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 PDF

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CN103382233B
CN103382233B CN201210147763.XA CN201210147763A CN103382233B CN 103382233 B CN103382233 B CN 103382233B CN 201210147763 A CN201210147763 A CN 201210147763A CN 103382233 B CN103382233 B CN 103382233B
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olefin
alpha
propylene
catalyzer
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CN103382233A (en
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付志峰
李瑛琦
闫新华
石艳
史君
朱景利
王健
姜明财
冯文元
张利仁
吕洁
张利粉
于贵春
郭洪元
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Petrochina Co Ltd
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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

The aqueous phase system polymerization process of the diimine catalysts of Bound moisture palladium (II)
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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