CN108467443A - A kind of new urea case linear low density polyethylene and preparation method thereof - Google Patents
A kind of new urea case linear low density polyethylene and preparation method thereof Download PDFInfo
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Abstract
A kind of new urea case linear low density polyethylene provided by the invention and preparation method thereof, by ethylene under the catalysis of catalyst for oligomerization, catalyst for copolymerization and co-catalyst in-situ polymerization and obtain, wherein, catalyst for oligomerization is loading type iron series catalysts, catalyst for copolymerization is carrier zirconium series catalysts, and co-catalyst is methylaluminoxane MAO.To have the characteristics that low melting point, low-density and excellent in mechanical performance.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, being that a kind of new urea case linea low density is poly-
Ethylene and preparation method thereof.
Background technology
Environment is not only polluted in the discharge of vehicle exhaust, but also endangers health of people, can all install selection on vehicle thus
Property catalysis system, using aqueous solution of urea as reducing agent by the conversion of nitrogen oxides in diesel exhaust gas as nitrogen.And it stores
Aqueous solution of urea must use urea box, and urea box is generally made by linear low density polyethylene (LLDPE) by rotational molding technique,
The quality of LLDPE affects the performance of urea box.
Catalyst has played important function in the preparation of LLDPE, and which determine the polymerization behavior of LLDPE, polymer beads
Form and polymer architecture and performance.It is described in the patent of invention of application number CN201010515021.9 a kind of linear low
Density polyethylene, using ethylene as raw material, bis (imino) pyridines iron, cobalt complex are catalyst for oligomerization major catalyst, and β-two is sub-
Amine titanium complex is catalyst for copolymerization major catalyst, and main group metal organic compound is unique co-catalyst, organizes work(in pairs
Energy catalyst system, one kettle way in-situ copolymerization obtain, and expensive alpha-olefin need not be added by having, and simplify production stream
Journey；Major catalyst preparation method is simple, and reaction condition is mild, and catalyst cost is relatively low；It is difunctional using single co-catalyst
There is no interfering with each other between catalyst, co-catalyst dosage is few；The features such as catalyzed ethylene polymerization activity is high, however the catalyst
It is higher uncontrollable in initial reaction stage activity, and there are serious glutinous kettle phenomenon, it is unfavorable for industrial applications.In application number
A kind of caltalyst of in-situ copolymerizing linear low-density polyethylene is described in the patent of invention of CN200510086486.6
System, by catalyst for oligomerization, (homogeneous or support type alpha-diimine pyridine Fe-series catalyst and alkylaluminoxane help the catalyst system
Catalyst) and catalyst for copolymerization (Titanium series catalyst and alkyl aluminum or alkylaluminoxane promoter), it is catalyzed the linear of generation
Low density polyethylene (LDPE) has the characteristics that the branch of low melting point, low-density, higher co-monomer insertion rate and different length, however
LLDPE made of the catalyst system and catalyzing does not have excellent mechanical property, to influence its practical application.
Invention content
The main purpose of the present invention is to provide a kind of new urea case linear low density polyethylene and preparation method thereof,
In view of the deficiencies of the prior art, have the characteristics that low melting point, low-density and excellent in mechanical performance.
To achieve the above objectives, the technical solution adopted by the present invention is a kind of new urea case linear low density polyethylene
Material by ethylene under the catalysis of catalyst for oligomerization, catalyst for copolymerization and co-catalyst in-situ polymerization and obtain, wherein oligomerisation is urged
Agent is loading type iron series catalysts, and catalyst for copolymerization is carrier zirconium series catalysts, and co-catalyst is methylaluminoxane MAO.
The co-catalyst is that methylaluminoxane MAO, MAO are lewis acid, metallocene compound can be made to be alkylated, and is produced
Raw cation activity center, at the same can also be in removing system impurity, so that cation activity central stabilizer is existed.
An embodiment according to the present invention, the catalyst for oligomerization are that metal-organic framework material/Fe (Salen) is heterogeneous
Catalyst, Fe (Salen) are immobilized in metal-organic framework material in the method for encapsulation.
