JP2018131515A - Hydrogenated styrene-based copolymer resin - Google Patents
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本発明は、水添スチレン系共重合樹脂に関するものであり、特にスチレン−ブタジエン共重合ゴム(以下、SBRと記す。)との相溶性に優れることからタイヤ、防振ゴム、ベルト、ホース、履物、接着剤等の各種用途で使用可能なSBR改質用として優れる水添スチレン系共重合樹脂に関するものである。 The present invention relates to a hydrogenated styrene-based copolymer resin, and is particularly excellent in compatibility with styrene-butadiene copolymer rubber (hereinafter referred to as SBR), so that it can be used for tires, anti-vibration rubbers, belts, hoses and footwear. The present invention relates to a hydrogenated styrene copolymer resin that is excellent for SBR modification that can be used in various applications such as adhesives.
タイヤ性能や加工性を向上することを目的に、ゴムに樹脂を配合することが提案されている。ゴムに相溶性の高い水素添加樹脂を配合することでウェットグリップ性を改良する方法が提案されている(例えば特許文献1〜4参照。)。水素化する原料の樹脂として、スチレン系樹脂、C9留分を重合して得られる石油樹脂、C5留分とC9留分を共重合して得られる石油樹脂等が提案されている。特許文献1には更に原料中のインデンの割合が40質量%以上の芳香族系石油樹脂が好ましいと提案されている。 In order to improve tire performance and workability, it has been proposed to blend a resin with rubber. A method of improving wet grip properties by blending a highly compatible hydrogenated resin with rubber has been proposed (see, for example, Patent Documents 1 to 4). As a raw material resin to be hydrogenated, a styrene resin, a petroleum resin obtained by polymerizing a C9 fraction, a petroleum resin obtained by copolymerizing a C5 fraction and a C9 fraction, and the like have been proposed. Patent Document 1 further suggests that an aromatic petroleum resin having a ratio of indene in the raw material of 40% by mass or more is preferable.
タイヤの初期グリップ性と走行安定性を改良するものとして、C5成分及び/又はC9成分から成る石油樹脂を水素化した軟化点120℃以上の水素化樹脂、更に軟化点140℃以上190℃以下のインデンを含有するC9樹脂をゴム成分に配合することが提案されている(例えば特許文献5参照。)。 For improving the initial grip and running stability of a tire, a hydrogenated resin having a softening point of 120 ° C. or higher obtained by hydrogenating a petroleum resin comprising a C5 component and / or a C9 component, and further having a softening point of 140 ° C. or higher and 190 ° C. or lower. It has been proposed to blend C9 resin containing indene into a rubber component (see, for example, Patent Document 5).
また、モノマー組成をインデン20重量%以下とし、ビニルトルエンを50重量%以上としたC9樹脂を水素化し、熱可塑性エラストマーに添加することが提案されている(例えば特許文献6、7参照。)。その際の熱可塑性エラストマーとしては、例えばスチレン−ブタジエン共重合体が挙げられている。 In addition, it has been proposed to hydrogenate a C9 resin having a monomer composition of 20% by weight or less of indene and 50% by weight or more of vinyltoluene and add it to a thermoplastic elastomer (see, for example, Patent Documents 6 and 7). As the thermoplastic elastomer at that time, for example, a styrene-butadiene copolymer is mentioned.
しかし、特許文献1〜5に提案の方法は、ゴムと樹脂の相溶性が不十分であり、ウェットグリップ性が不十分である、ゴムよりガラス転移点が高い樹脂を配合するため転がり抵抗が増加し低燃費性が悪化する、粘度が高くなるため加工性が悪化しシリカや末端変性ゴムの使用量が制限される、混練不良によりタイヤ性能が低下する、等の課題を有するものであった。 However, the methods proposed in Patent Documents 1 to 5 have insufficient compatibility between the rubber and the resin, the wet grip property is insufficient, and the rolling resistance is increased because the resin has a glass transition point higher than that of the rubber. However, the fuel efficiency deteriorates, the viscosity increases, the workability deteriorates, the amount of silica and terminal-modified rubber used is limited, and the tire performance deteriorates due to poor kneading.
また、特許文献6、7に提案の方法は、耐光性を改良するため、インデンを減量した水添C9樹脂を添加しており、相溶性の改良効果については何ら言及されていないものであった。 In addition, in the methods proposed in Patent Documents 6 and 7, hydrogenated C9 resin with a reduced amount of indene is added to improve light resistance, and no mention is made of the effect of improving compatibility. .
