CN104151575A - Chemically crosslinked polyethylene and preparation method thereof - Google Patents

Chemically crosslinked polyethylene and preparation method thereof Download PDF

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CN104151575A
CN104151575A CN201410353833.6A CN201410353833A CN104151575A CN 104151575 A CN104151575 A CN 104151575A CN 201410353833 A CN201410353833 A CN 201410353833A CN 104151575 A CN104151575 A CN 104151575A
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preparation
chemically crosslinked
crosslinked polyethylene
ethylene copolymer
processes
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CN104151575B (en
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高海洋
伍青
钱锦华
江如意
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China National Petroleum Corp
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China National Petroleum Corp
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Abstract

The invention provides a chemically crosslinked polyethylene and a preparation method thereof. The method comprises the following steps: carrying out copolymerization reaction on ethylene and polar monomer at 20-40 DEG C under the pressure of 1-30 atm ethylene for less than 1 hour by using a transition metal catalyst with favorable compatibility with the polar monomer, thereby obtaining an ethylene copolymer; and extruding the obtained ethylene copolymer to initiate chemical crosslinking at the extrusion forming temperature of 110-185 DEG C by using a double screw extruder to obtain the chemically crosslinked polyethylene. The invention also provides the chemically crosslinked polyethylene prepared by the preparation method. The preparation method provided by the invention has the advantages of high crosslinking efficiency, controllable structure of the crosslinking product, no influence of the byproduct or residue on the crosslinking product, and simple overall operation steps, and greatly saves the energy consumption.