Catalyst for oligomerization has played important function to the preparation of novel linear low-density polyethylene material.Salen passes through " in bottle
The mode of shipbuilding " is encapsulated into the duct of metal-organic framework material, and then, four water frerrous chlorides and the Salen in duct are anti-
It answers, forms metal-organic framework material/Fe (Salen) heterogeneous catalysis.
Preferably, the catalyst for copolymerization is metal-organic framework material/metallocene heterogeneous catalysis, metallocene chemical combination
Object is immobilized in metal-organic framework material in the method impregnated.
Preferably, the metallocene compound is Me2Si(Ind)2ZrCl2With Et (Ind)2ZrCl2One or both of,
Metallocene compound Me2Si(Ind)2ZrCl2Or Et (Ind)2ZrCl2Metal-organic framework material is arrived so that the method for dipping is immobilized
On, form metal-organic framework material/metallocene heterogeneous catalysis.
A kind of preparation method of novel linear low-density polyethylene material, specific preparation method are as follows：
Solvent hexamethylene is added in the autoclave with stirring S100, is warming up to 90-110 DEG C, stirs 10-
Hexamethylene is discharged after 30min；
S200 is kept for 90-110 DEG C and vacuumizes 0.5-2h, leads to nitrogen displacement three times, and ethylene displacement is primary, cools to required temperature
Degree opens ethylene valve, sequentially adds solvent hexamethylene and co-catalyst MAO, 10- is stirred under the conditions of 1500-3500r/min
Catalyst for oligomerization and catalyst for copolymerization are added after 20min, so that ethylene pressure is risen to 1*10 rapidly5Pa, and kept by surge tank
Ethylene pressure proceeds by in-situ copolymerization；
S300 closes ethylene valve after reacting 0.5-3h, stops reaction, and product is washed with aqueous hydrochloric acid solution, water and ethyl alcohol respectively
Afterwards, it is dried in vacuo, finished product.
Preferably, the addition of co-catalyst MAO accounts for the 0.4%-0.8% of solvent toluene quality, co-catalyst and oligomerisation
The molar ratio of catalyst is 200-400:1, the molar ratio of co-catalyst and catalyst for copolymerization is 200-300:1.
An embodiment according to the present invention, the catalyst for oligomerization preparation method, includes the following steps：
Metal-organic framework material and absolute ethyl alcohol are hybridly prepared into the suspension that mass fraction is 30-60% by S211
Afterwards, salicylide is added thereto, 10-30min is stirred under the conditions of 1000-2500r/min, mixed liquor is made, wherein salicylide
Addition account for the 50-80% of metal-organic framework material quality；
Ethylenediamine is added into the mixed liquor in S212, is heated to 60-80 DEG C, is reacted under the conditions of 500-1500r/min
The first reaction solution is made in 1-3h, wherein the molar ratio of salicylide and ethylenediamine is 1-3:1；
S213 is filtered by vacuum after being cooled to room temperature first reaction solution, and filter cake is placed in drying box in 50-80 DEG C
Under the conditions of dry 6-24h, the filter cake after drying is crushed to obtain intermediary metal organic framework materials/Salen compounds；
The metal-organic framework material/Salen compounds are hybridly prepared into mass fraction by S214 with absolute methanol
After the suspension of 20-50%, four water frerrous chlorides and natrium carbonicum calcinatum is added, 50-70 DEG C is heated to, in 500-1500r/min
Under the conditions of react 2-6h, be made the second reaction solution, wherein the addition of four water frerrous chlorides account for metal-organic framework material/
The addition of the 20-60% of Salen compound quality, natrium carbonicum calcinatum account for metal-organic framework material/Salen compound quality
0.2-1.5%；
S215 is filtered by vacuum after being cooled to room temperature second reaction solution, and filter cake is placed in drying box in 50-80 DEG C
Under the conditions of dry 6-24h, the filter cake after drying is crushed to obtain metal-organic framework material/Fe (Salen) heterogeneous catalysis,
It is spare.