そこで、本発明は、SBRとの相溶性に優れることからタイヤ、防振ゴム、ベルト、ホース、履物、接着剤等に使用可能となるSBR改質用として優れる水添スチレン系共重合樹脂を提供することを目的とするものである。 Accordingly, the present invention provides a hydrogenated styrene copolymer resin that is excellent for SBR modification and can be used for tires, anti-vibration rubbers, belts, hoses, footwear, adhesives and the like because of its excellent compatibility with SBR. It is intended to do.
本発明者らは、前記課題を解決すべく鋭意研究を進めた結果、特定の成分を共重合してなる水添スチレン系共重合樹脂がSBRとの著しい相溶性を改善することが可能となることを見出し、本発明を完成させるに至った。 As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention can improve the marked compatibility of the hydrogenated styrene copolymer resin obtained by copolymerizing specific components with SBR. As a result, the present invention has been completed.
即ち、本発明は、スチレン、ビニルトルエン、α−メチルスチレン、β−メチルスチレンからなる群から選択される少なくとも1種のスチレン系誘導体単位(A)99〜80重量%とインデン、メチルインデンからなる群から選択される少なくとも1種の誘導体単位(B)1〜20重量%を少なくとも構成単位とするスチレン系共重合樹脂を水素化してなり、芳香族環の水素化率が70%以上であることを特徴とする水添スチレン系共重合樹脂に関するものである。 That is, the present invention comprises 99 to 80% by weight of at least one styrene derivative unit (A) selected from the group consisting of styrene, vinyltoluene, α-methylstyrene, and β-methylstyrene, and indene and methylindene. A styrene copolymer resin having at least one derivative unit (B) of 1 to 20% by weight selected from the group is hydrogenated, and the hydrogenation rate of the aromatic ring is 70% or more. The present invention relates to a hydrogenated styrene copolymer resin.
以下に、本発明を詳細に説明する。 The present invention is described in detail below.
本発明の水添スチレン系共重合樹脂は、スチレン系共重合樹脂を水素化してなるものであり、該スチレン系共重合樹脂は、スチレン、ビニルトルエン、α−メチルスチレン、β−メチルスチレンからなる群から選択される少なくとも1種のスチレン系誘導体単位(A)99〜80重量%とインデン、メチルインデンからなる群から選択される少なくとも1種の誘導体単位(B)1〜20重量%を少なくとも構成単位とする共重合体であり、特に水素化した後の水添物がSBRとの相溶性、取扱い性に優れるものとなることから、スチレン系誘導体単位(A)95〜85重量%と誘導体単位(B)5〜15重量%を少なくとも構成単位とするものであることが好ましい。ここで、スチレン系誘導体単位(A)が80重量%未満である場合、又は99重量%を越える場合、SBRとの相溶性に劣るものとなる。 The hydrogenated styrene copolymer resin of the present invention is obtained by hydrogenating a styrene copolymer resin, and the styrene copolymer resin comprises styrene, vinyltoluene, α-methylstyrene, and β-methylstyrene. At least one styrene derivative unit (A) selected from the group of 99 to 80% by weight and at least one derivative unit (B) selected from the group consisting of indene and methylindene constitute at least 1 to 20% by weight Since the hydrogenated product after hydrogenation has excellent compatibility with SBR and excellent handleability, the styrene derivative unit (A) is 95 to 85% by weight and the derivative unit. (B) It is preferable that 5 to 15% by weight is at least a structural unit. Here, when the styrene derivative unit (A) is less than 80% by weight, or when it exceeds 99% by weight, the compatibility with SBR is poor.
本発明の水添スチレン系共重合樹脂は、スチレン系共重合樹脂を水素化してなるものであり、水素化の際には主にスチレン系共重合樹脂を構成する芳香族環の水素化が進行するものである。そして、特にSBRとの相溶性に優れる水添スチレン系共重合樹脂となることから該芳香族環の水素化率が70%以上のものであり、さらに水素化率が80%以上のものであることが好ましい。水素化率が70%未満である場合、SBRとの相溶性に劣るものとなる。 The hydrogenated styrene copolymer resin of the present invention is obtained by hydrogenating a styrene copolymer resin, and during the hydrogenation, hydrogenation of the aromatic ring mainly constituting the styrene copolymer resin proceeds. To do. And since it becomes a hydrogenated styrene copolymer resin excellent in compatibility with SBR in particular, the hydrogenation rate of the aromatic ring is 70% or more, and the hydrogenation rate is 80% or more. It is preferable. When the hydrogenation rate is less than 70%, the compatibility with SBR is poor.
