CN108715622A - A method of preparing atactic copolymerized polypropene - Google Patents
A method of preparing atactic copolymerized polypropene Download PDFInfo
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- CN108715622A CN108715622A CN201810417301.2A CN201810417301A CN108715622A CN 108715622 A CN108715622 A CN 108715622A CN 201810417301 A CN201810417301 A CN 201810417301A CN 108715622 A CN108715622 A CN 108715622A
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- Prior art keywords
- propylene
- atactic copolymerized
- copolymerized polypropene
- catalyst
- polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Abstract
The present invention provides a kind of methods preparing atactic copolymerized polypropene.This approach includes the following steps：1) propylene, alpha-olefin are refined, imurity-removal, hydrogen is dehydrated；2) alpha-olefin and propylene are mixed and is passed through hydrogen, and electron donor, catalyst for copolymerization and forth generation polypropylene Z-N catalyst is added and carries out polymerisation, stop polymerisation when polyacrylic conversion ratio reaches 70-80%；3) unconverted monomer in step 2) is recycled, to the polypropylene flash vaporization that polymerisation obtains, obtains the polypropylene powder without propylene, then being passed through air makes polypropylene powder inactivate, and obtains atactic copolymerized polypropene.The present invention the method for preparing atactic copolymerized polypropene every kettle yield between 5-6 tons, manufacturing cost economy, environmental protection, green, simply.
Description
Technical field
The present invention relates to functionalizationization before the polyolefin in high molecule plastic to be modified field, more particularly to a kind of using former
Position one-step method direct polymerization prepares the technical grade method of atactic copolymerized polypropene.
Background technology
Polyacrylic random copolymerization refers to the copolymer of propylene and alpha-olefin comonomer etc., and comonomer is on strand
Random distribution, comonomer are introduced into the stereoregularity destroyed in homopolypropylene strand, the crystalline rate of strand
Slack-off, overall crystallinity reduces, fusing point reduces.This analog copolymer has both high tenacity, high rigidity and intensity.Due to comonomer energy quilt
Included in polyacrylic α and γ crystallizations, polyacrylic crystallization is interfered few.For comonomer at 10% or so, crystallinity can
It is maintained between 50~60%, this is atactic copolymerized polypropene rigidity and the high reason of intensity.When co-monomer content 10% with
It when lower, both may include in α types crystallize, can also reside in the crystallization of γ types.The insertion of comonomer makes normal isotactic poly- third
Alkene segment sequence shortens, and results in the crystallization of γ types.After comonomer is higher than 10%, most of comonomer is included in α types
In crystallization, how much the translucency of this analog copolymer depends on spherocrystal, transparent rate can be made to be up to 90% with method for rapid cooling, and delays
Slow cool down, because of the presence of spherocrystal, light transmittance is down to 50%.Due to the reduction of crystallinity, spherocrystal is reduced, and makes random copolymer anti-impact
Hitting performance is improved, and when co-monomer content is 10%, fusing point is reduced to 135~145 DEG C.So atactic copolymerized polypropene
It can be widely applied to blowing, injection molding, film and sheet extrusion manufacture field, running water pipe, hot-water line, packaging material for food, doctor
Pack package material and common consumer product and bottle material etc..
Therefore, it is necessary to a kind of efficient and simple methods for preparing atactic copolymerized polypropene to become those skilled in the art urgently
Technical problem to be solved.
Invention content
The purpose of the present invention is to provide a kind of methods preparing atactic copolymerized polypropene.The preparation method of the present invention is not required to
Deliming takes off random object, solvent-free recycling, and flow is simple to operation, and whole process " three wastes " discharge is few.
Technical scheme is as follows：
According to the present invention, a kind of method preparing atactic copolymerized polypropene is provided, is included the following steps：
1) liquid propylene, alpha-olefin are refined, imurity-removal enters measuring tank, hydrogen is dehydrated；
2)12-23m3Polymeric kettle in, alpha-olefin and propylene are mixed and are passed through hydrogen, and electron donor, catalysis is added
Agent carries out polymerisation, stops polymerisation when polyacrylic conversion ratio reaches 70-80%；Unpolymerized propylene monomer is returned
It receives, opens and be cooled to blowing temperature opening bottom valve in cooling water to polymeric kettle, polypropylene powder sprays into flash vaporization kettle；
3) polypropylene flash vaporization obtained to polymerisation with flash evaporation in flash vaporization kettle obtains the polypropylene without propylene
Powder, then being passed through air makes polypropylene powder inactivate, and obtains atactic copolymerized polypropene；
4) by step 2) and 3), the middle propylene collected recycles after compressor compresses and liquefies.Wherein, step 2) and 3) middle receipts
The propylene integrated is propylene steam.
