CN107903349A - Functional rare earth EP rubbers and preparation method thereof - Google Patents
Functional rare earth EP rubbers and preparation method thereof Download PDFInfo
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- CN107903349A CN107903349A CN201711181691.XA CN201711181691A CN107903349A CN 107903349 A CN107903349 A CN 107903349A CN 201711181691 A CN201711181691 A CN 201711181691A CN 107903349 A CN107903349 A CN 107903349A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
Abstract
The invention belongs to Functional polymer materials technology field, is related to a kind of functional rare earth EP rubbers and preparation method thereof.Functional rare earth EP rubbers is the copolymer prepared by with rare earth catalyst catalysis ethene, propylene, functionalization alhpa olefin and alkadienes combined polymerization, wherein counted using molar content with reference to functionalization alhpa olefin as 0.5%-30%, be 0.5%-20% with reference to alkadienes.Functionalization alhpa olefin be selected from containing halogen, alkoxy, sulfenyl, tertiary amine, alkylphosphines, siloxanes, silane based functional groups one or both of alhpa olefin more than mixture.Alkadienes is selected from mixture more than one or both of bridged ring alkene, straight chain diene hydrocarbon, cyclodiene.Rare earth catalyst is made of two parts of A and B：A is rare earth compounding CpLnR2Xn, wherein：Cp is cyclopentadienyl ligand, and Ln is rare earth metal, and R is the alkyl being connected directly with rare earth metal, and X is the coordinating group on rare earth metal, n coordinating group numbers；B is organoboron reagent.
Description
Technical field
The invention belongs to Functional polymer materials technology field, is related to a kind of functional rare earth EP rubbers and its preparation.
Background technology
EP rubbers refers to the synthetic rubber prepared by ethene, propylene and alkadienes by copolymerization, because it has
Remarkable weatherability and ageing-resistant performance, obtains in fields such as automobile component, construction material, appliance material, rubber plastic blend products
It is widely applied.But general EP rubbers strand is made of nonpolar hydrocarbon atom, cause its adhesive property, printing and dyeing
Property and poor with the compatibility of other materials.Polar functional group is introduced in EP rubbers, EP rubbers can be significantly improved
The adhesion of material, surface property, solvent resistance, with the compatibility of other polymers and carbon black dispersion etc., widening it should
Use field.Functional group is introduced in EP rubbers at present mainly two methods：(1) post-modification is carried out to EP rubbers；(2) second
Alkene, propylene and the monomer copolymerization containing functional group.Functional group's species that post-modification can introduce is less, and easily occurs in modifying process
Degraded and cross-linking reaction, the quantity of functional group and distribution are uncontrollable.Ethene, propylene and the monomer direct copolymerization system containing functional group
Standby functionalization EP rubbers, can accurately control the structure and composition of polymer, be a kind of simple controllable preparation functionalization second
The method of third rubber.It is mainly at present tradition using the catalyst used in direct copolymerization process complex functionality EP rubbers material
Ziegler-Natta catalyst system and catalyzings and metallocene catalysis system.Use this two classes catalyst can obtain bromine, chlorine, hydroxyl with
And the ethylene propylene copolymer of furans functionalization, not only functional groups quantity is few, has obvious polyethylene for the copolymer of acquisition
Or the fusing point of polypropylene long-chain-segment, and there is no unsaturated double-bond can not carry out vulcanization crosslinking in copolymer.
Rare earth metal is due to its unique outer electronic structure so that has with the catalyst that rare earth element does central metal
Many unique performances, had obtained great concern catalyzing and synthesizing polyolefin field in recent years.Rare-earth metal catalyst activity
Height, dosage are few, rare-earth metal catalyst central metal valence stability different from transition-metal catalyst, gold in resulting polymers
Category ion residues amount is few, the ageing properties of high molecular material is influenced small, it is not necessary to be to prepare function by complicated deliming workshop section
Change the excellent catalyst of EP rubbers.The present invention is using rare earth catalyst catalysis ethene, propylene, functionalization alpha-olefin and alkadienes
Combined polymerization, improves functional groups quantity and species, and the feature of random copolymerization effectively eliminates the fusing point of polymer, and one
Walk processability it is excellent, number of functional groups species is controllable, can vulcanization crosslinking functionalization EP rubbers.