本発明の水添スチレン系共重合樹脂は、特にSBRとの相溶性に優れるものとなることから、ゲル浸透クロマトグラフィーを用い、標準ポリスチレン換算値として測定した際の重量平均分子量(Mw)が800〜3000のものが好ましく、更に800〜2000のものが好ましい。 Since the hydrogenated styrene copolymer resin of the present invention is particularly excellent in compatibility with SBR, the weight average molecular weight (Mw) when measured as a standard polystyrene conversion value using gel permeation chromatography is 800. -3000 are preferable, and 800-2000 are more preferable.
また、本発明の水添スチレン系共重合樹脂は、特にSBRとの相溶性や加工性に優れるものとなることから、JIS K−2207を準拠した軟化点が70〜140℃のものであることが好ましく、更に80〜130℃のものが好ましい。 The hydrogenated styrene copolymer resin of the present invention is particularly excellent in compatibility with SBR and processability, and therefore has a softening point of 70 to 140 ° C. based on JIS K-2207. Are preferred, and those having a temperature of 80 to 130 ° C. are preferred.
そして、本発明の水添スチレン系共重合樹脂は、SBRとの相溶性に悪影響を与えない範囲内で、該スチレン系誘導体単位(A)と該誘導体単位(B)以外の単位(C)を含んでも良い。その際の単位(C)としては、例えばジシクロペンタジエン及びその誘導体、イソプレン、ピペリレン、シクロペンタジエン等のC5単量体より誘導されたる単位を挙げることができる。 The hydrogenated styrene-based copolymer resin of the present invention contains units (C) other than the styrene-based derivative unit (A) and the derivative unit (B) within a range that does not adversely affect the compatibility with SBR. May be included. Examples of the unit (C) at that time include units derived from C5 monomers such as dicyclopentadiene and derivatives thereof, isoprene, piperylene, and cyclopentadiene.
本発明の水添スチレン系共重合樹脂とする際に水素化に供されるスチレン系共重合樹脂としては、本発明の水添スチレン系共重合樹脂とすることが可能であれば如何なるものであってもよく、例えばスチレン、ビニルトルエン、α−メチルスチレン、β−メチルスチレンからなる群から選択される少なくとも1種のスチレン系単量体(a)99〜80重量%とインデン、メチルインデンからなる群から選択される少なくとも1種の単量体(b)1〜20重量%とを少なくとも含む単量体を共重合に供することにより得ることが可能である。その際には、例えばジシクロペンタジエン及びその誘導体、イソプレン、ピペリレン、シクロペンタジエン等のC5単量体より誘導される単量体(c)を課題のない範囲で共重合することも可能である。 The styrene copolymer resin used for hydrogenation when the hydrogenated styrene copolymer resin of the present invention is used is not limited as long as it can be the hydrogenated styrene copolymer resin of the present invention. For example, at least one styrenic monomer (a) selected from the group consisting of styrene, vinyltoluene, α-methylstyrene, β-methylstyrene, 99 to 80% by weight, and indene and methylindene. It can be obtained by subjecting a monomer containing at least one monomer (b) 1 to 20% by weight selected from the group to copolymerization. In that case, for example, a monomer (c) derived from a C5 monomer such as dicyclopentadiene and derivatives thereof, isoprene, piperylene, cyclopentadiene, etc. can be copolymerized within a range where there is no problem.
そして、共重合を行う際に原料油(単量体混合物)の単量体組成を調製する方法としては、例えば純単量体を用い混合する方法、石油類の熱分解により得られる沸点範囲が140〜280℃の範囲にあるC9留分を蒸留精製する方法、純単量体とC9留分を混合する方法等が挙げられる。なお、C9留分は、一般的には該スチレン系単量体(a)、該単量体(b)、ジシクロペンタジエン及びその誘導体などの単量体を含み、一般に該スチレン系単量体(a)と該単量体(b)の合計量に占める該単量体(b)の割合が30〜45重量%と多く含まれるため、C9系石油樹脂を水素化した水添C9系石油樹脂はSBRとの相溶性は劣るものである。また、該水添C9系石油樹脂は、組成的にも本発明の水添スチレン系共重合樹脂とは異なるものである。 And as a method of preparing the monomer composition of the raw material oil (monomer mixture) at the time of copolymerization, for example, the method of mixing using pure monomers, the boiling point range obtained by pyrolysis of petroleums Examples include a method of distilling and purifying a C9 fraction in the range of 140 to 280 ° C., a method of mixing a pure monomer and a C9 fraction, and the like. The C9 fraction generally contains monomers such as the styrenic monomer (a), the monomer (b), dicyclopentadiene, and derivatives thereof. Since the proportion of the monomer (b) in the total amount of (a) and the monomer (b) is as high as 30 to 45% by weight, hydrogenated C9 petroleum obtained by hydrogenating a C9 petroleum resin The resin is inferior in compatibility with SBR. Further, the hydrogenated C9 petroleum resin is also different in composition from the hydrogenated styrene copolymer resin of the present invention.
