JP6012055B2 - チタン含有錯体及び縮合反応触媒、該触媒の調製方法、及び該触媒を含有する組成物 - Google Patents
チタン含有錯体及び縮合反応触媒、該触媒の調製方法、及び該触媒を含有する組成物 Download PDFInfo
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- 229940095064 tartrate Drugs 0.000 description 1
- 229920006250 telechelic polymer Polymers 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- VHXDHGALQPVNKI-UHFFFAOYSA-N thiadiazol-4-ylurea Chemical compound NC(=O)NC1=CSN=N1 VHXDHGALQPVNKI-UHFFFAOYSA-N 0.000 description 1
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical group CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 1
- 229960003231 thioacetazone Drugs 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LSZKGNJKKQYFLR-UHFFFAOYSA-J tri(butanoyloxy)stannyl butanoate Chemical compound [Sn+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O LSZKGNJKKQYFLR-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- LTQZKHRCYAXPAZ-UHFFFAOYSA-N triazin-4-ylsulfonylurea Chemical compound NC(=O)NS(=O)(=O)C1=CC=NN=N1 LTQZKHRCYAXPAZ-UHFFFAOYSA-N 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- PGVSPORIGRCPMG-UHFFFAOYSA-N triethoxy(1-triethoxysilylhexyl)silane Chemical compound CCCCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC PGVSPORIGRCPMG-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CPRPKIMXLHBUGA-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC CPRPKIMXLHBUGA-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- AXNJHBYHBDPTQF-UHFFFAOYSA-N trimethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OC)(OC)OC AXNJHBYHBDPTQF-UHFFFAOYSA-N 0.000 description 1
- ASEGJSMHCHEQSA-UHFFFAOYSA-N trimethoxy(undec-10-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCCC=C ASEGJSMHCHEQSA-UHFFFAOYSA-N 0.000 description 1
- MAFQBSQRZKWGGE-UHFFFAOYSA-N trimethoxy-[2-[4-(2-trimethoxysilylethyl)phenyl]ethyl]silane Chemical compound CO[Si](OC)(OC)CCC1=CC=C(CC[Si](OC)(OC)OC)C=C1 MAFQBSQRZKWGGE-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical class CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pyrane Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Furan Compounds (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
(A)チタン含有縮合反応触媒、及び
