CN106566065A - Application of organosilane, polyolefin in-kettle alloy and preparation method thereof - Google Patents
Application of organosilane, polyolefin in-kettle alloy and preparation method thereof Download PDFInfo
- Publication number
- CN106566065A CN106566065A CN201510658459.5A CN201510658459A CN106566065A CN 106566065 A CN106566065 A CN 106566065A CN 201510658459 A CN201510658459 A CN 201510658459A CN 106566065 A CN106566065 A CN 106566065A
- Authority
- CN
- China
- Prior art keywords
- dichlorosilane
- group
- alloy
- polyreaction
- organosilan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an application of organosilane, a polyolefin in-kettle alloy and a preparation method thereof. The preparation method for the polyolefin in-kettle alloy comprises the following steps: enabling a first olefin monomer to carry out first polymerization reaction in the presence of a catalyst; introducing a second olefin monomer into a polymerization reaction system to carry out second polymerization reaction, wherein the first olefin monomer is different from the second olefin monomer; first polymerization reaction and/or second polymerization reaction is carried out in the presence of organosilane with a general formula of R1mSiXn(OR2)k; R1 is C2-C20 alkyl and a R1 terminal comprises alpha-olefin double bonds, a norborneol alkenyl group, a cycloolefin group or a dicyclopentadiene group; X is halogen; R2 is a C1-C20 linear chain, a branched chain or isomerized alkyl; m is an integer number from 1 to 3; n is an integer number from 1 to 3; k is an integer number from 0 to 2; and m+n+k is equal to 4. Cross-linking degree of a rubber phase in the polyolefin in-kettle alloy obtained from the preparation method is relatively high, and the polyolefin in-kettle alloy has relatively high toughness and relatively low tensile breaking strength.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of organosilan is preparing conjunction in polyolefin kettle
The preparation method and the polyene prepared by the method for alloy in application, a kind of polyolefin kettle in gold
Alloy in hydrocarbon kettle.
Background technology
Polyolefin blend technology refer to by the homopolymer/homopolymer with the compatibility, homopolymer/copolymer,
The direct melt blending of copolymer/copolymer and make the technology of polymer alloy.And alloy is in polyolefin kettle
Refer to by way of being polymerized in kettle, directly polyolefin alloy is obtained by reaction monomers, so as to before instead of
By traditional blend method of polymers compositionss melt blending.Modal in alloy in polyolefin kettle is exactly poly-
Alloy in propylene kettle, which is typically polymerized in the presence of olefin polymerization catalysis by propylene and forms porous and gather
Particulate propylene, being passed through ethylene toward polymerization system again afterwards carries out copolyreaction with alpha-olefin comonomer,
The copolyreaction of both monomers is carried out in above-mentioned porous polypropylene granule, and the elastocopolymer of generation is filled out
Fill in the space of porous polypropylene granule and formed.
In recent years, although the olefinic polymerization modifying agent with new construction and new capability is constantly found and applies
In alloy high performance research in polyolefin kettle, but some have the high-performance poly of wide application prospect
In alkene kettle, alloy still lacks effective catalytic polymerization preparation means.For example, rubber mutually has cross-linked structure
Polypropylene-based thermoplastic elastomer (dynamic perduren, TPV) with excellent mechanical property and compared with
High added value, has broad application prospects in high-end applications field.But, current TPV products
It is main that (dynamic vulcanization crosslinking) is realized by the post-modification process that is polymerized, TPV is prepared by polymerization in kettle
Method have no report.
Realize that the crosslinking of rubber phase has many advantages by polymerization in kettle：First, change after eliminating
Property complicated technology and cost increase；2nd, in kettle, crosslinking technological has that the degree of cross linking is controllable, product is more more
The characteristics of sample, by the species and addition that adjust cross-linking monomer, can realize that controllable standby series is poly-
Alloy (rubber quality percentage ratio more than 50%) in alloy in alkene kettle, such as high rubber content polyolefin kettle,
Alloy, (rubber is mutually cross-linked structure) polypropylene-based thermoplastic elastomer in high impact poly alkene kettle
(TPV) etc.；3rd, it is relatively low to the dependency of polymerization catalyst and polymerization technique.
The content of the invention
The invention aims to providing a kind of organosilan is preparing answering in alloy in polyolefin kettle
Close in the polyolefin kettle prepared with the preparation method of alloy in a kind of, polyolefin kettle and by the method
Gold.
