CN106565883A - Applications of organosilanes, polyolefin resin and preparing method of the polyolefin resin - Google Patents
Applications of organosilanes, polyolefin resin and preparing method of the polyolefin resin Download PDFInfo
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- CN106565883A CN106565883A CN201510658460.8A CN201510658460A CN106565883A CN 106565883 A CN106565883 A CN 106565883A CN 201510658460 A CN201510658460 A CN 201510658460A CN 106565883 A CN106565883 A CN 106565883A
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Abstract
Applications of organosilanes, polyolefin resin and a preparing method of the polyolefin resin are provided. The method includes subjecting an olefin monomer to olefin polymerization under the existence of a catalyst. The method also includes adding organosilanes into the polymerization system before the olefin polymerization and/or in the olefin polymerization process. The general formula of the organosilanes is R<m><1>SiXn(OR<2>)k, wherein the R<1> is C2-C20 alkyl, the tail end of the R<1> comprises an alpha-olefin double bond, a norbornene group, a cycloolefin group or a dicyclopentadiene group, the X is halogen, the R<2> is C1-C20 straight-chain, branched or isomerized alkyl, the m is an integer ranging from 1 to 3, the n is an integer ranging from 1 to 3, the k is an integer ranging from 0 to 2, and the sum of the m, the n and the k is 4. The polyolefin resin prepared by the method has high melt strength and mechanical strength.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of organosilan is in vistanex is prepared
Application, a kind of preparation method of vistanex and the vistanex prepared by the method.
Background technology
In recent years, although the olefinic polymerization modifying agent with new construction and new capability is constantly found and applies
In the research of polyolefin high performance, but some have the High performance polyolefin resin of wide application prospect
Still lack effective catalytic polymerization preparation means.For example, the crosslinked polypropylene with high fondant-strength is blowing
The applications such as modeling, foaming have broad application prospects, but there is no the effective polymerization can be with present
This polypropylene is prepared in polymeric kettle directly.And for example, with impact copolymer polypropylene (hiPP) as representative
Polypropylene in alloy it is huge in automobile, instrument and equipment and durable consumer goods field application potential, but
It is in polypropylene, in alloy resin, have that interfacial adhesion between polypropylene and EP rubbers phase is low, phase point
From yardstick it is unstable the problems such as so that in the polypropylene, the melt strength of alloy resin is low and power
Poor-performing is learned, its performance has been had a strong impact on.
In order to improve the melt strength and mechanical strength of acrylic resin, presently mainly changed by radiation
Property, the means such as graft modification obtain the acrylic resin with long chain branching or cross-linked structure, or pass through
Introduce the means such as high molecular weight polypropylene component, inorganic filler, copolymerization component and improve the molten of acrylic resin
Body intensity and mechanical strength.But, although polyene can be improved to a certain extent using these methods
The melt strength of hydrocarbon resin simultaneously improves its mechanical property, but but there is production cost height, properties of product list
First-class defect.
The content of the invention
The invention aims to overcome the molten of the vistanex prepared using existing method
The defect of body low intensity, and a kind of application of organosilan in vistanex is prepared, Yi Zhongju are provided
The preparation method of olefin resin and the vistanex prepared by the method.
Specifically, the invention provides a kind of application of organosilan in vistanex is prepared, wherein,
The formula of the organosilan is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen at end
Element, R2For C1-C20Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n is 1-3
Integer, integers of the k for 0-2, and m+n+k=4.
Present invention also offers a kind of preparation method of vistanex, the method includes olefinic monomer exists
Olefinic polyreaction is carried out in the presence of catalyst, wherein, it is anti-that the method is additionally included in the olefinic polymerization
Organosilan, institute are added before answering and/or during the olefinic polyreaction toward polymerization reaction system
The formula for stating organosilan is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen,
R2For C1-C20Straight chain, side chain or isomerization alkyl, integers of the m for 1-3, n are whole for 1-3
Number, integers of the k for 0-2, and m+n+k=4.