(B)1分子当たり平均で1つ以上の加水分解性置換基を有するケイ素含有ベースポリマー(ベースポリマー)を含む。理論に縛られることを望むものではないが、Ti含有縮合反応触媒は、ベースポリマーの縮合反応に対し触媒作用を及ぼすのに効果的であると特徴づけることができると考えられる。ベースポリマーは縮合反応可能な加水分解性置換基を有する。ベースポリマーの縮合反応は反応生成物を調製する。この組成物は、場合により、1つ以上の追加の成分を更に含み得る。1つ以上の追加の成分は、成分(A)及び(B)とは異なる。好適な追加の成分は、(C)架橋剤;(D)乾燥剤;(E)増量剤、可塑剤又はこれらの組み合わせ;(F)充填剤;(G)充填剤処理剤;(H)殺生物剤;(J)難燃剤;(K)表面改質剤;(L)鎖延長剤;(M)末端封鎖剤;(N)非反応性結合剤;(O)老化防止添加剤;(P)水放出剤;(Q)顔料;(R)レオロジー添加剤;(S)賦形剤(例えば溶媒及び/又は希釈剤);(T)粘着付与剤;(U)腐食防止剤;並びにこれらの組み合わせにより例示される。
で表わされる一価の有機基(式中、*は、一般式(iii)中の窒素原子に結合する位置を示す)から選択され、Q3、A7、A8、A9、A10、及びA11は本明細書で定義されている通りである。適切な一価の炭化水素基としては、アルキル、アリール、アラルキル、及び炭素環基が挙げられる。
は単結合又は二重結合を表す。Q14は、O、P及びSから選択されるヘテロ原子である。Q14に選ばれたヘテロ原子の価数によって、また、Q14と炭素原子との間の結合が単結合か二重結合かによって、A40は存在しないか、又は水素原子である。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A46はそれぞれHであってもよい。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xiv)の配位子の例としては、表1に示される配位子20が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A51はアルキル又はアラルキルであってもよい。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xvii)の配位子の例としては、表1に示される配位子12が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xviii)の配位子の例としては、表1に示される配位子15が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。A62及びA63が互いに結合している場合、上述のとおり、それらは炭素環基、芳香族基、複素環基、又は複素芳香族基を形成してもよいが、縮合して五員複素環を形成する。一般式(xix)の配位子の例としては、表1に示される配位子18及び36が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A64はそれぞれ独立して、F、OH、Me、tBu、及びナフチルから選択される。一般式(xx)の配位子の例としては、表1に示される配位子59、83及び84が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xxi)の配位子の例としては、表1に示される配位子45が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xxii)の配位子の例としては、表1に示される配位子43が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。
(式中、*は結合の位置を示す)等の基)を含む。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xxiii)の配位子の例としては、表1に示される配位子41及び77が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。一般式(xxiv)の配位子の例としては、表1に示される配位子81が挙げられる。
は単結合又は二重結合を表す。Q24はO及びSから選択される。あるいは、Q24はOである。Q25、Q26、及びQ27はそれぞれ独立して、C、N、O、及びSから選択される。あるいは、Q25は、C、N、及びOから選択されてもよい。あるいは、Q26は、C、N、及びOから選択されてもよい。あるいは、Q26は、C及びNから選択されてもよい。あるいは、Q27は、C、N、及びOから選択されてもよい。