The content of the invention
In view of the problems of the existing technology, the present invention provides a kind of functional rare earth EP rubbers and preparation method thereof.
The technical scheme is that：
A kind of functional rare earth EP rubbers, the functional rare earth EP rubbers be rare earth catalyst catalysis ethene, propylene,
Copolymer prepared by functionalization alpha-olefin and alkadienes combined polymerization, number-average molecular weight is 5000-50 × 104, wherein functionalization α-
Alkene molar content is 0.5%-30%, and alkadienes molar content is 0.5%-20%；Added with ethene and propylene
Calculated with 100%, wherein the molar content of ethene is 10%-95%.Preferably, the functionalization EP rubbers
Number-average molecular weight is 2 × 104- 30 × 104, wherein functionalization alpha-olefin molar content is 1%-15%；Alkadienes mole
Percentage composition is 1%-10%；Calculated with ethene and propylene adduction 100%, wherein ethylene molar percentage composition is 40%-
75%.
The functionalization alpha-olefin is selected from containing halogen, alkoxy, sulfenyl, tertiary amine, alkylphosphines, siloxanes, silicon
Mixture more than one or both of alpha-olefin of alkyl functional group；Functionalization alpha-olefin has such as lower structure：
Wherein, R6Group refers to the alkyl containing 1-20 carbon, selected from-(CH2)n, n=1-20；- (CH2)m- CHR7-
(CH2)n-, m=1-18, n=1-18, wherein, R7Selected from CH3、CH2CH3、CH2CH2CH3、CH(CH3)2, cyclopropane base, ring penta
Alkyl, cyclohexyl.FG groups are selected from halogen F, Cl, Br, I；Alkoxy-OR8；Sulfenyl-SR8；Tertiary amine-NR8R9；Alkane
Base phosphine-PR8R9；Siloxanes-OSiR8R9；Silylation-SiR8R9R10；Wherein R8、R9、R10Selected from H, CH3、CH2CH3、i-Pr、n-
Pr、t-Bu、n-Bu, Ph, SiMe3；R8、R9、R10It can be the same or different.
The alkadienes is selected from more than one or both of bridged ring alkene, straight chain diene hydrocarbon, cyclodiene
Mixture.The specific alkadienes be selected from alkadienes be selected from 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene,
5- (2 '-acrylic) -2- norbornene, 5- (2- ethylidene -6- methyl -5- heptenyls) -2- norbornene, 5- (5- methyl -5-
Hexenyl) -2- norbornene, dicyclopentadiene, 1,4- hexadienes, 1,7- octadienes, 7- methyl isophthalic acids, 6- octadienes, 3,7- bis-
One or both of methyl isophthalic acid, 6- octadienes, 5,7- dimethyl -1,6- octadienes, butadiene, isoprene, laurene with
On mixing.
The rare earth catalyst is made of two parts of A and B：A is rare earth compounding CpLnR2Xn, wherein：Cp matches somebody with somebody for cyclopentadienyl
Body C5(R1)(R2)(R3)(R4)(R5), Ln is rare earth metal, selected from Nd, Sc, Y, Lu, Gd, Sm；R be and the direct phase of rare earth metal
Alkyl even, selected from CH2SiMe3, CH2C6H4NMe2- o, CH2Ph, CH2CH=CH2, 1,3-C3H4(Me), 1,3-C3H3
(SiMe3)2, CH (SiMe3)2, CH3, CH2CH3,i-Pr,t-Bu；X be with the coordinating group on rare earth metal, selected from containing O, N, P,
The heteroatomic lewis acids of S, n is lewis acidic number, selected from 0 or 1；R1, R2, R3, R4, R5Selected from H, CH3, CH2CH3,i-
Pr,t-Bu, Ph, CH2Ph, SiMe3, CH2SiMe3, R13, R14, R15, R16, R17It can be the same or different；Cyclopentadienyl ligand Cp is selected from
C5H5, C5Me5, C5Me4SiMe3, C5HMe4, C5H2Me3, C5Me3(SiMe3)2, C5H3(SiMe3)2, C5Ph5；Wherein Ph for phenyl,
Me is methyl, Pr is propyl group, Bu is butyl；
Rare earth compounding CpLnR2XnStructural formula
B is organoboron reagent, selected from [Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3In one kind or
Several mixtures.
