CN109796546A - A kind of preparation method and application of olefin polymerization heterogeneous catalysis - Google Patents
A kind of preparation method and application of olefin polymerization heterogeneous catalysis Download PDFInfo
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- CN109796546A CN109796546A CN201811552977.9A CN201811552977A CN109796546A CN 109796546 A CN109796546 A CN 109796546A CN 201811552977 A CN201811552977 A CN 201811552977A CN 109796546 A CN109796546 A CN 109796546A
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Abstract
A kind of preparation method of olefin polymerization heterogeneous catalysis, it is characterised in that include the following steps: that 1. polyolefin catalyst is dissolved in solvent, the concentration of polyolefin catalyst in a solvent is 50~5000 μm of ol/ml；2. auxiliary agent is added, and stir, so that polyolefin catalyst is agglomerated into particle in above-mentioned solvent, obtain heterogeneous catalysis agent solution, wherein the molar ratio of said polyolefins catalyst and auxiliary agent is 10~1000, and the partial size of particle is 50~900nm.The invention also discloses the applications of heterogeneous catalysis made from above-mentioned preparation method.Compared with prior art, preparation method of the invention is simple, and heterogeneous catalysis obtained can prepare the polyolefin products that grain diameter is big, bulk density is high, and will not generate reaction kettle in polymerization process and stick wall phenomenon；The activity of superelevation can be can be obtained under extremely low co-catalyst dosage simultaneously.
Description
Technical field
The invention belongs to olefin polymerization technical fields, and in particular to a kind of system of olefin polymerization heterogeneous catalysis
Preparation Method and application.
Background technique
Catalyst for olefines polymerizing mainly includes homogeneous catalyst and heterogeneous catalysis.Homogeneous catalyst is molten by catalyst
In solvent, catalysis reaction is carried out in the form of molecule.Homogeneous catalysis activity with higher, however, the polyolefin ten of preparation
Partial volume is also easy to produce the glutinous wall phenomenon of reactor, affects the continuous production of technique；Meanwhile the polyolefin particles partial size of preparation
Small, heap density is low, reduces the value of product；In addition, to obtain the catalyst of high activity, homogeneous catalyst is needed using a large amount of
Co-catalyst, the molar ratio of usual co-catalyst and catalyst is greater than 1000, can just obtain higher catalytic activity, this is significantly
Increase the production cost of technique.Heterogeneous catalysis can obtain particle in the course of the polymerization process to avoid the fouling of reactor wall face
Greatly, the high polyolefin products of heap density can direct plunge into use in existing commercial plant, be the important directions of catalyst development
One of.Currently, industrial about 70% polyethylene is produced by heterogeneous catalysis.Heterogeneous catalysis is by homogeneous catalyst
It is supported, i.e., catalyst is dissolved in solvent, is configured to after homogeneous catalyst through physical absorption or is chemically bonded close with carrier
It is connected.Be usually used in loading the carrier of homogeneous catalyst mainly including inorganic carrier and organic carrier, as silica, magnesium chloride,
Aluminium oxide, titanium oxide, carbon nanotubes, graphene, polystyrene, polyvinyl alcohol etc..When polymerization, due to chain growth generate it is huge
It is broken that carrier occurs for tension, broken to form nanoscale fragment and remain in the matrix of polyolefin, causes polyolefin nascent
Contain ash content inside particle, affects the following process of material；Simultaneously as the acidity and carrier surface of carrier surface are to activity
Point blocks, and causing the activity of heterogeneous catalysis is only 1/10th of homogeneous catalyst.It is different from homogeneous catalyst, it is non-equal
The co-catalyst dosage that phase catalyst is needed when obtaining high activity substantially reduces that (molar ratio of co-catalyst and catalyst is greater than
40)。
Summary of the invention
First technical problem to be solved by this invention is the status for the prior art, provides a kind of preparation process letter
The preparation method of olefin polymerization heterogeneous catalysis single, without using carrier, so that heterogeneous catalysis obtained is same
Has the effect of the heterogeneous catalysis that load in the prior art has carrier, and in the case where extremely low co-catalyst dosage, i.e.,
It can get efficient olefinic polymerization effect.
Second technical problem to be solved by this invention is the status for the prior art, provides a kind of above-mentioned preparation side
The application of olefin polymerization heterogeneous catalysis made from method.