(式中、下付き文字mは、0〜4、あるいは0〜3、あるいは0〜2、あるいは0〜1の整数であり、A84はそれぞれ独立して一価の有機基)を有してもよい。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A78はH及びMeから選択されてもよい。あるいは、A78はHであってもよい。あるいは、A80は存在しないか、シクロヘキシル等の炭素環、Ph等のアリール、及びエトキシ等のアルコキシから選択されてもよい。あるいは、A81は存在しないか、Hから選択されてもよい。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A79は存在しないか、フェニル等のアリール、及び
等のハロゲン化フェニルから選択されてもよい。一般式(xxv)の配位子の例としては、表1に示される配位子50、54、57、67、68、72、及び78が挙げられる。
(式中、*は結合の位置を示す)等の基)を含む。あるいは、A85及び/又はA86はそれぞれ独立して、複素芳香族基、アラルキルオキシ基、又は
から選択される基でもよい。一般式(xxvi)の配位子の例としては、表1に示される配位子73が挙げられる。
の3,5−ヘプタンジオン、又は式
の2−アセチル−1−テトラロンであってもよく、両者共にSigma−Aldrich,Inc.(St.Louis,Missouri,U.S.A.)より入手可能である。
式中、Dはそれぞれ独立して、酸素原子、二価の有機基、二価のシリコーン有機基、又は二価の炭化水素基と二価のシロキサン基との組み合わせを表し、Xはそれぞれ独立して加水分解性置換基を表し、Rはそれぞれ独立して一価の炭化水素基を表し、下付き文字cは0、1、2又は3を表し、下付き文字aは0、1又は2を表し、下付き文字bは0以上の値を有するが、但し、平均で少なくとも1つのXが式中に存在するように、(a+c)の合計は少なくとも1である。あるいは、添字bは、0〜18の範囲の値を有し得る。
)。あるいは、Dの例は酸素原子であり得、一方、Dの異なる例は二価の炭化水素基である。
式中、R1はそれぞれ独立して加水分解性置換基であり、R2はそれぞれ独立して一価の有機基であり、R3はそれぞれ独立して酸素原子又は二価の炭化水素基であり、下付き文字dはそれぞれ独立して1、2又は3であり、下付き文字eは、25℃にて少なくとも100mPa・sの粘度及び/又は少なくとも87のDPを、このポリジオルガノシロキサンに与えるのに十分な値を有する整数である。DPはポリスチレン標準液による校正を用いて、GPCにより測定してもよい。あるいは、添字eは、1〜200,000の範囲の値を有し得る。
)。あるいは、R1及びR2はそれぞれアルキルであってもよく、R3はそれぞれアルキレン(例えば、エチレン)であってもよく、下付き文字dはそれぞれ3であってもよい。
R29 wR30 (3−w)SiO1/2及びSiO4/2、(式中、R29及びR30は、一価の有機基(例えば、アルキル(例えば、メチル、エチル、プロピル、ペンチル、オクチル、デシル、ドデシル、ウンデシル及びオクタデシル)、シクロアルキル(例えば、シクロペンチル及びシクロヘキシル)、アリール(例えば、フェニル、トリル、キシリル及びベンジル)、及びアラルキル(例えば、2−フェニルエチル)により例示される一価の炭化水素基)、ハロゲン化炭化水素基(塩素化アルキル基(例えば、クロロメチル及びクロロプロピル基)、フッ素化アルキル基(例えば、フルオロメチル、2−フルオロプロピル、3,3,3−トリフルオロプロピル、4,4,4−トリフルオロブチル、4,4,4,3,3−ペンタフルオロブチル、5,5,5,4,4,3,3−ヘプタフルオロペンチル、6,6,6,5,5,4,4,3,3−ノナフルオロヘキシル、及び8,8,8,7,7−ペンタフルオロオクチル)、塩素化シクロアルキル基(例えば、2,2−ジクロロシクロプロピル、2,3−ジクロロシクロペンチル)及びフッ素化シクロアルキル(例えば、2,2−ジフルオロシクロプロピル、2,3−ジフルオロシクロブチル、3,4−ジフルオロシクロヘキシル、及び3,4−ジフルオロ−5−メチルシクロヘプチルにより例示される))、及び、他の一価の有機基(例えば、酸素原子で置換された炭化水素基(例えば、グリシドキシアルキル)及び窒素原子で置換された炭化水素基(例えば、アミノアルキル)及びシアノ官能基(例えば、シアノエチル及びシアノプロピル)であり、下付き文字wの各例は、0、1又は2である。あるいは、R29及びR30はそれぞれ、アルキル基であってもよい)MQ樹脂は、0.5:1〜1.5:1の、Mユニット対Qユニットのモル比(M:Q)を有し得る。これらのモル比は、Si29 NMR分光法により簡単に測定される。この技法は、シリコーン樹脂の総ヒドロキシル量に加えて、シリコーン樹脂及び最初のシリコーン樹脂中に存在したネオペンタマー(neopentamer)Si(OSiMe3)4から誘導されたR29 3 SiO1/2(「M」)単位とSiO4/2(「Q」)単位の濃度を量的に測定することができる。
の基を1分子当たり平均で少なくとも1つ有してもよい。(式中、R18は、水素原子又は一価の有機基を表す。あるいは、R18は、分枝状又は直鎖一価の炭化水素基を表してもよい。)一価の有機基は、4〜15個の炭素原子、あるいは9個〜12個の炭素原子のアルキル基といった、分枝状又は直鎖の一価の炭化水素基であり得る。好適な可塑剤は、アジピン酸塩、カルボン酸塩、フタル酸塩及びこれらの組み合わせからなる群より選択され得る。
