CN109810398A - A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof - Google Patents
A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of super high molecular weight isotactic polypropylene resin combinations and preparation method thereof, pass through preferred internal electron donor system, preparation Zigler-Natta catalyst is compounded by internal electron donor, the polypropylene that viscosity average molecular weigh is up to 3,000,000 has been synthesized using the catalyst, after entering flash distillation and inactivation kettle by the acrylic polymers generated in the second stage reactor simultaneously, the spray solution of heat stabilizer be will be enriched at this stage in prepared polypropylene powder particle surface, to obtain the polypropylene of uniform adhesion heat stabilizer, realize producing for the ultra high molecular weight resin product containing heat stabilizer, add, cost is relatively low, existing big device is convenient for operation, easily implement, it can effectively solve the production technology bottleneck of the poly- third allyl resin product of super high molecular weight isotactic.
Description
Technical field
The present invention relates to a kind of acrylic polymers, the molecular weight of the acrylic polymers is 1 × 106G/mol~4 × 106g/
Mol, isotacticity are greater than the preparation method of 90% and this acrylic polymers, and this method is suitable in continuity method propylene polymerization
High molecular weight isotactic polypropylene resin is produced in technique.
Background technique
Isotactic polypropylene has the characteristics that small density, easy processing, chemical stability are good, mechanical property is excellent etc., in building, packet
The fields extensive applications such as dress, automobile, household electrical appliances manufacture.The isotactic polypropylene resin of conventional method preparation, molecular weight usually exist
1000000 prepare various types of resins product hereinafter, being suitable for the processing methods such as injection molding, blown film, spinning.Super high molecular weight polymer (point
Son amount is usually 1,000,000 or more) there is very high mechanical strength and wearability, belong to high performance material.For example, super high molecular weight
Polyvinyl resin has been widely used in fiber production, and high performance ultra-high molecular weight polyethylene special fibre is made to obtain reality
Using.The synthesis of ultrahigh molecular weight polypropylene especially super high molecular weight isotactic polypropylene, always more slowly, this is main for development
It is to cause polymer that cannot reach higher molecular weight because propylene polymerization itself is easy to happen chain tra nsfer.Therefore synthesis superelevation
The key of molecular weight polypropylene is the exploitation of catalyst system.In addition, polypropylene molecular chain is due to containing a large amount of tertiary carbon atoms
(carbon atom being connected with methyl), when heating, are extremely easy to happen oxidative degradation and cause molecular weight and molecular weight, therefore heat stabilizer
Uniformly add it is extremely important, this give process propose requirements at the higher level.
So far, the synthetic method of super high molecular weight isotactic polypropylene only has few document report, such as Kaminsky
Metallocene catalyst Me is utilized Deng once report2Si(Ind)2ZrBz2Or metallocene catalyst Me2Si(2-Me-4-Ph-Ind)2ZrBz2With boranes co-catalyst [C (CH3)3][B(C6F5)4] composition catalyst system, at a lower temperature (0 DEG C~30 DEG C)
The isotactic polypropylene (Polymer, 2001,42,4017-4024) that molecular weight is 100~4,000,000, but polymerization activity can be obtained
It is not high.Also studies have reported that metallocene catalysis rac- [1- (9-h5-flu) -2- (2-methylbenzo [b] Indeno [4,5-d]
thiophen-1-h5-yl)ethane]H fMe2It can get the isotactic polypropylene that molecular weight is greater than 1,000,000 under certain condition
(Organometallics,2003,22,3495-3501).From the point of view of result reported in the literature, the conjunction of ultrahigh molecular weight polypropylene
It is required at the metallocene catalyst for being primarily dependent on a few class special constructions, and for the type of co-catalyst, it is necessary to adopt
Inhibit the generation of chain transfer reaction with boranes compound.Also, since reaction is homogeneous polymerization feature, resulting polymers do not have
There are controllable mode of appearance, only unformed powder.Recently, patent ZL201410181656, which reports one kind, can be used for 3D printing
Super high molecular weight isotactic polypropylene resin and its preparation method and application, the resin is to pass through Supported Metallocene Catalysts for Olefin Polymerization
It is catalyzed propylene polymerization to obtain, ultrasonic disperse in the solvent containing heat stabilizer then is added in above-mentioned acrylic resin again,
Again solvent evaporated and be made.Metallocene catalyst is used for the preparation of industrialization of isotactic polypropylene, in catalyst cost and polymerization work
There is significant bottleneck in terms of skill adaptability two, polymerizate also needs to return with bonding solvent using solution ultrasonic disperse addition heat stabilizer
Knock off skill, energy consumption is high, not environmentally.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art comprehensively, a kind of super high molecular weight isotactic poly- third is provided
Olefine resin composition.