According to one embodiment of present invention, this method also includes step：
The atactic copolymerized polypropene filtering that step 3) is obtained, into packaging process, into automatic packaging.
According to one embodiment of present invention, activator and molecular weight regulator are additionally added in the polymerisation of step 2).
According to one embodiment of present invention, activator is triethyl aluminum.
According to one embodiment of present invention, molecular weight regulator is hydrogen.
According to one embodiment of present invention, in step 1), imurity-removal includes：Desulfurization, one oxygen of deoxidation, dehydration and removal
Change carbon.
According to one embodiment of present invention, alpha-olefin is one or more of alpha-butylene, α-hexene, α-octene.
According to one embodiment of present invention, catalyst is the group of catalyst for copolymerization and forth generation polypropylene Z-N catalyst
It closes.
According to one embodiment of present invention, catalyst for copolymerization is two ethers electron donor type Z-N catalyst.
According to one embodiment of present invention, two ethers electron donor type Z-N catalyst can be TiCl4/ 1,3- diether/
MgCl2/AlEt3Class catalyst.
According to one embodiment of present invention, forth generation polypropylene Z-N catalyst can be TiCl4/ phthalic acid ester/
MgCl2/AlEt3。
According to one embodiment of present invention, the reaction condition of polymerisation is：Reaction time 3-4h, reaction pressure 2.2-
3.5MPa, 60-75 DEG C of reaction temperature.The polymerisation that heats up can be manual and automatic control.
According to one embodiment of present invention, the propylene in polymerisation, alpha-olefin, catalyst for copolymerization and forth generation poly- third
The combination of alkene Z-N catalyst, the proportioning of electron donor are 1:(0.01~0.15)：(0.02×10-3~0.03 × 10-3):
(0.02×10-3~0.05 × 10-3).Wherein, the quality proportioning of catalyst for copolymerization and forth generation polypropylene Z-N catalyst is
0.4:1~0.9:1.
According to the present invention, a kind of atactic copolymerized polypropene is provided, is prepared using method as described above.
The present invention is with intermittent liquid phase bulk polymerization polymerization technique in technical grade 12-23m3Polymeric kettle in-situ polymerization be made propylene with
Alpha-olefin atactic copolymerized polypropene realizes the Product industrialization and produces nearly about 2000 tons of products of 400 kettle.It is autonomous China has been filled up
The blank of intermittent liquid phase bulk polymerization production the atactic copolymerized polypropene technique and product of research and development, increases intermittent liquid phase bulk polymerization work
Skill produces the diversity of product.
The present invention is in 12-23m3A step direct polymerization in technical grade polymeric kettle is manufactured into per kettle yield between 5-6 tons
It is this economy, environmental protection, green, simple.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment, to the present invention
It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit
The fixed present invention.
Embodiment 1
Liquid propylene, alpha-olefin are refined, enter measuring tank, hydrogen after the impurity such as removing sulphur, oxygen, water and carbon monoxide
Gas uses after being dehydrated for polymerisation.
In 23m3In polymeric kettle, 11m is put into3Propylene, 1.02m3Butene-1,180g hydrogen, and sequentially add three second of activator
Base aluminium 2000ml, DDS (dimethoxydiphenylsilane) 250ml, catalyst for copolymerization (two ethers electron donor type Z-N catalyst
System) 80g, forth generation polypropylene Z-N catalyst 75g, kettle temperature is maintained at 70 DEG C, and kettle internal pressure, which is tried hard to keep, holds 3.0MPa, polymerization time
After stopping polymerisation, unreacted propylene is collected, is cooled to blowing temperature in balance, opening cooling water to polymeric kettle by 3h
Bottom valve is opened, polypropylene powder sprays into flash vaporization kettle.Make propylene and polypropylene powder with flash evaporation (repeatedly vacuumizing, inflated with nitrogen)
Material separation, then being passed through air makes polypropylene powder inactivate, blowing filters and packages to obtain atactic copolymerized polypropene powder product.
The propylene steam collected after polymerisation is recycled after compressor compresses and liquefies.
Embodiment 2
Liquid propylene, alpha-olefin are refined, enter measuring tank, hydrogen after the impurity such as removing sulphur, oxygen, water and carbon monoxide
Gas uses after being dehydrated for polymerisation.
