JP6901198B2 - アニオン重合のための官能性開始剤 - Google Patents
アニオン重合のための官能性開始剤 Download PDFInfo
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- JP6901198B2 JP6901198B2 JP2018525416A JP2018525416A JP6901198B2 JP 6901198 B2 JP6901198 B2 JP 6901198B2 JP 2018525416 A JP2018525416 A JP 2018525416A JP 2018525416 A JP2018525416 A JP 2018525416A JP 6901198 B2 JP6901198 B2 JP 6901198B2
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- polymerization
- active hydrogen
- ethylenically unsaturated
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- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Description
(式中、Mは、第1族金属であり、Qは、活性水素原子を含まず、S、P、Si又はSn原子を介してアリルアニオンのアリルC原子に結合している、官能基である)を有する開始化合物が提供される。
(式中、Qは、上記のように定義される)により定義されるアリル化合物と反応させることによって提供することができる。
(式中、Qは、上記のように定義され、π*は、カルバニオン(リビング)ポリマー、典型的には、ポリエンマーを含むものを表す)のうちの1つによって表すことができる。
「ポリマー」とは1つ以上のモノマーの重合生成物を意味し、ホモポリマー、コポリマー、ターポリマー、テトラポリマーなどを含む。
「マー」及び「マー単位」とは、単一の反応分子に由来するポリマーの一部分を意味する(例えば、エチレンマーは、一般式−CH2CH2−を有する)。
「コポリマー」は、2つの反応物質、通常はモノマーに由来するマー単位を含んだポリマーを意味し、ランダムコポリマー、ブロックコポリマー、セグメント化コポリマー、グラフトコポリマーなどを含む。
「インターポリマー」は、少なくとも2つの反応物質、通常はモノマーに由来するマー単位を含んだポリマーを意味し、コポリマー、ターポリマー、テトラポリマーなどを含む。
「ランダムインターポリマー」とは、本質的に非反復様式で組み込まれ、ブロック、すなわち、同じマーの3つ以上のセグメントを実質的に含まない各タイプの構成モノマーに由来するマー単位を有するインターポリマーを意味する。
「ゴムムーニー粘度」は、任意の充填剤(複数可)の添加前の未硬化ポリマーのムーニー粘度である。
「化合物ムーニー粘度」は、とりわけ、未硬化又は部分的に硬化されたポリマー及び粒状充填剤(複数可)を含む組成物のムーニー粘度である。
「置換」は、該当する基について意図した目的を阻害しないヘテロ原子又は官能基(例えば、ヒドロカルビル基)を含むものを意味する。
「直接結合」とは、介在する原子又は基がない状態で共有結合していることを意味する。
「ポリエン」は、最長部分又は分子鎖に少なくとも2つの二重結合が存在する分子を意味し、具体的にはジエン、トリエンなどが含まれる。
「ポリジエン」は、1つ以上のジエンのマー単位を含むポリマーを意味する。
「phr」とは、ゴム100重量部(pbw)当たりのpbwを意味する。
「ラジカル」又は「残基」とは、反応の結果、何らかの原子が得られるか又は失われるかに関わらず、別の分子と反応した後に残る分子の一部分を意味する。
「アリール基」は、フェニル基又は多環式芳香族ラジカルを意味する。
「環構造」は、環式基を意味し、
「末端」とは、ポリマー鎖の端部を意味する。
「末端部分」は、末端に位置する基又は官能基を意味し、
「反応性ポリマー」は、活性末端の存在により、他の分子と容易に反応する少なくとも1つの部位を有するポリマーを意味し、その用語は、とりわけ、カルバニオンポリマーを含んでいる。
(式中、それぞれのR1は、独立してエチレン性不飽和及び活性H原子を含まないヒドロカルビル基であり、それぞれのR2は、独立して、R1、NR1 2基、又はエチレン性不飽和及び活性H原子を含まない置換ヒドロカルビル基である)を含む。好ましいR1基は、C1〜C6アルキル基(特に直鎖アルキル基)、アリール(特にフェニル)基及びシクロアルキル(特にC5〜C6シクロアルキル)を含み、一方で、例示的なR2基(R1以外)は、それぞれのR1aが上記の好ましいR1基を表す−NR1a 2を含む。