Specifically, the invention provides a kind of organosilan is preparing the application in polyolefin kettle in alloy,
Wherein, the formula of the organosilan 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, R2For C1-C20Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n
For the integer of 1-3, integers of the k for 0-2, and m+n+k=4.
Present invention also offers in a kind of polyolefin kettle alloy preparation method, the method includes making the first alkene
Hydrocarbon monomer carries out the first polyreaction in the presence of a catalyst, and is then passed through toward polymerization reaction system
Diolefinic monomer carries out the second polyreaction, and first olefinic monomer is different from the second olefinic monomer, its
In, first polyreaction and/or the second polyreaction are carried out in the presence of organosilan, 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.
Additionally, present invention also offers alloy in the polyolefin kettle prepared by said method.
The present inventor has found that after further investigation above-mentioned formula is R1 mSiXn(OR2)kHave
Machine silane is Si (OR ') with formula4(wherein, R ' is C1-C20Alkyl) organosilan and formula
For SiX '4The halogenated silane of (wherein, X ' is halogen) table in the preparation process of alloy in the polyolefin kettle
Diverse behavior is revealed, by the experience needed for alloy preparation process in polyolefin kettle first polymerization
Reaction and/or the second polyreaction are placed in formula for R1 mSiXn(OR2)kOrganosilan in the presence of enter
OK, in the polyolefin kettle for obtaining, in alloy, the crosslinking degree of rubber phase is higher, and closes in the polyolefin kettle
Gold utensil has higher impact flexibility and relatively low tensile break strength.
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 2 or 3,
N is 1 or 2, k are 0, and during m+n+k=4, in the polyolefin kettle for obtaining in alloy rubber phase friendship
Connection degree is higher, and alloy has higher impact flexibility and lower tension failure in the polyolefin kettle
Intensity.
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 organosilan is preparing the application in polyolefin kettle in alloy, wherein, institute
The formula for stating organosilan is R1 mSiXn(OR2)k, wherein, the multiple R in same formula1Can with identical,
Can also be different, it is possible to be each independently C2-C20Alkyl and R1To contain alpha-olefin double for end
Key, norborene group, cycloolefins group or dicyclopentadiene group；Multiple X in same formula can
With identical, it is also possible to different, it is possible to be each independently halogen (including fluorine, chlorine, bromine, iodine)；
Multiple R in same formula2Can be with identical, it is also possible to different, it is possible to be each independently C1-C20
Straight chain, side chain or isomerization alkyl；Integers of the m for 1-3, integers of the n for 1-3, k is 0-2
Integer, 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 2 or 3, n are 1 or 2, k are 0, and m+n+k=4.Using the preferred organosilan as changing
Property agent is more beneficial for the raising of the crosslinking degree of rubber phase in alloy in polyolefin kettle, and is more beneficial for polyene
The raising of Impact Toughness of Alloy and the reduction of tensile break strength in hydrocarbon kettle.
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,
7- octenyl allyldichlorosilanes, 7- octenyl hydridovinyldichlorosilanes, 5- hexenyl pi-allyl dichloros
Silane, 7- octenyls two (pi-allyl) chlorosilane, two (7- octenyls) allyl chlorosilane, triallyl chlorine
At least one in silane etc..
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 H, R4For=CH-CH3, R5It is connected for ethylidene and with silicon atom, m=2,
When n=2, k=0, X are chlorine, the organosilan is 2- (5-ethylidene-2-norbornene base) allyl
Base dichlorosilane；Work as R1With the structure shown in formula (1), and R3For hydrogen atom, R4For ethylidene
And silicon atom is connected, R5For ethyl, m=2, n=2, k=0, when X is chlorine, the organosilan is two
[2- (5-ethylidene-2-norbornene base) ethyl] dichlorosilane.
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 trichlorosilane, 4- (2,7- cyclo-octadiene bases) butyl
Trichlorosilane, two [(2- (3- cyclohexenyl groups) ethyl)] dichlorosilane, 2- (bicyclic pentadiene) ethylidene allyl
At least one in base dichlorosilane and 2- (bicyclic pentadiene) ethylidene trichlorosilane etc..
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 R6For H, R7
For H, R8It is connected for ethylene and with silicon atom, m=2, n=2, k=0 are when X is chlorine, described
Organosilan is 2- (bicyclic pentadiene) ethylidene allyldichlorosilane；Work as R1With formula (2) institute
The structure shown, and R6And R7It is hydrogen atom, R8It is connected for ethylidene and with silicon atom, m=2, n=2,
When k=0, X are chlorine, the organosilan is two [2- (bicyclic pentadiene) ethylidene] dichlorosilane.
