CN109694432A - A kind of alkene-salt unsaturated carboxylic acid polymer and preparation method thereof - Google Patents
A kind of alkene-salt unsaturated carboxylic acid polymer and preparation method thereof Download PDFInfo
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- CN109694432A CN109694432A CN201711007935.2A CN201711007935A CN109694432A CN 109694432 A CN109694432 A CN 109694432A CN 201711007935 A CN201711007935 A CN 201711007935A CN 109694432 A CN109694432 A CN 109694432A
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- 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
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Abstract
The present invention relates to polymer arts, a kind of alkene-salt unsaturated carboxylic acid polymer and preparation method thereof is disclosed.The alkene-salt unsaturated carboxylic acid polymer is directly obtained by being copolymerized, and carboxylate content is 0.1~60mol%, preferably 0.2~30mol%；Number-average molecular weight is 1000~230000, preferably 8000~230000；Fusing point is 30~140 DEG C；Density is 0.900~1.000g/cm3.Using catalyst of the invention can the carry out Coordination copolymerization of directly catalyzed alkene and salt unsaturated carboxylic acid high activity at relatively low temperatures and pressures react, by controlling polymeric reaction condition, the molecular weight and the degree of branching of polymer can be regulated and controled in a wider range, alkene-salt unsaturated carboxylic acid polymer with different physical properties is made.
Description
Technical field
The present invention relates to polymer arts, alkene-salt unsaturated carboxylic acid polymer is used for more particularly, to one kind, one
Kind alkene-salt unsaturated carboxylic acid polymer preparation method, and alkene-salt unsaturated carboxylic acid as made from the preparation method gather
Close object.
Background technique
Ionomer refers to the high molecular polymer containing a small amount of ionic group on strand, also known as poly- from aggressiveness or ionomer
Close object.Due to the introducing of ionic group, the ionomer molecules physically or chemically effect no with general molecule: Ion-ion
Interaction；Ion-dipole interaction；The p- ion pair interaction of ion；Interaction of hydrogen bond；Metal combination phase interaction
With etc..This interaction assigns many unique performances of ionomer, makes it in polymer modification, function film, conductive material, doctor
Treat material, etc. have important application.
The more mature method of ionomer is prepared, mainly there is copolymerization process and Graft Method.Copolymerization process is ionomer synthesis
Main method polymerize mostly to promote alkene to be copolymerized with the monomer with acidic-group using high-pressure free radical, rear addition metal from
Son is neutralized into salt and obtains.Although directly carboxylic acids polar monomer can be introduced into polyolefin chain with high-pressure free radical copolymerization,
This method needs high-temperature and high-pressure conditions, and energy consumption is high, and cost of equipment is expensive, and the subsequent further metal salifying process of needs.
Coordination catalysis is copolymerized the polymer technology of preparing as a kind of normal temperature and pressure, because it is reducing energy consumption, improves reaction
The remarkable effect of efficiency etc. and have received widespread attention.Catalyst participates in reaction process and makes olefinic monomer and polar monomer
Copolyreaction activation energy be greatly lowered, to be conducive to the function of obtaining higher molecular weight at relatively low temperatures and pressures
Polymer.Currently, only a small amount of reported in literature is copolymerized using transient metal complex catalyzed alkene and unsaturated carboxylic acid.For example,
Document Journal of American Chemical Society, 2010,132,17690-17691,
Organometallics, 2017,36,1873-1879, Journal of Polymer Science:Part A:Polymer
Chemistry, 1999,37,2471-2480 disclose and can be catalyzed the same α of ethylene, β ethylenic bond insatiable hunger using transient metal complex
With carboxylic acid copolyreaction under conditions of toluene is solvent.However, using the same ethylenic bond of catalyst ethylene reported in the literature
When unsaturated carboxylic acid (olefin(e) acid) is copolymerized, catalyst amount is larger, and polymerization activity and resulting polymers molecular weight are lower.And
And further progress neutralization reaction is also needed for ionomer is made, process is increased, will cause yield reduction.