該スチレン系共重合樹脂を得る際の重合反応としては、例えばフリーデルクラフツ型触媒を用いたカチオン重合法を挙げることができ、該フリーデルクラフツ型触媒としては、例えば三塩化アルミニウム、三臭化アルミニウム、三フッ化ホウ素、これらのフェノール錯体、これらのブタノール錯体等が挙げられ、中でも三フッ化ホウ素フェノール錯体、三フッ化ホウ素ブタノール錯体が好ましい。重合温度は0〜100℃が好ましく、特に好ましくは0〜80℃である。また、フリーデルクラフツ型触媒の添加量としては、任意であり、その中でも特に生産効率に優れた製造方法となることから、該混合物100重量部に対して0.1〜2.0重量部であることが好ましい。さらに、重合時間としては、0.1〜10時間の範囲が好ましい。反応圧力は大気圧〜1MPaが好ましい。 Examples of the polymerization reaction for obtaining the styrene copolymer resin include a cationic polymerization method using a Friedel-Crafts type catalyst. Examples of the Friedel-Crafts type catalyst include aluminum trichloride and tribromide. Aluminum, boron trifluoride, these phenol complexes, these butanol complexes, etc. are mentioned, Among these, a boron trifluoride phenol complex and a boron trifluoride butanol complex are preferable. The polymerization temperature is preferably from 0 to 100 ° C, particularly preferably from 0 to 80 ° C. Further, the amount of the Friedel-Crafts-type catalyst added is arbitrary, and among them, the production method is particularly excellent in production efficiency, so 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the mixture. Preferably there is. Furthermore, the polymerization time is preferably in the range of 0.1 to 10 hours. The reaction pressure is preferably atmospheric pressure to 1 MPa.
本発明の水添スチレン系共重合樹脂は、該スチレン系共重合樹脂を水素化触媒存在下、公知の方法により水素化することで製造することが出来る。水素化触媒としては、例えばニッケル、コバルト、ルテニウム、ロジウム、パラジウム、白金、モリブデン等の酸化物、硫化物等の金属化合物が挙げられ、多孔質で表面積の大きい珪藻土、アルミナ、シリカ、カーボン、チタニア等の担体に担持したのものでも良い。 The hydrogenated styrene copolymer resin of the present invention can be produced by hydrogenating the styrene copolymer resin by a known method in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include nickel, cobalt, ruthenium, rhodium, palladium, platinum, molybdenum and other metal compounds such as sulfides, and porous, large surface area diatomaceous earth, alumina, silica, carbon, titania. It may be supported on a carrier such as.
水素化反応の条件は、所望の水素化率となるように水素圧、温度、触媒量、溶剤の使用量を適宜調整すればよい。 The conditions for the hydrogenation reaction may be adjusted as appropriate so that the hydrogen pressure, temperature, amount of catalyst, and amount of solvent used are adjusted to achieve a desired hydrogenation rate.
本発明の水添スチレン系共重合樹脂は、その性能に悪影響を与えない範囲内で他のゴム成分を1種または2種以上含んでも良い。ゴム成分としては、例えば天然ゴム、ポリイソプレンゴム、ポリブタジエンゴム、ブチルゴム、エチレン−プロピレン共重合体等が挙げられる。 The hydrogenated styrenic copolymer resin of the present invention may contain one or more other rubber components as long as the performance is not adversely affected. Examples of the rubber component include natural rubber, polyisoprene rubber, polybutadiene rubber, butyl rubber, ethylene-propylene copolymer, and the like.