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, 7- octenyl allyldichlorosilanes, 7- octenyl hydridovinyldichlorosilanes, 5- hexenyls
Allyldichlorosilane, 7- octenyls two (pi-allyl) chlorosilane, two (7- octenyls) allyl chlorosilane,
Triallyl chlorosilane, 2- (5-ethylidene-2-norbornene base) allyl ethyl dichlorosilane, two [2- (5-
Ethylidene -2- norbornenes) ethyl] dichlorosilane, 2- (5-ethylidene-2-norbornene base)-allyl
Base dichlorosilane, 2- (5-ethylidene-2-norbornene base) ethyl trichlorosilane, 2- (3- cyclohexenyl groups) ethyl
Trichlorosilane, 4- (2,7- cyclo-octadiene bases) butyl trichlorosilane, two [(2- (3- cyclohexenyl groups) ethyl)] dichloro
Silane), 2- (bicyclic pentadiene) ethylidene allyldichlorosilane, 2- (bicyclic pentadiene) ethylidene
Trichlorosilane, 2- (bicyclic pentadiene) ethylidene allyldichlorosilanes and two [2- (bicyclic pentadiene)
Ethylidene] at least one in dichlorosilane, preferably 7- octenyls allyldichlorosilane, 7- octenyls
Hydridovinyldichlorosilane, 5- hexenyl allyldichlorosilanes, 7- octenyls two (pi-allyl) chlorosilane,
Two (7- octenyls) allyl chlorosilane, two (7- octenyls) dichlorosilane, triallyl chlorosilane, two (alkene
Propyl group) dichlorosilane, 2- (5-ethylidene-2-norbornene base) allyl ethyl dichlorosilane, two [2- (5-
Ethylidene -2- norbornenes) ethyl] dichlorosilane, two [2- (3- cyclohexenyl groups) ethyl] dichlorosilane,
2- (bicyclic pentadiene) ethylidene allyldichlorosilanes and two [2- (bicyclic pentadiene) ethylidene] dichloro
At least one in silane.It is more beneficial in polyolefin kettle as modifying agent using the preferred organosilan
The raising of the crosslinking degree of rubber phase in alloy, and it is more beneficial for carrying for Impact Toughness of Alloy in polyolefin kettle
The reduction of high and tensile break strength.
In the polyolefin kettle that the present invention is provided, the preparation method of alloy includes making the first olefinic monomer in catalysis
The first polyreaction is carried out in the presence of agent, then the second olefinic monomer is passed through toward polymerization reaction system and is entered
The second polyreaction of row, first olefinic monomer are different from the second olefinic monomer, wherein, described first
Polyreaction and/or the second polyreaction are carried out in the presence of organosilan, the formula of the organosilan
For 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, R2For 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.
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
Total consumption of first olefinic monomer and the second olefinic monomer of amount part, total consumption of the organosilan
For 0.0001-20 weight portions, more preferably 0.0001-5 weight portions, more preferably 0.0005-1 weights
Amount part, most preferably 0.001-0.5 weight portions, so further can improve in the polyolefin kettle for obtaining
The impact flexibility of alloy simultaneously reduces its tensile break strength.
According to the preparation method of alloy in the polyolefin kettle that the present invention is provided, the first polyreaction can be put
Carry out in the presence of organosilan, it is also possible to enter in the presence of the second polyreaction is placed in organosilan
OK, can also carry out in the presence of the first polyreaction and the second polyreaction are placed in organosilan.
A preferred embodiment of the invention, first polyreaction not depositing in the organosilan
Carry out under, and second polyreaction is carried out in the presence of the organosilan, can so protect
Card only has the polymer that the second polyreaction is obtained to have cross-linked structure or branched structure.
In the polyolefin kettle that the present invention is provided, the main improvements of the preparation method of alloy are in polyolefin
Formula is added to be R in kettle in alloy preparation process1 mSiXn(OR2)kOrganosilan, and the first alkene list
The condition of body, the species of the second olefinic monomer and catalyst and the first polyreaction and the second polyreaction
Can be that the conventional of this area selects Deng.
