JP2018533667A - 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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- JP2018533667A JP2018533667A JP2018524475A JP2018524475A JP2018533667A JP 2018533667 A JP2018533667 A JP 2018533667A JP 2018524475 A JP2018524475 A JP 2018524475A JP 2018524475 A JP2018524475 A JP 2018524475A JP 2018533667 A JP2018533667 A JP 2018533667A
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- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 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
- 230000008685 targeting Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 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
- 230000000007 visual effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- B60C1/0016—Compositions of the tread
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- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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Abstract
Description
本国際出願は、2015年11月13日に出願の米国仮特許出願第62/255,151号の利益を主張し、この開示は参照により本明細書に組み込まれる。
式中、R1は置換若しくは非置換アリール基であり、R2はR1、水素原子、又は置換若しくは非置換(シクロ)−アルキル基であり、そしてRNは第二級アミン基である、開始化合物を提供する。R1及びR2の各々は、活性水素原子含有基を有していない。(活性水素原子の存在はZerewit−inoff測定法によって示される)。一般式(I)中のLi原子は、ベンジルC原子に共有結合しているとして示されているが、その結合はイオン性であってもよい。
式中、R1及びR2は上記のように定義される。上記反応に関与する第二級アミンのN原子は、2つのヒドロカルビル基に結合することができ、又は1個以上の環原子が置換基を含むことができる5〜8個の環原子を有する環状基の一部であり得る。
式中、R1、R2、及びRNは上で定義したものであり、π*はエチレン性不飽和、即ちエチレン性不飽和マーを含むカルバニオン性ポリマー鎖である。
「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」又は「マー単位」とは、単一の反応物分子由来の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、即ち、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」とは、あ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性(例えば、ヒドロカルビル基)を含むことを意味する。
「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」とは、その最長部分又は分子鎖に少なくとも2つの二重結合を有する分子を意味し、具体的にはジエン、トリエンなどが挙げられる。
「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かかわらず、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」とは、フェニル基又は多環状芳香族ラジカルを意味する。
「環構造」とは環状基を意味する。
「末端」とは、ポリマー鎖の端部を意味する。
「末端部分」とは、末端に位置する基又は官能性を意味する。
「反応性ポリマー」とは、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む。
が挙げられ;
置換若しくは非置換のアルカリール基、その特定の例としては、
が挙げられ;
置換若しくは非置換のシクロアルキル基、その特定の例としては、
が挙げられ;
又は、5〜7個の環原子を有する環状基の一部であるアミンN原子を介して結合した基、例えば、
が挙げられ、
式中、xは1〜6、好ましくは2〜4の両範囲値を含む整数である。式(IV−a)〜(IV−p)に示した特定の化合物は、当業者が相当数の類似体及び追加の種を構想するのに十分である。
式中、R2は上で定義され、FGは官能基(置換基)であり、nは0〜5の両範囲値を含む整数である。潜在的な置換基(FG)の非限定的な例としては、R2N−、R2P−、R3SiO−などが挙げられ、Rは、先に記載したようなヒドロカルビル基、特にC1〜C12アルキル、C5〜C8シクロアルキル又はアリール基、並びにピロリジニル及びピペリジニル基を含む複素環状部分を表す。これらの実施例は、限定と考えるのではなく、当業者は、一般式(II)及び(II−a)の範囲内に入る多くの他のかかる化合物を構想することができる。
Sigma−Aldrich Co.(St.Louis,Missouri)から、ピペリジン、N−(4−ピペリジノ)ピペリジン及び(3−グリシドキシプロピル)トリメトキシシラン(GLYMO、4.5M);
Gelest Inc.(Morrisville,Pennsylvania)から、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)。
実施例1〜4:対照重合、n−ブチルリチウム
サンプル2 − 0.5mLのMA2E溶液、
サンプル3 − 0.17mLのAP3E、及び
サンプル4 − 0.11mLのGLYMOを添加した。