A kind of super high molecular weight isotactic polypropylene resin combination is steady containing super high molecular weight isotactic polypropylene resin and heat
Determine agent, the composition is made by and the flash distillation workshop section of propylene continuous polymerization technique or inactivation workshop section add heat stabilizer.
The catalyst for preparing above-mentioned super high molecular weight isotactic polypropylene resin is economical Ziegler-Natta catalyst.
A kind of super high molecular weight isotactic polypropylene resin combination, it is poly- that the resin combination contains super high molecular weight isotactic
Allyl resin and thermal stability agent, the molecular weight (viscosimetry measurement) of the resin combination are 1 × 106G/mol~4 × 106g/
Mol, isotacticity (the method measurement that heptane extracts soluble matter) are more than or equal to 90%, and fusing point (differential scanning calorimetry measurement) is
160 DEG C~170 DEG C.
The heat stabilizer is in the macromolecular antioxidant of Hinered phenols, phosphorous acid kind antioxidant and sulphur ester antioxidant
Two or three of combination, preferably three kinds of combination, and the macromolecular antioxidant of Hinered phenols: phosphorous acid kind antioxidant: sulphur
Esters antioxidant is 1:0.5~2:0~1 (weight ratio).
Hindered phenol is one of most effective antioxidant, and-OH functional group is contained in structure, is easier to provide hydrogen atom,
By proton donation, to destroy free radical autoxidation chain reaction.Product currently on the market has 1010,1076,
730, BHA, BHT etc..Phosphorous acid kind antioxidant has the ability of hydroperoxide decomposition, so that autocatalytic reaction be inhibited to lead
The polymer of cause is degraded.Practice have shown that effect is complementary to one another, and not only may be used when hindered phenol and phosphorous acid kind antioxidant are used in compounding
There can also be chain termination with hydroperoxide decomposition.Product currently on the market is main 168.Sulphur ester antioxidant
Also can effective decomposing copolymer hydroperoxides, be allowed to be converted to stable product, domestic sulphur ester antioxidant mainly has
DLTP or DLTDP, DSTP or DSTDP etc..
Preferred following three kinds of combinations in the present invention: antioxidant 1010, it may be assumed that four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester；Irgasfos 168, it may be assumed that three [2.4- di-tert-butyl-phenyl] phosphite esters and anti-oxidant DLTP, it may be assumed that
The double dodecane esters of thio-2 acid.
The additional amount of the heat stabilizer is the 0.1~0.5% of super high molecular weight isotactic polypropylene weight resin.
The present invention also provides a kind of method for preparing above-mentioned super high molecular weight isotactic polypropylene resin combination, technical solutions
It is as follows:
According to the present invention, the preparation method of super high molecular weight isotactic polypropylene is for continuous polymerization reactor technology, example
As Spheripol double loop reactor technology carries out two stages propylene homo in succession and close instead in the reactor of two-stage series connection
It answers, adds heat stabilizer in inactivation/flash vaporization kettle, to obtain super high molecular weight isotactic polypropylene resin.
First stage: in the presence of Ziegler-Natta catalyst, polymerization temperature is 70~80 DEG C, is added without hydrogen
Under the conditions of, the liquid-phase bulk polymerization of propylene is carried out in the first stage reactor, polymerization pressure is surpassed in 4000~4500KPa
High-molecular-weight propylene homopolymer.