Summary of the invention
In order to solve the above technical problems existing in the prior art, the object of the present invention is to provide a kind of alkene-insatiable hungers
And carboxylate polymer, a kind of preparation method of alkene-salt unsaturated carboxylic acid polymer, and the alkene as made from the preparation method
Hydrocarbon-salt unsaturated carboxylic acid polymer.Catalyst of the invention polymerization activity with higher does not have to carry out salt unsaturated carboxylic acid
Alkyl aluminum protection, or be only added minimal amount of alkyl aluminum can high activity catalyzed alkene and salt unsaturated carboxylic acid combined polymerization it is direct
Ionomer is made, eliminates the processing step that metal ion is neutralized into salt.
The first aspect of the present invention provides a kind of alkene-salt unsaturated carboxylic acid polymer, the alkene-salt unsaturated carboxylic acid
Polymer is directly obtained by being copolymerized, and carboxylate content is 0.1~60mol%, preferably 0.2~30mol%；Number-average molecular weight
It is 1000~230000, preferably 8000~230000；Fusing point is 30~140 DEG C；Density is 0.900~1.000g/cm3。
The second aspect of the present invention provides a kind of preparation method of alkene-salt unsaturated carboxylic acid polymer, the preparation side
Method include: under the polymerization conditions, make alkene, salt unsaturated carboxylic acid, catalyst, hydrocarbon solvent and optional chain-transferring agent into
Row contact, the catalyst include major catalyst and co-catalyst；
The major catalyst is selected from least one of metal complex shown in formula (I):
In formula (I), R1And R4It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R2And R3It is identical or different, respectively
From selected from hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or miscellaneous
Ring group, and R2And R3It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；n
For the integer for meeting M valence state.
The third aspect of the present invention provides alkene-salt unsaturated carboxylic acid polymer made from a kind of above-mentioned preparation method.
Using catalyst of the invention can directly catalyzed alkene and salt unsaturated carboxylic acid it is high at relatively low temperatures and pressures
Active progress Coordination copolymerization reaction can regulate and control the molecular weight of polymer by controlling polymeric reaction condition in a wider range
And the degree of branching, be made with different physical properties alkene-salt unsaturated carboxylic acid polymer, catalyst of the invention have compared with
High catalytic activity, and under conditions of loading without catalyst and emulsifier is not added, it is good poly- to can be prepared by particle shape
Object is closed, there is wide prospects for commercial application.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with specific embodiment, the present invention will be described in detail, these realities
It applies mode and only serves illustrative, be not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of alkene-salt unsaturated carboxylic acid polymer, the alkene-
Salt unsaturated carboxylic acid polymer is directly obtained by being copolymerized, and carboxylate content is 0.1~60mol%, number-average molecular weight 1000
~230000, fusing point is 30~140 DEG C, and density is 0.900~1.000g/cm3。
Under preferable case, the alkene-salt unsaturated carboxylic acid polymer carboxylate content is 0.2~30mol%, and number is equal
Molecular weight is 8000~230000, and fusing point is 38~124 DEG C, and density is 0.902~0.965g/cm3。
Carboxylate content in the present invention refers to the content of unsaturated carboxylic acid salt monomer in polymer.
According to the second aspect of the invention, the present invention provides a kind of alkene-salt unsaturated carboxylic acid polymer preparation sides
Method, the preparation method include: under the polymerization conditions, to make alkene, salt unsaturated carboxylic acid, catalyst, hydrocarbon solvent and optional
Chain-transferring agent contacted, the catalyst include major catalyst and co-catalyst；
The major catalyst is selected from least one of metal complex shown in formula (I):
In formula (I), R1And R4It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R2And R3It is identical or different, respectively
From selected from hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or miscellaneous
Ring group, and R2And R3It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；n
For the integer for meeting M valence state.
Under preferable case, in formula (I), R2And R3Mutually cyclization.
According to one preferred embodiment, the major catalyst is selected from least one in metal complex shown in formula (II)
Kind:
In formula (II), R9And R10It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R5-R8It is identical or different, respectively
From selected from hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or miscellaneous
Ring group, and R5-R8It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；n
For the integer for meeting M valence state.
Under preferable case, in formula (II), R9And R10It is identical or different, it each is selected from substituted or unsubstituted C6-C30Aryl
Or C7-C30Aralkyl；R5-R8It is identical or different, it each is selected from hydrogen atom or C1-C20Alkyl, and R5And R8Mutually cyclization；M is
Group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is 2.
