CN106565883B - A kind of application of organosilan and polyolefin resin and preparation method thereof - Google Patents
A kind of application of organosilan and polyolefin resin and preparation method thereof Download PDFInfo
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- CN106565883B CN106565883B CN201510658460.8A CN201510658460A CN106565883B CN 106565883 B CN106565883 B CN 106565883B CN 201510658460 A CN201510658460 A CN 201510658460A CN 106565883 B CN106565883 B CN 106565883B
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Abstract
Application and polyolefin resin the present invention provides a kind of organosilan and preparation method thereof.The preparation method of the polyolefin resin includes that olefinic monomer is carried out olefin polymerization in the presence of a catalyst, wherein, this method further includes that organosilan is added into polymerization reaction system before the olefin polymerization and/or during the olefin polymerization, and the general formula of the organosilan is R1 mSiXn(OR2)k, wherein R1For C2‑C20Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group, X is halogen, R2For C1‑C20Straight chain, branch or the alkyl of isomerization, m is the integer of 1-3, and n is the integer of 1-3, and k is the integer of 0-2, and m+n+k=4.The polyolefin resin melt strength with higher and mechanical strength obtained using method provided by the invention.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of organosilan prepare the application in polyolefin resin,
A kind of preparation method of polyolefin resin and the polyolefin resin being prepared by this method.
Background technique
In recent years, although the olefinic polymerization modifying agent with new construction and new capability is constantly found and is applied to polyolefin
In high performance research, but some High performance polyolefin resins with wide application prospect still lack effective catalytic polymerization
Preparation means.For example, before the crosslinked polypropylene with high fondant-strength has wide application in application fields such as blow molding, foaming
Scape, but there is no effective polymerization that can directly prepare this polypropylene in polymeric kettle at present.For another example, poly- with crushing-resistant copolymerization
Propylene (hiPP) is that alloy is huge in automobile, instrument and equipment and durable consumer goods field application potential in the polypropylene of representative
Greatly, but there are interfacial adhesion is low between polypropylene and EP rubbers phase, mutually separates scale in alloy resin in polypropylene
The problems such as unstable, so that the melt strength of alloy resin is low in the polypropylene and mechanical property is poor, serious shadow
Its service performance is rung.
In order to improve the melt strength and mechanical strength of acrylic resin, presently mainly changed by radiation modification, grafting
Property etc. means obtain the acrylic resin with long chain branching or cross-linked structure, or by introducing high molecular weight polypropylene group
Point, inorganic filler, the means such as copolymerization component improve the melt strength and mechanical strength of acrylic resin.Although however, using
These methods can improve the melt strength of polyolefin resin to a certain extent and improve its mechanical property, but there is life
Produce the defects of at high cost, properties of product are single.
Summary of the invention
The purpose of the invention is to overcome the melt strength for the polyolefin resin being prepared using existing method low
Defect, and provide a kind of organosilan prepare the application in polyolefin resin, a kind of preparation method of polyolefin resin with
And the polyolefin resin being prepared by this method.
Specifically, the present invention provides a kind of organosilans to prepare the application in polyolefin resin, wherein described organic
The general formula of silane is R1 mSiXn(OR2)k, wherein R1For C2-C20Alkyl and R1End contain alpha-olefin double bond, norbornene
Group, cycloolefin group or dicyclopentadiene group, X are halogen, R2For C1-C20Straight chain, branch or the alkyl of isomerization, m
For the integer of 1-3, n is the integer of 1-3, and k is the integer of 0-2, and m+n+k=4.
The present invention also provides a kind of preparation method of polyolefin resin, this method includes by olefinic monomer in catalyst
In the presence of carry out olefin polymerization, wherein this method further includes before the olefin polymerization and/or in the alkene
Organosilan is added in polymerization process into polymerization reaction system, the general formula of the organosilan is R1 mSiXn(OR2)k,
In, R1For C2-C20Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene
Group, X are halogen, R2For C1-C20Straight chain, branch or the alkyl of isomerization, m is the integer of 1-3, and n is the integer of 1-3, and k is
The integer of 0-2, and m+n+k=4.