Additionally, present invention also offers the vistanex prepared by said method.
The present inventor has found that after further investigation above-mentioned formula is R1 mSiXn(OR2)kIt is organic
Silane is Si (OR ') with formula4(wherein, R ' is C1-C20Alkyl) organosilan and formula be
SiX’4The halogenated silane of (wherein, X ' is halogen) is shown during olefinic polyreaction completely not
Same behavior, toward polymerization reaction system before olefinic polyreaction and/or during olefinic polyreaction
Middle addition formula is R1 mSiXn(OR2)kOrganosilan, can be obtained with higher by polymerization in kettle
The vistanex of melt strength and mechanical strength.Additionally, the present invention provide prepare vistanex
Method can realize vistanex obtained by controllable adjustment by adjusting the species and consumption of organosilan
Branched or crosslinking degree purpose, be so obtained in that melt strength is adjustable, mechanical property is controllable is
Row high melt strength polyolefin resin, or even be obtained in that crosslinked polyolefin resin, so as to realize low cost,
The preparation of the various kettle interpolymerized olefins resin of high-performance, performance.
A preferred embodiment of the invention, the R in the organosilan1For C2-C20's
Alkyl and R1End contain alpha-olefin double bond, norborene group, cycloolefins group or bicyclic penta 2
Alkenyl group, X is halogen, R2For C1-C10Straight chain, side chain or isomerization alkyl, m be 1 or 2,
N is 2 or 3, k are 0, and during m+n+k=4, or work as R1For C2-C18Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen at end
Element, R2For C1-C5Straight chain, side chain or isomerization alkyl, m be 1, n be 3, k be 0 when,
The vistanex for obtaining has higher melt strength and mechanical strength.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of application of organosilan in vistanex is prepared, wherein, it is described to have
The formula of machine silane is R1 mSiXn(OR2)k, wherein, the multiple R in same formula1Can with identical,
Can be with difference, it is possible to be each independently C2-C20Alkyl and R1End contain alpha-olefin double bond,
Norborene group, cycloolefins group or dicyclopentadiene group；Multiple X in same formula can phase
Together, it is also possible to different, it is possible to be each independently halogen (including fluorine, chlorine, bromine, iodine)；It is same
Multiple R in formula2Can be with identical, it is also possible to different, it is possible to be each independently C1-C20It is straight
The alkyl of chain, side chain or isomerization；Integers of the m for 1-3, integers of the n for 1-3, k are whole for 0-2's
Number, and m+n+k=4.
In accordance with the present invention it is preferred that, the multiple R in same formula1Can be with identical, it is also possible to different,
And it is each independently C2-C20Alkyl and R1End contain alpha-olefin double bond, norborene group,
Cycloolefins group or dicyclopentadiene group；Multiple X in same formula can be with identical, it is also possible to different,
And it is each independently halogen (including fluorine, chlorine, bromine, iodine)；Multiple R in same formula2Can phase
Together, it is also possible to different, and it is each independently C1-C10Straight chain, side chain or isomerization alkyl；m
For 1 or 2, n are 2 or 3, k are 0, and m+n+k=4.It is highly preferred that multiple in same formula
R1Can be with identical, it is also possible to different, and it is each independently C2-C18Alkyl and R1End contain
Alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group；In same formula
Multiple X can be with identical, it is also possible to different, and is each independently halogen (including fluorine, chlorine, bromine, iodine)；
Multiple R in same formula2Can be with identical, it is also possible to different, and it is each independently C1-C5Straight chain,
The alkyl of side chain or isomerization；M be 1, n be 3, k be 0.Made using above-mentioned preferred organosilan
The raising of vistanex melt strength and mechanical strength is more beneficial for for modifying agent.
As the R1End contain alpha-olefin double bond (CH2=CH-) when, remove alpha-olefin double bond it
Outward, R1The structure of mid portion is not limited, including straight-chain alkyl (containing double bond, three keys etc.) or its isomer.
