CN105622805B - A kind of preparation method of 1- butene polymers - Google Patents
A kind of preparation method of 1- butene polymers Download PDFInfo
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- CN105622805B CN105622805B CN201410598390.7A CN201410598390A CN105622805B CN 105622805 B CN105622805 B CN 105622805B CN 201410598390 A CN201410598390 A CN 201410598390A CN 105622805 B CN105622805 B CN 105622805B
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Abstract
The invention discloses a kind of preparation method of 1 butene polymers, this method includes：In polymerization reaction kettle, in the presence of a catalyst, the monomer containing 1 butylene is subjected to polymerisation under olefin solution polymerization reaction condition, and obtained polymerization system is contacted with poor solvent, so that 1 butene polymers in the polymerization system separate out.For the method for the present invention in the case where ensureing that 1 obtained butene polymers have relatively low residual catalyst content, it is 0.1 0.4g/cm that can prepare bulk density3Powdered resin.
Description
Technical field
The present invention relates to a kind of preparation method of 1- butene polymers.
Background technology
Poly 1-butene (1-PB) has prominent creep resistance, environmental stress crack resistance, wearability, reelability and good
Mechanical performance, compared to other plastics (e.g., PVC, CPVC, HDPE, PP and crosslinking PE etc.), it can be less than 90 DEG C for a long time
Use, and in 105-110 DEG C of short-period used.Based on above characteristic, poly 1-butene is suitable for making tubing, food film and thin plate,
It even can be used for the hot water pipe and direct drinking water project pipe of domestic water, ensure water quality non-secondary pollution.In addition, and metal
Pipeline is compared, the energy consumption only respectively steel and the 1/8 of aluminium and 1/4, and poly 1-butene of the poly 1-butene tubing of production unit volume
Tubing is avoided that the problems such as the getting rusty of metal pipe material, galvano-cautery perforation.
High isotactic polybutene-1 can be produced and be machined using traditional polyolefin polymerization technology (such as：Squeeze
Pressure, injection or blow molding etc.).
In current industrial production, the poly- 1- fourths of the catalyst preparation based on Ziegler-Natta catalyst are mainly used
Alkene.The technique for carrying out 1- butene polymerizations using the catalyst mainly has substance law, vapor phase method and solwution method, with accomplished continuously or intermittently method
Production.
Domestic some producers carry out the production of poly 1-butene, batch of the poly 1-butene of this method production using mass polymerization
Secondary stability is poor and is not suitable for large-scale industrial production；Using gas phase polymerization process can obtain isotacticity it is higher, batch
The less poly 1-butene of secondary difference property, but the more difficult control of reaction process of this method.Solwution method since production process is relatively easy to control,
Polymerization technique is simple, is current more common method, and this method includes：1- butylene is carried out in the presence of solvent to polymerize anti-
Should, the last handling process then washed, separated and dried.The method of the post processing is similar to rubber, obtained resin
Easily assemble blocking.But solvent content is higher in block resin, extrusion of the resin in the follow-up processing such as extrusion can be caused
The block of molding failures, such as tube wall surface is raised, uneven color is even.
The content of the invention
The goal of the invention of the present invention is to overcome the 1- butene polymerizations resin synthesized in the prior art using solwution method to hold
Easily lump and influence the technical problem of product quality after machine-shaping, so as to provide a kind of preparation method of 1- butene polymers.
The present invention provides a kind of preparation method of 1- butene polymers, this method includes：In polymerization reaction kettle, urging
In the presence of agent, the monomer containing 1- butylene is subjected to polymerisation under olefin solution polymerization reaction condition, and will obtained
Polymerization system is contacted with poor solvent, so that the 1- butene polymers in the polymerization system separate out.
On the one hand the method for the present invention can guarantee that synthesized 1- butene polymers have relatively low residual catalyst content,
On the other hand the 1- butene polymers of powdery can also be obtained.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of 1- butene polymers, this method includes：In polymerization reaction kettle, urging
In the presence of agent, the monomer containing 1- butylene is subjected to polymerisation under olefin solution polymerization reaction condition, and will obtained
Polymerization system is contacted with poor solvent, so that the 1- butene polymers in the polymerization system separate out.
The method according to the invention,, can be with after the poor solvent is contacted with the polymerization system in polymerization reaction kettle
The remaining catalyst of unreacted monomer and part in the polymerization system is dissolved in poor solvent, when being vented monomer with
1- butene polymers in the polymerization system further separate, so that the 1- butene polymers of powdery be made.