It is highly preferred that the major catalyst is selected from least one of metal complex shown in formula (III):
In formula (III), R1-R10It is identical or different, it each is selected from hydrogen, saturated or unsaturated C1-C24Alkyl, oxyl or
Halogen, and R1-R10It is optionally mutually cyclic；M is group VIII metal, preferably nickel；X is identical or different, is selected from halogen, hydrocarbon
Base, oxyl.
It is further preferred that metal complex shown in formula (III) is following complex a, b or c:
According to another preferred embodiment, the major catalyst is selected from metal complex shown in formula (IV) at least
It is a kind of:
In formula (IV), R9And R10It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R11-R13It is identical or different,
It each is selected from hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or
Heterocycle, and R11-R13It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, hydrocarbon oxygen
Base；N is the integer for meeting M valence state.
Under preferable case, in formula (IV), R9And R10It is identical or different, it each is selected from substituted or unsubstituted C6-C30Aryl
Or C7-C30Aralkyl；R11-R13It is identical or different, it each is selected from hydrogen atom, C1-C20Alkyl, and R11-R13Optionally mutually
Cyclization；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is 2.
It is highly preferred that the major catalyst is selected from least one of metal complex shown in formula (V):
In formula (V), R1-R10It is identical or different, it each is selected from hydrogen, saturated or unsaturated C1-C24Alkyl, oxyl or halogen
Element, and R1-R10It is optionally mutually cyclic；M is group VIII metal, preferably nickel；X is identical or different, selected from halogen, alkyl,
Oxyl.
It is further preferred that metal complex shown in formula (V) is following complex d or e:
In the present invention, metal complex shown in formula (III) can refer to document Macromolecules 2009,42,7789-
Preparation method disclosed in 7796 is made, and metal complex shown in formula (V) can refer to document J.Am.Chem.Soc.1995, and 117,
Preparation method disclosed in 6414-6415 obtains, and related content disclosed in above-mentioned document can be all incorporated herein by reference,
Details are not described herein.
According to the present invention, the dosage of the major catalyst can be 0.00001~100mmol/L, preferably 0.0001~
1mmol/L, more preferably 0.001~0.5mmol/L.
In the present invention, the molar concentration (such as mmol/L) of material refers to the concentration of material in the reactor.
According to the present invention, the co-catalyst can be the conventional selection in olefin coordination polymerization reaction.Under preferable case,
The co-catalyst is selected from organo-aluminum compound and/or organoboron compound.
Wherein, the organo-aluminum compound can be AlR selected from alkylaluminoxane or general formulanX1 3-nOrganic compound.It is logical
Formula AlRnX1 3-nIn, R is hydrogen, C1-C20Alkyl or oxyl, preferably C1-C20Alkyl, C1-C20Alkoxy, C7-C20Aralkyl
Or C6-C20Aryl；X1For halogen, preferably chlorine or bromine；0 n≤3 <.
The specific example of the organo-aluminum compound includes but is not limited to: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium,
Tri-n-hexyl aluminum, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum,
The aluminum alkyl halides such as sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride and methylaluminoxane (MAO), modified methylaluminoxane
(MMAO).Preferably, the organo-aluminum compound is methylaluminoxane (MAO).
The organoboron compound can be selected from aryl boron and/or borate.The aryl boron preferably replace or not
Substituted phenyl boron, more preferably three pentafluorophenyl group boron.The borate is preferably N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group)
Borate and/or four (pentafluorophenyl group) boric acid trityl group salt.
When the co-catalyst is organo-aluminum compound, aluminium rubs with M in the major catalyst in the co-catalyst
Your ratio can be (10~10000000): 1, preferably (10~100000): 1, more preferably (100~10000): 1.It is helped when described
When catalyst choice organoboron compound, in the co-catalyst in boron and the major catalyst M molar ratio can for (0.1~
1000): 1, preferably (1~500): 1.
According to the present invention, the alkene can be selected from ethylene, C3-C16Alpha-olefin or cycloolefin.It is preferred that the alkene is second
Alkene.