The present invention solves technical solution used by above-mentioned first technical problem are as follows: a kind of olefin polymerization is heterogeneous to urge
The preparation method of agent, it is characterised in that include the following steps:
1. polyolefin catalyst is dissolved in solvent, the concentration of polyolefin catalyst in a solvent is 50~5000 μm of ol/
ml；
2. auxiliary agent is added, and stir, so that polyolefin catalyst is agglomerated into particle in above-mentioned solvent, obtains heterogeneous
Catalyst solution；Wherein the auxiliary agent includes ethers nucleating agent, esters nucleating agent, alkoxide compound, polysilsesquioxane, silicon
One of alkane coupling agent；The molar ratio of said polyolefins catalyst and auxiliary agent is 10~1000, the partial size of particle is 50~
900nm。
As an improvement, the polyolefin catalyst is Ziegler-Natta catalyst, metallocene catalyst, rear transition gold
At least one of metal catalyst, FI catalyst, chromium-based catalysts.
It improves, the solvent is at least one of toluene, normal heptane, tetrahydrofuran, chloroform.
The present invention solves technical solution used by above-mentioned second technical problem are as follows: a kind of preparation method as described above
The application of olefin polymerization heterogeneous catalysis obtained, including in olefin polymerization.
Above-mentioned application method is preferred are as follows: the temperature of polymer reactor is adjusted to -40~120 DEG C；And be added polymer solvent and
Above-mentioned olefin polymerization heterogeneous catalysis stirs 1~10min；Olefinic monomer is then added and co-catalyst polymerize instead
Answer, the reaction time is 1~120min, wherein the molar ratio of co-catalyst and above-mentioned olefin polymerization heterogeneous catalysis be 1~
40, the content i.e. polymerization pressure of olefinic monomer are 1~30bar.
Improved to be, the co-catalyst is alkyl aluminum compound, alkyl lithium compounds, alkyl zinc compound, boron alkyl
At least one of compound.
The olefinic monomer includes at least one of ethylene, propylene, isoprene, 1- butylene, 1- hexene, 1- octene.
Finally, the polymer solvent includes at least one of normal heptane, n-hexane, toluene.
Compared with the prior art, the advantages of the present invention are as follows: preparation method is simple, does not use any carrier, is not related to multiple
The reaction process of miscellaneous carrier and catalyst, only by the way that the auxiliary agent of trace is added, so that homogeneous catalyst is using auxiliary agent as core, shape
At cluster structure, grain diameter is obtained in the heterogeneous catalysis of 50~900nm.Since auxiliary agent makes catalyst molecule accumulate ten
Divide closely, strong interaction between catalyst molecule so that activated centre will not fall off when polymerization, therefore can prepare particle
The polyolefin products that diameter is big, bulk density is high.Meanwhile reaction kettle will not be generated in polymerization process and sticks wall phenomenon.It is worth mentioning
It is that when being applied in olefin polymerization using the heterogeneous catalysis that this method obtains, can be used in extremely low co-catalyst
Can be obtained the activity (molar ratio≤40 of 1≤co-catalyst and catalyst) of superelevation under amount, especially when co-catalyst with urge
When the molar ratio of agent is 1, catalyst is still able to maintain quite high activity.
Detailed description of the invention
Fig. 1 is the grain-size graph of heterogeneous catalysis particles in solution prepared by the embodiment of the present invention 1；
Fig. 2 is the optical microscope of heterogeneous catalysis agent solution prepared by the embodiment of the present invention 1；
Fig. 3 is polyethylene particle photo prepared by the embodiment of the present invention 1；
Fig. 4 is the wall surface photo of reaction kettle after 1 polymerization reaction of the embodiment of the present invention；
Fig. 5 is the wall surface photo of reaction kettle after comparative example polymerization reaction；
Fig. 6 is the polyethylene particle photo of comparative example preparation.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Embodiment 1:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 900 μm of ol
Agent TiCl4(Ziegler-Natta catalyst) is dissolved in the solvent n-heptane of 10mL, and the poly- silsesquioxane of auxiliary agent of 10 μm of ol is added
Alkane stirs 1h so that polyolefin catalyst is agglomerated into particle in normal heptane and obtains heterogeneous catalysis solvent.It is heterogeneous
Catalyst solution is after laser particle size monitors, and measuring the grain diameter to be formed is 375nm, as shown in Figure 1.Heterogeneous catalysis is molten
The optical microscope picture of liquid is as shown in Figure 2.Slurry polymerization temperature of reactor is adjusted to 60 DEG C, 400mL polymer solvent is added
Above-mentioned heterogeneous catalysis agent solution 1mL is added in normal heptane, stirs 10min, the co-catalyst triethyl aluminum of 90 μm of ol is then added
(molar ratio of co-catalyst and heterogeneous catalysis is 1), ethylene (3bar) polymerize 15min.It is heterogeneous made from the present embodiment
Polymerization catalyst activity is very high, obtains polyethylene 153.0g, and polymerizate particle is big, and average grain diameter is up to 3.5mm (such as Fig. 3 institute
Show), bulk density is high, reaches 385g/cm3, reactor, which is not present, sticks wall phenomenon, specifically refers to Fig. 4.