An embodiment according to the present invention, the preparation method of the catalyst for copolymerization include the following steps：
After metal-organic framework material and toluene are hybridly prepared into the suspension that mass fraction is 30-60% by S221, to
Metallocene compound is wherein added, is heated to 50-100 DEG C and is stirred under the conditions of 500-1500r/min, until solvent is evaporated completely
Entirely, wherein the addition of metallocene compound accounts for the 50-80% of metal-organic framework material quality；
Obtained solid is placed in drying box under the conditions of 50-80 DEG C dry 2-6h by S222, by the solid abrasive after drying
Metal-organic framework material/metallocene heterogeneous catalysis is obtained, it is spare.
An embodiment according to the present invention, the metal-organic framework material be MIL-100, be by Iron cluster and
Benzenetricarboxylic acid ligand assembles, and preparation method includes step：
The ferric chloride hexahydrate of corrresponding quality part is dissolved in deionized water by S231, is stirred fully dissolving, is added equal benzene
Tricarboxylic acid continues stirring 0.5 hour, is packed into 130 DEG C of autoclave and reacts 72 hours；
S232 is cooled to room temperature after reaction, is washed three times with hot water and methanol, and is handled 12 hours in boiling methanol,
150 DEG C are dried in vacuo 12 hours, obtain metal-organic framework material MIL-100, spare.
Wherein, the preparation of metal-organic framework material can be also made by microwave assisting method or mechanical mixing method.
The present invention compared with the existing technology, has the following advantages and beneficial effect：
(1) since the large space steric hindrance substituent group at catalyst for oligomerization ortho position is restricted to the β-H elimination reactions in activated centre
Effect, with the reduction of catalyst for oligomerization Salen molecular configuration space steric effects, β-H eliminate aggravation, lead to catalyst for oligomerization
Have to linear alpha-alkene more highly selective；Metal-organic framework material contains undersaturated metal coordination site so that metal is organic
Frame material can be used as Lewis acid catalysis center, cooperate with co-catalyst MAO, metallocene compound is facilitated to be alkylated, and generate sun
Ion activity center, stable cationic activated centre；Meanwhile metal-organic framework material large specific surface area, active site can
Contact is big, effect of the ethylene using the duct of metal-organic framework material as " microreactor " in catalyst for oligomerization activated centre
Lower generation high-purity linear alpha-alkene；Catalyst for copolymerization is single active center's metallocene compound, and copolymerization performance is excellent, then exists
Under the action of carrier metal organic framework materials and co-catalyst, linear alpha-alkene is set to be closed with in-situ copolymerization, directly by line
Property alpha-olefin is inserted on the polymer chain increased, generates LLDPE step by step.
(2) catalyst for oligomerization and catalyst for copolymerization are all loaded catalyst, and such design not only reduces co-catalysis
The dosage of agent reduces interfering with each other between catalyst, improves the catalytic activity of catalyst system, and efficiently control
The activity of initial reaction stage, eliminates serious glutinous kettle phenomenon；
(3) on the one hand catalyst carrier cooperates with co-catalyst MAO, and metallocene compound is facilitated to be alkylated, and generates cation
On the other hand activated centre, stable cationic activated centre are used as " microreactor " to provide more active sites for catalysis reaction
Point.
Specific implementation mode
It is described below for disclosing the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Chemical reagent used in the embodiment of the present invention is purchased in market：20% first of co-catalyst methylaluminoxane MAO Chemturas
Benzole soln is purchased from Nanjing Guo Chen Chemical Co., Ltd.s；Metallocene compound Me2Si(Ind)2ZrCl2With Et (Ind)2ZrCl2Purchase
From in Sigma-Aldrich；The production of ethylene Yangtze petrochemical industry is purchased from Nanjing Yao Jiang trade Co., Ltds；Z-N catalyst is purchased from three
Well Chemical Co., Ltd.；Other chemical reagent are purchased from Sinopharm Chemical Reagent Co., Ltd..