Now, the instantiation of the organosilan is included but is not limited to：7- octene base trichlorosilanes, 5- hexenes
Base trichlorosilane, allyltrichlorosilane, two (7- octenyls) dichlorosilane, two (pi-allyl) dichlorosilane
At least one in.
Work as R1End when containing norborene group, R1Structure preferably as shown in formula (1)：
Wherein, the group being connected with silicon atom can be R3, or R4, can also be R5, and
R3、R4And R5It is each independently H or C1-C10Alkyl (include alkene, alkynyl, cycloalkenyl group
Deng), but concrete structure is not limited, including straight-chain alkyl or its isomer.For example, work as R1With formula (1)
Shown structure, and R3For hydrogen atom, R4It is that ethylidene silicon atom are connected, R5For ethyl, m=1,
When n=3, k=0, X are chlorine, the organosilan is 2- (5-ethylidene-2-norbornene base) ethyl trichlorine
Silane.
Work as R1End when containing cycloolefins group, the carbon number of the cycloolefins group can be
3-10, wherein double bond quantity can be the carbon on the hydrocarbyl chain of 1-3, connection ring olefin group and silicon atom
Atomic number can be 1-10, and which includes straight-chain alkyl or its isomer.Additionally, the cycloolefins group
Side chain can be carried on ring, the side chain is preferably C1-C5Alkyl.Now, the tool of the organosilan
Body example includes but is not limited to 2- (3- cyclohexenyl groups) ethyl trichlorosilanes and/or 4- (2,7- cyclo-octadiene bases)
Butyl trichlorosilane.
Work as R1End when containing dicyclopentadiene group, R1Structure preferably as shown in formula (2)：
Wherein, the group being connected with silicon atom can be R6, or R7, can also be R8, and
R6、R7And R8It is each independently H or C1-C10Alkyl, but do not limit concrete structure, including straight
Chain alkylene or its isomer.For example, work as R1With the structure shown in formula (2), and R6And R7It is
Hydrogen atom, R8It is connected for ethylidene and with silicon atom, m=1, n=3, k=0 are when X is chlorine, described to have
Machine silane is 2- (bicyclic pentadiene) ethylidene trichlorosilane.
As described above, the instantiation of the organosilan is included but is not limited to：7- octene base trichlorosilanes,
5- hexenyltrichlorosilanes, allyltrichlorosilane, two (7- octenyls) dichlorosilane, two (pi-allyls)
Dichlorosilane, 2- (5-ethylidene-2-norbornene base) ethyl trichlorosilane, 2- (3- cyclohexenyl groups) ethyl three
Chlorosilane, 4- (2,7- cyclo-octadiene bases) butyl trichlorosilanes and 2- (bicyclic pentadiene) ethylidene trichlorine silicon
At least one in alkane.Preferably, the organosilan is 7- octene base trichlorosilanes, 5- hexenyls three
Chlorosilane, allyltrichlorosilane, 2- (5-ethylidene-2-norbornene base) ethyl trichlorosilane, 2- (3-
Cyclohexenyl group) ethyl trichlorosilane, 4- (2,7- cyclo-octadiene bases) butyl trichlorosilanes and 2- (dicyclopentadienes
Base) at least one in ethylidene trichlorosilane.Using above-mentioned preferred organosilan as modifying agent more
Be conducive to the raising of vistanex melt strength and mechanical strength.
The present invention provide vistanex preparation method include by olefinic monomer catalyst presence
Under carry out olefinic polyreaction, wherein, before the method is additionally included in the olefinic polyreaction and/or
Organosilan is added toward polymerization reaction system during the olefinic polyreaction, the organosilan
Formula is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1To contain alpha-olefin double for end
Key, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen, R2For C1-C20
Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n for 1-3 integer, k is 0-2
Integer, and m+n+k=4.
Additionally, the specifically chosen of the organosilan has been described above being described, therefore not to repeat here.