For example, first olefinic monomer and the second olefinic monomer various be able to can be carried out for existing
The monomer of olefinic polyreaction, is specifically as follows ethylene and/or alpha-olefin.Wherein, the alpha-olefin can
Think monoolefine of the existing various double bonds in strand end, for example, can for propylene, 1-butylene,
At least one in 1- amylenes, 1- hexenes and 1- octenes.It is particularly preferred that first olefinic monomer is
Propylene, and second olefinic monomer is ethylene and the mixture of alpha-olefin, the polyolefin kettle for now obtaining
Interior alloy is alloy in polypropylene.Now, in the second polymerization process, with the ethylene and α-
On the basis of the gross weight of alkene, the consumption of the ethylene can be 1-99 weight %, and preferably 20-50 is again
Amount %；The consumption of the alpha-olefin can be 1-99 weight %, preferably 50-80 weight %.Described
In one polymerization process in the consumption of propylene and the second polymerization process ethylene and alpha-olefin total use
The weight ratio of amount can be 0.2-100：1, preferably 0.5-10：1.Furthermore, it is necessary to explanation, institute
State species and the second alkene that the first olefinic monomer refers to the first olefinic monomer different from the second olefinic monomer
The species of monomer is incomplete same, can be with entirely different, it is possibility to have part is different.
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 first polyreaction and the second polyreaction.Example
Such as, it can be 30-90 DEG C that the condition of first polyreaction generally includes reaction temperature, preferably
40-80 DEG C, more preferably 60-75 DEG C；Response time can be 0.05-10 hours, and preferably 0.1-2 is little
When, more preferably 0.1-0.5 hours.Additionally, when the first olefinic monomer being passed through in the first polyreaction
For gaseous state when, the condition of first polyreaction also includes that reaction pressure can be 0-40 atmospheric pressure,
Preferably 1-35 atmospheric pressure, more preferably 5-10 atmospheric pressure.The condition of second polyreaction
It can be 60-120 DEG C, preferably 75-95 DEG C, more preferably 80-90 DEG C to generally include reaction temperature；Instead
Can be 0.1-10 hours, preferably 0.1-2 hours, more preferably 0.2-0.5 hours between seasonable.Additionally,
When the second olefinic monomer being passed through in the second polyreaction is gaseous state, the condition of second polyreaction
Also include reaction pressure can be 0.1-15 atmospheric pressure, preferably 0.2-10 atmospheric pressure, more preferably
4-6 atmospheric pressure.In the present invention, the pressure refers both to gauge pressure.Additionally, first polyreaction
And/or second polyreaction preferably carry out in the presence of hydrogen gas.In the first polymerization process, relatively
In the first olefinic monomer of 100 weight portions, the consumption of the hydrogen can be 0.001-0.5 weight portions,
Preferably 0.005-0.1 weight portions；In the second polymerization process, relative to the institute of 100 weight portions
State the second olefinic monomer, the consumption of the hydrogen can be 0.001-5 weight portions, preferably 0.02-0.15
Weight portion.
According to the preparation method of alloy in the polyolefin kettle that the present invention is provided, it is preferable that the method also includes
After second polyreaction is completed, the second polymeric reaction product for obtaining is adopted at 20-120 DEG C
Washed with water and/or alcohol, so can further be improved the branched or crosslinking journey of alloy in polyolefin kettle
Degree, so as to be more beneficial for the raising of its impact flexibility.Wherein, the species of the alcohol can be this area
Conventional to select, its instantiation is included but is not limited to：Methanol, ethanol, normal propyl alcohol, isopropanol, positive fourth
At least one in alcohol etc..
Additionally, present invention also offers alloy in the polyolefin kettle prepared by said method.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, in polyolefin kettle, the gel content of alloy is surveyed in accordance with the following methods
It is fixed：By alloy in polyolefin kettle in vacuum drying oven in 50 DEG C of dryings to constant weight, weigh, be designated as W1,
Then with alloy in the dried polyolefin kettle of xylene soluble, fully dissolve in 135 DEG C of vibrations, use 200
Purpose stainless (steel) wire is filtered, and collection remains in undissolved polymer on stainless (steel) wire, by rustless steel
Online undissolved polymer in vacuum drying oven, in 100 DEG C of dryings 4 hours, is weighed, is designated as W2,
In polyolefin kettle, the computing formula of the gel content of alloy is as follows：
Gel content (weight %)=(W2/W1) × 100 (weight %).