Embodiment 1
The specific preparation method of metal-organic framework material MIL-100 is as follows：
2.7g ferric chloride hexahydrates are dissolved in 50mL deionized waters, fully dissolving is stirred, adds the equal benzene front threes of 1.39g
Acid continues to stir 0.5h；Above-mentioned solution is packed into 130 DEG C of reaction 72h of autoclave again；It waits for being cooled to room temperature after reaction, use
Hot water and methanol are washed three times, and 12h is boiled in boiling methanol, and 150 DEG C of vacuum drying 12h obtain metal-organic framework material MIL-
100。
Catalyst for oligomerization is metal-organic framework material/Fe (Salen) heterogeneous catalysis, and specific preparation method is such as
Under：
After metal-organic framework material and absolute ethyl alcohol to be hybridly prepared into the suspension that mass fraction is 30%, thereto
Salicylide is added, stirs 30min under the conditions of 1000r/min, wherein the addition of salicylide accounts for metal-organic framework material matter
The 50% of amount；
Ethylenediamine is added into above-mentioned mixed liquor, is heated to 60 DEG C and reacts 3h under the conditions of 500r/min, wherein salicylide
Molar ratio with ethylenediamine is 1:1；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 50 DEG C
It is dry for 24 hours, the filter cake after drying is crushed to obtain intermediary metal organic framework materials/Salen compounds；
Above-mentioned gained metal-organic framework material/Salen compounds are hybridly prepared into mass fraction with absolute methanol is
After 20% suspension, four water frerrous chlorides and natrium carbonicum calcinatum is added, is heated to 50 DEG C and reacts 6h under the conditions of 500r/min,
Wherein, the addition of four water frerrous chlorides accounts for the 20% of metal-organic framework material/Salen compound quality, natrium carbonicum calcinatum
Addition account for the 0.2% of metal-organic framework material/Salen compound quality；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 50 DEG C
It is dry to crush the filter cake after drying to obtain metal-organic framework material/Fe (Salen) heterogeneous catalysis for 24 hours, it is spare.
Catalyst for copolymerization is metal-organic framework material/metallocene heterogeneous catalysis, and specific preparation method is as follows：
After metal-organic framework material and toluene to be hybridly prepared into the suspension that mass fraction is 30%, it is added thereto
Metallocene compound Me2Si(Ind)2ZrCl2, it is heated to 50 DEG C and is stirred under the conditions of 500r/min, until solvent volatilization is complete,
Wherein, the addition of metallocene compound accounts for the 50% of metal-organic framework material quality；
Obtained solid is placed in drying box under the conditions of 50 DEG C dry 6h, the solid abrasive after drying, which is obtained metal, to be had
Machine frame frame material/metallocene heterogeneous catalysis, it is spare.
A kind of specific preparation method of new urea case linear low density polyethylene is as follows：
Solvent hexamethylene is added in the autoclave with stirring, is warming up to 90 DEG C, is stirred hexamethylene after 30min
Discharge is kept for 90 DEG C and vacuumizes 2h；Three times, ethylene displacement is primary for logical nitrogen displacement；Required temperature is cooled to, ethylene valve is opened,
Sequentially add solvent hexamethylene and co-catalyst MAO, under the conditions of 1500r/min stir 20min after be added catalyst for oligomerization and
Catalyst for copolymerization makes ethylene pressure rise to 1*10 rapidly5Pa, and ethylene pressure is kept by surge tank, proceed by ethylogen
Position copolymerization；Ethylene valve is closed after reacting 3h, stops reaction, wherein the addition of co-catalyst MAO accounts for solvent toluene quality
0.4%, the molar ratio of co-catalyst and catalyst for oligomerization is 200:1, the molar ratio of co-catalyst and catalyst for copolymerization is 200:
1；After product is washed with aqueous hydrochloric acid solution, water and ethyl alcohol respectively, vacuum drying obtains novel linear low-density polyethylene material.
