 420,000. Wt m / 2I 0 (1−exp (−kt m )) V = 8.9 × 10 3 , ratio of the maximum value and the minimum value of W / 2 kIV 1.15
The same composition as in Example 1 was performed to obtain a soft vinyl chloride resin composition (B-4).
得られた軟質塩化ビニル系樹脂組成物（Ｂ−１）〜（Ｂ−４）について発泡性の評価を行った。結果を表１に示す。
・発泡性評価
各軟質塩化ビニル系樹脂組成物について、６インチロールを用い、ロール混練温度１５０℃で５分間混錬し、約１ｍｍのシートを成形した。得られたシートを各測定温度２００℃、２２０℃のギヤオーブン中に５分間設置して加熱し発泡させ、発泡倍率と表面外観を評価した。
発泡倍率は加熱前のシートに対する発泡後の高さおよび横の広がりを測定した。
○：発泡倍率が２．５倍を超える ×：発泡倍率が２．５倍以下
表面外観は、発泡後のシートの表面外観を目視で判断した。
○：ブツが全くなく、外観良好 ×：ブツが見られる
The resulting soft vinyl chloride resin compositions (B-1) to (B-4) were evaluated for foamability. The results are shown in Table 1.
-Evaluation of foamability Each soft vinyl chloride resin composition was kneaded for 5 minutes at a roll kneading temperature of 150 ° C using a 6-inch roll to form a sheet of about 1 mm. The obtained sheet was placed in a gear oven at each measurement temperature of 200 ° C. and 220 ° C. for 5 minutes, heated and foamed, and the expansion ratio and surface appearance were evaluated.
The expansion ratio was determined by measuring the height and lateral spread after foaming of the sheet before heating.
○: Foaming ratio exceeds 2.5 times ×: Foaming ratio is 2.5 times or less The surface appearance was determined by visual observation of the surface appearance of the foamed sheet.
○: No lumps and good appearance.
表１より明らかなように、高分子量かつ分子量分布が狭い本発明の実施例１、２は発泡性、表面外観共に良好なのに対し、滴下重合でなく分子量分布の広い比較例１は表面外観が損なわれている。また分子量分布が狭いが、平均分子量の低い比較例２では充分な発泡倍率は得られなかった。 As is apparent from Table 1, Examples 1 and 2 of the present invention having a high molecular weight and a narrow molecular weight distribution are good in foaming properties and surface appearance, whereas Comparative Example 1 having a broad molecular weight distribution rather than drop polymerization has a poor surface appearance. It is. Moreover, although the molecular weight distribution was narrow, in Comparative Example 2 having a low average molecular weight, a sufficient foaming ratio was not obtained.
Claims (3)
前記媒体が水であり、前記重合が乳化重合によるものであり、
単量体の滴下速度をＷ[mol/s]、熱分解性重合開始剤の初期濃度をＩ0[mol/m3]、熱分解性重合開始剤の濃度をＩ[mol/m3]、熱分解性重合開始剤の分解速度定数をｋ[1/s]、媒体の体積をＶ[m3]、滴下時間をｔm[s]とした場合に、
重合中、下記式１を満たし、かつ、
重合中のＷ／２ｋＩＶの最大値と最小値の比が１.５以下であることを特徴とするポリマーの製造方法。
式１：３×１０４＜Ｗｔm/（２Ｉ0（1−exp(−ｋｔm)）Ｖ）＜１.５×１０５ In the method for producing a polymer in which a vinyl monomer is dropped into a medium and polymerized in the presence of a thermally decomposable polymerization initiator,
The medium is water and the polymerization is by emulsion polymerization;
The monomer dropping rate is W [mol / s], the initial concentration of the thermal decomposable polymerization initiator is I 0 [mol / m 3 ], the concentration of the thermal decomposable polymerization initiator is I [mol / m 3 ], When the decomposition rate constant of the thermally decomposable polymerization initiator is k [1 / s], the volume of the medium is V [m 3 ], and the dropping time is t m [s],
During the polymerization, the following formula 1 is satisfied, and
A method for producing a polymer, wherein the ratio of the maximum value and the minimum value of W / 2 kIV during polymerization is 1.5 or less.
Formula 1: 3 × 10 4 <Wt m / (2I 0 (1−exp (−kt m )) V) <1.5 × 10 5
式２：τ−２０＜ｔ＜τ＋１０ The method for producing a polymer according to claim 1, wherein the polymerization initiation temperature t and the 10-hour half-life temperature τ of the thermally decomposable polymerization initiator satisfy the following formula 2.
Formula 2: τ−20 <t <τ + 10
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