Second stage: first order reactor product enters the second stage reactor and relays continuous propylene polymerization, is added appropriate
Hydrogen or non-hydrogenation carry out liquid phase bulk propylene polymerization, reaction temperature at 70~80 DEG C, polymerization pressure 4000~
4500KPa, generate have super high molecular weight isotactic polypropylene homopolymer, additional amount of the hydrogen in propylene be 0~
2000ppm, preferably 50~500ppm.
Phase III:, at this stage will be rich after the acrylic polymers that the second stage reactor generates enters flash distillation and inactivation kettle
Spray solution containing heat stabilizer is in prepared polypropylene powder particle surface, to obtain the super of uniform adhesion heat stabilizer
High molecular weight isotactic polypropylene composition.The heat stabilizer is scattered in solvent, and solvent is selected from the aqueous solution of ethyl alcohol, acetone
At least one of aqueous solution, the aqueous solution of preferred alcohol.
In the preparation process in accordance with the present invention, the Ziegler-Natta catalyst includes following components, (1) it is a kind of with magnesium,
Titanium and internal electron donor are the ingredient of solid catalyst of main component；(2) a kind of organo-aluminium component；(3) a kind of external electron donor
Component, wherein the mass ratio between component (1) and component (2) is calculated as 1:10~1:500 with titanium/aluminium ratio；Preferably 1:25~1:
100.The weight ratio of organo-aluminium component (2) and external electron donor component (3) is 1~50, preferably 2~20.
The component (1) is MgC12/TiC14/ ID loaded catalyst (such as patent CN1110281A；Patent
CN105985465A；Li Zhenhao, Li Huayi, Hu Youliang, two ethers Ziegler-Natta catalyst and its catalysis propylene polymerization
Progress, macromolecule notification, 2009, (5): 30-35；UmeshMakwan,Dhananjay G.Naik,Gurmeet Singh
Et al, Catalyst Letter, disclosed in the documents such as 2009,131:625-631).Wherein, ID is internal electron donor chemical combination
Object is selected from n-butyl phthalate, diethyl phthalate, diethyl succinate, dibutyl succinate, O-phthalic
Sour diisobutyl ester, diisooctyl phthalate, phthalic acid two (1- second, 2- fourth) ester, ethyl benzoate, to methoxybenzene
At least one of group composed by Ethyl formate, paraethoxybenxoic acid ethyl ester and succinate, ID is preferably selected from adjacent benzene two
At least one of formic acid di-n-butyl, diethyl phthalate and phthalic acid two (1- second, 2- fourth) ester.Wherein, with
Component (1) total weight, Ti content are 2.5%~3.5%, and content of magnesium is 16%~20%, internal electron donor carboxylate chemical combination
Object content is 5%~12%.
Component (2) is organo-aluminum compound, and optimizing alkyl aluminium compound, more preferable trialkylaluminium, wherein solids containing titanium is urged
The mass ratio of agent component and organo-aluminum compound cocatalyst component is calculated as 1:10~1:500 with titanium/aluminium ratio；Preferably 1:
25~1:100.
Component (3) specifically may include tetramethoxy-silicane, tetraethoxysilane, front three to be at least one of the following
Methoxylsilane, methyltrimethoxysilane, diphenyl diethoxy silane, dicyclopentyl dimethoxyl silane, methyl ring
Hexyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, diisopropyl dimethoxy silicon
Alkane.It is preferred that dicyclopentyl dimethoxyl silane, Cyclohexylmethyldimethoxysilane.
The control of the productivity ratio of the first stage reactor and the second stage reactor is in 30:70~70:30, preferably 40 in the present invention:
60~70:30.
Present invention is generally directed to continuous polymerization reactor technologies, especially Spheripol double loop reactor technology,
In one stage polymerization reaction, three kinds of catalytic components can be added directly into the first stage reactor, may also pass through industry
Pre- complexing and/or prepolymerization are known altogether and then are added in the first stage reactor.The purpose of the pre- complex reaction is to make to be catalyzed
The sufficiently effective mixing of agent each component energy, pre- complex reaction can carry out in continuous stirred tank reactor, annular-pipe reactor etc..