The present invention is not particularly limited to the consumption of the organosilan, it is preferable that relative to 100 weights
The olefinic monomer of amount part, the consumption of the organosilan is 0.0001-20 weight portions, further excellent
Elect 0.0001-5 weight portions, more preferably 0.0005-1 weight portions, most preferably 0.001-0.5 weight as
Part, so can further improve the melt strength and mechanical strength of the vistanex for obtaining.
The main improvements of the preparation method of the vistanex that the present invention is provided are poly- in the alkene
Before closing reaction and/or during the olefinic polyreaction, toward polymerization reaction system, addition formula is
R1 mSiXn(OR2)kOrganosilan, and the species and olefinic polyreaction of olefinic monomer and catalyst
Method and condition can be the conventional selection of this area.
For example, the olefinic monomer can be the existing various monomers that can carry out olefinic polyreaction,
It is specifically as follows ethylene and/or alpha-olefin.Wherein, the alpha-olefin can exist for existing various double bonds
The monoolefine of strand end, for example, can be pungent for propylene, 1-butylene, 1- amylenes, 1- hexenes and 1-
At least one in alkene.Adopt the vistanex that the olefinic polyreaction is obtained be homopolymerization polyene
Alloy etc. in hydrocarbon resin, copolymeric polyolefin resin, polyolefin kettle.When the vistanex gathers for copolymerization
During olefin resin, in olefinic monomer, the content of comonomer can be the conventional selection of this area, and here is not
Repeat.
The catalyst can carry out polyreaction for the existing various catalyzed alkene monomers that can be used in
Material, its instantiation are included but is not limited to：Ziegler-Natta catalyst, metallocene catalyst and non-
At least one in metallocene catalyst.Wherein, these catalyst specifically comprise people in the art
Member is known, and for example, the Ziegler-Natta catalyst can be MgCl2Supported catalyst system,
VOCl3-AlEt2Cl catalyst system and catalyzings etc..Specifically, MgCl2Usually contain in supported catalyst system
MgCl2、TiCl4, the internal electron donor that contains of alkyl aluminum and/or aluminum alkoxide and selectivity and/or outer
Electron donor, specifically known to those skilled in the art to know, therefore not to repeat here.
The present invention is not particularly limited to the condition of the olefinic polyreaction, generally includes polymerization temperature
It can be 30-90 DEG C, preferably 40-80 DEG C；Polymerization pressure can be 1-10 atmospheric pressure, preferably
1-7 atmospheric pressure；Polymerization time can be 0.05-10 hours, preferably 0.05-2 hours.In the present invention
In, the polymerization pressure refers both to gauge pressure.Additionally, the polyreaction can be slurry polymerization,
It can be bulk polymerization.When the polyreaction is slurry polymerization, the polyreaction is also
Should carry out in presence of organic solvent.The organic solvent can be C5-C10Alkane or C6-C8
Aromatic hydrocarbon, wherein, the C5-C10Alkane be preferably heptane, normal hexane and hexamethylene at least
One kind, the C6-C8Aromatic hydrocarbon be preferably toluene.Additionally, the consumption of the organic solvent can be
The conventional selection of this area, therefore not to repeat here.
Additionally, the melt index in order to adjust vistanex, generally can be with the vistanex
Preparation process in be passed through hydrogen toward polymerization reaction system.Relative to the alkene list of 100 weight portions
Body, the consumption of the hydrogen can be 0-10 weight portions, preferably 0-5 weight portions.
The preparation method of the vistanex provided according to the present invention, it is preferable that the method is additionally included in institute
State after olefinic polyreaction completes, the olefinic polyreaction product for obtaining is adopted at 20-120 DEG C water
And/or alcohol is washed, the olefinic polyreaction product for so enabling to has certain branched or friendship
It is coupled structure, so as to be more beneficial for the raising of its melt strength and mechanical strength.Wherein, the species of the alcohol
Can be that the conventional of this area selects, its instantiation is included but is not limited to：Methanol, ethanol, normal propyl alcohol,
At least one in isopropanol, n-butyl alcohol etc..