It is provided by the present invention it is a kind of prepare functional rare earth EP rubbers preparation method it is as follows：In inert nitrogen gas
Or under argon gas protection, organic solvent, functionalization alpha-olefin and alkadienes are added into the polymer reactor of dry deoxygenation by proportioning,
Stirring is warming up to polymerization temperature, is passed through ethene, propylene gas, reaction gas pressure 0.1MPa-6MPa, functionalization alpha-olefin
It is 1-50g/100mL with diene concentration, then adds rare earth catalyst, the molar ratio of rare earth catalyst component A and component B
For 1, rare earth catalyst agent concentration is 1.0 × 10-6- 4.0 × 10-7Mol/L, reacted at 0 DEG C -80 DEG C 5 minutes to 2 it is small when, adopt
Polymer is dried with traditional post-processing approach, obtains functional rare earth EP rubbers.Organic solvent be selected from n-hexane,
Mixture more than one or both of hexamethylene, normal heptane, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes.
Functional rare earth EP rubbers provided by the present invention and its preparation have following features：It is rare earth compounding with cyclopentadienyl
For major catalyst, simple in structure, synthesis easily, cost it is low；It is catalyzed ethene, propylene, functionalization alpha-olefin and alkadienes combined polymerization
Reactivity is high, and EP rubbers strand is linear structure, functionalization alpha-olefin and the diolefinic monomer group in EP rubbers chain
Into and distribution it is controllable.This method can excellent, number of functional groups species can in gentle reaction condition next step processability
Control, can vulcanization crosslinking functionalization EP rubbers, the feature of random copolymerization effectively eliminates the fusing point of polymer.
Embodiment
The present invention proposes following embodiments as further instruction, but the not model of limitation the claims in the present invention protection
Enclose.With carbon-13 nmr spectra (1H-NMR,13C-NMR) detection gained functionalization EP rubbers in combine each component content (mole
Percentage composition, %) and sequence distribution, with the molecular weight and molecualr weight distribution of gel permeation chromatograph (GPC) measure polymer
Index (the ratio between weight average molecular weight and number-average molecular weight), with the glass transition of differential scanning calorimetry instrument (DSC) measure polymer
Temperature (Tg) and fusing point (Tm)。
Embodiment 1, Dan Maoshuan alkyl scandium complexs (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2Preparation
13.500g (100mmol) N, N- dimethyl ortho-aminotoluene is added in 40mL diethyl ether solutions simultaneously in glove box
Stirring is opened, then adds 40mL (100mmol) n-butyllithium solution, reaction 3 days is stirred at room temperature.After completion of the reaction, vacuum is removed
Ether solvent is removed, residual solids are drained after n-hexane washs, and obtain 12.549g faint yellow solids LiCH2C6H4NMe2- o, production
Rate：89%.
1.513g (10mmol) ScCl is weighed in glove box3Powder is added in 8mL tetrahydrofurans.Weigh 4.234g
(30mmol) solid LiCH2C6H4NMe2- o is dissolved in 14mL tetrahydrofurans, and ScCl is added drop-wise to after it is completely dissolved3Tetrahydrochysene furan
Mutter in suspension, react 30min.After completion of the reaction, tetrahydrofuran solvent is removed in vacuum, it is molten to add 28mL toluene in residual solids
Solution, filtering, filter vacuum obtain 4.301g khaki powder Sc (CH after draining removing toluene2C6H4NMe2-o)3, yield：96%.
In glove box, 1.537g Sc (CH are weighed2C6H4NMe2-o)3(3.448mmol), which is put into, fills magnetic stir bar
In 50mLSchlenk bottles, add 10mL tetrahydrofuran solvents and dissolved.Weigh 0.671g C5Me4H(SiMe3)
(3.448mmol), after being dissolved with 5mL tetrahydrofurans, is added in Schlenk bottles at room temperature, and gloves are taken out after Schlenk bottles of sealing
Case is put into oil bath, is heated to 70 DEG C of stirring reaction 12h, and vacuum pumps solvent, and residue is dissolved in toluene after being washed with ether
In solution, -30 DEG C of refrigerator overnights are put into after concentrating toluene lysate, are recrystallized to give 1.450g yellow crystals (C5Me4SiMe3)
Sc(CH2C6H4NMe2-o)2, yield 83%.