In 23m3In polymeric kettle, 11.4m is put into3Propylene, 0.71m3Butene-1,110g hydrogen, and sequentially add activator three
Aluminium ethide 2000ml, DDS 250ml, catalyst for copolymerization (two ethers electron donor type Z-N catalyst systems) 60g, forth generation are poly-
Propylene Z-N catalyst 85g, kettle temperature are maintained at 68 DEG C, and kettle internal pressure, which is tried hard to keep, holds 2.7MPa, polymerization time 3h, after stopping polymerisation,
Unreacted propylene is collected, is cooled to blowing temperature opening bottom valve, polypropylene powder in balance, opening cooling water to polymeric kettle
Material sprays into flash vaporization kettle.Propylene is set to be detached with polypropylene powder with flash evaporation (repeatedly vacuumizing, inflated with nitrogen), then be passed through air to make
Polypropylene powder inactivates, and blowing filters and packages to obtain atactic copolymerized polypropene powder product.
The propylene steam collected after polymerisation is recycled after compressor compresses and liquefies.
Embodiment 3
Liquid propylene, alpha-olefin are refined, enter measuring tank, hydrogen after the impurity such as removing sulphur, oxygen, water and carbon monoxide
Gas uses after being dehydrated for polymerisation.
In 23m3In polymeric kettle, 11.9m is put into3Propylene, 0.3m3Butene-1, and sequentially add activator triethyl aluminum
AlEt32000ml, DDS 250ml, catalyst for copolymerization (two ethers electron donor type Z-N catalyst systems) 60g, forth generation poly- third
Alkene Z-N catalyst 90g, kettle temperature are maintained at 75 DEG C, and kettle internal pressure, which is tried hard to keep, holds 2.8MPa, polymerization time 3h, will after stopping polymerisation
Unreacted propylene is collected, is cooled to blowing temperature opening bottom valve, polypropylene powder in balance, opening cooling water to polymeric kettle
Spray into flash vaporization kettle.Propylene is set to be detached with polypropylene powder with flash evaporation (repeatedly vacuumizing, inflated with nitrogen), then be passed through air to make to gather
Propylene powder inactivates, and blowing filters and packages to obtain atactic copolymerized polypropene powder product.
The propylene steam collected after polymerisation is recycled after compressor compresses and liquefies.
Embodiment 4
Liquid propylene, alpha-olefin are refined, enter measuring tank, hydrogen after the impurity such as removing sulphur, oxygen, water and carbon monoxide
Gas uses after being dehydrated for polymerisation.
In 23m3In polymeric kettle, 11.7m is put into3Propylene, 0.5m3Butene-1,180g hydrogen, and sequentially add activator three
Aluminium ethide 2000ml, DDS 150ml, catalyst for copolymerization (two ethers electron donor type Z-N catalyst systems) 60g, forth generation are poly-
Propylene Z-N catalyst 95g, kettle temperature are maintained at 65 DEG C, and kettle internal pressure, which is tried hard to keep, holds 2.2MPa, polymerization time 3h, after stopping polymerisation,
Unreacted propylene is collected, is cooled to blowing temperature opening bottom valve, polypropylene powder in balance, opening cooling water to polymeric kettle
Material sprays into flash vaporization kettle.Propylene is set to be detached with polypropylene powder with flash evaporation (repeatedly vacuumizing, inflated with nitrogen), then be passed through air to make
Polypropylene powder inactivates, and blowing filters and packages to obtain atactic copolymerized polypropene powder product.
The propylene steam collected after polymerisation is recycled after compressor compresses and liquefies.
Embodiment 5
Liquid propylene, alpha-olefin are refined, enter measuring tank, hydrogen after the impurity such as removing sulphur, oxygen, water and carbon monoxide
Gas uses after being dehydrated for polymerisation.
In 23m3In polymeric kettle, 11.3m is put into3Propylene, 0.74m3Hexene -1,180g hydrogen, and sequentially add activator three
Aluminium ethide 2000ml, DDS150ml, catalyst for copolymerization (two ethers electron donor type Z-N catalyst systems) 60g, forth generation poly- third
Alkene Z-N catalyst 80g, kettle temperature are maintained at 60 DEG C, and kettle internal pressure, which is tried hard to keep, holds 3.5MPa, polymerization time 4h, will after stopping polymerisation
Unreacted propylene is collected, is cooled to blowing temperature opening bottom valve, polypropylene powder in balance, opening cooling water to polymeric kettle
Spray into flash vaporization kettle.Propylene is set to be detached with polypropylene powder with flash evaporation (repeatedly vacuumizing, inflated with nitrogen), then be passed through air to make to gather
Propylene powder inactivates, and blowing filters and packages to obtain atactic copolymerized polypropene powder product.