Embodiment 1
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Under vacuum conditions, 500 grams of propylene liguid monomers are added in reactors, then at 30 DEG C according to
Secondary addition 0.25mol triethyl aluminums, 20 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/ BMMF,
Wherein, BMMF be internal electron donor 9,9- dimethoxy fluorenes, MgCl2、TiCl4With the matter of BMMF
Amount is than being 80:12:8) reaction temperature is risen to 70 DEG C then and 0.2g hydrogen, to react 0.2 hour.
Then propylene monomer remaining in reactor is emptied and cools the temperature to 50 DEG C, add bis- (7- of 0.10mL
Octenyl) dichlorosilane, the gaseous mixture of 20g ethylene and 60g propylene is then passed through in reactor, will
Reaction temperature controls to continue reaction 0.2 hour at 90 DEG C, after the completion of reaction, adds acidic ethanol to terminate
Polyreaction, then respectively with the deionized water that temperature is 50 DEG C and the respectively washing 3 of ethanol that temperature is 50 DEG C
It is secondary, finally it is vacuum dried at 60 DEG C, obtains alloy in polypropylene.After testing, in the polypropylene
Two in alloy the concentration of (7- octenyls) dichlorosilane be 278ppm, rubber in alloy in the polypropylene
Mutually there is cross-linked structure, its gel content is 50 weight %.
Comparative example 1
The comparative example is used for the preparation method for illustrating alloy in the polyolefin kettle of reference.
Method according to embodiment 1 prepares alloy in polyolefin kettle, except for the difference that, does not add two (7- octenes
Base) dichlorosilane, obtain alloy in reference polypropylene kettle.
Comparative example 2
The comparative example is used for the preparation method for illustrating alloy in the polyolefin kettle of reference.
Method according to embodiment 1 prepares alloy in polyolefin kettle, except for the difference that, by two (7- octenyls)
The tetrachloro silicane of dichlorosilane same volume is substituted, and obtains alloy in reference polypropylene kettle.
Comparative example 3
The comparative example is used for the preparation method for illustrating alloy in the polyolefin kettle of reference.
Method according to embodiment 1 prepares alloy in polyolefin kettle, except for the difference that, by two (7- octenyls)
The tetramethoxy-silicane of dichlorosilane same volume is substituted, and obtains alloy in reference polypropylene kettle.
Embodiment 2
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Under vacuum conditions, 500 grams of propylene liguid monomers are added in reactors, then at 30 DEG C according to
Secondary addition 0.25mol triethyl aluminums, 20 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/ BMMF,
Wherein, BMMF be internal electron donor 9,9- dimethoxy fluorenes, MgCl2、TiCl4With the matter of BMMF
Amount is than being 80:15:5) reaction temperature is risen to 70 DEG C then and 0.2g hydrogen, to react 0.2 hour.
Then propylene monomer remaining in reactor is emptied and cools the temperature to 50 DEG C, add the two of 0.05mL
[2- (5-ethylidene-2-norbornene base) ethyl] dichlorosilane, be then passed through in reactor 20g ethylene and
The gaseous mixture of 60g propylene, reaction temperature is controlled to continue reaction 0.5 hour at 90 DEG C, and reaction is completed
Afterwards, acidic ethanol is added to terminate polyreaction, then respectively with the deionized water and temperature that temperature is 90 DEG C
For respectively washing 3 times of 80 DEG C of ethanol, finally it is vacuum dried at 60 DEG C, obtains alloy in polypropylene.
After testing, [2- (5-ethylidene-2-norbornene base) ethyl] dichlorosilane two in alloy in the polypropylene
Concentration is 125ppm, and in the polypropylene, in alloy, rubber mutually has cross-linked structure, its gel content
For 70 weight %.
Embodiment 3
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Under vacuum conditions, 500 grams of propylene liguid monomers are added in reactors, then at 30 DEG C according to
Secondary addition 0.25mol triethyl aluminums, 20 milligrams of olefin polymerization catalysis (MgCl2/TiCl4/ BMMF,
Wherein, BMMF be internal electron donor 9,9- dimethoxy fluorenes, MgCl2、TiCl4With the matter of BMMF
Amount is than being 78:12:10) reaction temperature is risen to 70 DEG C then and 0.2g hydrogen, to react 0.2 hour.
Then propylene monomer remaining in reactor is emptied and cools the temperature to 50 DEG C, add the two of 0.1mL
[2- (3- cyclohexenyl groups) ethyl] dichlorosilane, is then passed through 20g ethylene and 60g propylene in reactor
Gaseous mixture, reaction temperature is controlled to continue reaction 0.5 hour at 90 DEG C, after the completion of reaction, is gathered
Alloy in propylene kettle.After testing, [2- (3- cyclohexenyl groups) ethyl] dichloro silicon two in alloy in the polypropylene
The concentration of alkane is 210ppm, and in the polypropylene, in alloy, rubber mutually has cross-linked structure, its gel
Content is 65 weight %.