Embodiment 2, Dan Maoshuan alkyl scandium complexs (C5Me4SiMe3)Sc(CH2SiMe3) (THF) preparation
In glove box, 2.2695g ScCl are weighed3(15mmol) is put into the Schlenk bottles for filling magnetic stir bar,
Add 50mL tetrahydrofurans.After Schlenk bottles closed, take out glove box by Schlenk bottles and be stirred overnight at 80 DEG C.Will be living
ScCl after change3(THF)3White suspension is brought into glove box, weighs 4.2336g LiCH2SiMe3(45mmol) uses 15mL tetra-
Hydrogen furans dissolves, and is slowly added drop-wise to ScCl3(THF)3In white suspension, 30min is reacted.Then, solvent THF is taken in decompression away,
60mL n-hexane extractions are added, cold filtering is taken advantage of after extract is freezed out accessory substance, finally takes the n-hexane in filtrate away
To 4.4557g white powder Sc (CH2SiMe3)3(THF)2。
In glove box, 3.2681gSc (CH are weighed2SiMe3)3(THF)2(7.25mmol), which is put into, fills magnetic stir bar
100mL round-bottomed flasks in, add 10mL n-hexane solvent dissolving.Weigh 1.4092g trimethyl silicon substrates tetramethyl-ring penta 2
Alkene C5Me4H(SiMe3) (7.25mmol), after 1mL n-hexane dissolutions, it is added drop-wise at room temperature in reaction bulb.After 2h is stirred at room temperature,
Liquid is depressurized to 1mL or so, -35 DEG C of refrigerator overnights is put into, is recrystallized to give 2.7389g clear crystals (C5Me4SiMe3)Sc
(CH2SiMe3)2(THF)。
Embodiment 3, the preparation of ethene, propylene, ethylidene norbornene and the bromo- 1- decene quadripolymers of 10-
In glove box, added into 100mL stainless steel cauldrons 5mL chlorobenzene solutions, 1mmol ethylidene norbornenes and
Sealed after the bromo- 1- decene of 10mmol10-, by the catalyst (C prepared by 20 μm of ol above-described embodiments 25Me4SiMe3)Sc
(CH2SiMe3)2(THF) and equimolar amounts [Ph3C][B(C6F5)4] mixing 5mL chlorobenzene solutions sealed with needle seal after take out
Glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene molar ratio
For 1/2, reaction gas pressure 0.2MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, under inert gas shielding,
Catalyst solution is rapidly injected in reaction kettle, after polymerizeing 5min, stops being passed through for ethene and propylene, add methanol terminate it is anti-
Should, and use methanol washing copolymer, be dried in vacuo, obtain functionalization quaternary EP rubbers.Polymer architecture and performance evaluation knot
Fruit is as follows：Ethylene contents are 67% in mole percent, and ethylidene norbornene content is for the bromo- 1- decene contents of 3%, 10-
7%, number-average molecular weight is 6.5 × 104, molecular weight distributing index (Mw/Mn) it is 1.80, glass transition temperature TgFor -67 DEG C.
Embodiment 4, the preparation of ethene, propylene, dicyclopentadiene and the bromo- 1- decene quadripolymers of 10-
In glove box, added into 100mL stainless steel cauldrons 5mL chlorobenzene solutions, 1mmol dicyclopentadienes and
Sealed after the bromo- 1- decene of 10mmol10-, other polymerizing conditions are same as Example 3, obtain functionalization quaternary EP rubbers.It is poly-
Compound structure and results of performance analysis are as follows：Ethylene contents are 72% in mole percent, dicyclopentadiene content 4%,
The bromo- 1- decene contents of 10- are 7%, and number-average molecular weight is 9.5 × 104, molecular weight distributing index (Mw/Mn) it is 1.74, vitrifying
Transition temperature TgFor -55 DEG C.
