CN104151575B - A kind of processes for chemically crosslinked polyethylene and preparation method thereof - Google Patents
A kind of processes for chemically crosslinked polyethylene and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of processes for chemically crosslinked polyethylene and preparation method thereof.The method comprises the following steps: first by the late transition metal catalyst good to polar group tolerance under conditions of 20 40 DEG C and 1 30atm ethylene pressure, catalyzed ethylene and the copolyreaction of polar monomer, within reaction time is 1 hour, obtain ethylene copolymer；Then use double screw extruder, at a temperature of the extrusion molding of 110 185 DEG C, obtained ethylene copolymer is carried out extrusion and bring it about chemical crosslinking, obtain processes for chemically crosslinked polyethylene.Present invention also offers the processes for chemically crosslinked polyethylene that above-mentioned preparation method prepares.The cross-linking efficiency of the preparation method of processes for chemically crosslinked polyethylene provided by the present invention is high, the structure-controllable of cross-linking products, there is not accessory substance or residue affect the problem of cross-linking products performance, and whole operating procedure simply, is saved greatly energy consumption.
Description
Technical field
The present invention relates to a kind of processes for chemically crosslinked polyethylene and preparation method thereof, particularly belong to polyolefine material synthesis field.
Background technology
Polyethylene has excellent electrical property, toughness and chemical resistance, and is prone to processing, cheap, because forming
For one of general-purpose plastics that output and consumption figure are maximum, it is widely used in each neck of industrial production and daily life
Territory.But the fusing point of polyethylene is relatively low, poor heat resistance, mechanical strength is low, and ESC poor-performing, limit
Make it to be more widely applied.Therefore polyethylene is modified processing always polyethylene application and theoretical research
Emphasis and key, crosslinking is then one of PE modified ideal method.Through cross-linking modified, make have two
Dimension structure thermoplastic's linear polyethylene is changed into and has tridimensional network thermosetting plastics.Polyethylene becomes from linear structure
After network structure, the chemically and physically characteristic of material is the most significantly improved, and not only significantly improves polyethylene
Mechanical property, environmental stress cracking resistance, resistance to corrosive chemicals energy, creep resistance and electrical property etc. comprehensive
Performance, and be readily apparent that to improve temperature resistant grade, the heat resisting temperature of polyethylene can be made to bring up to 100 DEG C from 70 DEG C
Above, thus significantly widened the range of application of polyethylene.At present, crosslinked polyethylene be widely used in tubing,
The aspects such as film, CABLE MATERIALS and foamed product.
At present, the main cross-linking method of polyethylene has physical crosslinking i.e. crosslinking with radiation and chemical crosslinking two kinds, chemical crosslinking
It is divided into again crosslinked with silicane, peroxide crosslinking.Crosslinking with radiation and peroxide crosslinking processes be all by high-energy ray or
Add peroxide initiator and produce the polyethylene free radical of big molecule, then produced by the coupling reaction between strand
Raw crosslinking.Crosslinked with silicane is then to be drawn in Polyethylene Chain by grafting (can be divided into again one-step method and two-step method) or copolymerization
Enter silane group, then by hydrolyzing to form cross-linked structure.Although these crosslinking methods the most successfully achieve application,
But it is harsh to still suffer from operation condition, energy consumption is high, or the problem that there is the material property reduction that additive causes.
It is particularly noteworthy that be difficult to accurately control the molecular structure of polymerizate by the way of radical crosslinking, because of
And the most just cannot accurately control the physical property of final material.
Current ethylene-silane crosslinking copolymerization method is by controlling the input of silane copolymer monomer, it is possible to achieve silane is poly-
The distribution of rule on ethylene chain, shows relatively remarkable advantage, but its major defect to be cross-linking reaction speed relatively slow,
And the existence of catalyst dynamics model causes the molecular weight distribution of ethylene copolymer relatively wide.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide the preparation method of a kind of processes for chemically crosslinked polyethylene,
The method can efficiently control the molecular structure of cross-linking products, and then accurately controls the physical property of crosslinked polyethylene；
This cross-linking method need not any additive or catalyst simultaneously, and there is not residue affects the performance issue of cross-linking products；
And whole operating procedure is simple, it is possible to greatly save energy consumption.