Embodiment 4
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Method according to embodiment 1 prepares alloy in polyolefin kettle, except for the difference that, by two (7- octenyls)
2- (bicyclic pentadiene) the ethylidene trichlorosilane of dichlorosilane same volume is substituted, and obtains polypropylene
Alloy in kettle.After testing, 2- (bicyclic pentadiene) ethylidene trichlorosilane in alloy in the polypropylene
Concentration be 142ppm, in the polypropylene, in alloy, rubber mutually has cross-linked structure, and its gel contains
Measure as 45 weight %.
Embodiment 5
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Method according to embodiment 1 prepares alloy in polyolefin kettle, except for the difference that, by two (7- octenyls)
The 7- octenyl dimethoxys chlorosilane of dichlorosilane same volume is substituted, and obtains closing in polypropylene
Gold.After testing, in the polypropylene, in alloy, the concentration of 7- octenyls dimethoxy chlorosilane is
856ppm, in the polypropylene, in alloy, rubber mutually has branched or cross-linked structure, and its gel content is
20 weight %.
Embodiment 6
The embodiment is used for the preparation method for illustrating alloy in the polyolefin kettle for providing of the invention.
Under vacuum state, in reactor, then at 30 DEG C successively 450 grams of propylene liguid monomers are added
Add 0.25mol triethyl aluminums and 18 milligrams of olefin polymerization catalysis
(MgCl2/TiCl4/BMMF/rac-Me2Si(2-Me-4-PhInd)2ZrCl2/ aluminium methoxide, wherein,
BMMF is internal electron donor 9, and 9- dimethoxy fluorenes, rac- represent racemization, and Me is methyl, and Ph is benzene
Base, Ind is indenyl, MgCl2、TiCl4、BMMF、rac-Me2Si(2-Me-4-PhInd)2ZrCl2With
The mass ratio of aluminium methoxide is 60:8:5:1:16), reaction temperature control is at 70 DEG C, 30 points of polyreaction
Propylene monomer remaining in reactor is emptied and cools the temperature to 50 DEG C after the completion of polymerization by clock, is added
1.0mL allyltrichlorosilanes, are then passed through the gaseous mixture of 20g ethylene and 60g propylene in reactor
With 0.05 gram of hydrogen, reaction temperature is controlled to continue reaction 0.5 hour at 90 DEG C, after the completion of reaction,
Obtain alloy in polypropylene.After testing, in the polypropylene in alloy allyltrichlorosilane concentration
For 590ppm, in the polypropylene, in alloy, rubber mutually has cross-linked structure, and its gel content is
75%.
Test case
Test case is used for the test for illustrating alloy mechanical property in polyolefin kettle.
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.
Table 1
| Numbering | Gel content, quality % | Impact strength, kJ/m2 | Tensile break strength, MPa |
| Embodiment 1 | 50 | 55.0 | 13.0 |
| Comparative example 1 | 0 | 22.4 | 22.5 |
| Comparative example 2 | 0 | 18.6 | 25.4 |
| Comparative example 3 | 0 | 19.5 | 26.5 |
| Embodiment 2 | 70 | 59.0 | 10.1 |
| Embodiment 3 | 65 | 56.8 | 11.2 |
| Embodiment 4 | 45 | 50.0 | 14.5 |
| Embodiment 5 | 20 | 32.5 | 18.4 |
| Embodiment 6 | 75 | 50.6 | 9.8 |
As can be seen from the above results, close in the polyolefin kettle that the method for being provided using the present invention is prepared
In gold, the crosslinking degree of rubber phase is higher, and in the polyolefin kettle alloy resin have higher impact toughness and
Relatively low tensile break strength.Can be seen that from embodiment 1 with the contrast of embodiment 4-5 described to be had
R in machine silane1For C2-C20Alkyl and R1End contain alpha-olefin double bond, norborene group,
Cycloolefins group or dicyclopentadiene group, X is halogen, R2For C1-C10Straight chain, side chain or isomery
The alkyl of change, m is 2 or 3, n are 1 or 2, k are 0, and during m+n+k=4, the polyolefin for obtaining
In kettle, in alloy, the crosslinking degree of rubber phase is higher, and alloy has higher impact in the polyolefin kettle
Toughness and lower tensile break strength.This be can be seen that from contrast of the embodiment 1 with comparative example 2-3
The organosilan that invention is provided and the silicon tetrahalogen and tetraalkoxysilane table during olefinic polyreaction
Different behaviors are revealed, alloy has in the polyolefin kettle that the organosilan provided using the present invention is obtained
Higher impact flexibility and lower tensile break 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 (11)
1. a kind of organosilan is preparing the application in polyolefin kettle in alloy, it is characterised in that described
The formula of organosilan is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End contain
There are 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.