The polymerization reaction kettle can be suitable for what the monomer containing 1- butylene was polymerize for commonly used in the art
Reaction kettle, such as can be the autoclave of vertical type cylinder shape.
According to the present invention, the poor solvent refers to that in temperature be 20-90 DEG C, and pressure makes under conditions of being below 10MPa
The solubility of 1- butene polymers is less than the solvent of 0.01g.The poor solvent can exist in gaseous form at room temperature.
The poor solvent can be selected from C1-C7Aliphatic alcohol, C2-C3Aliphatic alkane and C2-C6Fatty monoethers
At least one of.
In the present invention, preferably described C1-C7Aliphatic alcohol be C1-C7Aliphatic saturated monohydroxy alcohol, its instantiation can
Think but be not limited to：Methanol, ethanol, normal propyl alcohol, isopropanol, 1- amylalcohols, 2- methyl isophthalic acids-propyl alcohol, 2- butanol, 2,3- dimethyl-
At least one of 3- amylalcohols.
In the present invention, the C2-C3The instantiation of aliphatic alkane can be but be not limited to：Ethane, n-propane and different
At least one of propane.
In the present invention, the C2-C6The instantiations of Fatty monoethers include but not limited to dimethyl ether, ether and n-butyl ether
At least one of.
From the angle for the bulk density for improving the 1- butene polymers powder, the poor solvent preferably is selected from first
At least one of alcohol, ethanol and isopropanol.
In the present invention, the dosage of the poor solvent can make choice according to the dosage of monomer.Usually, it is described bad
The mass ratio of solvent and the monomer containing 1- butylene can be 1:1-10.
The condition that the present invention contacts the polymerization system with poor solvent is not particularly limited, as long as can make the 1-
Butene polymers separate out in polymerization reaction kettle.Under preferable case, it is described contact temperature be 60-90 DEG C under conditions of into
OK, so the poor solvent can be made further to be uniformly mixed with polymerization system.Herein under preferable Contact Temperature, it is described not
The time of contact of good solvent and polymerization system can be 1-20 minutes.
The preparation method of the 1- butene polymers of the present invention can be used for the homopolymerization of 1- butylene, can be used for 1- fourths
The combined polymerization of alkene and other olefinic monomers.It is preferably described to contain from the angle for reducing the 1- butene polymers manufacturing cost
It also containing ethene, propylene and formula is CH to have the monomer of 1- butylene2At least one of alpha-olefin of=CHR, wherein R are C3-C10
Straight or branched alkyl.
In the present invention, the instantiation of the alpha-olefin includes but not limited to amylene (such as 1- amylenes), 4- methyl-1-pentenes
Alkene, hexene (such as 1- hexenes), heptene (such as 1- heptene) or octene (such as 1- octenes).
It is highly preferred that the monomer containing 1- butylene also contains ethene and/or propylene.
The method according to the invention, in the monomer containing 1- butylene, the content of 1- butylene can rub for 50-100
You are %, is preferably 60-100 moles of %.
In the present invention, the catalyst can be conventional selection when 1- butylene carries out polymerisation, for example, can be
Ziegler-Natta catalyst or metallocene catalyst.
The Ziegler-Natta catalyst can contain as the solid constituent of major catalyst, as co-catalyst
Organo-aluminum compound and optional external donor compound, the solid constituent can be titanium compound, magnesium compound and interior
The reaction product of electron donor compound.
According to the present invention, the titanium compound, magnesium compound all can be common selections in olefin polymerization catalysis.It is excellent
Selection of land, the titanium compound are titanium tetrachloride, and the magnesium compound is magnesium dichloride or dialkoxy magnesium.The internal electron donor
Compound can be diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, O-phthalic
At least one of sour diisopropyl ester, diethyl phthalate and repefral.
In the present invention, in the solid constituent, the titanium compound, internal electron donor compound and magnesium compound rub
Your ratio can be 0.01-50：0.01-50：1.The solid constituent is for example referred to the method described in CN102453150A
It is made, details are not described herein.
According to the present invention, the organo-aluminum compound can be various organo-aluminum compounds commonly used in the art.Such as can
Think the one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diethyl aluminum chloride.Preferably, it is described organic
Aluminium compound is triethyl aluminum.
External donor compound as optional catalyst component is preferably organo-silicon compound, described siliconated
Compound can be but be not limited only to：Tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, front three base oxethyl
Silane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, two phenoxy group dimethoxysilanes, phenyl trimethoxy
Silane, vinyltrimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane or diisobutyl two
Methoxy silane.
