CN103382233B - Aqueous phase system polymerization method of diimine catalyst combined with palladium (II) hydrate - Google Patents
Aqueous phase system polymerization method of diimine catalyst combined with palladium (II) hydrate Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 15
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000034 method Methods 0.000 title abstract 2
- 239000008346 aqueous phase Substances 0.000 title description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 230000009477 glass transition Effects 0.000 abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract 1
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 abstract 1
- 229920006126 semicrystalline polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 134
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 84
- 239000008367 deionised water Substances 0.000 description 42
- 229910021641 deionized water Inorganic materials 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 42
- 239000000126 substance Substances 0.000 description 25
- 238000013019 agitation Methods 0.000 description 21
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 21
- 238000003808 methanol extraction Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 238000001291 vacuum drying Methods 0.000 description 21
- 229920006125 amorphous polymer Polymers 0.000 description 20
- 239000007789 gas Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to a method for catalyzing olefin polymerization by a diimine catalytic system combined with palladium hydrate; the system employs a water-bound palladium diimine catalyst [ (ArN = c (an) -c (an) = NAr) Pd (CH)2)3C(O)OMe](BAr′4)·H2O(Ar=2,6-(i-Pr)2C6H3;Ar′=3,5-(CF3)2C6H3) As a catalyst, the catalyst is used for catalyzing ethylene, propylene and C under the condition that water is used as a solvent and no emulsifier is added6-C18Homopolymerization of alpha-olefins, or ethylene, propylene, C6-C18The copolymerization reaction of alpha-olefin, methyl acrylate and glycidyl acrylate for 18-20 hr can realize the homopolymerization or copolymerization of olefin at the polymerization temperature of 15-60 deg.c to produce semi-crystalline polymer with glass transition temperature and smelting point.
Description
Technical field
The present invention relates to and a kind ofly utilize the diimine of the palladium of Bound moisture (II) at water as solvent and catalyzed alkene CH under not adding any emulsifying agent condition
2the polymerization process of=CHR homopolymerization or copolymerization.Wherein, R is hydrogen or the alkyl with 1-16 carbon atom.Specifically, this polymerization process is with the diimine compounds of the Pb of Bound moisture (II) [(ArN=C (An)-C (An)=NAr) Pd (CH
2)
3c (O) OMe] (BAr '
4) H
2o (Ar=2,6-(i-Pr)
2c
6h
3; Ar '=3,5-(CF
3)
2c
6h
3) be catalyzer catalyzed ethylene, propylene, long-chain alpha-olefin (C at water as solvent and under not adding any emulsifying agent condition
6-C
18) polymerization form homopolymerization or multipolymer, ethene, propylene, C
6-C
18the copolymerization of alpha-olefin and methyl acrylate, glycidyl acrylate forms multipolymer.
Background technology
Guan in 1999 etc. obtain hyperbranched polyethylene with during alpha-diimine palladium catalyst catalyzed ethylene polymerization.Guan thinks, poly branching is the result of " chainpropagation " and " chain is walked " competing reaction.During polymerization, ethylene pressure is higher, and the speed of ethylene insertion " chainpropagation " is faster, tends to the branched polyethylene obtaining line style; When ethylene pressure is low, metal center can carry out " the chain walking " of more multistep after each ethylene insertion, causes generating hyperbranched polyethylene, even obtains dendroid polyethylene.The cationic palladium catalyst (see figure 1) containing alpha-diimine part such as Brookhart achieves the copolyreaction of ethene and methyl acrylate, its catalysate is the polymkeric substance of highly-branched degree, approximately containing 100 side chains in every 1000 carbon, ester group is random be distributed in branch terminals.Realize from High Linear to medium branched olefins the polymkeric substance even regulation and control of oligopolymer with selecting the part of different substituents by controlling reaction conditions simultaneously.
Diimine catalysts for the palladium (II) of alkene homopolymerization (ethene, propylene, hexene etc.) can be used for the multipolymer producing alkene and polar monomer, and the content of multipolymer Semi-polarity monomer is changed by the quantity term changing catalyst molecule structure and added monomer, thus produces many new type polyolefin products.The companies such as DuPond have applied for multiple patent about this type of catalyst olefinic polymerization (WO98/03521, WO99/05189, WO99/62968, US6,103,658).
