JP6829251B2 - アミノ及びポリメリル基のアルデヒド部分への付加を介する官能性ポリマーの調製プロセス - Google Patents
アミノ及びポリメリル基のアルデヒド部分への付加を介する官能性ポリマーの調製プロセス Download PDFInfo
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- JP6829251B2 JP6829251B2 JP2018512198A JP2018512198A JP6829251B2 JP 6829251 B2 JP6829251 B2 JP 6829251B2 JP 2018512198 A JP2018512198 A JP 2018512198A JP 2018512198 A JP2018512198 A JP 2018512198A JP 6829251 B2 JP6829251 B2 JP 6829251B2
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- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- UHOVQNZJYSORNB-MICDWDOJSA-N deuteriobenzene Chemical compound [2H]C1=CC=CC=C1 UHOVQNZJYSORNB-MICDWDOJSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical group [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012685 metal catalyst precursor Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MAMCJGWPGQJKLS-UHFFFAOYSA-N nona-2,7-diene Chemical compound CC=CCCCC=CC MAMCJGWPGQJKLS-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- QTYUSOHYEPOHLV-UHFFFAOYSA-N octa-1,3-diene Chemical compound CCCCC=CC=C QTYUSOHYEPOHLV-UHFFFAOYSA-N 0.000 description 1
- HYBLFDUGSBOMPI-UHFFFAOYSA-N octa-1,4-diene Chemical compound CCCC=CCC=C HYBLFDUGSBOMPI-UHFFFAOYSA-N 0.000 description 1
- HITROERJXNWVOI-UHFFFAOYSA-N octa-1,5-diene Chemical compound CCC=CCCC=C HITROERJXNWVOI-UHFFFAOYSA-N 0.000 description 1
- RJUCIROUEDJQIB-UHFFFAOYSA-N octa-1,6-diene Chemical compound CC=CCCCC=C RJUCIROUEDJQIB-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- IUXQFLRZZUQUPJ-UHFFFAOYSA-N prop-1-enyl benzoate Chemical compound CC=COC(=O)C1=CC=CC=C1 IUXQFLRZZUQUPJ-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/66—Preparation of compounds containing amino groups bound to a carbon skeleton from or via metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
元素の周期表に対する全ての参照は、CRC Press,Inc.,1990によって出版及び著作権化された元素の周期律表を指す。また、族(複数可)に対する参照は、族を番号付けするのにIUPACシステムを使用してこの元素の周期表に反映された族(複数可)に対するものとする。逆に述べない限り、文脈から黙示的でない限り、またはその技術で慣用でない限り、全ての部及びパーセントは重量を基準とし、全ての試験方法は本開示の出願日の時点で最新のものである。米国特許実務の目的のために、任意の参照された特許、特許出願、または刊行物の内容は、特に、合成技術、生成物、加工設計、ポリマー、触媒、定義(本開示で具体的に提供される任意の定義と矛盾しない範囲で)、及びその技術の一般的知識の開示に関して、それらの全体が参照により組み込まれる(またはその同等の米国版が全体として参照によりそのように組み込まれる)。
