JP2019535888A - 共役ジエン系共重合体の製造方法、それから製造された共役ジエン系共重合体、およびそれを含むゴム組成物 - Google Patents
共役ジエン系共重合体の製造方法、それから製造された共役ジエン系共重合体、およびそれを含むゴム組成物 Download PDFInfo
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- JP2019535888A JP2019535888A JP2019547567A JP2019547567A JP2019535888A JP 2019535888 A JP2019535888 A JP 2019535888A JP 2019547567 A JP2019547567 A JP 2019547567A JP 2019547567 A JP2019547567 A JP 2019547567A JP 2019535888 A JP2019535888 A JP 2019535888A
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- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
Description
[実施例1]
窒素置換された重合反応器(オートクレーブ)に、イオン交換水200重量部、単量体として、α−メチルスチレン48重量部、1,3−ブタジエン50重量部、ヒドロキシプロピルメタクリレート0.5重量部、乳化剤として、脂肪酸の石けんおよびロジン酸のアルカリ塩5重量部、開始剤としてクメンヒドロパーオキサイド0.5重量部、および分子量調節剤としてドデシルメルカプタン0.5重量部を一括投入し、反応温度10℃で反応させた。前記反応時に、重合転換率が15%、30%、および45%の時点で、単量体であるヒドロキシプロピルメタクリレートをそれぞれ0.5重量部ずつ一括投入した。重合転換率が60%である時点で反応を終了し、共役ジエン系共重合体ラテックスを製造した。
前記実施例1において、共役ジエン系共重合体ラテックスの製造時に、ヒドロキシプロピルメタクリレートを重合開始の前(重合転換率0%)と重合転換率30%の時点でそれぞれ1重量部ずつ一括投入したことを除き、前記実施例1と同様の方法により行った。
前記実施例1において、共役ジエン系共重合体ラテックスの製造時に、ヒドロキシプロピルメタクリレートの代わりに、ヒドロキシブチルメタクリレートを同回数で同量投入したことを除き、前記実施例1と同様の方法により行った。
前記実施例1において、共役ジエン系共重合体ラテックスの製造時に、α−メチルスチレンの代わりに、スチレンを同量投入したことを除き、前記実施例1と同様の方法により行った。
前記実施例1において、共役ジエン系共重合体ラテックスの製造時に、ヒドロキシプロピルメタクリレートを投入せず、α−メチルスチレン49重量部、1,3−ブタジエン51重量部を投入したことを除き、前記実施例1と同様の方法により行った。
前記実施例1において、共役ジエン系共重合体ラテックスの製造時に、ヒドロキシプロピルメタクリレート2重量部を重合開始の前(重合転換率0%)に一括投入したことを除き、前記実施例1と同様の方法により行った。
[実験例1]
前記実施例1〜3および比較例1〜3で製造された共役ジエン系共重合体の重量平均分子量、数平均分子量、分子量分布、ムーニー粘度(MV)、およびガラス転移温度(Tg)を、組成とともに下記表1に記載した。
重量平均分子量、数平均分子量は、GPC(Gel permeation chromatography)分析により測定し、分子量分布(MWD、Mw/Mn)は、測定された前記各分子量から計算した。具体的に、前記GPCには、PLgel Olexis(Polymer Laboratories社製)カラム2本とPLgel mixed−C(Polymer Laboratories社製)カラム1本を組み合わせて使用した。分子量の計算時に、GPC基準物質(Standard material)としてはPS(polystyrene)を使用して実施した。
MV−2000(ALPHA Technologies社製)により、100℃で、Rotor Speed 2±0.02rpm、Large Rotorを用いて測定した。この際、使用された試料は、室温(23±3℃)で30分以上放置した後、27±3gを採取してダイキャビティの内部に満たしておき、プラテン(Platen)を作動させて4分間測定した。
DSCを用いて、通常の方法により測定した。