More than invention provides a kind of good alpha-diimine palladium complex catalyst, can realize catalyzed ethylene polymerization in wide temperature range, prepare the multipolymer of ethene and polar monomer.But its polymerization system methylene dichloride makees solvent, toxicity is comparatively large, and in existing domestic olefin polymerization suitability for industrialized production, solvent for use is chain type stable hydrocarbon (C
6-C
8), also toxic.
Summary of the invention
The object of the present invention is to provide a kind of aqueous phase system polymerization process of diimine catalysts of Bound moisture palladium (II).Be catalyzer with the diimine of the Pd (II) of Bound moisture, water as solvent and do not add any emulsifying agent, catalyzed ethylene, propylene, long-chain alpha-olefin (C
6-C
18) polymerization form homopolymerization or multipolymer, ethene, propylene, C
6-C
18the copolymerization of alpha-olefin and methyl acrylate, glycidyl acrylate forms multipolymer, and the polymkeric substance generated is the semicrystalline polymeric with second-order transition temperature and fusing point.
The aqueous phase system polymerization process of the diimine catalysts of Bound moisture palladium (II) of the present invention, performing step is as follows:
The first step: the synthesis of catalyzer
Under nitrogen protection, in flask, add (ArN=C (An)-C (An)=NAr) PdMeCl (744mg, 1.13mmol), NaBAr '
4(1.00g, 1.13mmol), methyl acrylate 112uL, react two days at normal temperatures, product does solvent recrystallization with methylene dichloride at-30 DEG C.Obtain catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH
2)
3c (O) OMe] (BAr '
4) H
2o (Ar=2,6-(i-Pr)
2c
6h
3; Ar '=3,5-(CF
3)
2c
6h
3), its structural formula is as follows:
Second step: with the multipolymer of polycomplexation legal synthesizing polyethylene, alpha-olefin and ethene, propylene, alpha-olefin and methyl acrylate and glycidyl acrylate.
The invention provides a kind of polymerization process of diimine catalyst system catalyzed alkene of palladium, it is characterized in that:
Adopt diimine catalysts [(ArN=C (An)-C (An)=NAr) Pd (CH of the palladium of Bound moisture
2)
3c (O) OMe] (BAr '
4) H
2o (Ar=2,6-(i-Pr)
2c
6h
3; Ar '=3,5-(CF
3)
2c
6h
3) make catalyzer, adopt at water as solvent and do not add any emulsifying agent condition catalyzed ethylene, propylene, C
6-C
18the equal polyreaction of alpha-olefin, or ethene, propylene, C
6-C
18the copolymerization of alpha-olefin and methyl acrylate, glycidyl acrylate; 18-20 hour is reacted at 15-60 DEG C;
Wherein when the equal polyreaction of catalyzed ethylene or propylene, the pressure of ethene or propylene is under 1-3 normal atmosphere; As catalysis C
6-C
18during the equal polyreaction of alpha-olefin, C
6-C
18the mole number of alpha-olefin is 500-1500 times of palladium mole number in catalyzer;
As catalyzed ethylene, propylene, C
6-C
18the copolymerization of alpha-olefin and methyl acrylate, or ethene, propylene, C
6-C
18during the copolymerization of alpha-olefin and glycidyl acrylate, the pressure of ethene or propylene is under 1-3 normal atmosphere, and C
6-C
18the mole number of alpha-olefin is 500-1500 times of palladium mole number in catalyzer.
Diimine [(ArN=C (An)-C (An)=NAr) Pd (CH of the Pd (II) of the present invention's Bound moisture
2)
3c (O) OMe] (BAr '
4) H
2o (Ar=2,6-(i-Pr)
2c
6h
3; Ar '=3,5-(CF
3)
2c
6h
3) doing catalyst alkene or alkene and polar monomer copolymerization, the polymkeric substance simultaneously generated is the semicrystalline polymeric with second-order transition temperature and fusing point.This kind of catalyzer is insensitive to water and air, make solvent with water and greatly reduce costs the severe condition simultaneously reducing olefinic polymerization, simple to operate and water is as not firing, nontoxic environment amenable medium, to be a very important link this suitability for industrialized production for alkene and polycoordination research, have very important significance.