各ボトルを50℃の水浴中に置いた。約30分後、ボトルを取り出し、各ボトルの内容物を、BHTを含むイソプロパノール中で別々に凝固させた、次いでドラム乾燥させた。
実施例5〜8:比較重合、リチウム化ピペリジン
サンプル6 − 0.5mLのMA2E溶液、
サンプル7 − 0.17mLのAP3E、及び
サンプル8 − 0.12mLのECH3Mを添加した。
更なる加工は実施例1〜4に記載されたものと同じであった。これらのポリマーの特定の特性を以下の表2に要約する。
実施例9〜12:比較重合、リチウム化HMI
サンプル10 − 0.5mLのMA2E溶液、
サンプル11 − 0.17mLのAP3E、及び
サンプル12 − 0.5mLのSnCl4溶液を添加した。
更なる加工は実施例1〜4に記載されたものと同じであった。これらのポリマーの特定の特性を以下の表2に要約する。
実施例13〜16:官能化開始剤、スチレンとリチウム化HMIの付加物
サンプル14 − 0.5mLのMA2E溶液、
サンプル15 − 0.17mLのAP3E、及び
サンプル16 − 0.5mLのSnCl4溶液を添加した。
更なる加工は実施例1〜4に記載されたものと同じであった。これらのポリマーの特定の特性を以下の表に一覧にする。
実施例17〜19:官能化開始剤、スチレンとリチウム化ピペリジンの付加物
サンプル18 − 0.17mLのAP3E、及び
サンプル19 − 0.5mLのSnCl4溶液を添加した。
更なる加工は実施例1〜4に記載されたものと同じであった。これらのポリマーの特定の特性を以下の表3に要約する。
実施例20〜23:官能化開始剤、スチレンとリチウム化4−ピペリジンの付加物
サンプル21 − 0.5mLのMA2E溶液、
サンプル22 − 0.17mLのAP3E、及び
サンプル23 − 0.5mLのSnCl4溶液を添加した。
更なる加工は実施例1〜4に記載されたものと同じであった。これらのポリマーの特定の特性を以下の表3に要約する。
実施例24〜47:加硫物
実施例48〜51:連続重合
(1)約0.8g/秒のスチレン溶液(ヘキサン中31.8%)、
(2)約6.8g/秒の1,3−ブタジエン溶液(ヘキサン中21.7%)、
(3)約2.4g/秒のヘキサン、
(4)約0.11g/秒の2,2−ビス(2’−テトラヒドロフリル)プロパン溶液(ヘキサン中0.10M)、
(5)約2×10−9m3/秒の1,2−ブタジエン(ヘキサン中20%)、及び
(6)約0.097g/秒のn−BuLi溶液(ヘキサン中0.125M)。
約2.94g/秒の1,3−ブタジエン溶液の追加の流れを反応器の中間点に加えて、スチレンマーのブロックの形成を最小にした。ポリマーセメントを反応容器の上部から貯蔵容器に移した。4500±900秒の重合後、反応器は定常状態に達し、上部の温度は約99℃であり、底部の温度は約91℃であった。
実施例56 − MA2E、
実施例57及び60 − AP3E、及び
実施例58及び61 − ECH3M。
更なる加工は実施例1〜4に記載されたものと同じであった。
実施例52 − 実施例55及び59
実施例53 − 実施例56
実施例54 − 実施例57及び60
(例58及び61には比較例はない)。
Claims (20)
- 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)以下の一般式を有する開始化合物を提供することであって、
式中、
R1は、置換又は非置換フェニル基であり、
R2は、R1、水素原子、置換若しくは非置換アルキル基、又は置換若しくは非置換シクロアルキル基であり、
RNは、第二級アミン基のラジカルであり、
但し、R1及びR2の各々は、活性水素原子含有基を有していない、開始化合物を提供することと、
b)前記開始化合物を、1つ以上の有機液体と、少なくとも1つのポリエンを含む1つ以上のエチレン性不飽和化合物と、を含む、反応容器に導入することと、
c)前記1つ以上のエチレン性不飽和化合物を重合させ、それによって前記ポリマーを提供することと、
d)任意選択的に、前記ポリマーがカルバニオン形態であり、それを末端化合物、カップリング剤、又は連結剤と反応させて、前記ポリマーに末端官能性を提供することと、を含む、プロセス。 - 前記少なくとも1つのポリエンが、1つ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つ以上のエチレン性不飽和化合物が、少なくとも1つ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。
- 前記少なくとも1つのポリエンの各々が、共役ジエンである、請求項1に記載のプロセス。
- 前記1つ以上のエチレン性不飽和化合物が、少なくとも1つのビニル芳香族化合物を更に含む、請求項4に記載のプロセス。
- 前記1つ以上の有機液体が、少なくとも1つの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1つ以上の有機液体が、少なくとも1つのC5〜C12非環状アルカンである、請求項6に記載のプロセス。
- 前記第二級アミンのN原子が、2つのヒドロカルビル基に結合される、請求項8に記載のプロセス。
- 前記ヒドロカルビル基の各々が、アルキル基である、請求項9に記載のプロセス。
- 前記第二級アミンのN原子が、5〜8個の環原子を有する環状基の一部である、請求項8に記載のプロセス。
- 5〜8個の環原子を有する前記環状基のうちの少なくとも1個の環原子が、少なくとも1つの置換基を含む、請求項11に記載のプロセス。
- 前記少なくとも1つの置換基が、第三級アミン基を含む、請求項12に記載のプロセス。
- 前記第三級アミン基が、5〜8個の環原子を有する環状基の一部である、請求項13に記載のプロセス。
- 前記第二級アミンが、4−ピペリジノピペリジンである、請求項14に記載のプロセス。
- R1が、置換フェニル基である、請求項8に記載のプロセス。
- 前記置換フェニル基のうちの少なくとも1つの置換基が、少なくとも1つのP、O、又はSi原子を含む、請求項16に記載のプロセス。
- 前記ポリマーを回収及び単離することを更に含む、請求項1〜17のいずれかに記載のプロセス。
- 前記ポリマーを、少なくとも1つの粒状充填剤を含む成分とブレンドしてゴム化合物を提供することを更に含む、請求項18に記載のプロセス。
- 前記ゴム化合物を加硫して加硫物を提供することを更に含み、前記加硫物が任意選択的にタイヤ成分である、請求項19に記載のプロセス。
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