Present invention also offers the processes for chemically crosslinked polyethylene that above-mentioned preparation method prepares.
For reaching above-mentioned purpose, the present invention provides the preparation method of a kind of processes for chemically crosslinked polyethylene, wherein, the method bag
Include following steps:
Use the good late transition metal catalyst of polar group tolerance at 20-40 DEG C and 1-30atm ethylene pressure
Under the conditions of catalyzed ethylene and the copolyreaction of polar monomer, within the reaction time is 1 hour, obtain ethylene copolymer；
Chemistry friendship is there is in prepared ethylene copolymer double screw extruder at a temperature of 110-185 DEG C of extrusion molding
Connection, obtains the processes for chemically crosslinked polyethylene of fine structure.
The position of cross-linking reaction can be efficiently controlled in the method for the invention by controlling the insertion rate of polar monomer
Point, and then the structure of cross-linking products can be accurately controlled, therefore can obtain the processes for chemically crosslinked polyethylene of fine structure.
In above-mentioned preparation method, it is preferable that the late transition metal catalyst of employing is neutral α-amido imine nickel
Catalyst, its structure is as shown in formula 1 or formula 2:
Wherein, R1For hydrogen, methyl, isopropyl or the tert-butyl group；R2For phenyl, naphthyl or benzyl；L is trimethyl
Phosphine or triphenylphosphine.
In above-mentioned preparation method, it is preferable that R1For isopropyl, R2It is trimethyl-phosphine for benzyl, L.
In above-mentioned preparation method, it is preferable that the α of described neutrality-amido imine nickel catalyst through the following steps that
Preparation:
A, alpha-diimine compound under the reduction of trimethylaluminum compound, reduce one of them imido grpup
Group, obtains the part of α-amido imines；
B, below 0 DEG C in the α corresponding with described catalyst-amido group with imine moiety add KH, be warming up to
20-40 DEG C, react 8-16 hour, the proton on α-amido group with imine moiety removing amido, shape under the effect of KH
Become anion ligand；
C, make the precursor compound of described anion ligand and nickel under conditions of anhydrous and oxygen-free, 20-40 DEG C of reaction
8-12 hour, obtain neutral α-amido imine nickel complex.
In above-mentioned preparation method, it is preferable that for being warming up to 30 DEG C in step a.
In above-mentioned preparation method, it is preferable that the polar monomer of employing is isopropylidene malonate base substituted fall ice
Sheet alkene, its structure as shown in Equation 3:
This polar monomer can be by the abundantest cyclopentadiene monomers and isopropylidene malonate addition in petroleum industry
Reaction obtains, and its synthesis step is as shown in following formula 7:
In above-mentioned preparation method, it is preferable that the method comprises the following steps, the α-amido using above-mentioned neutrality is sub-
Amine Raney nickel, at co-catalyst MAO (MAO), modified methylaluminoxane (MMAO) or two (rings
1,5-diene) nickel (Ni (COD)2) effect under catalyzed ethylene and the substituted ENB copolymerization of isopropylidene malonate base,
Obtain the accurate ethylene copolymer of structure, its course of reaction as shown in Equation 4:
Wherein, the insertion rate of polar group can be controlled by the input amount of polar monomer, the molecular weight of polymer
Can also be controlled by reaction condition such as reaction temperature, ethylene pressure with the coefficient of dispersion.Polymerization in the present invention is anti-
Should carry out under the ethylene pressure of 1-30atm at 20-40 DEG C.Along with the rising of polymerization temperature, copolymer molecule
Amount reduces, and the coefficient of dispersion broadens, and polar monomer insertion rate increases.Along with the increase of ethylene pressure, copolymer molecule
Amount increases, and the coefficient of dispersion narrows, and polar monomer insertion rate reduces.