「遷移金属触媒」には、例えば、WO2005/090426、WO2005/090427、WO2009/012215、米国特許公開第2006/0199930号、同第2007/0167578号、同第2008/0311812号、及び米国特許第7,355,089B2号に開示されている触媒または触媒前駆体として機能する金属錯体、ならびにその技術で知られているものが含まれる。とりわけ、本開示は、少なくとも1種の重合触媒または触媒前駆体、少なくとも1種の共触媒、及び少なくとも1種の上述の鎖シャトリング剤を含む触媒組成物及び様々な方法を提供する。本開示はまた、少なくとも1種の重合触媒または触媒前駆体、少なくとも1種の共触媒、及び少なくとも1種の上述の鎖シャトリング剤を含む触媒組成物及び様々な方法であって、その少なくとも1種の重合触媒または触媒組成物がまた、その少なくとも1種の鎖シャトリング剤を調製するための触媒または触媒前駆体であるものを提供する。本明細書に開示された方法及び組成物で使用するのに好適な触媒または触媒前駆体には、所望の組成物または種類のポリマーを調製するために適応される任意の化合物または化合物の組み合わせが含まれる。不均一系及び均一系の触媒の両方が採用され得る。不均一系触媒の例には、第4族金属ハライド及びそれらの誘導体を含み、第2族金属ハライドまたは混合ハライド及びアルコキシドに担持された第4族金属ハライドを含み、よく知られたクロムまたはバナジウム系触媒を含む、よく知られたチーグラー・ナッタ組成物が含まれる。しかしながら、使用の容易さのため及び溶液中での狭い分子量のポリマーセグメントの生成のため、特に有用な触媒には、比較的純粋な有機金属化合物または金属錯体、特に元素の周期表の第3〜15族またはランタニドシリーズから選択される金属に基づく化合物または錯体を含む均一系触媒が含まれる。
上記のように、ジアルキル−亜鉛をアルデヒドに付加してエナンチオ選択性第2級アルコールを形成することは、文献(例えば、Luderer et al.,Tetrahedron:Asymmetry 2009,20,981−998;Genov et al.,Journal of Organometallic Chemistry 2008,693,2017−2020;Metzger et al.,Angew.Chem.Int.Ed.2010,49,4665−4668;Pisani et al.,Tetrahedron:Asymmetry 2008,19,1784−1789;Nugent,Organic Letters 2002,4(13),2133−2136;Larsson,et al.,Tetrahedron 2004,60,10659−10669;Binder et al.,Organic Preparation and Procedures International,2011,43:139−208;Yamakawa et al.,J.Am Chem.Soc.,1995,117,6327;Hevia et al.,Dalton Trans.,2010,39,520;Giacomelli et al.,J.Org.Chem.,1974,39,2736)で知られている。そのような付加反応を以下に示す。
文献に開示された上記の反応の実用性が限られていることを考慮して、本発明者らは、既存の溶液プロセスにおいてアルキル−亜鉛のアルデヒドへの付加を介してアルキル−亜鉛を官能化するための単純なβ−アミノ−アルコール促進剤、ジメチルアミノエタノール(DMAE)の使用を評価した。その反応は80℃で行ったが、その理由は、溶液プロセスに適応可能とするため、及び、ポリマーの溶解性を維持するために必要とされる最低温度と考えられたからである。この研究で使用された溶媒は、芳香族及び脂肪族炭化水素に限られていた。反応を水で冷却し、以下に記載の方法により得られたGCMS(ガスクロマトグラフィ質量分析)ピークの面積を積分することによって転化率を評価した。
ガスクロマトグラフ−質量分析(GCMS):Agilent Technologies 5975不活性XL質量選択検出器及びAgilent Technologies Capillaryカラム(HP1MS、15m×0.25mm、0.25ミクロン)を備えたAgilent Technologies 6890Nシリーズガスクロマトグラフで70eVで、電子衝撃イオン化(EI)を使用するタンデムガスクロマトグラフィ/低分解能質量分析を実施した。本開示のCSAのアリコートを水で冷却し、下記の方法を使用してGCMSによって分析した:
方法:
0分で50℃
次いで10分で300℃まで25℃/分
実行時間20分