According to the present invention, the salt unsaturated carboxylic acid can be linear chain or branched chain salt unsaturated carboxylic acid, can for containing
Naphthenic base, cycloalkyl-alkyl, aryl, alkylaryl, aryl alkyl salt unsaturated carboxylic acid, can for unsaturated carboxylic acid barium,
Lithium, sodium, zinc, bismuth, potassium, strontium, magnesium, calcium or aluminium salt, preferably sodium, zinc or sylvite.Preferably, the salt unsaturated carboxylic acid is to replace
Or unsubstituted C3-C30Olefin(e) acid salt, " the substituted C3-C30Olefin(e) acid salt " refers to " C3-C30Hydrogen atom or carbon in olefin(e) acid salt "
Atom is replaced halogen atom, oxygen atom, sulphur atom or nitrogen-atoms.It is highly preferred that the salt unsaturated carboxylic acid is C3-C20End
Alkenyl olefin(e) acid salt, the C3-C20End alkenyl olefin(e) acid salt be C3-C20End alkenyl olefin(e) acid sodium, C3-C20End alkenyl olefin(e) acid zinc or
C3-C20End alkenyl olefin(e) acid potassium.
The specific example of the salt unsaturated carboxylic acid includes but is not limited to: acrylates, methacrylate, maleic acid,
Fumaric acid, itaconic acid, 3-butenoic acid salt, 4- pentenoic acid salt, 9- decenoate, 10 hendecenoic acid salt, 7- octene hydrochlorate, 6- heptan
Olefin(e) acid salt, 5- hexene hydrochlorate.Under preferable case, the salt unsaturated carboxylic acid is 10 hendecenoic acid salt, 4- pentenoic acid salt or the 9- last of the ten Heavenly stems
Olefin(e) acid salt, more preferably zinc acrylate resin, potassium acrylate, sodium acrylate, Sodium methacrylate, zinc undecylenate.
According to the present invention, the dosage of the salt unsaturated carboxylic acid can be 0.01~6000mmol/L, preferably 0.1~
1000mmol/L, more preferably 1~500mmol/L.
According to the present invention, be optionally added chain-transferring agent in polymerization system, the chain-transferring agent can be selected from alkyl aluminum,
At least one of alkyl magnesium and zinc alkyl, preferably trialkylaluminium and/or dialkyl group zinc.
It is highly preferred that the chain-transferring agent is being selected from trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three just
At least one of hexyl aluminium, tri-n-octylaluminium, zinc methide and diethyl zinc.
The molar ratio of M can be (0.1~2000) in the dosage of the chain-transferring agent and the major catalyst: 1, preferably
(0.1~600): 1.
In the present invention, the salt unsaturated carboxylic acid can be handled first through part co-catalyst or chain-transferring agent, unsaturated carboxylic acid
Carboxylic acid radical content in salt can be 1000: 1~1: 10 with the molar ratio of co-catalyst or chain-transferring agent.Described herein helping is urged
Agent and chain-transferring agent are identical as above-mentioned co-catalyst and chain-transferring agent, but its dosage and above-mentioned dosage are relatively independent, no
In above-mentioned dosage.
Polymerization reaction of the invention can be carried out using following manner: in the presence of hydrocarbon solvent, in anhydrous and oxygen-free and
Under other polymeric reaction conditions, the catalyst is contacted with alkene and unsaturated carboxylic acid salt monomer.Wherein, the unsaturation
The components such as carboxylate, major catalyst and co-catalyst can be separately added into reactor, add again after each component can also being pre-mixed
Enter reactor, order of addition or mixed condition are not particularly limited.
In the present invention, the hydrocarbon solvent can be C3~C20Alkane or aromatic hydrocarbons, specific example includes: butane, isobutyl
At least one in alkane, pentane, hexane, heptane, octane, hexamethylene, toluene, dimethylbenzene etc., preferably hexane, hexamethylene and toluene
Kind.
According to the present invention, polymeric reaction condition includes: reaction temperature, reaction time and reaction pressure etc..
Wherein, the temperature of polymerization reaction can be selected in a big way, and reaction temperature can be -50 DEG C to 200 DEG C,
Preferably -20 to 150 DEG C, more preferably 0~120 DEG C.