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 2 or 3, n be 1 or 2, k be 0,
And m+n+k=4.
3. application according to claim 2, wherein, the organosilan is 7- octenyl allyls
Base dichlorosilane, 7- octenyl hydridovinyldichlorosilanes, 5- hexenyl allyldichlorosilanes, 7- octenes
Base two (pi-allyl) chlorosilane, two (7- octenyls) allyl chlorosilane, two (7- octenyls) dichlorosilane,
Triallyl chlorosilane, two (pi-allyl) dichlorosilane, 2- (5-ethylidene-2-norbornene base) allyl
Base dichlorosilane, two [2- (5-ethylidene-2-norbornene base) ethyl] dichlorosilane, two [2- (3- cyclohexene
Base) ethyl] dichlorosilane, 2- (bicyclic pentadiene) ethylidene allyldichlorosilanes and two [2- (bicyclic penta
Dialkylene) ethylidene] at least one in dichlorosilane.
4. in a kind of polyolefin kettle alloy preparation method, the method includes urging the first olefinic monomer
The first polyreaction is carried out in the presence of agent, the second olefinic monomer is then passed through toward polymerization reaction system
The second polyreaction is carried out, first olefinic monomer is different from the second olefinic monomer, it is characterised in that
First polyreaction and/or the second polyreaction are carried out in the presence of organosilan, the organosilicon
The formula of alkane is R1 mSiXn(OR2)k, wherein, R1For C2-C20Alkyl and R1End contain α-alkene
Hydrocarbon double bond, norborene group, cycloolefins group or dicyclopentadiene group, X is halogen, R2For
C1-C20Straight chain, side chain or isomerization alkyl, m for 1-3 integer, n for 1-3 integer, k
For the integer of 0-2, and m+n+k=4.
5. method according to claim 4, 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 2 or 3, n be 1 or 2, k be 0,
And m+n+k=4.
6. method according to claim 5, wherein, the organosilan is 7- octenyl allyls
Base dichlorosilane, 7- octenyl hydridovinyldichlorosilanes, 5- hexenyl allyldichlorosilanes, 7- octenes
Base two (pi-allyl) chlorosilane, two (7- octenyls) allyl chlorosilane, two (7- octenyls) dichlorosilane,
Triallyl chlorosilane, two (pi-allyl) dichlorosilane, 2- (5-ethylidene-2-norbornene base) allyl
Base dichlorosilane, two [2- (5-ethylidene-2-norbornene base) ethyl] dichlorosilane, two [2- (3- cyclohexene
Base) ethyl] dichlorosilane, 2- (bicyclic pentadiene) ethylidene allyldichlorosilanes and two [2- (bicyclic penta
Dialkylene) ethylidene] at least one in dichlorosilane.
7. the method according to any one in claim 4-6, wherein, relative to 100 weight
Part first olefinic monomer and the second olefinic monomer total consumption, total consumption of the organosilan is
0.0001-20 weight portions.
8. the method according to any one in claim 4-6, wherein, first polymerization is anti-
Should not carry out in the presence of the organosilan, and second polyreaction is in the organosilan
In the presence of carry out.
9. the method according to any one in claim 4-6, wherein, the catalyst is
At least one in Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst；
Preferably, first olefinic monomer is propylene, and second olefinic monomer be ethylene and α-
The mixture of alkene；
Preferably, the condition of first polyreaction includes that reaction temperature is 30-90 DEG C, the response time
For 0.05-10 hours；The condition of second polyreaction includes reaction temperature for 60-120 DEG C, reaction
Time is 0.1-10 hours.
10. the method according to any one in claim 4-6, wherein, the method is additionally included in
After second polyreaction is completed, the second polymeric reaction product for obtaining is adopted at 20-120 DEG C
Water and/or alcohol are washed.