Embodiment 2
The preparation method is the same as that of Example 1 by metal-organic framework material MIL-100.
Catalyst for oligomerization is metal-organic framework material/Fe (Salen) heterogeneous catalysis, and specific preparation method is such as
Under：
After metal-organic framework material and absolute ethyl alcohol to be hybridly prepared into the suspension that mass fraction is 60%, thereto
Salicylide is added, stirs 10min under the conditions of 2500r/min, wherein the addition of salicylide accounts for metal-organic framework material matter
The 80% of amount；
Ethylenediamine is added into above-mentioned mixed liquor, is heated to 80 DEG C and reacts 1h under the conditions of 1500r/min, wherein bigcatkin willow
The molar ratio of aldehyde and ethylenediamine is 3:1；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 80 DEG C
Dry 6h crushes the filter cake after drying to obtain intermediary metal organic framework materials/Salen compounds；
Above-mentioned gained metal-organic framework material/Salen compounds are hybridly prepared into mass fraction with absolute methanol is
After 250% suspension, four water frerrous chlorides and natrium carbonicum calcinatum is added, is heated to 70 DEG C and is reacted under the conditions of 1500r/min
2h, wherein the addition of four water frerrous chlorides accounts for the 60% of metal-organic framework material/Salen compound quality, Carbon Dioxide
The addition of sodium accounts for the 0.2% of metal-organic framework material/Salen compound quality；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 80 DEG C
Dry 6h crushes the filter cake after drying to obtain metal-organic framework material/Fe (Salen) heterogeneous catalysis, spare.
Catalyst for copolymerization is metal-organic framework material/metallocene heterogeneous catalysis, and specific preparation method is as follows：
After metal-organic framework material and toluene to be hybridly prepared into the suspension that mass fraction is 60%, it is added thereto
Metallocene compound Me2Si(Ind)2ZrCl2, it is heated to 80 DEG C and is stirred under the conditions of 1500r/min, until solvent volatilization is complete,
Wherein, the addition of metallocene compound accounts for the 80% of metal-organic framework material quality；
Obtained solid is placed in drying box under the conditions of 80 DEG C dry 2h, the solid abrasive after drying, which is obtained metal, to be had
Machine frame frame material/metallocene heterogeneous catalysis, it is spare.
A kind of specific preparation method of new urea case linear low density polyethylene is as follows：
Solvent hexamethylene is added in the autoclave with stirring, is warming up to 100 DEG C, is stirred hexamethylene after 30min
Alkane is discharged, and is kept for 100 DEG C and vacuumizes 0.5h；Three times, ethylene displacement is primary, cools to required temperature, opens second for logical nitrogen displacement
Alkene valve sequentially adds solvent hexamethylene and co-catalyst MAO, and oligomerization catalysis is added after stirring 10min under the conditions of 3500r/min
Agent and catalyst for copolymerization, make ethylene pressure rise to 1*10 rapidly5Pa, and ethylene pressure is kept by surge tank, proceed by second
Alkene in-situ copolymerization；Ethylene valve is closed after reacting 2h, stops reaction.Wherein, the addition of co-catalyst MAO accounts for solvent toluene quality
0.4%, the molar ratio of co-catalyst and catalyst for oligomerization is 200:1, the molar ratio of co-catalyst and catalyst for copolymerization is
200:1.After product is washed with aqueous hydrochloric acid solution, water and ethyl alcohol respectively, vacuum drying obtains urea box novel linear low-density
Polythene material.
Embodiment 3
The preparation method is the same as that of Example 1 by metal-organic framework material MIL-100.