他に述べていない限り、全ての化学試薬は受け取ったまま使用される。ZnEt2はAkzo Nobelから得られる。ZnBu2はFisher Scientificから得られる。ベンズアルデヒド、t−ブチルベンズアルデヒド、ジメチルアミノエタノール、MgCl2、MgBr2.OEt2、TiCl4、LiBr、ZrCl4、ZnCl2、Ti(OiPr)4、ClTi(OiPr)3は、Sigma−Aldrichから得られる。乾燥窒素でスパージすることによって溶媒を脱気し、使用前に活性化アルミナ(275℃のオーブンで5時間活性化)ビーズで乾燥させる。全ての実験は、窒素雰囲気下でグローブボックスまたはシュレンク(Schlenk)ラインのいずれかで行われる。
以下の表1に示されるように、既存の溶液プロセスにおいてアルキル−亜鉛のアルデヒドへの付加を介するアルキル−亜鉛の官能化について9種のルイス酸を評価する。表1に見られるように、得られた7つの化合物(すなわち、GCMS生成物)を同定する。表1において、時間の欄は、GCMS分析のためにアリコートを採取する時間を示している。これに関して、GCMS生成物に到達するための反応時間は、時間の欄の下に示された時間以下であることが理解される。
上記で論じたように、本発明者らは、驚くべきことに、予想外にも、以下に示す単純なワンポット反応がアルキル−亜鉛の官能化(例えば、アミノ官能基を有する化合物6及び7)をもたらすことを発見した。化合物6及び7は、それらの1H NMRスペクトルとともに図12に描かれている。化合物7の13C NMRスペクトルも図13に提供されている。
アルキル−亜鉛の官能化に加えて、本発明者らは、本開示の単純なワンポット反応を利用して、式(R2N)nMX4−nを有するルイス酸の存在下でポリメリル−亜鉛及びアルデヒドを採用することによってポリメリル−亜鉛を官能化することができ、以下の例によって実証されるように、また、以下に示す例示的な非限定的な反応に描かれているように(POはポリオクテンを指す)、そのポリメリル−亜鉛は、鎖シャトリング及び配位連鎖転移重合技術を介して形成され得ることを確認した。
Claims (12)
- 官能性ポリマーを生成するためのプロセスであって、
式(R2N)nMX4−nを有するルイス酸の存在下でアルデヒドを亜鉛組成体と反応させることを含み、
前記亜鉛組成体が、式ZnR’2またはR1Zn[R’Zn−]YR1を有し、
式中、
nが、1〜3の整数であり、
Xが、Cl、Br、またはIであり、
Rが、C1−10炭化水素であり、
Mが、第4族金属であり、
各場合におけるR’は、ポリマー組成体であり、
各場合において、R 1 は、独立して、ポリマー組成体、アルキル、水素、ハライド、アミド、ヒドロカルビル、ヒドロカルビルアミド、ジヒドロカルビルアミド、ヒドロカルビルオキシド、ヒドロカルビルスルフィド、ジヒドロカルビルホスフィド、トリ(ヒドロカルビル)シリル、少なくとも1つのハライド、アミド、ヒドロカルビルアミド、ジヒドロカルビルアミド、またはヒドロカルビルオキシドで置換されたもしくは非置換のヒドロカルビル基から選択され、R 1 の各炭素含有基は1〜50個の炭素原子を有し、
各場合において、Yが、平均で、1〜150の数である、プロセス。 - 前記ルイス酸が、(NMe2)2TiCl2である、請求項1に記載のプロセス。
- 前記ポリマー組成体が、重合プロセスによって形成され、前記重合プロセスが、重合条件下で、少なくとも1種の付加重合性モノマーを触媒組成物と接触させることを含み、前記触媒組成物が、少なくとも1種の触媒前駆体、少なくとも1種の共触媒、及び少なくとも1種の鎖シャトリング剤の接触生成物を含む、請求項1に記載のプロセス。
- 前記亜鉛組成体が、式R1Zn[R’Zn−]YR1を有し、前記少なくとも1種の鎖シャトリング剤が、多頭型または二頭型の鎖シャトリング剤である、請求項3に記載のプロセス。
- 前記反応工程が、70℃を超える温度で行われる、請求項1に記載のプロセス。
- 前記反応工程が、40分未満で完了する、請求項1に記載のプロセス。
- 前記官能性ポリマーが、少なくとも1つのアミノ基を含む、請求項1に記載のプロセス。
- 前記アルデヒドが、少なくとも1つの官能基を含む、請求項1に記載のプロセス。
- 前記少なくとも1つの官能基が、ビニル、アリルオキシ、またはスチリル基である、請求項8に記載のプロセス。
- 前記官能性ポリマーが、少なくとも1つのアミノ基及び更なる官能基を含み、前記更なる官能基が、ビニル、アリルオキシ、またはスチリル基である、請求項9に記載のプロセス。
- 前記亜鉛組成体が、式ZnR’ 2 を有し、ZnR’ 2 の両方のR’基が前記反応工程で反応する、請求項1に記載のプロセス。
- 前記官能性ポリマーが、テレキレックポリマーである、請求項4に記載のプロセス。
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