In addition, the present invention also provides polyolefin resins prepared by the above method.
The present inventor has found that above-mentioned general formula is R after further investigation1 mSiXn(OR2)kOrganosilan and general formula
For Si (OR ')4(wherein, R ' is C1-C20Alkyl) organosilan and general formula be SiX '4The halogenation of (wherein, X ' is halogen)
Silane shows entirely different behavior during olefin polymerization, before olefin polymerization and/or in alkene
It is R that general formula is added in polymerization process into polymerization reaction system1 mSiXn(OR2)kOrganosilan, kettle cohesion can be passed through
Close the polyolefin resin for obtaining and there is higher melt intensity and mechanical strength.In addition, provided by the invention prepare polyolefin resin
Method the branching or friendship of polyolefin resin obtained by controllable adjustment can be realized by the type and dosage for adjusting organosilan
The purpose of connection degree can obtain the serial high melt strength polyolefin resin that melt strength is adjustable, mechanical property is controllable in this way,
Crosslinked polyolefin resin even can be obtained, to realize the system of the kettle interpolymerized olefins resin of low cost, high-performance, performance multiplicity
It is standby.
A preferred embodiment of the invention, the R in the organosilan1For C2-C20Alkyl and R1End
Alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group are contained in end, and X is halogen, R2For C1-C10's
Straight chain, branch or the alkyl of isomerization, m are 1 or 2, and n is 2 or 3, k 0, and when m+n+k=4, or works as R1For C2-C18Hydrocarbon
Base and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group, X is halogen, R2
For C1-C5Straight chain, branch or the alkyl of isomerization, when m 1, n 3, k are 0, obtained polyolefin resin has higher molten
Body intensity and mechanical strength.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of organosilans to prepare the application in polyolefin resin, wherein the organosilan
General formula is R1 mSiXn(OR2)k, wherein multiple R in same general formula1It may be the same or different, and can be each independently
For C2-C20Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or bicyclic pentadiene
Group；Multiple X in same general formula may be the same or different, and can be each independently halogen (including fluorine, chlorine, bromine,
Iodine)；Multiple R in same general formula2It may be the same or different, and C can be each independently1-C20Straight chain, branch
Or the alkyl of isomerization；M is the integer of 1-3, and n is the integer of 1-3, and k is the integer of 0-2, and m+n+k=4.
In accordance with the present invention it is preferred that multiple R in same general formula1It may be the same or different, and each independently
For C2-C20Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or bicyclic pentadiene
Group；Multiple X in same general formula may be the same or different, and be each independently halogen (including fluorine, chlorine, bromine, iodine)；
Multiple R in same general formula2It may be the same or different, and be each independently C1-C10Straight chain, branch or isomerization
Alkyl；M is 1 or 2, and n is 2 or 3, k 0, and m+n+k=4.It is highly preferred that multiple R in same general formula1Can be identical,
Can be different, and it is each independently C2-C18Alkyl and R1End contain alpha-olefin double bond, norbornene group, cyclenes
Hydrocarbyl group or dicyclopentadiene group；Multiple X in same general formula may be the same or different, and be each independently halogen
Plain (including fluorine, chlorine, bromine, iodine)；Multiple R in same general formula2It may be the same or different, and be each independently C1-C5
Straight chain, branch or the alkyl of isomerization；M is 1, n 3, k 0.More had using above-mentioned preferred organosilan as modifying agent
Conducive to the raising of polyolefin resin melt strength and mechanical strength.
As the R1End contain alpha-olefin double bond (CH2=CH-) when, it removes except alpha-olefin double bond, R1Middle section
Structure it is unlimited, including straight-chain alkyl (containing double bond, three keys etc.) or its isomers.At this point, the specific example of the organosilan
Including but not limited to: 7- octene base trichlorosilane, 5- hexenyltrichlorosilane, allyltrichlorosilane, two (7- octenyls) two
At least one of chlorosilane, two (allyl) dichlorosilanes etc..