In the present invention, with Ti/Al molar ratio computings, the ratio between dosage of the solid constituent and the organo-aluminum compound can be with
For 1：25-1000；With the molar ratio computing of Al/Si, the organo-aluminum compound rubs with the external donor compound dosage
Your ratio can be 1-100：1, it is preferably 5-70：1.
The present invention is not particularly limited the dosage of Ziegler-Natta catalyst described in reaction system, Ke Yiwei
The content of field of olefin polymerisation routine.Usually, the molecular weight of polymerization rate and resulting polymers in order to balance, preferably
In the case of, in terms of major catalyst, the mass ratio with the dosage of the monomer containing 1- butylene of the Ziegler-Natta catalyst
Can be 1：103-106。
Usually, the metallocene catalyst usually contains metallocene compound and promoter aluminium alkyl oxygen alkane.
Wherein, the various metallocene compounds that the metallocene compound can be known to the skilled person, for example,
Can be bis cyclopentadienyl zirconium dichloride, (the 2- methyl 4-phenyls indenyl) zirconium dichloride of dimethyl silicon bridge two and (the 2- first of dimethyl silicon bridge two
At least one of base -4- naphthyls indenyl) zirconium dichloride.The metallocene compound can be conventional by commercially available or this area
Method is made, for example, can be by Organometallics1994, it is prepared by the method described in 13,954-963, or
The product that article No. purchased from Aladdin reagent is B124559.
The alkylaluminoxane can be selected from one kind in methylaluminoxane (MAO) and/or alkyl-modified methylaluminoxane
It is or a variety of.Wherein, the alkyl-modified methylaluminoxane refers to methylaluminoxane and C2-C5Alkylaluminoxane mixture or
Person is by trimethyl aluminium and C2-C5Alkyl aluminum mixture be hydrolyzed obtained from methylaluminoxane.The alkyl-modified methyl
Aikyiaiurnirsoxan beta is commercially available, and can also be prepared using well known to a person skilled in the art method.
In the present invention, the molar ratio of the aluminium in metallic element and alkylaluminoxane in the metallocene compound can be
1:500-10000, is preferably 1:500-5000.With elemental metal, metallocene compound in the metallocene catalyst with
The molar ratio of the butene monomers containing 1- can be 1:104-106。
A preferred embodiment of the invention, the catalyst are Ziegler-Natta catalyst, so can be with
Further improve the isotacticity of 1- butene polymers and reduce the residual catalyst content of 1- butene polymers.
In the present invention, preferably described polymerisation carries out in presence of hydrogen, carries out polymerisation in the presence of hydrogen gas,
With the 1- butene polymers strand of growth chain transfer reaction can occur for hydrogen, so that polymerisation terminates, obtain opposite
The less polymer of molecular weight, so as to play the role of adjusting 1- butene polymers relative molecular weights.
The method according to the invention, the olefin solution polymerization condition can under conditions of field of olefin polymerisation routine into
OK, preferably described olefin solution polymerization condition includes：Temperature is 20-120 DEG C.The time of the olefin solution polymerization can be
When 0.5-3 is small.
The method according to the invention, the polymerisation can be in the presence of optional inert hydrocarbon solvents, with liquid
1- butylene is carried out as polymerisation medium.Wherein, the inert hydrocarbon solvent can be in hexane, heptane, toluene and dimethylbenzene
One or more, are preferably hexane or toluene.
The method according to the invention, after obtained polymerization system is contacted with poor solvent, the method further includes：Will not
The monomer emptying of reaction.
In the present invention, the process that unreacted monomer is vented is preferably included to vacuumize, make the vacuum of polymerization reaction kettle
Reach below 0.1MPa, so as to further improve the bulk density of 1- butene polymers.
In a kind of preferred embodiment of the present invention, the preparation process of 1- butene polymers includes：Catalyst is each
Component is sent into polymerization reaction kettle and is mixed, and then passes to hydrogen, then will be sent into the polymerization containing the monomer of 1- butylene
In reaction kettle, contacted with the catalyst, hydrogen under olefin solution polymerization reaction condition, and the polymerization system that will be obtained
Contact with poor solvent, be then vented unreacted monomer, so as to obtain powdered 1- butene polymers.
The method according to the invention can obtain catalyst less residue and be powdered 1- butene polymers.
The invention will be further described by the following examples.