Isopropylidene malonate in ethylene copolymer shows the highest reactivity worth, and multiple chemistry can be occurred anti-
Should, the ketenes group with high reaction activity can be cracked into by heating isopropylidene malonate, ketenes group is permissible
There is dimerization coupling reaction efficiently.By the dimerization coupling reaction of ketenes group, it becomes possible to obtain the crosslinking of narrow ditribution
Polyethylene.The insertion rate of isopropylidene malonate group can be controlled, it becomes possible to effective by copolyreaction above
Control the site of cross-linking reaction, it is thus possible to accurately control the structure of cross-linking products.
In above-mentioned preparation method, it is preferable that the method uses double screw extruder the extrusion temperature of 110-185 DEG C
To above-mentioned ethylene copolymer extrusion molding under degree, there is chemical crosslink reaction in situ, obtain processes for chemically crosslinked polyethylene,
Its course of reaction is as shown in Equation 5:
The high temperature of the present invention is to be provided by the heater of double screw extruder, the head temperature of the extruder used
For 165-195 DEG C, preferably 185 DEG C.Now, course of reaction is as shown in Equation 6.In the above-mentioned methods, twin-screw
Extruder can be respectively set to the temperature of charging aperture 5 sections from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C,
110 DEG C, but it is not limited to this.
Present invention also offers a kind of processes for chemically crosslinked polyethylene, it is the preparation side by above-mentioned processes for chemically crosslinked polyethylene
Method prepares.
The processes for chemically crosslinked polyethylene that the present invention provides is to be total to by late transition metal catalyst catalyzed ethylene and polar monomer
Poly-and obtain, preparation process can efficiently control site and the number of crosslinking, and then can effectively realize right
The control of processes for chemically crosslinked polyethylene crosslinking degree.
In the preparation process in accordance with the present invention, cross-linking reaction can be carried out under gentle operating condition, and cross-linking efficiency is high, hands over
Co-product structure-controllable.And, the cross-linking method that the present invention provides need not any additive or catalyst, does not exists
Accessory substance or residue affect the performance issue of cross-linking products.Cross-linking reaction has only to the extrusion procedure temperature at polyethylene
Under complete, extrusion molding and cross-linking process synchronously complete；And whole operating procedure is simple, relative to radiation
Crosslinking, is saved greatly energy consumption.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
In order to state ligands and complexes to simplicity and clarity in an embodiment, wherein R1For isopropyl, it is described as follows:
L1: α-amido imine ligand
1: α-amido imine nickel complex
2: α-amido imine nickel complex
Embodiment 1
Synthesis α-amido imine nickel complex 1, specifically follows the steps below:
In a nitrogen atmosphere, in the Schlenk bottle with stirrer, addition 0.63g (1.50mmol) α-amido is weighed sub-
Amine ligand L1, is injected into 20mL anhydrous tetrahydro furan, then adds 80mg KH (2mmol) at 0 DEG C, slow
Slowly being warming up to normal temperature, stir 12 hours, after removing insoluble matter with core filter ball, vacuum evaporation removes solvent, adds
Enter 20mL dichloromethane solvent to dissolve, be subsequently adding 0.33g Ni (CH2Ph)Cl(P(CH3)3)2Compound, reacted
At night, filtering, filter vacuum is concentrated into 5mL, then squeezes into 20mL n-hexane and make complex be precipitated out, and uses core mistake
Filter bulb filters, and vacuum is drained, and obtains the blackish green pulverulent solids of 0.63g, i.e. α-amido imine nickel complex 1, produces
Rate is 65%.
1H NMR(500MHz,C6D6): 7.14 7.02 (m, 5H, Ph), 6.82 (m, 1H, Ph), 6.50 (m, 1H,
Ph)、6.28(m,2H,Ph)、6.00(d,1H,Ph)、5.38(s,2H,CH2)、3.25(sp,2H,CH(Me3)2、2.93(sp,
2H,CH(Me3)2)、2.67(s,6H,Me)、2.07(s,6H,Me)、1.51(s,3H,Me)、1.26(s,3H,Me)、
1.18(s,9H,Me)、1.16-1.02(m,12H,CH(CH3)2)、0.80(s,3H,Me)。
31P NMR(203MHz,C6D6) :-36.0.