本発明の水添スチレン系共重合樹脂は、さらに通常樹脂組成物やゴム組成物に配合される添加剤を使用してもよい。例えば、硫黄を始めとする架橋剤、加硫促進剤、加硫促進助剤、ステアリン酸、亜鉛華、可塑剤、オイル、老化防止剤、シリカやカーボンブラック等のフィラーなどの配合剤を加えても良い。これらの配合剤としては市販品を好適に使用することができる。さらに、通常樹脂組成物、ゴム組成物に配合される添加剤、例えばフェノール系抗酸化剤、リン系抗酸化剤、硫黄系抗酸化剤、ラクトン系抗酸化剤、紫外線吸収剤、顔料、炭酸カルシウム、ガラスビーズなどを配合しても良い。 The hydrogenated styrene copolymer resin of the present invention may further use an additive that is usually blended in a resin composition or a rubber composition. For example, by adding compounding agents such as sulfur and other crosslinking agents, vulcanization accelerators, vulcanization acceleration aids, stearic acid, zinc white, plasticizers, oils, anti-aging agents, silica and carbon black fillers, etc. Also good. Commercial products can be suitably used as these compounding agents. Furthermore, additives usually incorporated in resin compositions and rubber compositions, such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, UV absorbers, pigments, calcium carbonate Glass beads may be blended.
本発明により、SBRとの相溶性に優れることからタイヤ、防振ゴム、ベルト、ホース、履物、接着剤等の各種用途で使用出来るSBR改質用として優れる水添スチレン系共重合樹脂を提供することが可能となる。 The present invention provides a hydrogenated styrene copolymer resin that is excellent for SBR modification and can be used in various applications such as tires, anti-vibration rubbers, belts, hoses, footwear, and adhesives because of its excellent compatibility with SBR. It becomes possible.
以下に、実施例および比較例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例、比較例において用いた原料、分析、試験法は下記の通りである。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The raw materials, analysis, and test methods used in Examples and Comparative Examples are as follows.
1.原料
(1)スチレン系共重合樹脂原料
スチレン;和光純薬製試薬。
ビニルトルエン;p−メチルスチレン、和光純薬製試薬。
α−メチルスチレン;和光純薬製試薬。
インデン;和光純薬製試薬。
トルエン;和光純薬製試薬、超脱水グレード。
C9油;ナフサの熱分解により得られる沸点範囲140〜280℃のC9留分。
精製C9油;C9油を蒸留精製したもの。
所定の組成となるように重合に用いる原料を調製した。原料の組成を表1に示す。なお、表1中のDCPDはジシクロペンタジエンの略記である。
重合触媒;三フッ化ホウ素フェノール(ステラケミファ製)。
1. Raw material (1) Styrene copolymer resin raw material styrene; Reagent made by Wako Pure Chemical Industries.
Vinyl toluene; p-methylstyrene, a reagent manufactured by Wako Pure Chemical Industries.
α-methylstyrene; a reagent manufactured by Wako Pure Chemical Industries.
Inden: Wako Pure Chemicals reagent.
Toluene: Wako Pure Chemicals reagent, ultra-dehydrated grade.
C9 oil: C9 fraction having a boiling point range of 140 to 280 ° C. obtained by thermal decomposition of naphtha.
Refined C9 oil: Distilled and refined C9 oil.
The raw material used for superposition | polymerization was prepared so that it might become a predetermined composition. Table 1 shows the composition of the raw materials. In Table 1, DCPD is an abbreviation for dicyclopentadiene.
Polymerization catalyst; boron trifluoride phenol (manufactured by Stella Chemifa).
(2)スチレン系共重合樹脂の水素化
水素化触媒;パラジウム−硫酸バリウム(アルドリッチ製、パラジウム10%)。
溶媒;シクロヘキサン(和光純薬製試薬)
2.分析方法
(1)スチレン系共重合樹脂用原料油の組成:ガスクロJIS K−0114(2000年)に準拠してガスクロマトグラフ法により測定した。
(2)軟化点:JIS K−2207に従って測定。
(3)分子量:ポリスチレンを標準物質としてゲル浸透クロマトグラフィーにより測定した。
(4)水素化率:重クロロホルム中で核磁気共鳴測定装置(日本電子製、商品名JNM−ECZ400S/LI、周波数400MHz)により1H−NMRスペクトルを測定し、7ppm付近の芳香族由来のピーク面積を基に、以下の式により水素化率を算出した。
水素化率=(1−(水添樹脂のピーク面積/原料樹脂のピーク面積))×100(%)。
(5)相溶性:粘弾性測定装置(レオメトリックス社製)を使用し、温度−100〜100℃、昇温速度2℃/分、周波数10Hz、剪断モードでtanδを測定し、tanδのピーク値(高さ)を相溶性の指標とした。基準として水添スチレン系共重合体樹脂を添加していない比較例1及び8の測定値(tanδ)を基準値(100)として設定した。該基準値に対する相対値が大きい程、相溶性が良好であると判断した。
相溶性指数=((測定tanδ値)/(比較例1,8のtanδ))×100
製造例1(原料油の調製)
表1に示す原料油A〜Dは市販の原料を用いて所定の濃度に調製した。原料油Eはナフサの熱分解により得られる沸点範囲140〜280℃のC9留分をそのまま用いた。原料油Fは原料油Eを蒸留し、高沸点留分を中心に除去して精製した。原料油の組成を表1に示す。
(2) Hydrogenation catalyst for styrene copolymer resin; palladium-barium sulfate (Aldrich, 10% palladium).