Description

A kind of processes for chemically crosslinked polyethylene and preparation method thereof
Technical field
The present invention relates to a kind of processes for chemically crosslinked polyethylene and preparation method thereof, specifically belong to the synthetic field of polyolefine material.
Background technology
Polyethylene has good electrical property, toughness and chemical resistant properties, and is easy to processing, cheap, thereby becomes one of general-purpose plastics of turnout and consumption maximum, is widely used in the every field of industrial production and daily life.But poly fusing point is lower, poor heat resistance, physical strength is low, and environmental stress cracking poor-performing, has limited it and has applied more widely.Therefore polyethylene is carried out to emphasis and the key that modification is polyethylene application and theoretical investigation always, crosslinked be one of PE modified comparatively desirable method.Through cross-linking modified, make to have the linear polyethylene of two-dirnentional structure thermoplasticity and change into and there is tridimensional network thermosetting resin.Polyethylene is from linear structure becomes reticulated structure, chemistry and the physical property of material are also significantly improved, the over-all propertieies such as poly mechanical property, environmental stress cracking resistance, resistance to corrosive chemicals energy, creep resistance and electrical property are not only significantly improved, and improve very significantly temperature resistant grade, can make poly heat resisting temperature bring up to more than 100 DEG C from 70 DEG C, thereby greatly widen poly range of application.At present, crosslinked polyethylene has been widely used in the aspects such as tubing, film, CABLE MATERIALS and foam article.
At present, it is two kinds of radiation crosslinking and chemically crosslinkeds that poly main cross-linking method has physical crosslinking, and chemically crosslinked is divided into again crosslinked with silicane, peroxide crosslinking.Radiation crosslinking and peroxide crosslinking method are all by energetic ray or add peroxide initiator to produce macromolecular polyethylene free radical, then produce crosslinked by the linked reaction between molecular chain.Crosslinked with silicane is in Polyethylene Chain, to introduce silane group by grafting (can be divided into again single stage method and two-step approach) or copolymerization, then forms crosslinking structure by hydrolysis.Although these crosslinking methods have successfully been obtained application, still there is operation condition harshness, energy consumption is high, or the problem that exists material property that additive causes to reduce.Especially it should be noted that the molecular structure that is difficult to accurately control polymerisate by the mode of radical crosslinking, thereby also just cannot accurately control the physicals of final material.
Current ethylene-silane crosslinking copolymerization method is by controlling the input of silane copolymer monomer, can realize the distribution of silane rule in Polyethylene Chain, demonstrate relatively remarkable advantage, but its main drawback is that crosslinking reaction speed is slower, and the existence of catalyzer dynamics model causes the molecular weight distribution of ethylene copolymer wider.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of processes for chemically crosslinked polyethylene, the method can be controlled the molecular structure of cross-linking products effectively, and then accurately controls the physicals of crosslinked polyethylene; This cross-linking method, without any need for additive or catalyzer, does not exist residue to affect the performance issue of cross-linking products simultaneously; And whole operation steps is simple, widely energy efficient.
The processes for chemically crosslinked polyethylene that the present invention also provides above-mentioned preparation method to prepare.
For achieving the above object, the invention provides a kind of preparation method of processes for chemically crosslinked polyethylene, wherein, the method comprises the following steps:
Use the copolyreaction to the good late transition metal catalyst of polar group tolerance catalyzed ethylene and polar monomer under the condition of 20-40 DEG C and 1-30atm ethylene pressure, the reaction times is in 1 hour, obtains ethylene copolymer;
Prepared ethylene copolymer issues biochemical crosslinked 110-185 DEG C of extrusion moulding temperature with twin screw extruder, obtain the meticulous processes for chemically crosslinked polyethylene of structure.
Can, by controlling the insertion rate of polar monomer, effectively control the site of crosslinking reaction, and then can accurately control the structure of cross-linking products in the method for the invention, therefore can obtain the meticulous processes for chemically crosslinked polyethylene of structure.
In above-mentioned preparation method, preferably, the late transition metal catalyst of employing is neutral α-amido imines nickel catalyzator, its structure suc as formula 1 or formula 2 shown in:
Wherein, R 1for hydrogen, methyl, sec.-propyl or the tertiary butyl; R 2for phenyl, naphthyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
In above-mentioned preparation method, preferably, R 1for sec.-propyl, R 2for benzyl, L are trimethyl-phosphine.
In above-mentioned preparation method, preferably, α-amido imines nickel catalyzator of described neutrality is prepared by following steps:
The compound of a, alpha-diimine, under the reductive action of trimethyl aluminium compound, reduces one of them imine group, obtains the part of α-amido imines;
B, below 0 DEG C, in the α-amido group with imine moiety corresponding with described catalyzer, add KH, be warming up to 20-40 DEG C, reaction 8-16 hour, under the effect of KH, α-amido group with imine moiety removes the proton on amido, forms anion ligand;
C, make the precursor compound of described anion ligand and nickel under the condition of anhydrous and oxygen-free, 20-40 DEG C of reaction 8-12 hour, obtains neutral α-amido imine nickel complex.
In above-mentioned preparation method, preferably, in step a for being warming up to 30 DEG C.
In above-mentioned preparation method, preferably, the polar monomer of employing be isopropylidene malonate base replace norbornylene, its structure as shown in Equation 3:
This polar monomer can obtain by cyclopentadiene monomers very abundant in petroleum industry and isopropylidene malonate addition reaction, and its synthesis step is as shown in the formula shown in 7:
In above-mentioned preparation method, preferably, the method comprises the following steps, use α-amido imines nickel catalyzator of above-mentioned neutrality, at promotor methylaluminoxane (MAO), modified methylaluminoxane (MMAO) or two (ring 1,5-diene) nickel (Ni (COD) 2) effect under the norbornylene copolymerization that replaces of catalyzed ethylene and isopropylidene malonate base, obtain out the accurate ethylene copolymer of structure, its reaction process as shown in Equation 4:
Wherein, the insertion rate of polar group can be controlled by the input amount of polar monomer, and the molecular weight of polymkeric substance and dispersion coefficient also can be controlled as temperature of reaction, ethylene pressure by reaction conditions.Polyreaction in the present invention can be at 20-40 DEG C, under the ethylene pressure of 1-30atm, carries out.Along with the rising of polymerization temperature, molecular weight of copolymer reduces, and dispersion coefficient broadens, and polar monomer insertion rate increases.Along with the increase of ethylene pressure, molecular weight of copolymer increases, and dispersion coefficient narrows, and polar monomer insertion rate reduces.
Isopropylidene malonate in ethylene copolymer has demonstrated very high reactivity worth, can there is number of chemical reaction, can be cracked into the ketenes group with high reaction activity by heating isopropylidene malonate, can there is dimerization linked reaction in ketenes group efficiently.By the dimerization linked reaction of ketenes group, just can obtain the crosslinked polyethylene of narrow distribution.Can control the insertion rate of isopropylidene malonate group by copolyreaction above, just can effectively control the site of crosslinking reaction, thereby can accurately control the structure of cross-linking products.
In above-mentioned preparation method, preferably, the method use twin screw extruder under the extrusion temperature of 110-185 DEG C to above-mentioned ethylene copolymer extrusion moulding, original position generation chemical crosslink reaction, obtains processes for chemically crosslinked polyethylene, its reaction process as shown in Equation 5:
High temperature of the present invention is to be provided by the heating unit of twin screw extruder, and the head temperature of the forcing machine adopting is 165-195 DEG C, is preferably 185 DEG C.Now, reaction process as shown in Equation 6.In aforesaid method, twin screw extruder can be set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C, but be not limited to this.
The present invention also provides a kind of processes for chemically crosslinked polyethylene, and it is to prepare by the preparation method of above-mentioned processes for chemically crosslinked polyethylene.
Processes for chemically crosslinked polyethylene provided by the invention obtains by late transition metal catalyst catalyzed ethylene and polar monomer copolymerization, in preparation process, crosslinked site and number can be effectively controlled, and then the control to processes for chemically crosslinked polyethylene crosslinking degree can be effectively realized.
In preparation method of the present invention, crosslinking reaction can be carried out under gentle operational condition, and cross-linking efficiency is high, and cross-linking products structure is controlled.And cross-linking method provided by the invention, without any need for additive or catalyzer, does not exist by product or residue to affect the performance issue of cross-linking products.Crosslinking reaction only need to complete under poly extrusion molding service temperature, and extrusion moulding and cross-linking process synchronously complete; And whole operation steps is simple, with respect to radiation crosslinking, save widely energy consumption.
Embodiment
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
In order concisely clearly to explain in an embodiment ligands and complexes, wherein R 1for sec.-propyl, be described as follows:
L1: α-amido imine ligand
1: α-amido imine nickel complex
2: α-amido imine nickel complex
Embodiment 1
Synthetic α-amido imine nickel complex 1, specifically carries out according to following steps:
Under nitrogen atmosphere, to weighing and add 0.63g (1.50mmol) α-amido imine ligand L1 in the Schlenk bottle with stirrer, be injected into 20mL anhydrous tetrahydro furan, then at 0 DEG C, add 80mg KH (2mmol), be slowly warming up to normal temperature, stir 12 hours, remove after insolubles with core filter ball, vacuum-evaporation, except desolventizing, adds 20mL dichloromethane solvent to dissolve, and then adds 0.33g Ni (CH 2ph) Cl (P (CH 3) 3) 2compound, reaction is spent the night, and filters, and filtrate vacuum concentration is to 5mL, then squeezes into 20mL normal hexane title complex is precipitated out, and filters with core filter ball, and vacuum is drained, and obtains the blackish green pulverulent solids of 0.63g, i.e. α-amido imine nickel complex 1, productive rate is 65%.
1H?NMR(500MHz,C 6D 6)：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,CH 2)、3.25(sp,2H,CH(Me 3) 2、2.93(sp,2H,CH(Me 3) 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(CH 3) 2)、0.80(s,3H,Me)。
31P?NMR(203MHz,C 6D 6)：-36.0。
Ultimate analysis (C 39h 59n 2niP) theoretical value: C:72.56, H:9.21, N:4.34.Measured value: C:72.40, H:9.18, N:4.35.
Embodiment 2
Synthetic α-amido imine nickel complex 2, specifically carries out according to following steps:
Press the synthetic method in embodiment 1, with the part replacement dimethyl diketone skeleton part of acenaphthenequinone skeleton, prepare α-amido imine nickel complex 2 with 68% productive rate.
1H?NMR(500MHz,C 6D 6)：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,CH 2),3.19-3.01(m,4H,CH( iPr) 2)、1.96(s,3H,CH 3)、1.26(d,3H,CH 3)、1.18(d,3H,CH 3)、1.09(s,6H,CH 3)、0.80(s,9H,Me)，0.95(t,6H,CH 3)、0.59(s,6H,CH 3)。
31P?NMR(203MHz,C 6D 6)：-35.4。
Ultimate analysis (C 39h 59n 2niP) 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 norbornylene that synthetic isopropylidene malonate base replaces, specifically carries out according to following steps:
In the solution of Michaelis acid (Meldrum ' s acid), add excessive formic acid and pyridine, stir 8 hours, then drain solvent, remove excessive formic acid and pyridine, add the mixed solvent of acetic acid and acetonitrile, then add cyclopentadiene monomers, react 24 hours, obtain the norbornene monomer that isopropylidene malonate base replaces.
1H?NMR(500MHz,CDCl 3)：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,CDCl 3)：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。
Ultimate analysis (C 12h 14o 4) theoretical value: C:64.85, H:6.35.Measured value: C:64.32, H:6.08.
Embodiment 4
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, the norbornene monomer, the 2mmol modified methylaluminoxane that replace to the α-amido imine nickel complex 1 that adds in the polymerization bottle of 100mL 6.44mg (10 μ mol) embodiment 1 to prepare, 100mL dry toluene, 2mmol isopropylidene malonate base, polymerization 1 hour under 20 DEG C, 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.78g ethylene copolymer.