In the present invention, the pressure of polymerization reaction is not particularly limited, as long as monomer can be made to carry out Coordination copolymerization reaction
?.When olefin polymerization is ethylene, from reducing cost and simplifying the angle of polymerization technique, in the reactor, preferably
1~1000atm of pressure of ethylene, further preferably 1~200atm, more preferably 1~50atm.
Catalyst of the invention can be catalyzed to high activity monomer and carry out polymerization reaction, therefore reacting can be complete in a short time
At the reaction time can be 10~200min, preferably 20~60min.
In addition, the polymerization methods that this field routine can be used in polymerization reaction of the invention carry out, catalyst of the invention is equal
It is applicable in.Such as continuous polymerization or batchwise polymerization mode, preferably continuous solution polymerization mode can be used in polymerization reaction of the invention.
Specifically, catalyst and selected solvent, auxiliary agent, cleanser and polymerization reaction auxiliary agent etc. are continuously supplied into reaction zone
Domain, while continuously removing polymerizate.
The present invention can loaded and be not added without catalyst by the regulation to catalyst in catalyst system and polymerizing condition
Under conditions of emulsifier, the good olefin polymer containing carboxylate of particle shape is made.
According to the third aspect of the invention we, the present invention provides a kind of alkene made from above-mentioned preparation method-unsaturation carboxylics
Silicate polymer.
The alkene-salt unsaturated carboxylic acid polymer carboxylate content is 0.1~60mol%, number-average molecular weight 1000
~230000, fusing point is 30~140 DEG C, and density is 0.900~1.000g/cm3。
Under preferable case, the alkene-salt unsaturated carboxylic acid polymer carboxylate content is 0.2~30mol%, and number is equal
Molecular weight is 8000~230000.
The present invention will be described in detail by way of examples below.
In embodiment and comparative example below:
The number-average molecular weight and co-monomer content (carboxylate content) of polymer: it uses13The measurement of C H NMR spectroscopy,
On 400 nuclear magnetic resonance chemical analyser of 400MHz Bruker Avance, using 13 probe of 10mm PASEX, with deuterium at 130 DEG C
Analysis test is carried out for tetrachloroethanes dissolution polymer samples to obtain.
The fusing point of polymer is tested using differential scanning calorimetry (DSC): 10mg sample being placed in crucible, in Pekin
It is measured on 8500 differential scanning calorimeter of Elmer DSC.Under nitrogen atmosphere, it is risen with the heating rate of 10 DEG C/min from 50 DEG C
Temperature keeps the temperature 1min to 180 DEG C, is down to 50 DEG C with 10 DEG C/min, keeps the temperature 3min, then rises to 180 DEG C with 10 DEG C/min, record the
Secondary temperature elevation scan data.
The density of polymer: it referring to GB/T1033-1986 the method, is tested using infusion process.
Embodiment 1-19 is for illustrating alkene of the invention-salt unsaturated carboxylic acid polymer and preparation method thereof.
Embodiment 1
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
10mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 30 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 2
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 30 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 3
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L) keeps the ethylene pressure of 10atm, is stirred to react at 30 DEG C
30min.It is finally neutralized with the ethanol solution that 1 volume % hydrochloric acid is acidified, obtains polymer.The performance of polymerization activity and polymer
Parameter is as shown in table 1.
Embodiment 4
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 5
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 0.25mL diethyl zinc (hexane solution of 1mol/L), 3mL methylaluminoxane
(MAO) (toluene solution of 1.53mol/L) keeps the ethylene pressure of 10atm, is stirred to react 30min at 60 DEG C.Finally with 1
The ethanol solution of volume % hydrochloric acid acidification neutralizes, and obtains polymer.The performance parameter of polymerization activity and polymer such as 1 institute of table
Show.
Embodiment 6
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 0.5mL diethyl zinc (hexane solution of 1mol/L), 3mL methylaluminoxane
(MAO) (toluene solution of 1.53mol/L) keeps the ethylene pressure of 10atm, is stirred to react 30min at 60 DEG C.Finally with 1
The ethanol solution of volume % hydrochloric acid acidification neutralizes, and obtains polymer.The performance parameter of polymerization activity and polymer such as 1 institute of table
Show.