Additionally, present invention also offers the vistanex prepared by said method.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the gel content of vistanex is determined in accordance with the following methods：
By vistanex in vacuum drying oven in 50 DEG C of dryings to constant weight, weigh, be designated as W1, so
The dried vistanex of xylene soluble is used afterwards, is fully dissolved in 135 DEG C of vibrations, is used 200 purposes
Stainless (steel) wire is filtered, and collection remains in undissolved polymer on stainless (steel) wire, by stainless (steel) wire
Undissolved polymer in vacuum drying oven, in 100 DEG C of dryings 4 hours, is weighed, is designated as W2, polyene
The computing formula of the gel content of hydrocarbon resin is as follows：
Gel content (weight %)=(W2/W1) × 100 (weight %).
Embodiment 1
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Slurry polymerization：Under vacuum conditions, 450 grams of propylene steam monomers are filled with reactor, then
Sequentially add n-heptane solution 3mL, 7- octenyl three of 50mL hexanes, the triethyl aluminum containing 5.5mmol
Chlorosilane 0.1mL and 20 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/ BMMF, wherein, BMMF
For internal electron donor 9,9- dimethoxy fluorenes, MgCl2、TiCl4Mass ratio with BMMF is 80:12:8),
And by the Stress control in reactor in 5.0 atmospheric pressure, reaction temperature control at 60 DEG C, polyreaction
0.5 hour, polymerization added acidic ethanol to terminate polyreaction after completing, and then used temperature to be 60 DEG C respectively
Deionized water and respectively washing 3 times of ethanol that temperature is 50 DEG C, be finally vacuum dried at 60 DEG C, obtain
To 20.0 grams of HOPP resins.After testing, 7- octenyl trichlorine silicon in the HOPP resin
The concentration of alkane is 5000ppm, and the HOPP resin has branched or cross-linked structure, and its gel contains
Measure as 20 weight %.
Embodiment 2
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Polymerisation in bulk：Under vacuum state, 450 grams of propylene liguids are added in reactor, is then added successively
Enter 0.25mol triethyl aluminums, 0.005 gram of hydrogen, 7- octenes base trichlorosilane 0.02mL and 18 milligrams
Olefin polymerization catalysis (MgCl2/TiCl4/ BMMF, wherein, MgCl2、TiCl4With the matter of BMMF
Amount is than being 80:12:8), reaction temperature control is at 70 DEG C, polyreaction 30 minutes, after the completion of polymerization,
Gas in reactor is vented, is discharged, then products therefrom is washed with hot water (90 DEG C), and
It is vacuum dried at 60 DEG C, obtains HOPP resin.After testing, in the HOPP resin
The concentration of 7- octene base trichlorosilanes be 57ppm, the HOPP resin have it is branched or crosslinking knot
Structure, its gel content are 1.1 weight %.
Embodiment 3
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Method according to embodiment 2 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with the 7- octenyl dimethoxys chlorosilane of same volume, obtain HOPP resin.After testing,
In the HOPP resin concentration of 7- octenyls dimethoxy chlorosilane be 250ppm, the homopolymerization
Acrylic resin has branched or cross-linked structure, and its gel content is 1 weight %.
Comparative example 1
The comparative example is used for the preparation method of the vistanex for illustrating reference.
Method according to embodiment 2 prepares vistanex, except for the difference that, does not add 7- octenyl trichlorines
Silane, obtains reference HOPP resin.
Comparative example 2
The comparative example is used for the preparation method of the vistanex for illustrating reference.
Method according to embodiment 2 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with the tetrachloro silicane of same volume, obtain reference HOPP resin.
Comparative example 3
The comparative example is used for the preparation method of the vistanex for illustrating reference.
Method according to embodiment 2 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with the tetramethoxy-silicane of same volume, obtain reference HOPP resin.