Embodiment 5, the preparation of ethene, propylene, isoprene and the bromo- 1- decene quadripolymers of 10-
In glove box, added into 100mL stainless steel cauldrons 5mL chlorobenzene solutions, 1mmol dicyclopentadienes and
Sealed after the bromo- 1- decene of 10mmol10-, other polymerizing conditions are same as Example 3, obtain functionalization quaternary EP rubbers.It is poly-
Compound structure and results of performance analysis are as follows：Ethylene contents are 63% in mole percent, isoprene content 7%, 10-
Bromo- 1- decene content is 6%, and number-average molecular weight is 7.8 × 104, molecular weight distributing index (Mw/Mn) it is 1.64, glass transition
Temperature TgFor -56 DEG C.
Embodiment 6, the preparation of ethene, propylene, laurene and 5- (N, N- diethyl) -1- amylene quadripolymers
In glove box, 10mL chlorobenzene solutions, 1mmol laurenes and 4mmol5- are added into 100mL stainless steel cauldrons
Sealed after (N, N- diethyl) -1- amylenes, by the catalyst (C prepared by 20 μm of ol above-described embodiments 15Me4SiMe3)Sc
(CH2C6H4NMe2-o)2With [the Ph of equimolar amounts3C][B(C6F5)4] mixing 5mL chlorobenzene solutions sealed with needle seal after take out
Glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene molar ratio
For 1/3, reaction gas pressure 0.4MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, under inert gas shielding,
Catalyst solution is rapidly injected in reaction kettle, after polymerizeing 10min, stops being passed through for ethene and propylene, add methanol terminate it is anti-
Should, and use methanol washing copolymer, be dried in vacuo, obtain functionalization quaternary EP rubbers.Polymer architecture and performance evaluation knot
Fruit is as follows：Ethylene contents are 67% in mole percent, and laurene content is 5%, 5- (N, N- diethyl) -1- amylene contents
For 20%, number-average molecular weight is 0.6 × 104, molecular weight distributing index (Mw/Mn) it is 1.92, glass transition temperature TgFor -70
℃。
Embodiment 7, the preparation of ethene, propylene, 1,7- octadienes and 5- (N, N- diethyl) -1- amylene quadripolymers
In glove box, add 10mL chlorobenzene solutions, 2mmol1 into 100mL stainless steel cauldrons, 7- octadienes and
Sealed after 4mmol5- (N, N- diethyl) -1- amylenes, other polymerizing conditions are same as Example 6, obtain functionalization quaternary second third
Rubber.Polymer architecture is as follows with results of performance analysis：Ethylene contents are 73% in mole percent, 1,7- octadiene content
It is 10% for 9%, 5- (N, N- diethyl) -1- amylenes contents, number-average molecular weight is 3.1 × 104, molecular weight distributing index (Mw/
Mn) it is 1.67, glass transition temperature TgFor -66 DEG C.
Embodiment 8, ethene, propylene, isoprene and 4-N, the preparation of TMSDEA N diethylamine base styrene quadripolymer
In glove box, added into 100mL stainless steel cauldrons 10mL toluene solutions, 2mmol isoprene and
2mmol4-N, seals after TMSDEA N diethylamine base styrene, by the catalyst (C prepared by 20 μm of ol above-described embodiments 25Me4SiMe3)
Sc(CH2SiMe3)2(THF) and equimolar amounts [Ph3C][B(C6F5)4] mixing 5mL toluene solutions sealed with needle seal after take
Go out glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene mole
Than for 1/5, reaction gas pressure 0.2MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, in inert gas shielding
Under, catalyst solution is rapidly injected in reaction kettle, after polymerizeing 15min, stops being passed through for ethene and propylene, methanol is added and terminates
Reaction, and use methanol washing copolymer, be dried in vacuo, obtain functionalization ethylene propylene diene rubber.Polymer architecture and performance evaluation
As a result it is as follows：Ethylene contents are 51% in mole percent, isoprene content 8%, 4-N, TMSDEA N diethylamine base styrene
Content is 5%, and number-average molecular weight is 5.2 × 104, molecular weight distributing index (Mw/Mn) it is 1.57, glass transition temperature TgFor-
51℃。
Embodiment 9, the preparation of ethene, propylene, isoprene and 10- dimethylsilane -1- decene quadripolymers
In glove box, added into 100mL stainless steel cauldrons 10mL toluene solutions, 1mmol isoprene and
Sealed after 4mmol10- dimethylsilane -1- decene, by the catalyst (C prepared by 20 μm of ol above-described embodiments 25Me4SiMe3)
Sc(CH2SiMe3)2(THF) and equimolar amounts [Ph3C][B(C6F5)4] mixing 5mL toluene solutions sealed with needle seal after take
Go out glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene mole
Than for 1/5, reaction gas pressure 0.2MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, in inert gas shielding
Under, catalyst solution is rapidly injected in reaction kettle, after polymerizeing 2min, stops being passed through for ethene and propylene, methanol is added and terminates
Reaction, and use methanol washing copolymer, be dried in vacuo, obtain functionalization ethylene propylene diene rubber.Polymer architecture and performance evaluation
As a result it is as follows：Ethylene contents are 54% in mole percent, isoprene content 4%, 10- dimethylsilane -1- decene
Content is 12%, and number-average molecular weight is 2.8 × 104, molecular weight distributing index (Mw/Mn) it is 1.92, glass transition temperature Tg
For -48 DEG C.