The propylene steam collected after polymerisation is recycled after compressor compresses and liquefies.
The two ethers electron donor type Z-N catalyst that embodiment 1-5 is used can be TiCl4/ 1,3- diether/MgCl2/
AlEt3Class catalyst.Forth generation polypropylene Z-N catalyst can be TiCl4/ phthalic acid ester/MgCl2/AlEt3。
The foregoing is merely presently preferred embodiments of the present invention, practical range not for the purpose of limiting the invention；If do not taken off
It from the spirit and scope of the present invention, modifies or equivalently replaces the present invention, should all cover in the claims in the present invention
In protection domain.
Claims (9)
1. a method of preparing atactic copolymerized polypropene, which is characterized in that include the following steps：
1) propylene, alpha-olefin are refined, imurity-removal, hydrogen is dehydrated；
2) alpha-olefin and propylene are mixed and is passed through hydrogen, and electron donor, catalyst for copolymerization and forth generation polypropylene Z-N is added
The combination of catalyst carries out polymerisation, stops polymerisation when polyacrylic conversion ratio reaches 70-80%；
3) unconverted monomer in step 2) is recycled, to the polypropylene flash vaporization that polymerisation obtains, is obtained poly- without propylene
Propylene powder, then being passed through air makes polypropylene powder inactivate, and obtains atactic copolymerized polypropene.
2. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the method further includes will
Unreacted propylene and the middle propylene detached of step 3) are collected in step 2), and are recycled after compressor compresses and liquefies.
3. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the polymerization of the step 2)
Activator and molecular weight regulator are additionally added in reaction.
4. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the alpha-olefin is α-fourth
One or more of alkene, α-hexene, α-octene.
5. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the catalyst for copolymerization is
Two ethers electron donor Z-N catalyst.
6. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the polymerisation it is anti-
The condition is answered to be：Reaction time 3-4h, reaction pressure 2.2-3.5MPa, 60-75 DEG C of reaction temperature.
7. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that the polymerisation is in body
Product is 12-23m3Polymeric kettle in carry out.
8. the method according to claim 1 for preparing atactic copolymerized polypropene, which is characterized in that in the polymerisation
The propylene, the alpha-olefin, the combining of the catalyst for copolymerization and forth generation polypropylene Z-N catalyst, the electron donor
Quality proportioning be 1:(0.01~0.15)：(0.02×10-3~0.03 × 10-3):(0.02×10-3~0.05 × 10-3)。
9. a kind of atactic copolymerized polypropene is prepared using such as claim 1-8 any one of them method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171205A (en) * | 2020-03-02 | 2020-05-19 | 石家庄联合石化有限公司 | Production method of polypropylene |
| CN112358560A (en) * | 2020-10-21 | 2021-02-12 | 中国石油化工股份有限公司 | System and method for producing odorless polypropylene granular product |
| CN113583167A (en) * | 2021-08-27 | 2021-11-02 | 云南云天化石化有限公司 | Device and method for producing propylene-butylene random copolymerization polypropylene by gas phase process |
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| CN103772571A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of propylene-alpha-olefin random copolymer |
| CN104774394A (en) * | 2015-03-30 | 2015-07-15 | 青岛科技大学 | Preparation methods for polyolefin alloy |
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2018
- 2018-05-04 CN CN201810417301.2A patent/CN108715622A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772571A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of propylene-alpha-olefin random copolymer |
| CN104774394A (en) * | 2015-03-30 | 2015-07-15 | 青岛科技大学 | Preparation methods for polyolefin alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171205A (en) * | 2020-03-02 | 2020-05-19 | 石家庄联合石化有限公司 | Production method of polypropylene |
| CN111171205B (en) * | 2020-03-02 | 2021-05-28 | 石家庄联合石化有限公司 | Production method of polypropylene |
| CN112358560A (en) * | 2020-10-21 | 2021-02-12 | 中国石油化工股份有限公司 | System and method for producing odorless polypropylene granular product |
| CN113583167A (en) * | 2021-08-27 | 2021-11-02 | 云南云天化石化有限公司 | Device and method for producing propylene-butylene random copolymerization polypropylene by gas phase process |
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Application publication date: 20181030 |