Embodiment 4
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Polymerisation in bulk：Under vacuum state, 450 grams of propylene liguids are added in reactor, is then added successively
Enter 0.25mol triethyl aluminums, 0.025mL Cyclohexylmethyldimethoxysilanes, 7- octenyl trichlorine silicon
Alkane 0.05mL and 18 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/ DIBP, wherein, DIBP
For internal electron donor diisobutyl phthalate, MgCl2、TiCl4Mass ratio with DIBP is
85:8:7), reaction temperature control is at 70 DEG C, polyreaction 30 minutes, after the completion of polymerization, by reactor
Middle gas emptying, discharging obtain 300 grams of HOPP resins.After testing, the HOPP tree
In fat the concentration of 7- octenes base trichlorosilane be 167ppm, the HOPP resin have it is branched or
Cross-linked structure, its gel content are 0.2 weight %.
Embodiment 5
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Polymerisation in bulk：Under vacuum state, 450 grams of propylene liguids are added in reactor, is then added successively
Enter 0.25mol MAOs, 7- octenes base trichlorosilane 0.02mL and 0.0025g transition metals
Compound rac-Me2Si(2-Me-4-PhInd)2ZrCl2(wherein, rac- represents racemization, and Me is methyl, Ph
For phenyl, Ind is indenyl), reaction temperature control at 70 DEG C, polyreaction 30 minutes, polymerization is completed
Afterwards, gas in reactor is vented, discharges, obtain 300 grams of HOPP resins.After testing, should
In HOPP resin the concentration of 7- octenes base trichlorosilane be 67ppm, the HOPP resin
With branched or cross-linked structure, its gel content is 15.2 weight %.
Embodiment 6
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Polymerisation in bulk：Under vacuum state, 450 grams of propylene liguids are added in reactor, is then added successively
Enter 0.25mol alkylaluminoxanes, 7- octenes base trichlorosilane 0.01mL and 0.0025g transition metals
Compound Me2C(Cp)(Flu)ZrCl2(Me is methyl, and Cp is cyclopentadienyl group, and Flu is fluorenyl), instead
Answer temperature control at 70 DEG C, polyreaction 30 minutes, after the completion of polymerization, gas in reactor is vented,
Discharging, obtains 360 grams of HOPP resins.After testing, 7- octenyls in the HOPP resin
The concentration of trichlorosilane is 28ppm, and the HOPP resin has branched or cross-linked structure, and which coagulates
Glue content is 12.0 weight %.
Embodiment 7
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Method according to embodiment 6 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with 2- (5-ethylidene-2-norbornene base) ethyl trichlorosilane of same volume, obtain homopolymerization poly- third
Olefine resin.After testing, 2- (5-ethylidene-2-norbornene base) ethyl trichlorine in the HOPP resin
The concentration of silane is 150ppm, and the HOPP resin has branched or cross-linked structure, its gel
Content is 8.5 weight %.
Embodiment 8
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Method according to embodiment 6 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with 2- (3- cyclohexenyl groups) ethyl trichlorosilane of same volume, obtain HOPP resin.Jing
Detection, in the HOPP resin, the concentration of 2- (3- cyclohexenyl groups) ethyl trichlorosilane is 60ppm,
The HOPP resin has branched or cross-linked structure, and its gel content is 5.2 weight %.
Embodiment 9
The embodiment is used for the preparation method of the vistanex for illustrating present invention offer.
Method according to embodiment 6 prepares vistanex, except for the difference that, by 7- octene base trichlorosilanes
Substituted with 2- (bicyclic pentadiene) the ethylidene trichlorosilane of same volume, obtain HOPP resin.
After testing, in the HOPP resin, the concentration of 2- (bicyclic pentadiene) ethylidene trichlorosilane is
120ppm, the HOPP resin have branched or cross-linked structure, and its gel content is 6.0 weights
Amount %.
Test case
Test case is used for the test for illustrating properties of polyolefin resin.