Solvent: Cyclohexane (Wako Pure Chemicals Reagents)
2. Analysis method (1) Composition of raw material oil for styrene-based copolymer resin: Measured by gas chromatography in accordance with Gas Chroma JIS K-0114 (2000).
(2) Softening point: Measured according to JIS K-2207.
(3) Molecular weight: Measured by gel permeation chromatography using polystyrene as a standard substance.
(4) Hydrogenation rate: 1 H-NMR spectrum was measured with a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, trade name JNM-ECZ400S / LI, frequency 400 MHz) in deuterated chloroform, and an aromatic-derived peak near 7 ppm. Based on the area, the hydrogenation rate was calculated by the following formula.
Hydrogenation rate = (1− (peak area of hydrogenated resin / peak area of raw material resin)) × 100 (%).
(5) Compatibility: Using a viscoelasticity measuring apparatus (manufactured by Rheometrics), measure tan δ at a temperature of −100 to 100 ° C., a heating rate of 2 ° C./min, a frequency of 10 Hz, and a shear mode, and a peak value of tan δ (Height) was used as an indicator of compatibility. As a reference, the measured value (tan δ) of Comparative Examples 1 and 8 to which no hydrogenated styrene copolymer resin was added was set as a reference value (100). The greater the relative value with respect to the reference value, the better the compatibility.
Compatibility index = ((measured tan δ value) / (tan δ of Comparative Examples 1 and 8)) × 100
Production Example 1 (Preparation of raw oil)
Raw material oils A to D shown in Table 1 were prepared to a predetermined concentration using commercially available raw materials. As the raw material oil E, a C9 fraction having a boiling point range of 140 to 280 ° C. obtained by thermal decomposition of naphtha was used as it was. The feedstock F was refined by distilling the feedstock E and removing mainly high-boiling fractions. Table 1 shows the composition of the feedstock oil.
製造例2(スチレン系共重合体の製造)
内容積2リットルのガラス製オートクレーブに表1に示す原料油500gを仕込んだ。次に、窒素雰囲気下で40℃に加熱した後、フリーデルクラフツ型触媒として三フッ化ホウ素フェノール錯体(ステラケミファ(株)三フッ化ホウ素フェノール)を原料油100重量部に対して、0.8重量部を加えて80℃で2時間重合した。苛性ソーダ水溶液を添加した後、水相を除去した。
Production Example 2 (Production of styrene copolymer)
500 g of the raw material oil shown in Table 1 was charged into a glass autoclave having an internal volume of 2 liters. Next, after heating to 40 ° C. in a nitrogen atmosphere, 0.03 parts by weight of boron trifluoride phenol complex (Stella Chemifa Co., Ltd., boron trifluoride phenol) as a Friedel-Crafts type catalyst is added to 0.1 parts by weight of the raw material oil. 8 parts by weight was added and polymerization was carried out at 80 ° C. for 2 hours. After adding the aqueous sodium hydroxide solution, the aqueous phase was removed.
そして、窒素導入管、温度計および脱気管が付いた0.5リットルセパラブルフラスコに得られた油相400gを添加した。窒素導入管より7ml/分の流速で窒素を導入し、30分かけて220℃に昇温した後、更に30分加熱し未反応油の蒸留除去を行い、スチレン系共重合樹脂を得た。 Then, 400 g of the obtained oil phase was added to a 0.5 liter separable flask equipped with a nitrogen introduction tube, a thermometer, and a deaeration tube. Nitrogen was introduced from the nitrogen introduction tube at a flow rate of 7 ml / min, the temperature was raised to 220 ° C. over 30 minutes, and the mixture was further heated for 30 minutes to distill off unreacted oil to obtain a styrene copolymer resin.