In following embodiments and comparative example, solid constituent is used in CN102453150A in Ziegler-Natta catalyst
The method that embodiment 1 describes obtains, and internal electron donor compound therein is n-butyl phthalate.
The heap density of 1- butene polymers is measured using method as defined in GB/T 1636-2008.
The measure of 1- butene polymers isotacticities：Measured not after 1- butene polymers are extracted 48h in the ether of boiling
Percentage composition shared by molten thing.
Metal element content measures in 1- butene polymers：By 1- butene polymers at 800 DEG C after high temperature sintering, hydrochloric acid
It is dissolved into the content of trace meter in using plasma emission spectrometer (ICP) measure polymer after aqueous solution.Icp analysis instrument
Device composes direct-reading ICP spectrometers (PE companies of the U.S.) entirely for 8300 types of Optima, and operating condition is high frequency power 1300W, plasma
Gas 15L/min, atomization gas 0.55L/min, aid in gas 0.2L/min, wriggling pump speed 1.50mL/min, time of integration 5s, plasma
Body axial observation.
Embodiment 1
The present embodiment is used for the preparation method for illustrating the 1- butene polymers of the present invention.
The heating of 5L autoclaves is vacuumized, inflated with nitrogen, repeatedly for three times, add the hexane solution (three of 9mL triethyl aluminums
The concentration of aluminium ethide is 0.88mmol/mL), the outer electron of the diisopropyl dimethoxy silane of 10mg solid constituents and 1.5mL
The hexane solution (concentration of external electron donor is 0.1mmol/mL) of body, stirs evenly.Backward reaction kettle in be passed through 0.4MPa
H2, then the 1- butylene of 800g is passed through, while heated to reaction kettle, polymerisation is carried out at 40 DEG C, after reacting 1h, stops stirring
Mix, polymerization system temperature is increased to 80 DEG C, 100g methanol is added into reaction kettle, after stirring 20min, be in vacuum
Unreacted 1- butene monomers are vented under conditions of below 0.01MPa, reaction kettle is opened, obtains the 1- butene polymerizations of powdery
Thing, the property of the polymer are as shown in table 1.
Embodiment 2
The present embodiment is used for the preparation method for illustrating the 1- butene polymers of the present invention.
The heating of 5L autoclaves is vacuumized, inflated with nitrogen, repeatedly for three times, add the hexane solution (three of 9mL triethyl aluminums
The concentration of aluminium ethide is 0.88mmol/mL), the outer electron of the diisopropyl dimethoxy silane of 10mg solid constituents and 1.5mL
The hexane solution (concentration of external electron donor is 0.1mmol/mL) of body, stirs evenly.Backward reaction kettle in be passed through 0.4MPa
H2, then the 1- butylene and 20g ethene of 780g are passed through, start to stir, while heated to reaction kettle, carry out polymerizeing at 50 DEG C anti-
Should, after reacting 1h, stop stirring, polymerization system temperature is increased to 70 DEG C, 100g isopropanols, stirring are added into reaction kettle
After 20min, unreacted 1- butylene and vinyl monomer are vented under conditions of vacuum is below 0.1MPa, open reaction
Kettle, obtains the 1- butene polymers of powdery, and the property of the polymer is as shown in table 1.
Embodiment 3
The present embodiment is used for the preparation method for illustrating the 1- butene polymers of the present invention.
1- butene polymers are prepared using method same as Example 1, the difference is that the propane generation with phase homogenous quantities
For the methanol in embodiment 1, so that the 1- butene polymers of powdery be made, the property of the polymer is as shown in table 1.
Embodiment 4
The present embodiment is used for the preparation method for illustrating the 1- butene polymers of the present invention.
1- butene polymers are prepared using method same as Example 1, the difference is that the ethane generation with phase homogenous quantities
For the methanol in embodiment 1, so that the 1- butene polymers of powdery be made, the property of the polymer is as shown in table 1.
Embodiment 5
The present embodiment is used for the preparation method for illustrating the 1- butene polymers of the present invention.
The heating of 5L autoclaves is vacuumized, inflated with nitrogen, repeatedly for three times, the MAO for adding 20mL (is tried purchased from Aladdin
Agent, article No. M201049) and 20mL toluene, then add 15mg bis cyclopentadienyl zirconium dichloride (be purchased from Aladdin reagent, concentration is
98%), stir evenly.Backward reaction kettle in be passed through the H of 0.4MPa2, then the 1- butylene and 20g propylene of 780g are passed through, at the same time
Heated to reaction kettle, polymerisation carried out at 50 DEG C, after reacting 1h, stopped stirring, polymerization system temperature is increased to 70 DEG C,
100g isopropanols are added into reaction kettle, after stirring 20min, by unreacted 1- under conditions of vacuum is below 0.1MPa
Butylene and propylene monomer emptying, open reaction kettle, obtain the 1- butene polymerization resins of powdery, the property such as table 1 of the polymer
It is shown.