Work as R1End when containing norbornene 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 R5Respectively solely
It is on the spot H or C1-C10Alkyl (including alkene, alkynyl, cycloalkenyl group etc.), but do not limit specific structure, including straight-chain alkyl
Or its isomers.For example, working as R1With structure shown in formula (1), and R3For hydrogen atom, R4For ethylidene and silicon atom is connected, R5
For ethyl, m=1, n=3, when k=0, X are chlorine, the organosilan is 2- (5- ethylidene -2- norbornene) ethyl trichlorine
Silane.
Work as R1End when containing cycloolefin group, the carbon atom number of the cycloolefin group can be 3-10, wherein double
Bond number amount can be 1-3, and the carbon atom number on the hydrocarbyl chain of connection ring olefin group and silicon atom can be 1-10 comprising directly
Chain alkylene or its isomers.In addition, can have branch on the ring of the cycloolefin group, which is preferably C1-C5Alkane
Base.At this point, the specific example of the organosilan includes but is not limited to 2- (3- cyclohexenyl group) ethyl trichlorosilane and/or 4-
(2,7- cyclo-octadiene base) 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 R8Respectively solely
It is on the spot H or C1-C10Alkyl, but do not limit specific structure, including straight-chain alkyl or its isomers.For example, working as R1With formula
(2) structure shown in, and R6And R7It is hydrogen atom, R8It is connected for ethylidene and with silicon atom, m=1, n=3, k=0, X are chlorine
When, the organosilan is 2- (bicyclic pentadiene) ethylidene trichlorosilane.
As described above, the specific example of the organosilan includes but is not limited to: 7- octene base trichlorosilane, 5- hexenyl
Trichlorosilane, allyltrichlorosilane, two (7- octenyl) dichlorosilanes, two (allyl) dichlorosilanes, 2- (5- ethylidene-
2- norbornene) ethyl trichlorosilane, 2- (3- cyclohexenyl group) ethyl trichlorosilane, 4- (2,7- cyclo-octadiene base) butyl three
At least one of chlorosilane and 2- (bicyclic pentadiene) ethylidene trichlorosilane.Preferably, the organosilan is that 7- is pungent
Alkenyl trichlorosilane, 5- hexenyltrichlorosilane, allyltrichlorosilane, 2- (5- ethylidene -2- norbornene) ethyl three
Chlorosilane, 2- (3- cyclohexenyl group) ethyl trichlorosilane, 4- (2,7- cyclo-octadiene base) butyl trichlorosilane and 2- (bicyclic penta 2
At least one of alkenyl) ethylidene trichlorosilane.Polyene is more advantageous to as modifying agent using above-mentioned preferred organosilan
The raising of hydrocarbon resin melt strength and mechanical strength.
The preparation method of polyolefin resin provided by the invention includes that olefinic monomer is carried out alkene in the presence of a catalyst
Polymerized hydrocarbon reaction, wherein this method further includes before the olefin polymerization and/or in the olefin polymerization process
In be added organosilan into polymerization reaction system, the general formula of the organosilan is R1 mSiXn(OR2)k, wherein R1For C2-C20
Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group, X is halogen
Element, R2For C1-C20Straight chain, branch or the alkyl of isomerization, m be 1-3 integer, n be 1-3 integer, k be 0-2 integer,
And m+n+k=4.
In addition, the specific choice of the organosilan has been described herein above, therefore not to repeat here.
The present invention is not particularly limited the dosage of the organosilan, it is preferable that relative to described in 100 parts by weight
Olefinic monomer, the dosage of the organosilan are 0.0001-20 parts by weight, further preferably 0.0001-5 parts by weight, more excellent
It is selected as 0.0005-1 parts by weight, most preferably 0.001-0.5 parts by weight, the polyolefin resin that can be further increased in this way
Melt strength and mechanical strength.
The main improvements of the preparation method of polyolefin resin provided by the invention be the olefin polymerization it
It is preceding and/or during the olefin polymerization into polymerization reaction system be added general formula be R1 mSiXn(OR2)kOrganosilicon
Alkane, and the method and condition of the type and olefin polymerization of olefinic monomer and catalyst all can be this field conventional choosing
It selects.