Embodiment 10, the preparation of ethene, propylene, isoprene and 8- diphenylphosphine -1- octene quadripolymers
In glove box, added into 100mL stainless steel cauldrons 10mL chlorobenzene solutions, 2mmol isoprene and
Sealed after 1mmol8- diphenylphosphine -1- octenes, by the catalyst (C prepared by 20 μm of ol above-described embodiments 15Me4SiMe3)Sc
(CH2C6H4NMe2-o)2With [the Ph of equimolar amounts3C][B(C6F5)4] mixing 5mL chlorobenzene solutions sealed with needle seal after take out
Glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene molar ratio
For 1/5, reaction gas pressure 0.4MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, under inert gas shielding,
Catalyst solution is rapidly injected in reaction kettle, after polyase 13 0min, stops being passed through for ethene and propylene, add methanol terminate it is anti-
Should, and use methanol washing copolymer, be dried in vacuo, obtain functionalization quaternary EP rubbers.Polymer architecture and performance evaluation knot
Fruit is as follows：Ethylene contents are 71% in mole percent, isoprene content 15%, 8- diphenylphosphine -1- octene contents
For 5%, number-average molecular weight is 4.7 × 104, molecular weight distributing index (Mw/Mn) it is 1.52, glass transition temperature TgFor -50
℃。
Embodiment 11, the preparation of ethene, propylene, isoprene and 10- thiophenyl -1- decene quadripolymers
In glove box, added into 100mL stainless steel cauldrons 10mL toluene solutions, 2mmol isoprene and
Sealed after 2mmol10- thiophenyl -1- decene, by the catalyst (C prepared by 20 μm of ol above-described embodiments 25Me4SiMe3)Sc
(CH2SiMe3)2(THF) and equimolar amounts [Ph3C][B(C6F5)4] mixing 5mL toluene solutions sealed with needle seal after take out
Glove box.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene molar ratio
For 1/5, reaction gas pressure 0.2MPa, polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, under inert gas shielding,
Catalyst solution is rapidly injected in reaction kettle, after polyase 13 0min, stops being passed through for ethene and propylene, add methanol terminate it is anti-
Should, and use methanol washing copolymer, be dried in vacuo, obtain functionalization ethylene propylene diene rubber.Polymer architecture and performance evaluation knot
Fruit is as follows：Ethylene contents are 57% in mole percent, isoprene content 8%, and 10- thiophenyl -1- decene contents are
6%, number-average molecular weight is 6.3 × 104, molecular weight distributing index (Mw/Mn) it is 1.47, glass transition temperature TgFor -55 DEG C.