The temperature of pre- complex reaction controls between -10~60 DEG C, and preferably 10~30 DEG C.The time control of pre- complex reaction 30~
100min, preferably 5~30min.
Bulk propylene or slurry prepolymerization can be also carried out with or without the catalyst being complexed in advance, it can be continuous
It being carried out in blender or annular-pipe reactor, the temperature of prepolymerization controls between -10~60 DEG C, and preferably 10~30 DEG C.In advance
The multiple of polymerization is controlled at 30~300 times, and preferably 50~150 times.
Under the conditions of the Ziegler-Natta catalyst of general performance, polypropylene of the molecular weight less than 1,000,000 is usually obtained
Resin can get molecular weight under specific polymerization process condition as 100~1,500,000 acrylic resin, but high molecular weight
Acrylic resin is degradable to be difficult to store for a long time, it is necessary to add heat stabilizer (i.e. in resin by the method for extruding pelletization
Antioxidant) to guarantee to stablize storage.However, melt viscosity increases, and especially molecular weight reaches with the raising of polymer molecular weight
To after 1,500,000 or more, extruding pelletization energy consumption is high, difficult work is difficult, and heat stabilizer is in super high molecular weight isotactic polypropylene resin
It is added to technical bottleneck.The invention reside in by preferred internal electron donor system, is compounded and prepared by internal electron donor
Zigler-Natta catalyst has synthesized the polypropylene that viscosity average molecular weigh is up to 3,000,000 using the catalyst, while by
After the acrylic polymers that two-stage generates enters flash distillation and inactivation kettle (workshop section), the solution spray of heat stabilizer will be enriched at this stage
It spills in prepared polypropylene powder particle surface, to obtain the polypropylene of uniform adhesion heat stabilizer, realizes containing heat
The i.e. production of the ultra high molecular weight resin product of stabilizer is added, and can carry out powder packaging immediately, cost is relatively low, existing
Big device is easily implemented convenient for operation, can effectively solve the production technology bottle of the poly- third allyl resin product of super high molecular weight isotactic
Neck.
Detailed description of the invention
Fig. 1 is the dynamic shear rheological curve of 1 polymer melt of comparative example.
Fig. 2 is the dynamic shear rheological curve of 2 polymer melt of comparative example.
Fig. 3 is the dynamic shear rheological curve of 1 polymer melt of embodiment.
Fig. 4 is the dynamic shear rheological curve of 2 polymer melt of embodiment.
Fig. 5 is the dynamic shear rheological curve of 3 polymer melt of embodiment.
Fig. 6 is the dynamic shear rheological curve of 4 polymer melt of embodiment.
Fig. 7 is the dynamic shear rheological curve of 5 polymer melt of embodiment.
Fig. 8 is that the complex viscosity of polymer melt compares.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, it is to be noted that the content of present invention is simultaneously
It is not limited to this.
The related data of polymer are obtained by following test method in embodiment:
(1) it viscosity-average molecular weight (viscosimetry): is surveyed according to GB T 1632-1993 dilute polymer viscosity number and intrinsic viscosity
Determine standard test.
(2) polymer xylene soluble content measures: measuring by ASTM D5492.
(3) Rheological Behavior of Polymer Melt is tested: plate rheometer, 210 DEG C, is tested under nitrogen atmosphere.
Embodiment 1
The component (1) (the solid catalyst activity component of titaniferous) of Ziegler-Natta catalyst uses Chinese patent
The method that CN201310552108 embodiment 1 describes obtains, Ti content: 2.76%, content of magnesium: and 18.0%, phthalic acid
Di-n-butyl content: 5.28%, diethyl phthalate content: 2.26%.