For example, the olefinic monomer can be the existing various monomers for being able to carry out olefin polymerization, it specifically can be with
For ethylene and/or alpha-olefin.Wherein, the alpha-olefin can be monoolefine of the existing various double bonds in strand end, example
It such as, can be at least one of propylene, 1- butylene, 1- amylene, 1- hexene and 1- octene.It is obtained using the olefin polymerization
The polyolefin resin arrived can be alloy in homopolymerization polyolefin resin, copolymeric polyolefin resin, polyolefin kettle etc..When the polyene
When hydrocarbon resin is copolymeric polyolefin resin, the content of comonomer can be the conventional selection of this field in olefinic monomer, herein
It does not repeat.
The catalyst can be the existing various substances that can be used in catalyzed alkene monomer and carry out polymerization reaction, tool
Body example includes but is not limited to: at least one in Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst
Kind.Wherein, the concrete composition of these catalyst is known to the skilled person, for example, the Ziegler-Natta catalyst
It can be MgCl2Supported catalyst system, VOCl3-AlEt2Cl catalyst system etc..Specifically, MgCl2In supported catalyst system
Usually contain MgCl2、TiCl4, alkyl aluminum and/or aluminum alkoxide and the internal electron donor selectively contained and/or outer electron
Body, specifically known to those skilled in the art to know, therefore not to repeat here.
The present invention is not particularly limited the condition of the olefin polymerization, and generally including polymerization temperature 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
Think 0.05-10 hours, preferably 0.05-2 hours.In the present invention, the polymerization pressure refers both to gauge pressure.In addition, described poly-
Closing reaction can be slurry polymerization, or bulk polymerization.When the polymerization reaction is slurry polymerization,
The polymerization reaction should also carry out in presence of organic solvent.The organic solvent can be C5-C10Alkane or C6-
C8Aromatic hydrocarbon, wherein the C5-C10Alkane be preferably at least one of heptane, n-hexane and hexamethylene, the C6-C8
Aromatic hydrocarbon be preferably toluene.In addition, the dosage of the organic solvent can be the conventional selection of this field, do not go to live in the household of one's in-laws on getting married herein
It states.
In addition, in order to adjust the melt index of polyolefin resin, it usually can also be in the preparation of the polyolefin resin
Hydrogen is passed through in journey into polymerization reaction system.Relative to the olefinic monomer of 100 parts by weight, the dosage of the hydrogen can be with
For 0-10 parts by weight, preferably 0-5 parts by weight.
The preparation method of the polyolefin resin provided according to the present invention, it is preferable that this method further includes poly- in the alkene
After closing reaction completion, obtained olefin polymerization product is washed at 20-120 DEG C using water and/or alcohol, in this way
The olefin polymerization product enabled to have certain branching or cross-linked structure, thus be more advantageous to its melt strength and
The raising of mechanical strength.Wherein, the type of the alcohol can be the conventional selection of this field, and specific example includes but unlimited
In: at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol etc..
In addition, the present invention also provides polyolefin resins prepared by the above method.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the gel content of polyolefin resin measures in accordance with the following methods:
Polyolefin resin is dry to constant weight in 50 DEG C in a vacuum drying oven, and weighing is denoted as W1, then molten with dimethylbenzene
Polyolefin resin after solution is dry is filtered, collection remains in 135 DEG C of oscillations sufficiently dissolution with the stainless (steel) wire of 200 mesh
Undissolved polymer on stainless (steel) wire, by polymer undissolved on stainless (steel) wire in a vacuum drying oven in 100 DEG C dry 4
Hour, weighing is denoted as W2, the calculation formula of the gel content of polyolefin resin is as follows:
Gel content (weight %)=(W2/W1) × 100 (weight %).