Comparative example 1
1- butene polymers are prepared using method same as Example 1, the difference is that after discontinuation of the stirring, not rising
Warm polymerization system, is also added without methanol, but is directly vented 1- butene monomers with the method for embodiment 1, obtains the 1- of bulk
Butene polymers, the property of the polymer are as shown in table 1.
Comparative example 2
1- butene polymers are prepared using method same as Example 5, the difference is that after discontinuation of the stirring, not rising
Warm polymerization system, is also added without isopropanol, but is directly vented 1- butylene and propylene monomer with the method for embodiment 5, obtains
Block 1- butene polymers, the property of the polymer are as shown in table 1.
Table 1
| Numbering | Poor solvent | Heap density (g/cm3) | Aluminium content (ppm) | Isotacticity (%) |
| Embodiment 1 | Methanol | 0.38 | 83 | 98.6 |
| Embodiment 2 | Isopropanol | 0.35 | 129 | 98.3 |
| Embodiment 3 | Propane | 0.19 | 183 | 97.9 |
| Embodiment 4 | Ethane | 0.23 | 85 | 97.5 |
| Embodiment 5 | Isopropanol | 0.31 | 165 | 97.6 |
| Comparative example 1 | - | - | 256 | 98.1 |
| Comparative example 2 | - | - | 284 | 97.3 |
1- butylene made from the method for the present invention gathers it can be seen from above example and comparative example and the result of table 1
The isotacticity of compound reaches more than 97.5%, and this method can make obtained 1- butene polymers have relatively low residual catalyst
Content, and it is 0.1-0.4g/cm that bulk density, which can be made,3Powdered resin.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (7)
1. a kind of preparation method of 1- butene polymers, it is characterised in that this method includes：In polymerization reaction kettle, it is being catalyzed
In the presence of agent, the monomer containing 1- butylene is subjected to polymerisation under olefin solution polymerization reaction condition, and it is poly- by what is obtained
Zoarium system contacts with poor solvent, so that the 1- butene polymers in the polymerization system separate out；
Wherein, the temperature of the contact is 60-90 DEG C, and the time is 1-20 minutes；
The poor solvent is C2-C3Aliphatic alkane and/or C2-C6Fatty monoethers.
2. according to the method described in claim 1, wherein, the mass ratio of the poor solvent and the monomer containing 1- butylene
For 1:1-10.
3. according to the method described in claim 1, wherein, the monomer containing 1- butylene also contains ethene and/or propylene.
4. according to the method described in claim 3, wherein, in the monomer containing 1- butylene, the content of 1- butylene is 50-
100 moles of %.
5. according to the method described in claim 1, wherein, the catalyst is Ziegler-Natta catalyst.
6. according to the method described in claim 1, wherein, the olefin solution polymerization reaction condition includes：Temperature is 20-120
℃。
7. according to the method described in any one in claim 1-6, wherein, obtained polymerization system is contacted with poor solvent
Afterwards, the method further includes：Unreacted monomer is vented.
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| CN103173149A (en) * | 2011-12-20 | 2013-06-26 | 日东电工株式会社 | Bonding sheet |
| CN103289588A (en) * | 2012-03-02 | 2013-09-11 | 日东电工株式会社 | Adhesive sheet |
| WO2013161833A1 (en) * | 2012-04-26 | 2013-10-31 | 三井化学株式会社 | Method for producing olefin polymer |
| CN103429690A (en) * | 2011-03-17 | 2013-12-04 | 日东电工株式会社 | Adhesive tape |
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| CN103429690A (en) * | 2011-03-17 | 2013-12-04 | 日东电工株式会社 | Adhesive tape |
| CN103173149A (en) * | 2011-12-20 | 2013-06-26 | 日东电工株式会社 | Bonding sheet |
| CN103289588A (en) * | 2012-03-02 | 2013-09-11 | 日东电工株式会社 | Adhesive sheet |
| WO2013161833A1 (en) * | 2012-04-26 | 2013-10-31 | 三井化学株式会社 | Method for producing olefin polymer |
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