Accompanying drawing explanation
Fig. 1 is the GPC spectrogram of embodiment 4
Fig. 2 is embodiment 18
1hNMR spectrogram
Embodiment
The diimine compounds aqueous catalysis alkene homopolymerization of Bound moisture Pd (II)
Embodiment 1:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), magnetic agitation 5min, blast ethylene gas in reaction solution, finally continues to pass into ethene, keeps 3 normal atmosphere, and at ethene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtains 2.0 grams of white solid state shapes and with certain elastic polymkeric substance, is amorphous polymer, its glass transition temperature Tg=-30 DEG C, Tm=41 DEG C.And the catalytic efficiency of this kind of catalyst system is 23.50kgmol
-1pd, records polymer average molecular weight Mw=40000, molecular weight distribution mw/mn=1.42 during reaction end.
Embodiment 2:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), magnetic agitation 5min, blast propylene gas in reaction solution, finally continues to pass into propylene, keeps 3 normal atmosphere, and at propylene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtains 1.8 grams of white solid state shapes and with certain elastic polymkeric substance, is amorphous polymer, its glass transition temperature Tg=-32 DEG C, Tm=38 DEG C.And the catalytic efficiency of this kind of catalyst system is 21.17kgmol
-1pd, records polymer average molecular weight Mw=35000, molecular weight distribution mw/mn=1.51 during reaction end.
Embodiment 3:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-hexene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) 0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtains 1.56 grams of white solid state shapes and with certain elastic polymkeric substance, is amorphous polymer, its glass transition temperature Tg=-35.3 DEG C, Tm=35 DEG C.And the catalytic efficiency of this kind of catalyst system is 18.35kgmol
-1pd, records polymer average molecular weight Mw=30000, molecular weight distribution mw/mn=1.61 during reaction end.
Embodiment 4:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-octene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH2) 3C (O) OMe] (BAr ' 4) H successively
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.32 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-54.7 DEG C, melt temperature Tm=27.27 DEG C.And the catalytic efficiency of this kind of catalyst system is 15.53kgmol
-1pd, records polymer average molecular weight Mw=24000, molecular weight distribution mw/mn=1.21 during reaction end.
Embodiment 5:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-certain herbaceous plants with big flowers alkene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH2) 3C (O) OMe] (BAr ' 4) H successively
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.21 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-43.7 DEG C, melt temperature Tm=26 DEG C.And the catalytic efficiency of this kind of catalyst system is 14.23kgmol
-1pd, records polymer average molecular weight Mw=26000, molecular weight distribution mw/mn=1.65 during reaction end.
Embodiment 6:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-laurylene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.17 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-41.5 DEG C melt temperature Tm=24.2 DEG C.And the catalytic efficiency of this kind of catalyst system is 13.76kgmol
-1pd, records polymer average molecular weight Mw=22500, molecular weight distribution mw/mn=1.73 during reaction end.
Embodiment 7:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-tetradecylene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.10 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-42.6 DEG C melt temperature Tm=22 DEG C.And the catalytic efficiency of this kind of catalyst system is 12.94kgmol
-1pd, records polymer average molecular weight Mw=23200, molecular weight distribution mw/mn=1.72 during reaction end.
Embodiment 8:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-hexadecylene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 0.80 gram of white solid state shape and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-44.1 DEG C melt temperature Tm=23.2 DEG C.And the catalytic efficiency of this kind of catalyst system is 9.41kgmol
-1pd, records polymer average molecular weight Mw=24500, molecular weight distribution mw/mn=1.61 during reaction end.
Embodiment 9:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the 1-octadecylene of 10mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 0.55 gram of white solid state shape and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-46.1 DEG C, melt temperature Tm=21.4 DEG C.And the catalytic efficiency of this kind of catalyst system is 6.47kgmol
-1pd, records polymer average molecular weight Mw=27000, molecular weight distribution mw/mn=1.85 during reaction end.