原料油A〜Fを用いて得られたスチレン系共重合樹脂をそれぞれ樹脂A〜Fとした。重合収率、および樹脂A〜Fの物性(分子量、軟化点)を表2に示す。 Styrenic copolymer resins obtained using raw material oils A to F were designated as resins A to F, respectively. Table 2 shows the polymerization yield and the physical properties (molecular weight, softening point) of the resins A to F.
実施例1
1Lオートクレーブに樹脂Aを100g、水素化触媒としてパラジウム−硫酸バリウム触媒を樹脂Aに対して5重量%、及びシクロヘキサン100gを添加した。250℃に昇温し、水素圧10MPaで6時間水素化を行った。
Example 1
100 g of resin A was added to a 1 L autoclave, 5% by weight of a palladium-barium sulfate catalyst as a hydrogenation catalyst with respect to resin A, and 100 g of cyclohexane were added. The temperature was raised to 250 ° C., and hydrogenation was performed at a hydrogen pressure of 10 MPa for 6 hours.
水素化の後、濾過により水素化触媒の除去を行い、窒素導入管、温度計および脱気管が付いた1リットルセパラブルフラスコに得られた水添スチレン系共重合樹脂溶液を添加し、窒素導入管より7ml/分の流速で窒素を導入し、30分かけて220℃に昇温した後、更に30分加熱しシクロヘキサンの蒸留除去を行い、水添スチレン系共重合樹脂A1を得た。 After hydrogenation, the hydrogenation catalyst is removed by filtration, and the hydrogenated styrene copolymer resin solution obtained is added to a 1-liter separable flask equipped with a nitrogen introduction tube, thermometer and deaeration tube, and nitrogen is introduced. Nitrogen was introduced from the tube at a flow rate of 7 ml / min, the temperature was raised to 220 ° C. over 30 minutes, and the mixture was further heated for 30 minutes to distill off cyclohexane to obtain hydrogenated styrene copolymer resin A1.
水素化反応条件、及び得られた水添スチレン系共重合樹脂A1の物性(水素化率、分子量、軟化点)を表3に示す。 Table 3 shows the hydrogenation reaction conditions and the physical properties (hydrogenation rate, molecular weight, softening point) of the obtained hydrogenated styrene copolymer resin A1.
そして、バイアル瓶(20ml)に溶液重合品の末端未変性スチレン−ブタジエン共重合体ゴム(SBR1)((株)JSR製、(商品名)SL552)100重量部、水素化スチレン共重合樹脂A1を30重量部加え、スターラーを用いてトルエン1000重量部に溶解した。アルミカップ上に溶液を流延し、窒素気流下で予備乾燥後、60℃で真空乾燥した。 Then, 100 parts by weight of hydrogenated styrene copolymer resin A1 and terminal polymer unmodified styrene-butadiene copolymer rubber (SBR1) (manufactured by JSR Co., Ltd., (trade name) SL552) are placed in a vial (20 ml). 30 parts by weight was added and dissolved in 1000 parts by weight of toluene using a stirrer. The solution was cast on an aluminum cup, pre-dried under a nitrogen stream, and then vacuum-dried at 60 ° C.
得られたSBR配合物の相溶性を測定した。その結果を表4に示す。 The compatibility of the obtained SBR formulation was measured. The results are shown in Table 4.
実施例2〜4
樹脂の種類、水素化触媒の量を表3に示す通りとした以外は、実施例1と同様の方法により、水添スチレン系共重合樹脂(A2、B1、B2)を得た。
Examples 2-4
A hydrogenated styrene copolymer resin (A2, B1, B2) was obtained in the same manner as in Example 1 except that the type of resin and the amount of the hydrogenation catalyst were as shown in Table 3.
水素化反応条件、及び得られた水添スチレン系共重合樹脂(A2、B1、B2)の物性(水素化率、分子量、軟化点)を表3に示す。 Table 3 shows the hydrogenation reaction conditions and the physical properties (hydrogenation rate, molecular weight, softening point) of the obtained hydrogenated styrene copolymer resins (A2, B1, B2).
水添スチレン系共重合樹脂A1の代わりに、水添スチレン系共重合樹脂(A2,B1,B2)を用いた以外は、実施例1と同様の方法によりSBR配合物を得た。その結果を表4に示す。 An SBR formulation was obtained in the same manner as in Example 1 except that the hydrogenated styrene copolymer resin (A2, B1, B2) was used instead of the hydrogenated styrene copolymer resin A1. The results are shown in Table 4.