Embodiment 7
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 4.14g zinc acrylate resin is added,
10mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 8
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 1.88g sodium acrylate is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 9
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.20g potassium acrylate is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 10
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 4.32g undecenoic acid is added
Zinc, 5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), 60
At DEG C, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
To polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 11
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 2.16g methacrylic acid is added
Sodium, 5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), 60
At DEG C, the ethylene pressure of 10atm is kept, 30min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
To polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 12
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.5mg (2.5 μm of ol) complex b, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 30 DEG C
Under, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 13
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.5mg (2.5 μm of ol) complex b, 4.32g undecenoic acid is added
Zinc, 5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), 60
At DEG C, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
To polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 14
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.4mg (2.5 μm of ol) complex c, 4.32g undecenoic acid is added
Zinc, 5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), 60
At DEG C, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
To polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 15
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 4.32g undecenoic acid is added
Zinc, 5mL AlEt32.5mL N is added in (hexane solution of 1.0mol/L), N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate
Toluene solution (toluene solution of 1mmol/L), makes Ni/B=1, at 60 DEG C, keeps the ethylene pressure of 10atm, is stirred to react
30min.It is finally neutralized with the ethanol solution that 1 volume % hydrochloric acid is acidified, obtains polymer.The performance of polymerization activity and polymer
Parameter is as shown in table 1.
Embodiment 16
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex a, 4.32g undecenoic acid is added
Zinc, 5mL AlEt33mL AlEt is added in (hexane solution of 1.0mol/L)2Cl (hexane solution of 2mmol/L), at 60 DEG C,
The ethylene pressure for keeping 10atm, is stirred to react 30min.It is finally neutralized, is gathered with the ethanol solution that 1 volume % hydrochloric acid is acidified
Close object.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 17
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex d, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 30 DEG C
Under, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 18
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.6mg (2.5 μm of ol) complex d, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Embodiment 19
It will vacuumize while hot equipped with churned mechanically 1L stainless steel polymeric kettle at 130 DEG C of continuous drying 6h and use N2Gas is set
It changes 3 times.To the hexane of polymerization system injection 500mL, while 1.8mg (2.5 μm of ol) complex e, 2.07g zinc acrylate resin is added,
5mL AlEt3(hexane solution of 1.0mol/L), 3mL methylaluminoxane (MAO) (toluene solution of 1.53mol/L), at 60 DEG C
Under, the ethylene pressure of 10atm is kept, 60min is stirred to react.It is finally neutralized, is obtained with the ethanol solution that 1 volume % hydrochloric acid is acidified
Polymer.The performance parameter of polymerization activity and polymer is as shown in table 1.
Table 1
As can be seen from Table 1, catalyst ethylene of the invention with unsaturated carboxylic acid salt monomer be copolymerized when, show compared with
High polymerization activity, Copolymerization activity reach as high as 25.7 × 106g·mol-1(Ni)·h-1, the co-monomer content of polymer compared with
Height, and the molecular weight of polymer can be regulated and controled in a wider range according to the addition of chain-transferring agent.In addition, passing through regulation polymerization
The good polymer of particle shape can be made in condition.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of alkene-salt unsaturated carboxylic acid polymer, which is characterized in that the alkene-salt unsaturated carboxylic acid polymer is by being copolymerized
It directly obtains, carboxylate content is 0.1~60mol%, preferably 0.2~30mol%；Number-average molecular weight be 1000~
230000, preferably 8000~230000；Fusing point is 30~140 DEG C；Density is 0.900~1.000g/cm3。
2. a kind of alkene-salt unsaturated carboxylic acid polymer preparation method, which is characterized in that the preparation method includes: to polymerize
Under reaction condition, contact alkene, salt unsaturated carboxylic acid, catalyst, hydrocarbon solvent and optional chain-transferring agent, it is described to urge
Agent includes major catalyst and co-catalyst；
The major catalyst is selected from least one of metal complex shown in formula (I):
In formula (I), R1And R4It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R2And R3It is identical or different, it is each free
From hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or heterocycle,
And R2And R3It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is full
The integer of sufficient M valence state.