Elementary analysis (C39H59N2NiP) theoretical value: C:72.56, H:9.21, N:4.34.Measured value: C:72.40,
H:9.18, N:4.35.
Embodiment 2
Synthesis α-amido imine nickel complex 2, specifically follows the steps below:
By the synthetic method in embodiment 1, replace diacetyl framework counterpart with the part of acenaphthenequinone skeleton, with the product of 68%
Rate prepares α-amido imine nickel complex 2.
1H NMR(500MHz,C6D6): 7.81 (d, 1H, Ph), 7.64 (d, 1H, Ph), 7.31-7.21 (m, 10H, Ph),
7.12(t,1H,Ph,)、7.02(d,2H,Ph)、6.53(d,1H,Ph)、6.36(d,1H,Ph)、5.28(s,2H,
CH2),3.19-3.01(m,4H,CH(iPr)2)、1.96(s,3H,CH3)、1.26(d,3H,CH3)、1.18(d,3H,CH3)、
1.09(s,6H,CH3), 0.80 (s, 9H, Me), 0.95 (t, 6H, CH3)、0.59(s,6H,CH3)。
31P NMR(203MHz,C6D6) :-35.4.
Elementary analysis (C39H59N2NiP) theoretical value: C:68.75, H:8.15, N:3.31.Measured value: C:68.36,
H:8.03, N:3.15.
Embodiment 3
The synthesis substituted ENB of isopropylidene malonate base, specifically follows the steps below:
In the solution of Michaelis acid (Meldrum ' s acid), add formic acid and the pyridine of excess, stir 8 hours, then take out
Dry solvent, removes formic acid and the pyridine of excess, adds acetic acid and the mixed solvent of acetonitrile, be subsequently adding cyclopentadiene list
Body, reacts 24 hours, obtains the substituted norbornene monomer of isopropylidene malonate base.
1H NMR(500MHz,CDCl3): 6.50 (dd, 1H), 5.94 (dd, 1H), 3.46 (s, 1H), 3.15 (s, 1H),
2.55 (dd, 2H), 2.09 (d, J=9Hz, 2H), 1.89 (s, 3H), 1.86 (s, 1H), 1.74 (s, 3H), 1.70 (s, 1H),
1.48 (d, J=8.4Hz, 1H).
13C NMR(125MHz,CDCl3): 169.6,168.1,141.7,130.5,104.9,56.9,56.1,
47.7、43.4、36.9、29.9、28.8。
IR:2977 (w) cm-1、1766(m)cm-1、1731(s)cm-1、1385(m)cm-1、1300(s)cm-1、
1209(m)cm-1、1050(m)cm-1、1020(w)cm-1、983(m)cm-1、911(w)cm-1、789(w)cm-1、
736(m)cm-1。
Elementary analysis (C12H14O4) theoretical value: C:64.85, H:6.35.Measured value: C:64.32, H:6.08.
Embodiment 4
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, the α that in the polymerization bottle of 100mL prepared by addition 6.44mg (10 μm ol) embodiment 1-
Amido imine nickel complex 1,100mL dry toluene, 2mmol isopropylidene malonate base substituted ENB list
Body, 2mmol modified methylaluminoxane, 20 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.78g ethylene copolymer.
Catalysis activity can be calculated by polymers obtained weight.It is computed the catalysis of above-mentioned ethylene copolymer
Activity for 78.0kg PE/ (molNi h), polymer number-average molecular weight be 131.0kg/mol, polydispersity coefficient be 1.51,
Polar monomer insertion rate is 0.45mol%.
Embodiment 5
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 6.44mg (10 μm ol) embodiment 1 preparation-
Amido imine nickel complex 1,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 4mmol
Monomer, 2mmol modified methylaluminoxane, at 20 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.51g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 51.0kg PE/ (molNi h), polymer number-average molecular weight is
86.0kg/mol, polydispersity coefficient are 1.59, polar monomer insertion rate is 0.83mol%.