The diimine compounds catalyzed alkene aqueous phase copolymerization of the Pd (II) of Bound moisture
Embodiment 10
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), after magnetic agitation 5min, blasts ethylene gas, finally continues to pass into ethene in reaction solution, keeps 3 normal atmosphere, and at ethene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.41 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-32.1 DEG C melt temperature Tm=46.6 DEG C.And the catalytic efficiency of this kind of catalyst system is 16.58kgmol
-1pd, records polymer average molecular weight Mw=40000, molecular weight distribution mw/mn=1.61 during reaction end.
After embodiment 11 is clean by the mouth flask of 100mL with deionized water, puts into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), after magnetic agitation 5min, blasts ethylene gas, finally continues to pass into ethene in reaction solution, keeps 3 normal atmosphere, and at ethene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.31 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-35.2 DEG C melt temperature Tm=44.3 DEG C.And the catalytic efficiency of this kind of catalyst system is 15.41kgmol
-1pd, records polymer average molecular weight Mw=39000, molecular weight distribution mw/mn=1.52 during reaction end
Embodiment 12:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr ' 4) H
2o0.1g (0.085mmol), after magnetic agitation 5min, blasts propylene gas, finally continues to pass into ethene in reaction solution, keeps 3 normal atmosphere, and at propylene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.05 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-33.4 DEG C, melt temperature Tm=45.2 DEG C.And the catalytic efficiency of this kind of catalyst system is 12.35kgmol
-1pd, records polymer average molecular weight Mw=38000, molecular weight distribution mw/mn=1.63 during reaction end.
Embodiment 13:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), after magnetic agitation 5min, blasts propylene gas, finally continues to pass into propylene in reaction solution, keeps 3 normal atmosphere, and at propylene atmosphere lower seal reaction flask.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.15 grams of white solid state shapes and with certain elastic polymkeric substance, its glass transition temperature Tg=-36.1 DEG C melt temperature Tm=47.4 DEG C.And the catalytic efficiency of this kind of catalyst system is 13.53kgmol
-1pd, records polymer average molecular weight Mw=37500, molecular weight distribution mw/mn=1.56 during reaction end.
Embodiment 14:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL, 10mL1-hexene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.38 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-41.3 DEG C, melt temperature Tm=49.5 DEG C.And the catalytic efficiency of this kind of catalyst system is 16.23kgmol
-1pd, records polymer average molecular weight Mw=37000, molecular weight distribution mw/mn=1.54 during reaction end.
Embodiment 15:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL, 10mL1-hexene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.29 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-38.4 DEG C, melt temperature Tm=51.6 DEG C.And the catalytic efficiency of this kind of catalyst system is 15.18kgmol
-1pd, records polymer average molecular weight Mw=38000, molecular weight distribution mw/mn=1.56 during reaction end.
Embodiment 16:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL, 10mL1-heptene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.27 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-47.6 DEG C, melt temperature Tm=53.1 DEG C.And the catalytic efficiency of this kind of catalyst system is 14.94kgmol
-1pd, records polymer average molecular weight Mw=37500, molecular weight distribution mw/mn=1.32 during reaction end.
Embodiment 17:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL, 10mL1-heptene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.05 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-48.8 DEG C, melt temperature Tm=56.3 DEG C.And the catalytic efficiency of this kind of catalyst system is 12.35kgmol
-1pd, records polymer average molecular weight Mw=37800, molecular weight distribution mw/mn=1.79 during reaction end.
Embodiment 18:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL, 10mL1-octene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.07 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-52 DEG C, melt temperature Tm=84.2 DEG C.And the catalytic efficiency of this kind of catalyst system is 12.59kgmol
-1pd, records polymer average molecular weight Mw=33000, molecular weight distribution mw/mn=2.06 during reaction end.
Embodiment 18:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL, 10mL1-octene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 1.01 grams of white solid state shapes and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-56 DEG C, melt temperature Tm=84.2 DEG C.And the catalytic efficiency of this kind of catalyst system is 11.88kgmol
-1pd, records polymer average molecular weight Mw=34000, molecular weight distribution mw/mn=1.77 during reaction end.