Catalyst for oligomerization is metal-organic framework material/Fe (Salen) heterogeneous catalysis, and specific preparation method is such as
Under：
After metal-organic framework material and absolute ethyl alcohol to be hybridly prepared into the suspension that mass fraction is 60%, thereto
Salicylide is added, stirs 130min under the conditions of 2500r/min, wherein the addition of salicylide accounts for metal-organic framework material
The 80% of quality；
Ethylenediamine is added into above-mentioned mixed liquor, is heated to 80 DEG C and reacts 1h under the conditions of 1500r/min, wherein bigcatkin willow
The molar ratio of aldehyde and ethylenediamine is 3:1；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 80 DEG C
Dry 6h crushes the filter cake after drying to obtain intermediary metal organic framework materials/Salen compounds；
Above-mentioned gained metal-organic framework material/Salen compounds are hybridly prepared into mass fraction with absolute methanol is
After 50% suspension, four water frerrous chlorides and natrium carbonicum calcinatum is added, is heated to 70 DEG C and reacts 6h under the conditions of 500r/min,
Wherein, the addition of four water frerrous chlorides accounts for the 60% of metal-organic framework material/Salen compound quality, natrium carbonicum calcinatum
Addition account for the 1.5% of metal-organic framework material/Salen compound quality；
It is filtered by vacuum after above-mentioned gained reaction solution is cooled to room temperature, filter cake is placed in drying box and is done under the conditions of 50 DEG C
It is dry to crush the filter cake after drying to obtain metal-organic framework material/Fe (Salen) heterogeneous catalysis for 24 hours, it is spare.
Catalyst for copolymerization is metal-organic framework material/metallocene heterogeneous catalysis, and specific preparation method is as follows：
After metal-organic framework material and toluene to be hybridly prepared into the suspension that mass fraction is 60%, it is added thereto
Metallocene compound Et (Ind)2ZrCl2, it is heated to 100 DEG C and is stirred under the conditions of 1500r/min, until solvent volatilization is complete,
In, the addition of metallocene compound accounts for the 80% of metal-organic framework material quality；
Obtained solid is placed in drying box under the conditions of 50 DEG C dry 6h, the solid abrasive after drying, which is obtained metal, to be had
Machine frame frame material/metallocene heterogeneous catalysis, it is spare.
A kind of specific preparation method of new urea case linear low density polyethylene material is as follows：
Solvent hexamethylene is added in the autoclave with stirring, is warming up to 110 DEG C, is stirred hexamethylene after 10min
Alkane is discharged, and is kept for 110 DEG C and vacuumizes 0.5；Three times, ethylene displacement is primary, cools to required temperature, opens ethylene for logical nitrogen displacement
Valve sequentially adds solvent hexamethylene and co-catalyst MAO, and catalyst for oligomerization is added after stirring 10min under the conditions of 3500r/min
And catalyst for copolymerization, so that ethylene pressure is risen to 1*10 rapidly5Pa, and ethylene pressure is kept by surge tank, proceed by ethylene
In-situ copolymerization.Ethylene valve is closed after reacting 0.5h, stops reaction.Wherein, the addition of co-catalyst MAO accounts for solvent toluene quality
0.8%, the molar ratio of co-catalyst and catalyst for oligomerization is 400:1, the molar ratio of co-catalyst and catalyst for copolymerization is
300:1.After product is washed with aqueous hydrochloric acid solution, water and ethyl alcohol respectively, vacuum drying obtains novel linear low density polyethylene (LDPE) material
Material.
Embodiment 4
A kind of preparation method of new urea case linear low density polyethylene material is with embodiment 2, only oligomerization catalysis
Agent is only Salen, and catalyst for copolymerization is only metallocene compound Me2Si(Ind)2ZrCl2。
Embodiment 5
A kind of preparation method of new urea case linear low density polyethylene material only uses commercially available with embodiment 2
Z-N catalyst systems.
Embodiment 6
A kind of preparation method of new urea case linear low density polyethylene material is with embodiment 2, only oligomerization catalysis
Agent is only metal-organic framework material, and catalyst for copolymerization is only metal-organic framework material.