(1) test of melt strength：
Determine the experimental provision of melt strength by the single screw extrusion machine and Gottfert for being furnished with capillary tube
Rheotens melt strengths analyzer is constituted.First by the vistanex melt of melt strength to be measured from squeeze
Machine outlet mould is extruded, then by the melt extrusion beam batten for obtaining two motion sides being mounted on equalizer bar
Draw to contrary roller.Melt beam be stretched when institute's stress be roll speed and time function.Roller
Uniform to accelerate to rotate, until melt beam ruptures, when melt beam is ruptured, to be defined as melt strong for suffered power
Degree.Acquired results are as shown in table 1.
(2) Mechanics Performance Testing：
Impact strength is measured according to method specified in ASTM D256A, as a result as shown in table 1.
Tensile strength is measured according to method specified in ISO527-2-5A, as a result as shown in table 1.
Bending moduluses are measured according to method specified in ASTM 638-V, as a result as shown in table 1.
Table 1
| Numbering | Melt strength, cN | Impact strength, kJ/m2 | Tensile strength, MPa | Bending moduluses, MPa |
| Embodiment 1 | 650 | 15.2 | 74.5 | 1600 |
| Embodiment 2 | 150 | 7.2 | 64.5 | 1460 |
| Embodiment 3 | 12.0 | 6.9 | 35.6 | 1260 |
| Comparative example 1 | 9.0 | 2.1 | 32.2 | 1200 |
| Comparative example 2 | 8.9 | 1.8 | 32.5 | 1210 |
| Comparative example 3 | 8.0 | 1.3 | 30.8 | 1090 |
| Embodiment 4 | 27 | 5.4 | 40.2 | 1300 |
| Embodiment 5 | 520 | 10.8 | 59.0 | 1450 |
| Embodiment 6 | 480 | 11.5 | 46.0 | 1320 |
| Embodiment 7 | 75.0 | 15.0 | 44.2 | 1350 |
| Embodiment 8 | 48.0 | 10.0 | 41.2 | 1450 |
| Embodiment 9 | 50.0 | 13.6 | 44.0 | 1470 |
As can be seen from the above results, the vistanex tool that the method for being provided using the present invention is prepared
There are higher melt strength and mechanical strength.Can be seen that with the contrast of embodiment 3 from embodiment 2 and work as
R in the organosilan1For C2-C18Alkyl and R1End contain alpha-olefin double bond, norborneol
Alkenyl group, cycloolefins group or dicyclopentadiene group, X is halogen, R2For C1-C5Straight chain,
The alkyl of chain or isomerization, m be 1, n be 3, k be 0 when, the vistanex for obtaining have it is higher
Melt strength and mechanical strength.The present invention be can be seen that from contrast of the embodiment 3 with comparative example 2-3
The organosilan of offer is shown during olefinic polyreaction with silicon tetrahalogen and tetraalkoxysilane
Different behavior, the vistanex that the organosilan provided using the present invention is obtained have higher molten
Body intensity and mechanical strength.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (12)
1. application of a kind of organosilan in vistanex is prepared, it is characterised in that described organic
The formula of silane is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End contain α-
Olefinic double bonds, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen, R2
For C1-C20Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n for 1-3 integer,
Integers of the k for 0-2, and m+n+k=4.
2. application according to claim 1, wherein, R1For C2-C20Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen,
R2For C1-C10Straight chain, side chain or isomerization alkyl, m be 1 or 2, n be 2 or 3, k be 0,
And m+n+k=4.
3. application according to claim 2, wherein, R1For C2-C18Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen,
R2For C1-C5Straight chain, side chain or isomerization alkyl, m be 1, n be 3, k be 0.
4. application according to claim 3, wherein, the organosilan is 7- octenyl trichlorines
Silane, 5- hexenyltrichlorosilanes, allyltrichlorosilane, 2- (5-ethylidene-2-norbornene base) second
Base trichlorosilane, 2- (3- cyclohexenyl groups) ethyl trichlorosilane, 4- (2,7- cyclo-octadiene bases) butyl trichlorine silicon
At least one in alkane and 2- (bicyclic pentadiene) ethylidene trichlorosilane.