Embodiment 12, the preparation of ethene, propylene, laurene and 4- pentenyl phenyl ether quadripolymers
In glove box, 10mL toluene solutions, 2mmol laurenes and 1mmol4- are added into 100mL stainless steel cauldrons
Sealed after pentenyl phenyl ether, by the catalyst (C prepared by 20 μm of ol above-described embodiments 15Me4SiMe3)Sc(CH2C6H4NMe2-
o)2With [the Ph of equimolar amounts3C][B(C6F5)4] mixing 5mL toluene solutions sealed with needle seal after take out glove box.Will reaction
Kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, ethylene/propene molar ratio is 1/5, reacting gas
Pressure is 0.4MPa, and polymerization temperature is 25 DEG C, and quick stirring is fast by catalyst solution under inert gas shielding after 2 minutes
In speed injection reaction kettle, after polyase 13 0min, stop being passed through for ethene and propylene, add methanol and terminate reaction, and washed with methanol
Polymer, vacuum drying, obtains functionalization quaternary EP rubbers.Polymer architecture is as follows with results of performance analysis：With moles hundred
Fraction meter ethylene contents are 69%, and laurene content is that 17%, 4- pentenyl phenyl ether content is 6%, number-average molecular weight 8.9
×104, molecular weight distributing index (Mw/Mn) it is 1.59, glass transition temperature TgFor -57 DEG C.
Embodiment 13, ethene, propylene, laurene and trimethyl (10- undecenyls epoxide) silane quadripolymer
Prepare
In glove box, 10mL toluene solutions, 1mmol laurenes and 1mmol tri- are added into 100mL stainless steel cauldrons
Sealed after methyl (10- undecenyls epoxide) silane, by the catalyst prepared by 20 μm of ol above-described embodiments 1
(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2With [the Ph of equimolar amounts3C][B(C6F5)4] mixing 5mL toluene solutions seal
Glove box is taken out after pin sealing.Reaction kettle is connected on polymerization line, after displaced air, is passed through ethylene/propene gaseous mixture, second
Alkene/propylene molar ratio is 1/5, reaction gas pressure 0.4MPa, and polymerization temperature is 25 DEG C, quick stirring, after 2 minutes, lazy
Property gas shield under, catalyst solution is rapidly injected in reaction kettle, after polyase 13 0min, stops being passed through for ethene and propylene, is added
Enter methanol terminate reaction, and use methanol washing copolymer, be dried in vacuo, obtain functionalization quaternary EP rubbers.Polymer architecture
It is as follows with results of performance analysis：Ethylene contents are 59% in mole percent, and laurene content is 5%, trimethyl (10- ten
One carbene base epoxide) silane contents be 6%, number-average molecular weight be 10.2 × 104, molecular weight distributing index (Mw/Mn) it is 1.48,
Glass transition temperature TgFor -51 DEG C.
Claims (7)
1. a kind of functional rare earth EP rubbers, its feature are as follows：Functional rare earth EP rubbers is rare earth catalyst catalysis second
Copolymer prepared by alkene, propylene, functionalization alpha-olefin and alkadienes combined polymerization, number-average molecular weight is 5000-50 × 104, wherein
Functionalization alpha-olefin molar content is 0.5%-30%, and alkadienes molar content is 0.5%-20%；With ethene
Calculated with propylene adduction 100%, wherein the molar content of ethene is 10%-95%；
The functionalization alpha-olefin is selected from containing halogen, alkoxy, sulfenyl, tertiary amine, alkylphosphines, siloxanes, silylation
Mixture more than one or both of alpha-olefin of functional group；The alkadienes is selected from selected from bridged ring alkene, straight chain two
Mixture more than one or both of alkene, cyclodiene；The rare earth catalyst is made of two parts of A and B：A
For rare earth compounding CpLnR2Xn, wherein：Cp is cyclopentadienyl ligand C5(R1)(R2)(R3)(R4)(R5), Ln is rare earth metal, selected from Nd,
Sc、Y、Lu、Gd、Sm；R is the alkyl being connected directly with rare earth metal, selected from CH2SiMe3, CH2C6H4NMe2- o, CH2Ph, CH2CH
=CH2, 1,3-C3H4(Me), 1,3-C3H3(SiMe3)2, CH (SiMe3)2, CH3, CH2CH3,i-Pr,t-Bu；X is and rare earth metal
On coordinating group, selected from containing the heteroatomic lewis acid of O, N, P, S, n is lewis acidic number, selected from 0 or 1；R1, R2,
R3, R4, R5Selected from H, CH3, CH2CH3,i-Pr,t-Bu, Ph, CH2Ph, SiMe3, CH2SiMe3, R13, R14, R15, R16, R17Can phase
Together can not also be same；Cyclopentadienyl ligand Cp is selected from C5H5, C5Me5, C5Me4SiMe3, C5HMe4, C5H2Me3, C5Me3(SiMe3)2, C5H3
(SiMe3)2, C5Ph5；Wherein Ph is phenyl, Me is methyl, Pr is propyl group, Bu is butyl；
Rare earth compounding CpLnR2XnStructural formula
B is organoboron reagent, selected from [Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3In one or more
Mixture.