(式中、Z基は、3個以上の炭素原子、あるいは3〜15個の炭素原子を有する炭素環基を表す。添字sは、1〜12の範囲の値を有し得る。Z基は、飽和又は芳香族であり得る。R20はそれぞれ独立して水素原子、又は分枝状若しくは直鎖の一価の有機基である。R19の一価の有機基は、メチル、エチル、又はブチルといった、アルキル基であってもよい。あるいは、R20の一価の有機基は、エステル官能基であってもよい。R19はそれぞれ独立して、4〜15個の炭素原子のアルキル基といった、分枝状又は直鎖の一価の炭化水素基である。)
(式中、下付き文字rは、1,500までの値を有する)。
トリアジニルスルホニル尿素除草剤(例えば、チフェンスルフロン3−(4−メトキシ−6−メチル−1,3,5−トリアジン−2−イルカルバモイルスルファモイル)チオフェン−2−カルボン酸)、チアジアゾリル尿素除草剤(例えば、テブチウロン1−(5−tert−ブチル−1,3,4−チアジアゾール−2−イル)−1,3−ジメチル尿素)、並びに/又は、未分類の除草剤(例えば、クロルフェナック(2,3,6−トリクロロフェニル)酢酸、メタゾール2−(3,4−ジクロロフェニル)−4−メチル−1,2,4−オキサジアゾリジン−3,5−ジオン、トリタック(tritac)(RS)−1−(2,3,6−トリクロロベンジルオキシ)プロパン−2−オール、2,4−D、クロリムロン、及びフェノキサプロップ)、並びにこれらの組み合わせが挙げられる。
前駆体溶液は、前駆体と、Ti(ethoxide)4又はTi(benzyl)4(濃度:0.025M)のどちらかとを、トルエンと混合することにより調製された。前駆体溶液は無色であった。上記表1に示される各配位子の溶液もまた、配位子(濃度:0.025M)を、トルエンと混合することにより調製された。
上記(実施例1)の錯形成反応の完了後、210mg(ミリグラム)のPDMS 1(235.7μL、すなわち50μモルに相当)及び17.8mg(19.1μL、すなわち100μモルに相当)のn−BuSi(O−Me)3が、ドライボックス内の金属−配位子錯体を含む各バイアル瓶に注入された。その後、各バイアル瓶内の合計量が325μLとなるように、更にトルエンが加えられた。実施例2のサンプルはこのように調製された。陰性対照サンプルもまた上記前駆体を使用して調製したが、配位子は含まずに調製した。陰性対照サンプルには、210mgのPDMS 1、17.8mgのn−BuSi(O−Me)3、及びトルエン(合計量が325μLになるのに十分な量)が、前駆体の入ったバイアル瓶に注入された。追加の陰性対照サンプルもまた上記表1に示す配位子を使用して調製したが、前駆体は含まずに調製した。これらの追加の陰性対照サンプルには、210mgのPDMS 1、17.8mgのn−BuSi(O−Me)3、及びトルエン(合計量が325μLになるのに十分な量)が、配位子の入ったバイアル瓶に注入された。
Claims (15)
- (A)触媒的に有効量の、成分i)と成分ii)との反応の触媒活性反応生成物、ここで、
前記成分i)は、式Ti−A4であるTi前駆体であり(式中、Aはそれぞれ独立して一価の有機基を表す);
前記成分ii)は、下記配位子[1]から[84]および[86]から[111]の中の一つであり、
[90]一般式(iii)の配位子:
[90]一般式(iv)の配位子:
[91]一般式(v)の配位子:
[92]一般式(vi)の配位子:
[93]一般式(vii)の配位子:
[94]一般式(viii)の配位子:
[95]一般式(ix)の配位子:
[96]一般式(x)の配位子:
[97]一般式(xi)の配位子:
[98]一般式(xiii)の配位子:
[99]一般式(xiv)の配位子:
であり、A47はそれぞれ独立して一価の有機基であり、下付き文字cは0〜5の整数である);又は
[102]一般式(xvii)の配位子:
[103]一般式(xviii)の配位子:
[104]一般式(xix)の配位子:
[105]一般式(xx)の配位子:
[106]一般式(xxi)の配位子:
[107]一般式(xxii)の配位子:
[108]一般式(xxiii)の配位子:
[109]一般式(xxiv)の配位子:
[110]一般式(xxv)の配位子:
[111]一般式(xxvi)の配位子:
(B)1分子当たり平均で1つ以上の加水分解性置換基を有するケイ素含有ベースポリマー、
を含む、組成物。 - 条件(a)〜(d)のうち1つが満たされる組成物であって、
条件(a)は、各Aがアルコキシ基であること;又は
条件(b)は、各Aがエトキシ基であること;又は
条件(c)は、各Aがアラルキル基であること;又は
条件(d)は、各Aがベンジル基であること;