Embodiment 2:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 500 μm of ol
Agent TiCl3(Ziegler-Natta catalyst) is dissolved in the solvents tetrahydrofurane of 10mL, and the auxiliary agent ether of 50 μm of ol is added (certainly
Other ethers such as dimethyl ether, silicon ether, amidogen ether can also be used as nucleating agent), 1h is stirred, so that polyolefin catalyst is in tetrahydrofuran
In be agglomerated into particle, obtain heterogeneous catalysis solvent.Heterogeneous catalysis agent solution measures to be formed after laser particle size monitors
Grain diameter be 50nm.Slurry polymerization temperature of reactor is adjusted to 120 DEG C, addition 400mL polymer solvent toluene, in addition
State heterogeneous catalysis agent solution 1mL, stir 1min, be then added 250 μm of ol co-catalyst n-BuLi (co-catalyst with it is non-
The molar ratio of homogeneous catalyst is that 5), propylene (30bar) polymerize 15min.The polymerization of heterogeneous catalysis made from the present embodiment is lived
Property it is very high, obtain polypropylene 103.0g, polymerizate particle is big, and average grain diameter reaches 2.5mm, and bulk density is high, reaches 355g/
cm3, reactor, which is not present, sticks wall phenomenon.
Embodiment 3:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 50mmol
Agent VCl4(Ziegler-Natta catalyst) is dissolved in the solvent chloroform of 10mL, and the auxiliary agent ethyl acetate of 50mol is added (certainly
Other esters such as methyl formate, acrylate, aliphatic ester can be used as nucleating agent), 1h is stirred, so that polyolefin catalyst exists
It is agglomerated into particle in chloroform, obtains heterogeneous catalysis solvent.Heterogeneous catalysis agent solution measures after laser particle size monitors
The grain diameter of formation is 900nm.Slurry polymerization temperature of reactor is adjusted to 0 DEG C, 400mL polymer solvent n-hexane is added,
Above-mentioned heterogeneous catalysis agent solution 1mL is added, stirs 1min, the co-catalyst aluminium diethyl monochloride that 5mmol is then added (is helped and urged
Agent and the molar ratio of heterogeneous catalysis are that 1), isoprene (1bar) polymerize 15min.It is heterogeneous made from the present embodiment
Polymerization catalyst activity is very high, obtains polyisoprene 23.0g, and polymerizate particle is big, and average grain diameter reaches 1.2mm, accumulation
Density is high, reaches 355g/cm3, reactor, which is not present, sticks wall phenomenon.
Embodiment 4:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.The polyolefin of 9000 μm of ol is urged
Agent bis cyclopentadienyl zirconium dichloride (metallocene catalyst) is dissolved in the solvent toluene of 10mL, and the auxiliary agent trimethyl aikyiaiurnirsoxan beta of 9 μm of ol is added, stirs
1h is mixed, so that polyolefin catalyst is agglomerated into particle in toluene, obtains heterogeneous catalysis solvent.Heterogeneous catalysis is molten
For liquid after laser particle size monitors, measuring the grain diameter to be formed is 500nm.Slurry polymerization temperature of reactor is adjusted to 90 DEG C,
400mL polymer solvent toluene is added, above-mentioned heterogeneous catalysis agent solution 1mL is added, stirs 1min, helping for 36mmol is then added
Catalyst trimethyl aikyiaiurnirsoxan beta (molar ratio of co-catalyst and heterogeneous catalysis is 40), 1- butylene (10bar), polymerization
15min.Heterogeneous catalysis polymerization activity made from the present embodiment is very high, obtains polybutene 43.0g, polymerizate particle
Greatly, average grain diameter reaches 2.2mm, and bulk density is high, reaches 375g/cm3, reactor, which is not present, sticks wall phenomenon.