The method for testing performance of embodiment institute prepared material
A certain amount of polymer is weighed, is tested on differential scanning calorimeter, heating rate is 10 DEG C/min, calefactive interzone
It it is 40~180 DEG C, polymer's heat history, second of melting point values that sample is recorded when heating up are eliminated in heating for the first time；Sample is in warm
It is rapid to quench in 150 DEG C of press molds on press, the density of sample is measured after film is dried with density gradient method；By reaction product
It is filtered after metering, for liquid product through GC-MS qualitative and quantitative analysis, solid product is dried under vacuum to constant weight at 40 DEG C, and catalysis is lived
Property acquired by reacting front and back weight change.Tensile property test is with reference to standard GB/T/T1040-2006, test speed：
100mm/min；Impact property test is by with reference to standard GB/T/T 1843-2008.
Vinyl material performance test made 1 embodiment 1-6 of table
Embodiment 7 to 13
The preparation method of new urea case linear low density polyethylene material in embodiment 7~13 is with embodiment 2, no
It is with place, co-catalyst is different from the molar ratio of catalyst for oligomerization, and respectively 50:1、100:1、150:1、250:1、300:
1、400:1、500:1, performance test is shown in Table 2
The main performance index of LLDPE samples made 2 embodiment 7-13 of table
Embodiment 14 is to embodiment 20
The preparation method of new urea case linear low density polyethylene in embodiment 14~20 is different with embodiment 2
Place is that the content that the co-catalyst accounts for solvent toluene quality is different, and the molar ratio of co-catalyst and catalyst for oligomerization is
200:1, the molar ratio of co-catalyst and catalyst for copolymerization is 200:1, the co-catalyst of embodiment 14~20 accounts for solvent toluene matter
The content of amount is respectively 0.1%, 0.3%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, and performance test is shown in Table 3.
The main performance index of LLDPE samples made 3 embodiment 14-20 of table
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection domain by appended claims and its
Equivalent defines.
Claims (9)
1. a kind of new urea case linear low density polyethylene, which is characterized in that be catalyzed in catalyst for oligomerization, copolymerization by ethylene
In-situ polymerization under agent and the catalysis of co-catalyst and obtain, wherein catalyst for oligomerization be loading type iron series catalysts, copolymerization catalysis
Agent is carrier zirconium series catalysts, and co-catalyst is methylaluminoxane MAO.
2. new urea case linear low density polyethylene according to claim 1, which is characterized in that the oligomerization catalysis
Agent is metal-organic framework material/Fe (Salen) heterogeneous catalysis, and Fe (Salen) has so that the method for encapsulation is immobilized to metal
On machine frame frame material.
3. new urea case linear low density polyethylene according to claim 2, which is characterized in that the copolymerization catalysis
Agent is metal-organic framework material/metallocene heterogeneous catalysis, and metallocene compound has so that the method impregnated is immobilized to metal
On machine frame frame material.
4. new urea case linear low density polyethylene according to claim 3, which is characterized in that the metallocene
Conjunction object is Me2Si(Ind)2ZrCl2With Et (Ind)2ZrCl2One or both of, metallocene compound Me2Si(Ind)2ZrCl2
Or Et (Ind)2ZrCl2It is immobilized in metal-organic framework material in the method for dipping, form metal-organic framework material/cyclopentadienyl
Metal heterogeneous catalysis.
5. a kind of preparation method of new urea case linear low density polyethylene as described in any in Claims 1 to 4, packet
Include following steps：
Solvent hexamethylene is added in the autoclave with stirring S100, is warming up to 90-110 DEG C, after stirring 10-30min
Hexamethylene is discharged；
S200 is kept for 90-110 DEG C and vacuumizes 0.5-2h, leads to nitrogen displacement three times, and ethylene displacement is primary, cools to required temperature,
Ethylene valve is opened, solvent hexamethylene and co-catalyst MAO is sequentially added, 10-20min is stirred under the conditions of 1500-3500r/min
Catalyst for oligomerization and catalyst for copolymerization are added afterwards, so that ethylene pressure is risen to 1*10 rapidly5Pa, and ethylene pressure is kept by surge tank
Power proceeds by in-situ copolymerization；
S300 closes ethylene valve after reacting 0.5-3h, stops reaction, after product is washed with aqueous hydrochloric acid solution, water and ethyl alcohol respectively,
Vacuum drying, finished product.