2. functional rare earth EP rubbers according to claim 1, it is characterised in that the functionalization EP rubbers
Number-average molecular weight is 2 × 104- 30 × 104, wherein functionalization alpha-olefin molar content is 1%-15%；Alkadienes mole
Percentage composition is 1%-10%；Calculated with ethene and propylene adduction 100%, wherein ethylene molar percentage composition is 40%-
75%.
3. functional rare earth EP rubbers according to claim 1 or 2, it is characterised in that the functionalization alpha-olefin
With such as lower structure：
Wherein R6Group refers to the alkyl containing 1-20 carbon, selected from-(CH2)n, n=1-20；- (CH2)m- CHR7-
(CH2)n-, m=1-18, n=1-18, wherein, R7Selected from CH3、CH2CH3、CH2CH2CH3、CH(CH3)2, cyclopropane base, ring penta
Alkyl, cyclohexyl；FG groups are selected from halogen F, Cl, Br, I；Alkoxy-OR8；Sulfenyl-SR8；Tertiary amine-NR8R9；Alkane
Base phosphine-PR8R9；Siloxanes-OSiR8R9；Silylation-SiR8R9R10；Wherein R8、R9、R10Selected from H, CH3、CH2CH3、i-Pr、n-
Pr、t-Bu、n-Bu, Ph, SiMe3；R8、R9、R10It can be the same or different.
4. functional rare earth EP rubbers according to claim 1 or 2, it is characterised in that the alkadienes is selected from 5-
Ethylidene -2- norbornene, 5- vinyl -2- norbornene, 5- (2 '-acrylic) -2- norbornene, 5- (2- ethylidene -6-
Methyl -5- heptenyls) -2- norbornene, 5- (5- methyl -5- hexenyls) -2- norbornene, dicyclopentadiene, 1,4- oneself two
Alkene, 1,7- octadienes, 7- methyl isophthalic acids, 6- octadienes, 3,7- dimethyl -1,6- octadienes, 5,7- dimethyl -1,6- octadienes,
Mixing more than one or both of butadiene, isoprene, laurene.
5. functional rare earth EP rubbers according to claim 3, it is characterised in that the alkadienes is selected from 5- Asias second
Base -2- norbornene, 5- vinyl -2- norbornene, 5- (2 '-acrylic) -2- norbornene, 5- (2- ethylidene -6- first
Base -5- heptenyls) -2- norbornene, 5- (5- methyl -5- hexenyls) -2- norbornene, dicyclopentadiene, 1,4- hexadienes,
1,7- octadienes, 7- methyl isophthalic acids, 6- octadienes, 3,7- dimethyl -1,6- octadienes, 5,7- dimethyl -1,6- octadienes, fourth two
Mixing more than one or both of alkene, isoprene, laurene.
6. the preparation method of any functional rare earth EP rubbers of claim 1-5, it is characterised in that：In indifferent gas
Under body nitrogen or argon gas protection, added by proportioning into the polymer reactor of dry deoxygenation organic solvent, functionalization alpha-olefin and
Alkadienes, stirring are warming up to polymerization temperature, are passed through ethene, propylene gas, reaction gas pressure 0.1MPa-6MPa, functionalization
Alpha-olefin and diene concentration are 1-50g/100mL；Add rare earth catalyst, mole of rare earth catalyst component A and component B
Than for 1, rare earth catalyst agent concentration is 1.0 × 10-6- 4.0 × 10-7mol/L；Reacted at 0 DEG C -80 DEG C 5 minutes to 2 it is small when,
Polymer is dried using traditional post-processing approach, obtains functional rare earth EP rubbers.
7. preparation method according to claim 6, it is characterised in that the organic solvent be selected from n-hexane, hexamethylene,
Mixture more than one or both of normal heptane, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes.
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