Embodiment 1
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Slurry polymerization: under vacuum conditions, 450 grams of propylene steam monomers is filled in reaction kettle, are then sequentially added
50mL hexane, n-heptane solution 3mL, 7- octene base trichlorosilane 0.1mL of triethyl aluminum containing 5.5mmol and 20 milligrams of alkene are poly-
Close catalyst (MgCl2/TiCl4/ BMMF, wherein BMMF is internal electron donor 9,9- dimethoxy fluorenes, MgCl2、TiCl4With
The mass ratio of BMMF is 80:12:8), and by the pressure control in reaction kettle in 5.0 atmospheric pressure, reaction temperature is controlled 60
DEG C, polymerization reaction 0.5 hour, it polymerize after completing and acidic ethanol termination polymerization reaction is added, then using temperature respectively is 60 DEG C
Deionized water and temperature be that 50 DEG C of ethyl alcohol respectively washs 3 times, be finally dried in vacuo at 60 DEG C, obtain 20.0 grams of homopolymerizations poly- third
Olefine resin.Through detecting, the concentration of 7- octene base trichlorosilane is 5000ppm, the homopolymerization poly- third in the homopolypropylene resin
Olefine resin has branching or cross-linked structure, and gel content is 20 weight %.
Embodiment 2
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Bulk polymerization: under vacuum state, 450 grams of propylene liguids is added in reaction kettle, 0.25mol tri- is then sequentially added
Aluminium ethide, 0.005 gram of hydrogen, 7- octene base trichlorosilane 0.02mL and 18 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/
BMMF, wherein MgCl2、TiCl4Mass ratio with BMMF is 80:12:8), reaction temperature is controlled at 70 DEG C, and polymerization reaction 30 is divided
After the completion of polymerization, gas in reaction kettle is vented for clock, and discharging then washs products therefrom with hot water (90 DEG C), and in
It is dried in vacuo at 60 DEG C, obtains homopolypropylene resin.Through detecting, 7- octene base trichlorosilane in the homopolypropylene resin
Concentration is 57ppm, and the homopolypropylene resin has branching or cross-linked structure, and gel content is 1.1 weight %.
Embodiment 3
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Polyolefin resin is prepared according to the method for embodiment 2, unlike, by 7- octene base trichlorosilane same volume
7- octenyl dimethoxy chlorosilane substitution, obtain homopolypropylene resin.Through detecting, 7- is pungent in the homopolypropylene resin
The concentration of alkenyl dimethoxy chlorosilane is 250ppm, and the homopolypropylene resin has branching or cross-linked structure, gel
Content is 1 weight %.
Comparative example 1
The comparative example is used to illustrate the preparation method of the polyolefin resin of reference.
Polyolefin resin is prepared according to the method for embodiment 2, unlike, 7- octene base trichlorosilane is not added, obtains
Reference homopolypropylene resin.
Comparative example 2
The comparative example is used to illustrate the preparation method of the polyolefin resin of reference.
Polyolefin resin is prepared according to the method for embodiment 2, unlike, by 7- octene base trichlorosilane same volume
Tetrachloro silicane substitution, obtain reference homopolypropylene resin.
Comparative example 3
The comparative example is used to illustrate the preparation method of the polyolefin resin of reference.
Polyolefin resin is prepared according to the method for embodiment 2, unlike, by 7- octene base trichlorosilane same volume
Tetramethoxy-silicane substitution, obtain reference homopolypropylene resin.
Embodiment 4
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Bulk polymerization: under vacuum state, 450 grams of propylene liguids is added in reaction kettle, 0.25mol tri- is then sequentially added
Aluminium ethide, 0.025mL Cyclohexylmethyldimethoxysilane, 7- octene base trichlorosilane 0.05mL and 18 milligrams of olefinic polymerizations
Catalyst (MgCl2/TiCl4/ DIBP, wherein DIBP is internal electron donor diisobutyl phthalate, MgCl2、TiCl4With
The mass ratio of DIBP is 85:8:7), reaction temperature is controlled at 70 DEG C, polymerization reaction 30 minutes, will be in reaction kettle after the completion of polymerization
Gas emptying, discharging obtain 300 grams of homopolypropylene resins.Through detecting, 7- octenyl trichlorine silicon in the homopolypropylene resin
The concentration of alkane is 167ppm, and the homopolypropylene resin has branching or cross-linked structure, and gel content is 0.2 weight %.