Sigma−Aldrich Co.(St.Louis,Missouri)製−アリルメチルスルフィド、アリル(ジエチルアミノ)−ジメチルシラン、アリルトリメチルシラン、アリルトリブチルスタンナン、及びアリルジフェニルホスフィン、
Gelest Inc.(Morrisville,Pennsylvania)製−3−(1,3−ジメチルブチリデン)アミノプロピルトリエトキシシラン(AP3E、3.0M)及び2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン(ECH3M;4.3M)。
撹拌機を備えたN2パージした反応器に、1.36kgのヘキサン、0.45kgのスチレン溶液、及び3.14kgのブタジエン溶液を添加した。反応器に3.6mLのn−BuLi溶液、続いて、1.1mLの2,2−bis(2’−テトラヒドロフリル)プロパン溶液を投入した。反応器ジャケットを50℃まで加熱し、約33分後、バッチ温度は約65℃でピークに達した。
試料2−0.17mLのAP3E、
試料3−0.12mLのECH3M、及び
試料4−0.5mLのSnCl4溶液(ヘキサン中で0.25M)を添加した。
それぞれの瓶を50℃湯浴に入れた。約30分後、瓶を取り除き、それぞれの内容物をBHT含有イソプロパノール中で別々に凝固させた後、ドラム乾燥させた。
実施例5〜8:重合、P−アリル系開始剤
乾燥シクロヘキサン10mL及びアリルトリブチルスタンナン(3.22M)1.7mLの混合物に、3.6mLのn−BuLi溶液、続いて1.1mLの2,2−ビス(2’−テトラヒドロフリル)−プロパン溶液を添加した。内容物を室温で更に約15分間攪拌した。
乾燥シクロヘキサン10mL及びアリルトリメチルシラン(6.29M)0.87mLの混合物に、3.6mLのn−BuLi溶液、続いて1.1mLの2,2−ビス(2’−テトラヒドロフリル)−プロパン溶液を添加した。内容物を室温で更に約15分間攪拌した。
乾燥シクロヘキサン10mL及びアリル(ジエチルアミノ)ジメチルシラン(4.64M)1.18mLの混合物に、3.6mLのn−BuLi溶液、続いて1.1mLの2,2−ビス(2’−テトラヒドロフリル)−プロパン溶液を添加した。内容物を室温で更に約15分間攪拌した。
乾燥シクロヘキサン10mL及びアリルメチルスルフィド(9.10M)0.6mLの混合物に、3.6mLのn−BuLi溶液、続いて1.1mLの2,2−ビス(2’−テトラヒドロフリル)−プロパン溶液を添加した。内容物を室温で更に約15分間攪拌した。
上記の表1a及び表1bからの配合を使用して、補強充填剤を含有する加硫可能なエラストマー性化合物を試料5〜8及び16〜24から調製した。化合物を約15分間171℃で硬化させて、加硫物25〜48がもたらされた。
Claims (5)
- エチレン性不飽和を含むポリマーを提供するためのプロセスであって、
a)一般式:
(式中、Mは、第1族金属であり、Qは、活性水素原子を含まず、S、P、若しくはSn原子を介して、それぞれアリルアニオンのアリルC原子に結合している官能基、又はR 2 R 1 2 Si基であり、それぞれのR 1 が独立してヒドロカルビル基であり、R 2 がR 1 、NR 1 2 基、又はエチレン性不飽和及び活性水素原子を含まない置換ヒドロカルビル基である)を有する開始化合物を提供することと、
b)1種以上の有機液体と、少なくとも1種のポリエンを含む1種以上のエチレン性不飽和化合物と、を含む反応容器に、前記開始化合物を、導入することと、
c)前記1種以上のエチレン性不飽和化合物を重合させ、その重合により前記ポリマーを提供することと、を含む、プロセス。 - 前記少なくとも1種のポリエンは、1種以上の共役ジエンを含む、請求項1に記載のプロセス。
- 前記1種以上のエチレン性不飽和化合物は、少なくとも1種のビニル芳香族化合物を更に含む、請求項2に記載のプロセス。
- 前記1種以上の有機液体は、少なくとも1種のC5〜C12非環状アルカンを含む、請求項1に記載のプロセス。
- 前記Qは、活性水素原子を含まず、S、P、又はSn原子を介して、それぞれアリルアニオンのアリルC原子に結合している官能基である場合において、前記Qは以下に示す(a)〜(c)のいずれかであり、
(a)前記Qは、R1S基であり、R1がエチレン性不飽和及び活性水素原子を含まないヒドロカルビル基であり、
(b)前記Qは、R1 2P基であり、それぞれのR1が独立してエチレン性不飽和及び活性水素原子を含まないヒドロカルビル基であり、
(c)前記Qは、R1 3Sn基であり、それぞれのR1が独立してエチレン性不飽和及び活性水素原子を含まないヒドロカルビル基である、
請求項1に記載のプロセス。
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