Embodiment 6
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 6.44mg (10 μm ol) embodiment 1 preparation-
Amido imine nickel complex 1,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 2mmol
Monomer, 2mmol modified methylaluminoxane, at 40 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.68g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 68.0kg PE/ (molNi h), polymer number-average molecular weight is
108.0kg/mol, polydispersity coefficient are 1.62, polar monomer insertion rate is 0.48mol%.
Embodiment 7
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 6.44mg (10 μm ol) embodiment 1 preparation-
Amido imine nickel complex 1,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 4mmol
Monomer, 2mmol modified methylaluminoxane, at 40 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.45g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 45.0kg PE/ (molNi h), polymer number-average molecular weight is
32kg/mol, polydispersity coefficient are 1.78, polar monomer insertion rate is 1.08mol%.
Embodiment 8
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 16.91mg (10 μm ol) embodiment 2 preparation-
Amido imine nickel complex 2,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 2mmol
Monomer, 2mmol modified methylaluminoxane, at 20 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 1.08g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 108kg PE/ (molNi h), polymer number-average molecular weight is
142kg/mol, polydispersity coefficient are 1.58, polar monomer insertion rate is 0.52mol%.
Embodiment 9
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 16.91mg (10 μm ol) embodiment 2 preparation-
Amido imine nickel complex 2,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 4mmol
Monomer, 2mmol modified methylaluminoxane, at 20 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.67g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 67kg PE/ (molNi h), polymer number-average molecular weight is
98kg/mol, polydispersity coefficient are 1.74, polar monomer insertion rate is 0.88mol%.
Embodiment 10
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 16.91mg (10 μm ol) embodiment 2 preparation-
Amido imine nickel complex 2,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 2mmol
Monomer, 2mmol modified methylaluminoxane, at 40 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.96g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 96kg PE/ (molNi h), polymer number-average molecular weight is
112kg/mol, polydispersity coefficient are 1.61, polar monomer insertion rate is 0.68mol%.
Embodiment 11
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the α of addition 16.91mg (10 μm ol) embodiment 2 preparation-
Amido imine nickel complex 2,100mL dry toluene, the substituted ENB of isopropylidene malonate base of 4mmol
Monomer, 2mmol modified methylaluminoxane, at 40 DEG C, be polymerized 1 hour under 5atm ethylene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and filters, and polymer ethanol washs 3 times, vacuum at 60 DEG C
It is dried, obtains 0.56g ethylene copolymer.
The catalysis activity of above-mentioned ethylene copolymer is 56kg PE/ (molNi h), polymer number-average molecular weight is
48kg/mol, polydispersity coefficient are 1.93, polar monomer insertion rate is 1.14mol%.
The reaction condition of embodiment 4-11 and the various parameters of product are as shown in table 1.
Table 1
Embodiment 12
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 4, double screw extruder is from head
Temperature to charging aperture 5 sections arranges and is respectively as follows: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 14MPa, and elongation at break is 350%, brittle temperature
Less than-70 DEG C, Vicat softening point is 93 DEG C.
Embodiment 13
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 5, double screw extruder is from head
Temperature to charging aperture 5 sections is respectively set to: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 21MPa, and elongation at break is 450%, brittle temperature
Less than-70 DEG C, Vicat softening point is 96 DEG C.
Embodiment 14
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 6, double screw extruder is from head
Temperature to charging aperture 5 sections is respectively set to: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 18MPa, and elongation at break is 400%, brittle temperature
Less than-70 DEG C, Vicat softening point is 94 DEG C.
Embodiment 15
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 7, double screw extruder is from head
Temperature to charging aperture 5 sections is respectively set to: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 25MPa, and elongation at break is 500%, brittle temperature
Degree is less than-70 DEG C, and Vicat softening point is 98 DEG C.
Embodiment 16
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 8, double screw extruder is from head
Temperature to charging aperture 5 sections is respectively set to: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 17MPa, and elongation at break is 350%, brittle temperature
Less than-70 DEG C, Vicat softening point is 93 DEG C.