Catalytic activity can calculate by polymers obtained weight.The catalytic activity of above-mentioned ethylene copolymer is that 78.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 131.0kg/mol, polydispersity coefficient are 1.51, polar monomer insertion rate is 0.45mol% as calculated.
Embodiment 5
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 1 prepared by 6.44mg (10 μ mol) embodiment 1,100mL dry toluene, 4mmol to replace, at 20 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.51g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 51.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 86.0kg/mol, polydispersity coefficient are 1.59, polar monomer insertion rate is 0.83mol%.
Embodiment 6
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 1 prepared by 6.44mg (10 μ mol) embodiment 1,100mL dry toluene, 2mmol to replace, at 40 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.68g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 68.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 108.0kg/mol, polydispersity coefficient are 1.62, polar monomer insertion rate is 0.48mol%.
Embodiment 7
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 1 prepared by 6.44mg (10 μ mol) embodiment 1,100mL dry toluene, 4mmol to replace, at 40 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.45g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 45.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 32kg/mol, polydispersity coefficient are 1.78, polar monomer insertion rate is 1.08mol%.
Embodiment 8
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 2 prepared by 16.91mg (10 μ mol) embodiment 2,100mL dry toluene, 2mmol to replace, at 20 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 1.08g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 108kg PE/ (molNih), polymkeric substance number-average molecular weight are that 142kg/mol, polydispersity coefficient are 1.58, polar monomer insertion rate is 0.52mol%.
Embodiment 9
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 2 prepared by 16.91mg (10 μ mol) embodiment 2,100mL dry toluene, 4mmol to replace, at 20 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.67g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 67kg PE/ (molNih), polymkeric substance number-average molecular weight are that 98kg/mol, polydispersity coefficient are 1.74, polar monomer insertion rate is 0.88mol%.
Embodiment 10
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 2 prepared by 16.91mg (10 μ mol) embodiment 2,100mL dry toluene, 2mmol to replace, at 40 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.96g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 96kg PE/ (molNih), polymkeric substance number-average molecular weight are that 112kg/mol, polydispersity coefficient are 1.61, polar monomer insertion rate is 0.68mol%.
Embodiment 11
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, the norbornene monomer, the 2mmol modified methylaluminoxane that add the isopropylidene malonate base of α-amido imine nickel complex 2 prepared by 16.91mg (10 μ mol) embodiment 2,100mL dry toluene, 4mmol to replace, at 40 DEG C, polymerization 1 hour under 5atm ethylene pressure;
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 DEG C, obtains 0.56g ethylene copolymer.
The catalytic activity of above-mentioned ethylene copolymer is that 56kg PE/ (molNih), polymkeric substance number-average molecular weight are that 48kg/mol, polydispersity coefficient are 1.93, polar monomer insertion rate is 1.14mol%.
The various parameters of the reaction conditions of embodiment 4-11 and product are as shown in table 1.
Table 1
Embodiment 12
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 4 twin screw extruder extrusion moulding, twin screw extruder is respectively to the temperature setting of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 14MPa, and elongation at break is 350%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 93 DEG C.
Embodiment 13
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 5 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 21MPa, and elongation at break is 450%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 96 DEG C.
Embodiment 14
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 6 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 18MPa, and elongation at break is 400%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 94 DEG C.
Embodiment 15
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 7 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 25MPa, and elongation at break is 500%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 98 DEG C.
Embodiment 16
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 8 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 17MPa, and elongation at break is 350%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 93 DEG C.
Embodiment 17
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 9 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 23MPa, and elongation at break is 490%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 97 DEG C.
Embodiment 18
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 10 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 20MPa, and elongation at break is 450%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 96 DEG C.
Embodiment 19
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 11 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 185 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 32MPa, and elongation at break is 600%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 99 DEG C.
Embodiment 20
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 11 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 165 DEG C, 155 DEG C, 150 DEG C, 140 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 31MPa, and elongation at break is 500%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 94 DEG C.
Embodiment 21
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 11 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 175 DEG C, 165 DEG C, 150 DEG C, 140 DEG C, 110 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 31MPa, and elongation at break is 540%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 95 DEG C.
Embodiment 22
The present embodiment provides a kind of preparation method of processes for chemically crosslinked polyethylene, and it comprises the following steps:
By ethylene copolymer prepared embodiment 11 twin screw extruder extrusion moulding, twin screw extruder is set to respectively to the temperature of 5 sections of opening for feeds from head: 195 DEG C, 185 DEG C, 170 DEG C, 160 DEG C, 120 DEG C;
The tensile strength of the processes for chemically crosslinked polyethylene obtaining is 32MPa, and elongation at break is 560%, and embrittlement temperature is less than-70 DEG C, and Vicat softening point is 96 DEG C.