Embodiment 5
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Bulk polymerization: under vacuum state, 450 grams of propylene liguids is added in reaction kettle, 0.25mol first is then sequentially added
Base aikyiaiurnirsoxan beta, 7- octene base trichlorosilane 0.02mL and 0.0025g transistion metal compound rac-Me2Si(2-Me-4-
PhInd)2ZrCl2(wherein, rac- indicates racemization, and Me is methyl, and Ph is phenyl, and Ind is indenyl), reaction temperature is controlled 70
DEG C, polymerization reaction 30 minutes, after the completion of polymerization, gas in reaction kettle is vented, discharges, obtain 300 grams of homopolypropylene resins.
Through detecting, the concentration of 7- octene base trichlorosilane is 67ppm in the homopolypropylene resin, and the homopolypropylene resin has
Branching or cross-linked structure, gel content are 15.2 weight %.
Embodiment 6
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Bulk polymerization: under vacuum state, 450 grams of propylene liguids is added in reaction kettle, 0.25mol alkane is then sequentially added
Base aikyiaiurnirsoxan beta, 7- octene base trichlorosilane 0.01mL and 0.0025g transistion metal compound Me2C(Cp)(Flu)ZrCl2(Me
For methyl, Cp is cyclopentadienyl group, and Flu is fluorenyl), reaction temperature is controlled at 70 DEG C, polymerization reaction 30 minutes, and polymerization is completed
Afterwards, gas in reaction kettle is vented, discharges, obtains 360 grams of homopolypropylene resins.Through detecting, in the homopolypropylene resin
The concentration of 7- octene base trichlorosilane is 28ppm, and the homopolypropylene resin has branching or cross-linked structure, gel content
For 12.0 weight %.
Embodiment 7
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Polyolefin resin is prepared according to the method for embodiment 6, unlike, by 7- octene base trichlorosilane same volume
2- (5- ethylidene -2- norbornene) ethyl trichlorosilane substitution, obtain homopolypropylene resin.Through detecting, the homopolymerization
The concentration of 2- (5- ethylidene -2- norbornene) ethyl trichlorosilane is 150ppm, the homopolymerization poly- third in acrylic resin
Olefine resin has branching or cross-linked structure, and gel content is 8.5 weight %.
Embodiment 8
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Polyolefin resin is prepared according to the method for embodiment 6, unlike, by 7- octene base trichlorosilane same volume
2- (3- cyclohexenyl group) ethyl trichlorosilane substitution, obtain homopolypropylene resin.Through detecting, in the homopolypropylene resin
The concentration of 2- (3- cyclohexenyl group) ethyl trichlorosilane is 60ppm, and the homopolypropylene resin has branching or cross-linked structure,
Its gel content is 5.2 weight %.
Embodiment 9
The embodiment is used to illustrate the preparation method of polyolefin resin provided by the invention.
Polyolefin resin is prepared according to the method for embodiment 6, unlike, by 7- octene base trichlorosilane same volume
2- (bicyclic pentadiene) ethylidene trichlorosilane substitution, obtain homopolypropylene resin.Through detecting, the homopolypropylene tree
In rouge the concentration of 2- (bicyclic pentadiene) ethylidene trichlorosilane be 120ppm, the homopolypropylene resin have branching or
Cross-linked structure, gel content are 6.0 weight %.
Test case
Test case is used to illustrate the test of properties of polyolefin resin.
(1) test of melt strength:
Determine that the experimental provision of melt strength is melted by being furnished with the single screw extrusion machine of capillary and Gottfert Rheotens
Body intensity measuring device composition.The polyolefin resin melt of melt strength to be measured is squeezed out from extruding dies first, is then incited somebody to action
To the roller traction of using two directions of motion on the equalizer bar opposite of melt extrusion beam batten.Melt beam is stretched when institute
Stress is the function of roll speed and time.Roller uniformly accelerates to rotate, suffered when melt beam is broken, and melt beam is broken
To power be defined as melt strength.Acquired results are as shown in table 1.
(2) Mechanics Performance Testing:
Impact strength is measured according to method specified in ASTM D256A, and the results are shown in Table 1.
Tensile strength is measured according to method specified in ISO527-2-5A, and the results are shown in Table 1.
Bending modulus is measured according to method specified in ASTM 638-V, and the results are shown in Table 1.