3. preparation method according to claim 2, wherein in formula (I), R2And R3Mutually cyclization；It is preferred that the major catalyst
Selected from least one of metal complex shown in formula (II):
In formula (II), R9And R10It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R5-R8It is identical or different, it is each free
From hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or heterocycle,
And R5-R8It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is to meet
The integer of M valence state.
4. preparation method according to claim 3, wherein in formula (II), R9And R10It is identical or different, it each is selected from substitution
Or unsubstituted C6-C30Aryl or C7-C30Aralkyl；R5-R8It is identical or different, it each is selected from hydrogen atom or C1-C20Alkyl, and
R5And R8Mutually cyclization；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is 2；
It is preferred that the major catalyst is selected from least one of metal complex shown in formula (III):
In formula (III), R1-R10It is identical or different, it each is selected from hydrogen, saturated or unsaturated C1-C24Alkyl, oxyl or halogen
Element, and R1-R10It is optionally mutually cyclic；M is group VIII metal, preferably nickel；X is identical or different, selected from halogen, alkyl,
Oxyl.
5. preparation method according to claim 2, wherein in formula (I), R2And R3Mutually cyclization；It is preferred that major catalyst is selected from
At least one of metal complex shown in formula (IV):
In formula (IV), R9And R10It is identical or different, it each is selected from C1-C30Alkyl or miscellaneous alkyl；R11-R13It is identical or different, respectively
Selected from hydrogen atom, chlorine atom, C1-C20Alkyl, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom heterochain alkyl or heterocycle
Base, and R11-R13It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；n
For the integer for meeting M valence state.
6. preparation method according to claim 5, wherein in formula (IV), R9And R10It is identical or different, it each is selected from substitution
Or unsubstituted C6-C30Aryl or C7-C30Aralkyl；R11-R13It is identical or different, it each is selected from hydrogen atom, C1-C20Alkyl,
And R11-R13It is optionally mutually cyclic；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl；N is 2；
It is preferred that the major catalyst is selected from least one of metal complex shown in formula (V):
In formula (V), R1-R10It is identical or different, it each is selected from hydrogen, saturated or unsaturated C1-C24Alkyl, oxyl or halogen,
And R1-R10It is optionally mutually cyclic；M is group VIII metal, preferably nickel；X is identical or different, is selected from halogen, alkyl, hydrocarbon oxygen
Base.
7. preparation method according to claim 2, wherein the co-catalyst is selected from organo-aluminum compound and/or organic
Boron compound；The organo-aluminum compound is preferably alkylaluminoxane and/or aluminum alkyl halide；The organoboron compound is excellent
It is selected as aryl boron and/or borate；
The dosage of the major catalyst is 0.00001~100mmol/L, preferably 0.0001~1mmol/L；The co-catalyst
The molar ratio of M is (10~10000000) in middle aluminium and the major catalyst: 1 or the co-catalyst in boron and the main reminder
The molar ratio of M is (0.1~1000) in agent: 1.
8. preparation method according to claim 2, wherein the alkene is selected from ethylene, C3-C16Alpha-olefin or cyclenes
Hydrocarbon, preferably ethylene；The salt unsaturated carboxylic acid is substituted or unsubstituted C3-C30Olefin(e) acid salt, preferably C3-C20End alkenyl
Olefin(e) acid salt；The dosage of the salt unsaturated carboxylic acid is 0.01~6000mmol/L, preferably 0.1~1000mmol/L.
9. preparation method according to claim 2, wherein the chain-transferring agent is selected from alkyl aluminum, alkyl magnesium and zinc alkyl
At least one of, preferably trialkylaluminium and/or dialkyl group zinc；M in the dosage of the chain-transferring agent and the major catalyst
Molar ratio be (0.1~2000): 1.
10. alkene made from preparation method described in any one of claim 2-9-salt unsaturated carboxylic acid polymer.
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| CN115260365A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Branched olefin polymers, process for their preparation and their use |
| CN115260359A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Method for preparing olefin-unsaturated carboxylic ester copolymer, copolymer and application |
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| CN115260365A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Branched olefin polymers, process for their preparation and their use |
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| CN115260359A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Method for preparing olefin-unsaturated carboxylic ester copolymer, copolymer and application |
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