Claims (7)

1. a preparation method for processes for chemically crosslinked polyethylene, wherein, the method comprises the following steps:
Use the copolyreaction to the good late transition metal catalyst of polar group tolerance catalyzed ethylene and polar monomer under the condition of 20-40 DEG C and 1-30atm ethylene pressure, the reaction times is in 1 hour, obtains ethylene copolymer;
Prepared ethylene copolymer is extruded and made it that chemically crosslinked occur at the extrusion moulding temperature of 110-185 DEG C with twin screw extruder, obtain processes for chemically crosslinked polyethylene.
2. preparation method according to claim 1, wherein, described late transition metal catalyst is neutral α-amido imines nickel catalyzator, its structure suc as formula 1 or formula 2 shown in:
Wherein, R 1for hydrogen, methyl, sec.-propyl or the tertiary butyl; R 2for phenyl, naphthyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
3. preparation method according to claim 2, wherein, R 1for sec.-propyl, R 2for benzyl, L are trimethyl-phosphine.
4. preparation method according to claim 1, wherein, described polar monomer be isopropylidene malonate base replace norbornylene, its structure as shown in Equation 3:
5. preparation method according to claim 2, wherein, the method comprises the following steps:
Use α-amido imines nickel catalyzator of described neutrality, at promotor methylaluminoxane, modified methylaluminoxane and two (ring 1,5-diene) catalyzed ethylene and isopropylidene malonate base replace under the effect of nickel norbornylene generation copolyreaction, obtain ethylene copolymer, its reaction process as shown in Equation 4:
6. preparation method according to claim 5, wherein, the method is used twin screw extruder under the extrusion temperature of 110-185 DEG C, described ethylene copolymer to be carried out to extrusion moulding, original position generation chemical crosslink reaction, obtain processes for chemically crosslinked polyethylene, its reaction process as shown in Equation 5:
7. a processes for chemically crosslinked polyethylene, it is to obtain by the preparation method described in claim 1-6 any one.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745410A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 Preparation method of in-situ crosslinked polyethylene with high thermal stability

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087677A (en) * 1989-07-08 1992-02-11 Hoechst Aktiengesellschaft Process for the preparation of cycloolefin polymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087677A (en) * 1989-07-08 1992-02-11 Hoechst Aktiengesellschaft Process for the preparation of cycloolefin polymers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JANIAK ET AL.: ""Metal catalysts for the vinyl polymerization of norbornene"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 *
黄宪: ""丙二酸亚异丙酯在有机合成中的应用"", 《有机化学》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745410A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 Preparation method of in-situ crosslinked polyethylene with high thermal stability

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