Embodiment 17
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 9, double screw extruder is from head
Temperature to charging aperture 5 sections is respectively set to: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 23MPa, and elongation at break is 490%, brittle temperature
Less than-70 DEG C, Vicat softening point is 97 DEG C.
Embodiment 18
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 10, double screw extruder is from machine
Head is respectively set to the temperature of charging aperture 5 sections: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 20MPa, and elongation at break is 450%, brittle temperature
Less than-70 DEG C, Vicat softening point is 96 DEG C.
Embodiment 19
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 11, double screw extruder is from machine
Head is respectively set to the temperature of charging aperture 5 sections: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 32MPa, and elongation at break is 600%, brittle temperature
Less than-70 DEG C, Vicat softening point is 99 DEG C.
Embodiment 20
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 11, double screw extruder is from machine
Head is respectively set to the temperature of charging aperture 5 sections: 165 DEG C, 155 DEG C, 150 DEG C, 140 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 31MPa, and elongation at break is 500%, brittle temperature
Less than-70 DEG C, Vicat softening point is 94 DEG C.
Embodiment 21
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 11, double screw extruder is from machine
Head is respectively set to the temperature of charging aperture 5 sections: 175 DEG C, 165 DEG C, 150 DEG C, 140 DEG C, 110 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 31MPa, and elongation at break is 540%, brittle temperature
Less than-70 DEG C, Vicat softening point is 95 DEG C.
Embodiment 22
Present embodiments providing the preparation method of a kind of processes for chemically crosslinked polyethylene, it comprises the following steps:
By the ethylene copolymer double screw extruder extrusion molding prepared by embodiment 11, double screw extruder is from machine
Head is respectively set to the temperature of charging aperture 5 sections: 195 DEG C, 185 DEG C, 170 DEG C, 160 DEG C, 120 DEG C；
The hot strength of obtained processes for chemically crosslinked polyethylene is 32MPa, and elongation at break is 560%, brittle temperature
Less than-70 DEG C, Vicat softening point is 96 DEG C.
Claims (6)
1. a preparation method for processes for chemically crosslinked polyethylene, wherein, the method comprises the following steps:
Use the good late transition metal catalyst of polar group tolerance at the bar of 20-40 DEG C and 1-30atm ethylene pressure
Under part, catalyzed ethylene and the copolyreaction of polar monomer, within the reaction time is 1 hour, obtain ethylene copolymer；
At a temperature of the extrusion molding of 110-185 DEG C, prepared ethylene copolymer is carried out extrusion with double screw extruder to make
It is chemically crosslinked, and obtains processes for chemically crosslinked polyethylene；
Described polar monomer is the substituted ENB of isopropylidene malonate base, its structure as shown in Equation 3:
Preparation method the most according to claim 1, wherein, described late transition metal catalyst is neutral α-amine
Base imine nickel catalyst, its structure is as shown in formula 1 or formula 2:
Wherein, R1For hydrogen, methyl, isopropyl or the tert-butyl group；R2For phenyl, naphthyl or benzyl；L be trimethyl-phosphine or
Triphenylphosphine.
Preparation method the most according to claim 2, wherein, R1For isopropyl, R2It is trimethyl for benzyl, L
Phosphine.
Preparation method the most according to claim 2, wherein, the method comprises the following steps:
Use the α-amido imine nickel catalyst of described neutrality, co-catalyst MAO, modified methylaluminoxane and
Under the effect of two (ring 1,5-diene) nickel, catalyzed ethylene and the substituted ENB of isopropylidene malonate base are copolymerized instead
Should, obtain ethylene copolymer, its course of reaction as shown in Equation 4:
Preparation method the most according to claim 4, wherein, the method uses double screw extruder at 110-185 DEG C
Extrusion temperature under described ethylene copolymer carried out extrusion molding, there is chemical crosslink reaction in situ, obtain chemistry friendship
Connection polyethylene, its course of reaction as shown in Equation 5:
6. a processes for chemically crosslinked polyethylene, it is to be obtained by the preparation method described in any one of claim 1-5.
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| "丙二酸亚异丙酯在有机合成中的应用";黄宪;《有机化学》;19861231(第5期);第329-335页 * |
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