Polymerization reaction carries out on Spheripol double loop reactor device.Catalytic component (1), component (2) (three second
Base aluminium), after 20min is complexed in advance under the conditions of 10 DEG C in component (3) external electron donor (Cyclohexylmethyldimethoxysilane), be added
Pre-polymerization reactor carries out pre-polymerization reactor, wherein each component ratio being added in pre- complex reaction kettle is that titanium/aluminium ratio is calculated as
1:50 (mass ratio), triethyl aluminum/Cyclohexylmethyldimethoxysilane mass ratio are 10:1.Prepolymerization is in propylene liquid-phase bulk
It is carried out under environment, reaction temperature is 15 DEG C, residence time 4min, and the pre-polymerization multiple of catalyst is about 120~150 under this condition
Times.
1) slurries after prepolymerization enter the first stage reactor, and polymeric reaction temperature is 70 DEG C, and reaction pressure is
4000KPa, reaction obtain super high molecular weight Noblen；
2) super high molecular weight Noblen enters the second stage reactor, and polymeric reaction temperature is 70 DEG C, and reaction pressure is
The hydrogen of 200ppm is added in polymerization process by 4000KPa；
3) reaction product after the second stage reactor is after flash distillation process, into the processing of deactivation kettle, in deactivation kettle
Ethanol solution containing antioxidant 1010 and irgasfos 168 mixture is sprayed on polymer, wherein antioxidant 1010 and anti-
168 ratio of oxygen agent is 0.5:1, and additional amount is the 0.3% of total resin weight.The superelevation of final obtained uniform adhesion heat stabilizer
Molecular weight isotactic polypropylene composition.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Embodiment 2
Embodiment 2 is similar to Example 1, and difference is changed in catalytic component (1) composition, concrete composition are as follows:
Ti content: 2.60%, content of magnesium: 18.5%, n-butyl phthalate content: 5.25%, diethyl phthalate contains
Amount: 1.18%, phthalic acid two (1- second, 2- fourth) ester: 1.26%.It is other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Embodiment 3
Embodiment 3 is similar to Example 2, the difference is that catalytic component (2) is changed to triisobutyl by triethyl aluminum
Aluminium, component (3) external electron donor are changed to dicyclopentyl dimethoxyl silane by Cyclohexylmethyldimethoxysilane, meanwhile, the
Second reactor density of hydrogen is adjusted to 0 by 200ppm, other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Embodiment 4
Embodiment 4 is similar to Example 3, the difference is that heat stabilizer added in deactivation kettle be antioxidant 1010,
The ethanol solution of irgasfos 168 and the mixture of anti-oxidant DLTP three, ratio 1:1:1, additional amount are total resin weight
0.3%.It is other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Embodiment 5
Embodiment 5 is similar to Example 4, the difference is that catalytic component (3) external electron donor is by bicyclopentyl two
Methoxy silane is changed to diisopropyl dimethoxy silane (Donor P).It is other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Comparative example 1
Comparative example 1 is similar to Example 1, the difference is that catalytic component (1) composition changes, concrete composition
Are as follows: Ti content: 2.60%, content of magnesium: 18.5%, n-butyl phthalate content: 7.45%, it is other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
Comparative example 2
Comparative example 1 is similar to Example 5, the difference is that urging the difference is that the thermostabilization being not added in deactivation kettle
Agent, it is other identical.
The performance test results of polymerization technique and fluoropolymer resin are shown in Table 1.
1 embodiment process conditions of table and polymer performance
It can be seen that comparative example 1 and embodiment 1 from the data in table 1, pass through control catalyst composition and polymerization technique
The viscosity average molecular weigh of condition, gained acrylic resin significantly improves, and increases to 1,020,000 by 270,000；And then pass through catalyst group again
At and polymerization technique control, the higher acrylic resin of molecular weight can be obtained, as the polypropylene molecule amount of embodiment 5 reaches
To 3,120,000；Obtained polymer obtains the evenly dispersed polymer powder for having heat stabilizer after inactivation workshop section addition heat stabilizer
Material, and can store for a long time.