Embodiment 19:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the methyl acrylate of 2mL, 10mL1-certain herbaceous plants with big flowers alkene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 0.85 gram of white solid state shape and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-56.4 DEG C, melt temperature Tm=77.6 DEG C.And the catalytic efficiency of this kind of catalyst system is 10.0kgmol
-1pd, records polymer average molecular weight Mw=32000, molecular weight distribution mw/mn=1.81 during reaction end.
Embodiment 20:
After the mouth flask of 100mL is clean with deionized water, put into magnet rotor and add 40mL deionized water, the glycidyl acrylate of 2mL, 10mL1-certain herbaceous plants with big flowers alkene and catalyzer [(ArN=C (An)-C (An)=NAr) Pd (CH successively
2)
3c (O) OMe] (BAr '
4) H
2o0.1g (0.085mmol), sealed reaction bottle after magnetic agitation 5min.This reaction stops after stirring reaction 18h at normal temperatures, and reaction system is black and band toughness.Use hydrochloric acid-methanol dilute solution termination reaction again.Resulting polymers dissolves with tetrahydrofuran (THF) again, methanol extraction, so in triplicate, final sample puts into vacuum drying oven room temperature dries 24 hours, obtain 0.96 gram of white solid state shape and with certain elastic polymkeric substance, for amorphous polymer, its glass transition temperature Tg=-57.3 DEG C, melt temperature Tm=63.9 DEG C.And the catalytic efficiency of this kind of catalyst system is 11.29kgmol
-1pd, records polymer average molecular weight Mw=33500, molecular weight distribution mw/mn=1.78 during reaction end.
Claims (1)
1. a polymerization process for the diimine catalyst system catalyzed alkene of Bound moisture palladium (II), is characterized in that: comprise the following steps:
Adopt diimine compounds [(ArN=C (An)-C (An)=NAr) Pd (CH of Pd (II)
2)
3c (O) OMe] (BAr '
4) H
2o (Ar=2,6-(i-Pr)
2c
6h
3; Ar '=3,5-(CF
3)
2c
6h
3) make catalyzer, adopt at water as solvent and do not add the polymerization process catalyzed ethylene of any emulsifying agent, propylene or C
6-C
18the equal polyreaction of alpha-olefin, ethene, propylene or C
6-C
18the copolymerization of alpha-olefin and methyl acrylate, or ethene, propylene or C
6-C
18the copolymerization of alpha-olefin and glycidyl acrylate, reacts 18 ~ 20 hours at 15-60 DEG C; Wherein, described catalyzer has following structural formula:
Wherein when the equal polyreaction of catalyzed ethylene or propylene, the pressure of ethene or propylene is under 1 ~ 3 normal atmosphere;
As catalysis C
6-C
18during the equal polyreaction of alpha-olefin, C
6-C
18the mole number of alpha-olefin is 500-1500 times of palladium mole number in catalyzer;
As catalyzed ethylene, propylene or C
6-C
18the copolymerization of alpha-olefin and methyl acrylate or glycidyl acrylate, C
6-C
18the mole number of alpha-olefin is 500-1500 times of palladium mole number in catalyzer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998037110A1 (en) * | 1997-02-25 | 1998-08-27 | Eastman Chemical Company | Polymers containing functionalized olefin monomers |
| CN1326473A (en) * | 1998-06-01 | 2001-12-12 | 伊斯曼化学公司 | Supported group 8-10 transition metal olefin polymerization catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998037110A1 (en) * | 1997-02-25 | 1998-08-27 | Eastman Chemical Company | Polymers containing functionalized olefin monomers |
| CN1326473A (en) * | 1998-06-01 | 2001-12-12 | 伊斯曼化学公司 | Supported group 8-10 transition metal olefin polymerization catalysts |
Non-Patent Citations (1)
| Title |
|---|
| 乙烯/极性单体共聚钯基催化剂的研究进展;傅智盛等;《合成树脂及塑料》;20101231;第27卷(第3期);69-74 * |
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