である請求項1に記載の組成物。 - 前記成分(A)及び(B)とは異なる少なくとも1種の追加の成分を更に含む組成物であって、前記少なくとも1種の追加の成分が、(C)架橋剤;(D)乾燥剤;(E)増量剤、可塑剤、又はこれらの組み合わせ;(F)充填剤;(G)処理剤;(H)殺生物剤;(J)難燃剤;(K)表面改質剤;(L)鎖延長剤;(M)末端封鎖剤;(N)非反応性のバインダー;(O)老化防止添加剤;(P)水放出剤;(Q)顔料;(R)レオロジー添加剤;(S)賦形剤;(T)粘着付与剤;(U)腐食防止剤;及びこれらの組み合わせからなる群より選ばれる、請求項1又は2に記載の組成物。
- 請求項1〜3のいずれか一項に記載の組成物を製造する方法であって、前記組成物を製造するために、成分(A)及び成分(B)を含む成分を混合する工程を含む、方法。
- 反応生成物を調製するために、請求項1〜3のいずれか一項に記載の組成物を水分に曝露する工程を含む、方法。
- i)式Ti−A4であるTi前駆体(式中、Aはそれぞれ独立して一価の有機基を表す)と、
ii)配位子[1]、[2]、[3]、[4]、[6]、[7]、[8]、[9]、[10]、[11]、[12]、[13]、[14]、[15]、[16]、[17]、[18]、[19]、[20]、[21]、[22]、[23]、[24]、[25]、[26]、[27]、[31]、[32]、[33]、[34]、[35]、[36]、[37]、[38]、[39]、[40]、[41]、[42]、[43]、[44]、[45]、[46]、[47]、[48]、[49]、[50]、[51]、[52]、[53]、[55]、[58]、[59]、[60]、[63]、[64]、[65]、[66]、[67]、[68]、[70]、[71]、[73]、[74]、[75]、[79]、[81]、[82]、[83]、[84]、[86]、[87]、及び[88](下記に示す)からなる群より選ばれる配位子と、
を反応させる工程を含む、1分子当たり平均で1つ以上の加水分解性置換基を有するケイ素含有ベースポリマーの縮合反応のためのTi含有触媒を調製するための方法。
- 条件(a)〜(d)のうち1つが満たされる方法であって、
条件(a)は、各Aがアルコキシ基であること;又は
条件(b)は、各Aがエトキシ基であること;又は
条件(c)は、各Aがアラルキル基であること;又は
条件(d)は、各Aがベンジル基であること;
である請求項6に記載の方法。 - 前記配位子が配位子[2]、[7]、[8]、[9]、[11]、[13]、[14]、[15]、[16]、[17]、[18]、[19]、[20]、[21]、[22]、[23]、[25]、[26]、[27]、[32]、[34]、[35]、[36]、[37]、[38]、[39]、[40]、[41]、[42]、[43]、[44]、[45]、[47]、[48]、[49]、[50]、[51]、[52]、[53]、[55]、[58]、[59]、[60]、[63]、[64]、[65]、[67]、[68]、[70]、[71]、[73]、[74]、[79]、[81]、[82]、[83]、[84]、[86]、[87]、及び[88]からなる群より選ばれる配位子である、又は
前記配位子が、
前記配位子が、
- 前記Ti前駆体と前記配位子を加熱する工程を更に含む、請求項6〜8のいずれか一項
に記載の方法。 - 前記反応生成物から副生成物を取り除く工程であって、前記副生成物を含まないTi−配位子錯体を生成する、工程を更に含む、請求項6〜9のいずれか一項に記載の方法。
- (A)触媒的に有効量の、成分i)と成分ii)との反応の触媒活性反応生成物、ここで、
成分i)は、式Ti−A4であるTi前駆体であり(式中、Aはそれぞれ独立して一価の有機基を表す);
成分ii)は、3,5−ヘプタンジオン及び2−アセチル−1−テトラロンからなる群より選ばれ;及び
(B)1分子当たり平均で1つ以上の加水分解性置換基を有するベースポリマー、
を含む組成物。 - 条件(a)〜(d)のうち1つが満たされる組成物であって、
条件(a)は、各Aがアルコキシ基であること;又は
条件(b)は、各Aがエトキシ基であること;又は
条件(c)は、各Aがアラルキル基であること;又は
条件(d)は、各Aがベンジル基であること;
である請求項11に記載の組成物。 - i)式Ti−A4であるTi前駆体(式中、Aはそれぞれ独立して一価の有機基を表す)と、
ii)3,5−ヘプタンジオン及び2−アセチル−1−テトラロンからなる群より選ばれる配位子と、
を反応させる工程を含む、方法。 - 条件(a)〜(d)のうち1つが満たされる方法であって、
条件(a)は、各Aがアルコキシ基であること;又は
条件(b)は、各Aがエトキシ基であること;又は
条件(c)は、各Aがアラルキル基であること;又は
条件(d)は、各Aがベンジル基であること;
である請求項13に記載の方法。 - 前記Ti前駆体と前記配位子を加熱する工程を更に含む、請求項13又は14に記載の方法。
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