FIG. 1 to FIG. 7 illustrates the dynamic shear rheological curve of resulting polymers in embodiment and comparative example, 1 He of comparative example
Comparative example 2 is common molecular weight polymers, is the storage modulus of sample at 0.01rad/s in shearing frequency in rheological curve
G ' is respectively 1.83Pa and 182Pa, it is seen that as molecular weight improves, the storage modulus of polymer melt rises (loss modulus G "
Also same).The polymer samples of Examples 1 to 5 are respectively 3156Pa cutting frequency as the storage modulus G ' at 0.01rad/s,
3997Pa, 5006Pa, 8522Pa and 10370Pa are significantly higher than the polymer of convenient molecular weight, especially 5 gained sample of embodiment
The storage modulus G ' of product is more than 5000 times and 57 times of 2 sample of comparative example 1 and comparative example respectively, with viscosity average molecular weight determination result
Unanimously, show to successfully synthesize ultrahigh molecular weight polypropylene resin.
It compared the complex viscosity of each sample in Fig. 8, it can be seen that super high molecular weight polymer (0.01rad/ at low frequency
S) there is the complex viscosity value significantly increased, the complex viscosity of sample is respectively 1998 Hes in comparative example 1 and comparative example 2
92080Pa.s, the complex viscosity of Examples 1 to 5 sample are respectively 670400,813800,957400,1331000 and
1725000Pa.s shows that the polymer of this patent method preparation has the hyperviscosity feature of super high molecular weight polymer, simultaneously
Polymer highly viscous in this way, be can not realize what heat stabilizer added by way of melt blending, and can only by this specially
The method of polymerization latter end addition described in benefit realizes heat stabilizer dispersion.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. a kind of super high molecular weight isotactic polypropylene resin combination, which is characterized in that the resin combination contains superelevation point
Son amount isotactic polypropylene resin and heat stabilizer, the molecular weight of the resin combination are 1 × 106G/mol~4 × 106G/mol,
Isotacticity is more than or equal to 90%, and fusing point is 160 DEG C~170 DEG C.
2. resin combination according to claim 1, which is characterized in that the heat stabilizer is that Hinered phenols are macromolecular
Two or three of combination in antioxidant, phosphorous acid kind antioxidant and sulphur ester antioxidant.
3. resin combination according to claim 1 or 2, which is characterized in that the heat stabilizer is that Hinered phenols divide greatly
The composition of subtype antioxidant, phosphorous acid kind antioxidant and sulphur ester antioxidant, the macromolecular antioxidant of Hinered phenols: phosphorous acid
Kind antioxidant: the weight ratio of sulphur ester antioxidant is 1:0.5~2:0~1.
4. resin combination according to claim 1 or 2, which is characterized in that the heat stabilizer is antioxidant 1010, resists
The composition of oxygen agent 168 and anti-oxidant DLTP, the heat stabilizer content are super high molecular weight isotactic polypropylene weight resin
0.1~0.5%.
5. a kind of preparation method of the super high molecular weight isotactic polypropylene resin combination as described in Claims 1 to 4, feature
It is, in continuous polymerization reactor, the preparation process is as follows:
1) in the presence of Ziegler-Natta catalyst, polymerization temperature is 70~80 DEG C, is added without under conditions of hydrogen, the
The liquid-phase bulk polymerization of propylene is carried out in first-stage reactor, polymerization pressure obtains super high molecular weight propylene in 4000~4500KPa
Homopolymer；
2) first order reactor product enters the continuous propylene polymerization of the second stage reactor relaying, and appropriate amount of hydrogen is added or hydrogen is not added
Gas carries out liquid phase bulk propylene polymerization, and for reaction temperature at 70~80 DEG C, polymerization pressure generates tool in 4000~4500KPa
There is an isotactic polypropylene resin of higher molecular weight, additional amount of the hydrogen in propylene is 0~2000ppm, preferably 50~
500ppm；
3) after the acrylic polymers that the second stage reactor generates enters flash distillation and inactivation kettle, it will be enriched in heat stabilizer at this stage
Spray solution is in prepared polypropylene powder particle surface, to obtain the super high molecular weight isotactic of uniform adhesion heat stabilizer
Polypropylene resin composite.