Table 1
| Number | Melt strength, cN | Impact strength, kJ/m2 | Tensile strength, MPa | Bending modulus, 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 polyolefin resin being prepared using method provided by the invention is with higher
Melt strength and mechanical strength.It can be seen that from the comparison of embodiment 2 and embodiment 3 as the R in the organosilan1For C2-
C18Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group, X and be
Halogen, R2For C1-C5Straight chain, branch or the alkyl of isomerization, m 1, n 3, k be 0 when, obtained polyolefin resin has
Higher melt strength and mechanical strength.It can be seen that from the comparison of embodiment 3 and comparative example 2-3 provided by the invention organic
Silane shows different behaviors from silicon tetrahalogen and tetraalkoxysilane during olefin polymerization, using the present invention
The polyolefin resin that the organosilan of offer obtains has higher melt strength and mechanical strength.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of polyolefin resin, this method includes that olefinic monomer is carried out to alkene in the presence of a catalyst to gather
Close reaction, which is characterized in that this method further includes before the olefin polymerization and/or in the olefin polymerization mistake
Organosilan is added in journey into polymerization reaction system, the general formula of the organosilan is R1 mSiXn(OR2)k, wherein R1For C2-
C20Alkyl and R1End contain alpha-olefin double bond, norbornene group, cycloolefin group or dicyclopentadiene group, X and be
Halogen, R2For C1-C20Straight chain, branch or the alkyl of isomerization, m be 1-3 integer, n be 1-3 integer, k be 0-2 it is whole
Number, and m+n+k=4, the organosilan are added when preparing catalytic component.
2. according to the method described in claim 1, wherein, R1For C2-C20Alkyl and R1End contain alpha-olefin double bond, drop
Borneol alkenyl group, cycloolefin group or dicyclopentadiene group, X are halogen, R2For C1-C10Straight chain, branch or isomerization
Alkyl, m are 1 or 2, and n is 2 or 3, k 0, and m+n+k=4.
3. according to the method described in claim 2, wherein, R1For C2-C18Alkyl and R1End contain alpha-olefin double bond, drop
Borneol alkenyl group, cycloolefin group or dicyclopentadiene group, X are halogen, R2For C1-C5Straight chain, branch or the alkane of isomerization
Base, m 1, n 3, k 0.
4. according to the method described in claim 3, wherein, the organosilan is 7- octene base trichlorosilane, 5- hexenyl three
Chlorosilane, allyltrichlorosilane, 2- (5- ethylidene -2- norbornene) ethyl trichlorosilane, 2- (3- cyclohexenyl group) second
In base trichlorosilane, 4- (2,7- cyclo-octadiene base) butyl trichlorosilane and 2- (bicyclic pentadiene) ethylidene trichlorosilane
It is at least one.
5. method described in any one of -4 according to claim 1, wherein relative to the olefinic monomer of 100 parts by weight,
The dosage of the organosilan is 0.0001-20 parts by weight.
6. method described in any one of -4 according to claim 1, wherein the catalyst is Ziegler-Natta catalysis
At least one of agent, metallocene catalyst and non-metallocene catalyst.
7. according to the method described in claim 6, wherein, the olefinic monomer is ethylene and/or alpha-olefin.
8. according to the method described in claim 7, wherein, the alpha-olefin is propylene, 1- butylene, 1- amylene, 1- hexene and 1-
At least one of octene.
9. method described in any one of -4 according to claim 1, wherein this method further includes in the olefin polymerization
After completion, obtained olefin polymerization product is washed at 20-120 DEG C using water and/or alcohol.
10. the polyolefin resin that the method as described in any one of claim 1-9 is prepared.
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| CN111138575B (en) * | 2018-11-05 | 2021-06-11 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
| CN111635482B (en) * | 2019-03-01 | 2022-05-20 | 叶平山 | High-melt-strength polypropylene resin and preparation method thereof |
| 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 |
| 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 |
| CN115746204B (en) * | 2022-11-25 | 2023-09-12 | 安徽建筑大学 | Intrinsic flame-retardant polydicyclopentadiene elastomer material and preparation method thereof |
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