Embodiment 5:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 900 μm of ol
Agent FI catalyst is dissolved in the solvent toluene of 10mL, and the auxiliary agent dimethyl siloxane of 0.9 μm of ol is added, and 1h is stirred, so that polyolefin
Catalyst is agglomerated into particle in toluene, obtains heterogeneous catalysis solvent.Heterogeneous catalysis agent solution is supervised through laser particle size
After survey, measuring the grain diameter to be formed is 700nm.Slurry polymerization temperature of reactor is adjusted to -40 DEG C, 400mL polymerization is added
Above-mentioned heterogeneous catalysis agent solution 1mL is added in solvent toluene, stirs 1min, the co-catalyst diethyl of 450 μm of ol is then added
Zinc (molar ratio of co-catalyst and heterogeneous catalysis is 5), 1- hexene (10bar) polymerize 15min.Made from the present embodiment
Heterogeneous catalysis polymerization activity is very high, obtains polyhexene 63.0g, and polymerizate particle is big, and average grain diameter reaches 1.2mm, heap
Product density is high, reaches 305g/cm3, reactor, which is not present, sticks wall phenomenon.
Embodiment 6:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 900 μm of ol
Agent ferric acetyl acetonade/pyridine diimine catalyst (late transition metal catalyst) is dissolved in the solvent toluene of 10mL, and 0.9 μm of ol is added
Auxiliary agent vinyltrimethoxysilane, stir 1h so that polyolefin catalyst is agglomerated into particle in toluene, obtain it is non-
Phase catalyst solvent.For heterogeneous catalysis agent solution after laser particle size monitors, measuring the grain diameter to be formed is 350nm.It will slurry
Liquid polymer reactor temperature is adjusted to 30 DEG C, and 400mL polymer solvent toluene is added, above-mentioned heterogeneous catalysis agent solution 1mL is added,
1min is stirred, the co-catalyst boron triethyl of 450 μm of ol is then added, and (molar ratio of co-catalyst and heterogeneous catalysis is
5), 1- octene (25bar) polymerize 15min.Heterogeneous catalysis polymerization activity made from the present embodiment is very high, obtains gathering pungent
Alkene 53.0g, polymerizate particle is big, and average grain diameter reaches 2.2mm, and bulk density is high, reaches 385g/cm3, reactor, which is not present, sticks wall
Phenomenon.
Embodiment 7:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyzed polyolefin of 900 μm of ol
Agent chrome green (chromium-based catalysts) is dissolved in the solvent chloroform of 10mL, and the auxiliary agent vinyl trimethoxy silicon of 0.9 μm of ol is added
Alkane stirs 1h so that polyolefin catalyst is agglomerated into particle in chloroform and obtains heterogeneous catalysis solvent.It is heterogeneous to urge
For agent solution after laser particle size monitors, measuring the grain diameter to be formed is 350nm.By slurry polymerization temperature of reactor adjust to
120 DEG C, 400mL polymer solvent toluene is added, above-mentioned heterogeneous catalysis agent solution 1mL is added, stirs 1min, 450 μ is then added
The co-catalyst boron triethyl (molar ratio of co-catalyst and heterogeneous catalysis is 5) of mol, 1- octene (2bar), polymerization
15min.Heterogeneous catalysis polymerization activity made from the present embodiment is very high, obtains polyoctenamer 233.0g, polymerizate particle
Greatly, average grain diameter reaches 3.2mm, and bulk density is high, reaches 405g/cm3, reactor, which is not present, sticks wall phenomenon.
Comparative example:
Reaction unit is purged with high pure nitrogen, removes air and water in reaction unit.By the catalyst of 900 μm of ol
TiCl4(Ziegler-Natta catalyst) is dissolved in the solvent n-heptane of 10mL, stirs 1h, and catalyst solution is made.Catalyst is molten
Liquid no signal after laser particle size monitors shows catalyst and not formed nanoscale heterogeneous catalyst particles.Slurries are gathered
It closes reactor to adjust to 60 DEG C, 400ml polymer solvent normal heptane is added, above-mentioned catalyst solution 1mL is added, stir 10min, with
The co-catalyst triethyl aluminum (molar ratio of co-catalyst and catalyst solution is 1) of 90 μm of ol is added afterwards, ethylene (3bar) gathers
Close 15min.Polymerization catalyst activity is low, only obtains polyethylene 3.0g, and polymerizate sticks wall very much, as shown in Figure 5.Polymerizate
Has no particle shape, as shown in Figure 6.