前記実施例1および比較例3の共役ジエン系共重合体の製造時に、重合転換率による共重合体中のヒドロキシアルキル(メタ)アクリレート単量体由来の繰り返し単位の含量をNMRにより分析し、下記表2および図1に示した。
前記実施例1〜3および比較例1〜3で製造された共役ジエン系共重合体を含むゴム組成物、およびそれから製造された成形品の物性を比較分析するために、下記のようにゴム試験片を製造し、製造されたゴム試験片を用いて、ムーニー粘度、耐磨耗性、および粘弾性特性を下記の方法によりそれぞれ測定し、その結果を表4に示した。
実施例1〜3および比較例1〜3の共役ジエン系共重合体100重量部、およびブタジエンゴム(エルジー・ケム・リミテッド社製、grade名BR1208)30重量部を原料ゴムとして、下記表3に示した配合条件で配合した。表3中の原料は、共役ジエン系共重合体100重量部を基準とした各重量部である。
MV−2000(ALPHA Technologies社製)により、100℃で、Rotor Speed 2±0.02rpm、Large Rotorを用いて測定した。この際、使用された試料は、室温(23±3℃)で30分以上放置した後、27±3gを採取してダイキャビティの内部に満たしておき、プラテン(Platen)を作動させて4分間測定した。
No.152 Akron Type Abrasion Test(日本Yasuda社製)を用いて、常温で10lb積載下で、500回の予備摩耗を行った後、3,000回の本摩耗を行い、体積の減少分を測定して示した。
DMTS 500N(ドイツGabo社製)を用いて、周波数10Hz、Prestrain5%、Dynamic Strain0.5%で、−40℃〜70℃の温度範囲内で2℃/minで昇温しながら温度Sweepを行って、tanδを測定した。tanδグラフにおいて、変曲点のX軸の値からCompound Tgを示した。低温である0℃でのtanδが高いほど、ウェットグリップ性に優れることを意味し、高温である60℃でのtanδが低いほど、ヒステリシス損が少なく、低走行抵抗性(燃費性)に優れることを意味する。
Claims (8)
- α−メチルスチレン単量体、共役ジエン系単量体、およびヒドロキシアルキル(メタ)アクリレート単量体を含んで乳化重合させるステップ(S10)を含み、
前記α−メチルスチレン単量体および共役ジエン系単量体は、前記乳化重合の重合転換率が0%である時点で一括投入し、前記ヒドロキシアルキル(メタ)アクリレート単量体は、前記乳化重合の重合転換率が0%〜80%である時点で2回以上に分割投入して、
単量体の全含量に対して、前記α−メチルスチレン単量体は10重量%〜50重量%、前記共役ジエン系単量体は49重量%〜89重量%、および前記ヒドロキシアルキル(メタ)アクリレート単量体は0.1重量%〜5重量%で投入する、共役ジエン系共重合体の製造方法。 - 前記ヒドロキシアルキル(メタ)アクリレート単量体は、前記乳化重合の重合転換率が0%〜60%である時点で2回〜4回に分割投入する、請求項1に記載の共役ジエン系共重合体の製造方法。
- 前記ヒドロキシアルキル(メタ)アクリレート単量体に由来の繰り返し単位の含量は、前記乳化重合の重合転換率による各共役ジエン系共重合体の全含量に対して、偏差±2重量%の範囲内で維持される、請求項1に記載の共役ジエン系共重合体の製造方法。
- 前記ヒドロキシアルキル(メタ)アクリレート単量体に由来の繰り返し単位の含量は、前記乳化重合の重合転換率による各共役ジエン系共重合体の全含量に対して、0.1重量%〜5重量%の範囲内で維持される、請求項3に記載の共役ジエン系共重合体の製造方法。
- 共役ジエン系共重合体に含まれる単量体由来の繰り返し単位の全含量に対して、α−メチルスチレン単量体由来の繰り返し単位10重量%〜50重量%、共役ジエン系単量体由来の繰り返し単位49重量%〜89重量%、およびヒドロキシプロピルメタクリレート単量体由来の繰り返し単位0.1重量%〜5重量%を含み、前記ヒドロキシアルキル(メタ)アクリレート単量体由来の繰り返し単位の含量は、重合転換率による各共役ジエン系共重合体の全含量に対して、偏差±2重量%の範囲内で維持される、共役ジエン系共重合体。
- 請求項5に記載の共役ジエン系共重合体を含む原料ゴムを含むゴム組成物。
- 前記原料ゴム100重量部に対して、1重量部〜200重量部のシリカ系充填剤を含む、請求項6に記載のゴム組成物。
- 前記シリカ系充填剤は、湿式シリカ、乾式シリカ、ケイ酸カルシウム、ケイ酸アルミニウム、およびコロイドシリカからなる群から選択される1種以上である、請求項7に記載のゴム組成物。
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