5. a kind of preparation method of vistanex, the method include the depositing in catalyst by olefinic monomer
Olefinic polyreaction is carried out under, it is characterised in that the method be additionally included in the olefinic polyreaction it
It is front and/or organosilan is added toward polymerization reaction system during the olefinic polyreaction, it is described to have
The formula of machine silane is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End contain
Alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen, R2
For C1-C20Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n for 1-3 integer,
Integers of the k for 0-2, and m+n+k=4.
6. method according to claim 5, wherein, R1For C2-C20Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen,
R2For C1-C10Straight chain, side chain or isomerization alkyl, m be 1 or 2, n be 2 or 3, k be 0,
And m+n+k=4.
7. method according to claim 6, wherein, R1For C2-C18Alkyl and R1End
Containing alpha-olefin double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen,
R2For C1-C5Straight chain, side chain or isomerization alkyl, m be 1, n be 3, k be 0.
8. method according to claim 7, wherein, the organosilan is 7- octenyl trichlorines
Silane, 5- hexenyltrichlorosilanes, allyltrichlorosilane, 2- (5-ethylidene-2-norbornene base) second
Base trichlorosilane, 2- (3- cyclohexenyl groups) ethyl trichlorosilane, 4- (2,7- cyclo-octadiene bases) butyl trichlorine silicon
At least one in alkane and 2- (bicyclic pentadiene) ethylidene trichlorosilane.
9. the method according to any one in claim 5-8, wherein, relative to 100 weight
The olefinic monomer of part, the consumption of the organosilan is 0.0001-20 weight portions.
10. the method according to any one in claim 5-8, wherein, the catalyst is
At least one in Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst；
Preferably, the olefinic monomer is ethylene and/or alpha-olefin；
Preferably, the alpha-olefin be propylene, 1-butylene, 1- amylenes, 1- hexenes and 1- octenes in extremely
Few one kind.
11. methods according to any one in claim 5-8, wherein, the method is additionally included in
After the olefinic polyreaction is completed, the olefinic polyreaction product for obtaining is adopted at 20-120 DEG C
Water and/or alcohol are washed.
The vistanex that 12. methods by described in any one in claim 5-11 are prepared.
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| CN111138470A (en) * | 2018-11-05 | 2020-05-12 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
| CN111138575A (en) * | 2018-11-05 | 2020-05-12 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
| CN111635482A (en) * | 2019-03-01 | 2020-09-08 | 叶平山 | High-melt-strength polypropylene resin and preparation method thereof |
| CN112142897A (en) * | 2019-09-25 | 2020-12-29 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
| CN112142896A (en) * | 2019-07-15 | 2020-12-29 | 中国科学院化学研究所 | Application of organosilane, polypropylene in-kettle alloy and preparation method thereof |
| CN115073644A (en) * | 2021-03-11 | 2022-09-20 | 中国石油天然气股份有限公司 | Copolymerized high-melt-strength polypropylene resin and preparation method and application thereof |
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| CN111138470B (en) * | 2018-11-05 | 2021-04-23 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
| CN111138575A (en) * | 2018-11-05 | 2020-05-12 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
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| CN111635482A (en) * | 2019-03-01 | 2020-09-08 | 叶平山 | High-melt-strength polypropylene resin and preparation method thereof |
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| CN112142896B (en) * | 2019-07-15 | 2021-06-29 | 中国科学院化学研究所 | Application of organosilane, polypropylene in-kettle alloy and preparation method thereof |
| CN112142897A (en) * | 2019-09-25 | 2020-12-29 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
| CN112142897B (en) * | 2019-09-25 | 2021-07-27 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
| CN115073644A (en) * | 2021-03-11 | 2022-09-20 | 中国石油天然气股份有限公司 | Copolymerized high-melt-strength polypropylene resin and preparation method and application thereof |
| CN115746204A (en) * | 2022-11-25 | 2023-03-07 | 安徽建筑大学 | Intrinsic flame-retardant polydicyclopentadiene elastomer material and preparation method thereof |
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