6. the preparation method of super high molecular weight isotactic polypropylene resin combination according to claim 5, which is characterized in that
The Ziegler-Natta catalyst includes following components: (1) a kind of consolidating using magnesium, titanium and internal electron donor as main component
Body catalyst component；(2) a kind of organo-aluminium component；(3) a kind of external electron donor component, wherein component (1) and component (2) it
Between mass ratio 1:10~1:500, preferably 1:25~1:100 are calculated as with titanium/aluminium ratio；The weight ratio of component (2) and component (3)
Example is 1~50, preferably 2~20；The component (1) is MgC12/ TiC14/ID loaded catalyst, wherein ID is interior electron
Body compound: n-butyl phthalate, diethyl phthalate, diethyl succinate, dibutyl succinate, neighbour are selected from
Phthalic acid diisobutyl ester, diisooctyl phthalate, phthalic acid two (1- second, 2- fourth) ester, ethyl benzoate, to first
At least one of group, is preferably selected from neighbour composed by p-methoxybenzoic acid ethyl ester, paraethoxybenxoic acid ethyl ester and succinate
At least one of phthalic acid di-n-butyl, diethyl phthalate and phthalic acid two (1- second, 2- fourth) ester,
In, with component (1) total weight, Ti content is 2.5%~3.5%, and content of magnesium is 16%~20%, internal electron donor carboxylate
Compounds content is 5%~12%；Component (2) is alkyl aluminum compound, preferred trialkylaluminium, wherein solids containing titanium catalyst group
Divide the mass ratio with organo-aluminum compound cocatalyst component, 1:10~1:500, preferably 1:25~1 be calculated as with titanium/aluminium ratio:
100；Component (3) is selected from tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, two
Diethylamino phenyl oxysilane, dicyclopentyl dimethoxyl silane, Cyclohexylmethyldimethoxysilane, diisobutyl dimethoxy
At least one of silane, di-t-butyl dimethoxysilane and diisopropyl dimethoxy silane, are preferably selected from bicyclopentyl
At least one of dimethoxysilane, Cyclohexylmethyldimethoxysilane.
7. the preparation method of super high molecular weight isotactic polypropylene resin combination according to claim 6, which is characterized in that
Three kinds of components of the Ziegler-Natta catalyst are added in first reactor after the processing of complexing in advance, and pre- complexing is anti-
Answering device is continuous stirred tank reactor or annular-pipe reactor, and pre- complex reaction temperature is between -10~60 DEG C preferably 10~30
DEG C, the pre- complex reaction time is 30~100min, preferably 5~30min.
8. the preparation method of super high molecular weight isotactic polypropylene resin combination according to claim 6 or 7, feature exist
In the Ziegler-Natta catalyst carries out bulk propylene or slurry prepolymerization in continuous stirred tank reactor or annular-pipe reactor
Reaction, prepolymerization temperature be -10~60 DEG C between, preferably 10~30 DEG C, prepolymerization multiple be 30~300 times, preferably 50
~150 times.
9. the preparation method of super high molecular weight isotactic polypropylene resin combination according to claim 6, which is characterized in that
The heat stabilizer is scattered in solvent, and solvent is selected from least one of the aqueous solution of ethyl alcohol, aqueous solution of acetone.
10. the preparation method of super high molecular weight isotactic polypropylene resin combination according to claim 6, feature exist
In the productivity ratio of the first stage reactor and the second stage reactor is controlled in 30:70~70:30, preferably 40:60~70:30.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114874370A (en) * | 2022-06-13 | 2022-08-09 | 中国科学院长春应用化学研究所 | Ultrahigh molecular weight functionalized isotactic polypropylene and preparation method thereof |
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| CN114874370A (en) * | 2022-06-13 | 2022-08-09 | 中国科学院长春应用化学研究所 | Ultrahigh molecular weight functionalized isotactic polypropylene and preparation method thereof |
| CN114874370B (en) * | 2022-06-13 | 2023-05-26 | 中国科学院长春应用化学研究所 | Ultra-high molecular weight functionalized isotactic polypropylene and preparation method thereof |
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