Claims (8)
1. a kind of preparation method of olefin polymerization heterogeneous catalysis, it is characterised in that include the following steps:
1. polyolefin catalyst is dissolved in solvent, the concentration of polyolefin catalyst in a solvent is 50~5000 μm of ol/ml；
2. auxiliary agent is added, and stir, so that polyolefin catalyst is agglomerated into particle in above-mentioned solvent, obtains heterogeneous catalysis
Agent solution；Wherein the auxiliary agent includes ethers nucleating agent, esters nucleating agent, alkoxide compound, polysilsesquioxane, silane idol
Join one of agent；The molar ratio of said polyolefins catalyst and auxiliary agent is 10~1000, and the partial size of particle is 50~900nm.
2. preparation method according to claim 1, it is characterised in that: the polyolefin catalyst is Ziegler-Natta
At least one of catalyst, metallocene catalyst, late transition metal catalyst, FI catalyst, chromium-based catalysts.
3. preparation method according to claim 1, it is characterised in that: the solvent be toluene, normal heptane, tetrahydrofuran,
At least one of chloroform.
4. olefin polymerization heterogeneous catalysis made from a kind of preparation method as described in any claim of claims 1 to 3
Using, including in olefin polymerization.
5. application according to claim 4, it is characterised in that method are as follows: the temperature of polymer reactor is adjusted to -40~120
℃；And polymer solvent and above-mentioned olefin polymerization heterogeneous catalysis is added, stir 1~10min；Then be added olefinic monomer and
Co-catalyst carries out polymerization reaction, and the reaction time is 1~120min, wherein co-catalyst with above-mentioned olefin polymerization is heterogeneous urges
The molar ratio of agent is 1~40, and the content i.e. polymerization pressure of olefinic monomer are 1~30bar.
6. application according to claim 5, it is characterised in that: the co-catalyst is alkyl aluminum compound, alkyl lithiumation
Close at least one of object, alkyl zinc compound, alkyl boron compound.
7. application according to claim 5, it is characterised in that: the olefinic monomer include ethylene, propylene, isoprene,
At least one of 1- butylene, 1- hexene, 1- octene.
8. application according to claim 5, it is characterised in that: the polymer solvent includes normal heptane, n-hexane, in toluene
At least one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698578A (en) * | 2019-09-30 | 2020-01-17 | 宁波大学 | Process for preparing blends of ultrahigh molecular weight polyolefins and low molecular weight polyolefins |
| CN114891140A (en) * | 2022-04-29 | 2022-08-12 | 浙江大学 | Preparation method of polyolefin copolymer with low ash content and high comonomer content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503659C (en) * | 2001-12-19 | 2009-06-24 | 玻利阿黎斯技术有限公司 | Production of olefin polymerisation catalysts |
| CN102209732A (en) * | 2008-11-10 | 2011-10-05 | 北欧化工公司 | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
| CN110922512A (en) * | 2018-09-19 | 2020-03-27 | 杭州双安科技有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
-
2018
- 2018-12-19 CN CN201811552977.9A patent/CN109796546A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503659C (en) * | 2001-12-19 | 2009-06-24 | 玻利阿黎斯技术有限公司 | Production of olefin polymerisation catalysts |
| CN102209732A (en) * | 2008-11-10 | 2011-10-05 | 北欧化工公司 | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
| CN110922512A (en) * | 2018-09-19 | 2020-03-27 | 杭州双安科技有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698578A (en) * | 2019-09-30 | 2020-01-17 | 宁波大学 | Process for preparing blends of ultrahigh molecular weight polyolefins and low molecular weight polyolefins |
| CN110698578B (en) * | 2019-09-30 | 2021-11-23 | 宁波大学 | Process for preparing blends of ultrahigh molecular weight polyolefins and low molecular weight polyolefins |
| CN114891140A (en) * | 2022-04-29 | 2022-08-12 | 浙江大学 | Preparation method of polyolefin copolymer with low ash content and high comonomer content |
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Application publication date: 20190524 |