6. preparation method according to claim 5, which is characterized in that the addition of co-catalyst MAO accounts for solvent toluene matter
The molar ratio of the 0.4%-0.8% of amount, co-catalyst and catalyst for oligomerization is 200-400:1, co-catalyst and catalyst for copolymerization
Molar ratio be 200-300:1.
7. preparation method according to claim 6, which is characterized in that the catalyst for oligomerization preparation method, including it is as follows
Step：
After metal-organic framework material and absolute ethyl alcohol are hybridly prepared into the suspension that mass fraction is 30-60% by S211, to
Salicylide is wherein added, 10-30min is stirred under the conditions of 1000-2500r/min, mixed liquor is made, wherein salicylide adds
Enter the 50-80% that amount accounts for metal-organic framework material quality；
Ethylenediamine is added into the mixed liquor in S212, is heated to 60-80 DEG C, reacts 1-3h under the conditions of 500-1500r/min,
The first reaction solution is made, wherein the molar ratio of salicylide and ethylenediamine is 1-3:1；
S213 is filtered by vacuum after being cooled to room temperature first reaction solution, and filter cake is placed in drying box in 50-80 DEG C of condition
Lower dry 6-24h crushes the filter cake after drying to obtain intermediary metal organic framework materials/Salen compounds；
It is 20- that the metal-organic framework material/Salen compounds and absolute methanol are hybridly prepared into mass fraction by S214
After 50% suspension, four water frerrous chlorides and natrium carbonicum calcinatum is added, 50-70 DEG C is heated to, in 500-1500r/min conditions
The second reaction solution is made, wherein it is multiple that the addition of four water frerrous chlorides accounts for metal-organic framework material/Salen in lower reaction 2-6h
The 20-60% of amount of substance is closed, the addition of natrium carbonicum calcinatum accounts for the 0.2- of metal-organic framework material/Salen compound quality
1.5%；
S215 is filtered by vacuum after being cooled to room temperature second reaction solution, and filter cake is placed in drying box in 50-80 DEG C of condition
Lower dry 6-24h crushes the filter cake after drying to obtain metal-organic framework material/Fe (Salen) heterogeneous catalysis, standby
With.
8. preparation method according to claim 7, which is characterized in that the preparation method of the catalyst for copolymerization, including such as
Lower step：
After metal-organic framework material and toluene are hybridly prepared into the suspension that mass fraction is 30-60% by S221, thereto
Metallocene compound is added, is heated to 50-100 DEG C and is stirred under the conditions of 500-1500r/min, until solvent volatilization is complete,
In, the addition of metallocene compound accounts for the 50-80% of metal-organic framework material quality；
Obtained solid is placed in drying box under the conditions of 50-80 DEG C dry 2-6h by S222, and the solid abrasive after drying is obtained
Metal-organic framework material/metallocene heterogeneous catalysis, it is spare.
9. preparation method according to claim 8, which is characterized in that the metal-organic framework material is MIL-100,
It is to be assembled by Iron cluster and trimesic acid ligand, preparation method includes step：
The ferric chloride hexahydrate of corrresponding quality part is dissolved in deionized water by S231, is stirred fully dissolving, is added equal benzene front three
Acid continues stirring 0.5 hour, is packed into 130 DEG C of autoclave and reacts 72 hours；
S232 is cooled to room temperature after reaction, is washed three times with hot water and methanol, and is handled 12 hours, 150 DEG C in boiling methanol
Vacuum drying 12 hours obtains metal-organic framework material MIL-100, spare.
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Non-Patent Citations (2)
| Title |
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| 王丽苹等: "羧基配体金属有机骨架材料作为催化剂的研究进展", 《分子催化》 * |
| 艾宁等: "《化学化工实验教学改革与创新》", 30 September 2016, 浙江大学出版社 * |
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