実施例5、6
樹脂の種類、水素化触媒の量を表3に示す通りとした以外は、実施例1と同様の方法により、水添スチレン系共重合樹脂(F1、F2)を得た。
Examples 5 and 6
Hydrogenated styrene copolymer resins (F1, F2) were obtained by the same method as in Example 1 except that the type of resin and the amount of the hydrogenation catalyst were as shown in Table 3.
水素化反応条件、及び得られた水添スチレン系共重合樹脂(F1、F2)の物性(水素化率、分子量、軟化点)を表3に示す。 Table 3 shows the hydrogenation reaction conditions and the physical properties (hydrogenation rate, molecular weight, softening point) of the obtained hydrogenated styrene copolymer resins (F1, F2).
溶液重合品の末端未変性スチレン−ブタジエン共重合体ゴム(SBR1)((株)JSR製、(商品名)SL552)の代わりに、溶液重合品の末端変性スチレン−ブタジエン共重合体ゴム(SBR2)((株)JSR製、(商品名)HPR350)を用い、水添スチレン系共重合樹脂A1の代わりに、水添スチレン系共重合樹脂(F1、F2)を用いた以外は、実施例1と同様の方法によりSBR配合物を得た。その結果を表5に示す。 Instead of the solution-modified end-modified styrene-butadiene copolymer rubber (SBR1) (manufactured by JSR, (trade name) SL552), the solution-polymerized end-modified styrene-butadiene copolymer rubber (SBR2) Example 1 except that hydrogenated styrene copolymer resins (F1, F2) were used instead of hydrogenated styrene copolymer resin A1 (made by JSR Corporation, (trade name) HPR350). An SBR formulation was obtained in a similar manner. The results are shown in Table 5.
比較例1
水添スチレン系共重合樹脂A1を用いずにSBR1のみで、実施例1と同様の方法により評価を行った。その結果を表4に示す。
Comparative Example 1
Evaluation was carried out in the same manner as in Example 1 using only SBR1 without using the hydrogenated styrene copolymer resin A1. The results are shown in Table 4.
比較例2〜7
樹脂の種類、水素化触媒の量、水素化時間を表3に示す通りとした以外は、実施例1と同様の方法により、水添共重合樹脂(A3、B3、C1,C2、D1、D2)を得た。
Comparative Examples 2-7
A hydrogenated copolymer resin (A3, B3, C1, C2, D1, D2) was prepared in the same manner as in Example 1 except that the type of resin, the amount of hydrogenation catalyst, and the hydrogenation time were as shown in Table 3. )
水素化反応条件、及び得られた水添共重合樹脂(A3、B3、C1,C2、D1、D2)の物性(水素化率、分子量、軟化点)を表3に示す。 Table 3 shows the hydrogenation reaction conditions and the physical properties (hydrogenation rate, molecular weight, softening point) of the resulting hydrogenated copolymer resin (A3, B3, C1, C2, D1, D2).
水添スチレン系共重合樹脂A1の代わりに、水添共重合樹脂(A3、B3、C1,C2、D1、D2)を用いた以外は、実施例1と同様の方法によりSBR配合物を得た。その結果を表4に示す。 An SBR formulation was obtained in the same manner as in Example 1 except that the hydrogenated copolymer resin (A3, B3, C1, C2, D1, D2) was used instead of the hydrogenated styrene copolymer resin A1. . The results are shown in Table 4.
比較例8
SBR2のみで評価を行った。その結果を表5に示す。
Comparative Example 8
Evaluation was performed using only SBR2. The results are shown in Table 5.
比較例9〜12
水添共重合樹脂F1の代わりに、水添共重合樹脂(E1,E2,E3,F3)を用いた以外は、実施例5と同様の方法によりSBR配合物を得た。その結果を表5に示す。
Comparative Examples 9-12
An SBR formulation was obtained in the same manner as in Example 5 except that the hydrogenated copolymer resin (E1, E2, E3, F3) was used instead of the hydrogenated copolymer resin F1. The results are shown in Table 5.
本発明の水添スチレン系共重合樹脂は、スチレン−ブタジエンゴム(SBR)改質用として優れたものであり、特にSBRとの相溶性に優れることからタイヤ、防振ゴム、ベルト、ホース、履物、接着剤等に使用可能となり、その産業的価値は極めて高いものである。 The hydrogenated styrene copolymer resin of the present invention is excellent for modifying styrene-butadiene rubber (SBR), and particularly excellent in compatibility with SBR, so that it is tire, vibration-proof rubber, belt, hose, footwear. It can be used for adhesives and the like, and its industrial value is extremely high.
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