Close in the polyolefin kettle that 11. methods by described in any one in claim 4-10 are prepared
Gold.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658459.5A CN106566065B (en) | 2015-10-12 | 2015-10-12 | Alloy and preparation method thereof in a kind of application of organosilan and polyolefin kettle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658459.5A CN106566065B (en) | 2015-10-12 | 2015-10-12 | Alloy and preparation method thereof in a kind of application of organosilan and polyolefin kettle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106566065A true CN106566065A (en) | 2017-04-19 |
| CN106566065B CN106566065B (en) | 2019-07-19 |
Family
ID=58508640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510658459.5A Active CN106566065B (en) | 2015-10-12 | 2015-10-12 | Alloy and preparation method thereof in a kind of application of organosilan and polyolefin kettle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106566065B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912735A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院化学研究所 | The preparation method of olefin polymerization catalysis external electron donor, catalyst system and polyolefin |
| WO2019237582A1 (en) * | 2018-06-13 | 2019-12-19 | 大连理工大学 | Complex of silica and ethylene propylene rubber and preparation method therefor |
| 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 |
| CN111138469A (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 |
| 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 |
| CN111138572A (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 |
| CN111138573A (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 |
| CN111892778A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Impact-resistant co-polypropylene and polypropylene composition and respective preparation method |
| CN111944079A (en) * | 2019-05-17 | 2020-11-17 | 中国科学院化学研究所 | Polyolefin in-kettle alloy and preparation method thereof |
| CN111944234A (en) * | 2019-05-17 | 2020-11-17 | 中国科学院化学研究所 | Method for preparing polyolefin in-kettle alloy and polyolefin in-kettle alloy prepared by method |
| 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 |
| CN112143114A (en) * | 2020-04-27 | 2020-12-29 | 中国科学院化学研究所 | Long-chain branched polypropylene impact copolymer 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 |
| CN112851892A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Preparation method of polypropylene with high melt strength |
| CN113683837A (en) * | 2020-05-19 | 2021-11-23 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665203A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Solid catalyst component for olefinic polymerization and catalyst |
-
2015
- 2015-10-12 CN CN201510658459.5A patent/CN106566065B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665203A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Solid catalyst component for olefinic polymerization and catalyst |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912735A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院化学研究所 | The preparation method of olefin polymerization catalysis external electron donor, catalyst system and polyolefin |
| WO2019237582A1 (en) * | 2018-06-13 | 2019-12-19 | 大连理工大学 | Complex of silica and ethylene propylene rubber and preparation method therefor |
| CN111138573A (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 |
| CN111138469A (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 |
| 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 |
| CN111138572A (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 |
| 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 |
| 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 |
| 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 |
| CN111138573B (en) * | 2018-11-05 | 2021-04-27 | 中国科学院化学研究所 | Organosilane compound, polyolefin resin, and preparation method and application thereof |
| CN111892778A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Impact-resistant co-polypropylene and polypropylene composition and respective preparation method |
| CN111944079A (en) * | 2019-05-17 | 2020-11-17 | 中国科学院化学研究所 | Polyolefin in-kettle alloy and preparation method thereof |
| CN111944234A (en) * | 2019-05-17 | 2020-11-17 | 中国科学院化学研究所 | Method for preparing polyolefin in-kettle alloy and polyolefin in-kettle alloy prepared by method |
| CN111944234B (en) * | 2019-05-17 | 2022-01-11 | 中国科学院化学研究所 | Method for preparing polyolefin in-kettle alloy and polyolefin in-kettle alloy prepared by method |
| CN111944079B (en) * | 2019-05-17 | 2021-10-22 | 中国科学院化学研究所 | Polyolefin in-kettle alloy and preparation method 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 |
| 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 |
| CN112851892A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Preparation method of polypropylene with high melt strength |
| CN112143114A (en) * | 2020-04-27 | 2020-12-29 | 中国科学院化学研究所 | Long-chain branched polypropylene impact copolymer and preparation method thereof |
| CN113683837A (en) * | 2020-05-19 | 2021-11-23 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| CN113683837B (en) * | 2020-05-19 | 2023-11-28 | 中国石油天然气股份有限公司 | Impact-resistant copolymerized polypropylene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106566065B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106566065A (en) | Application of organosilane, polyolefin in-kettle alloy and preparation method thereof | |
| KR101576697B1 (en) | Long chain branched (lcb), block or interconnected copolymers of ethylene in combination with one other polymer | |
| CN105814101B (en) | The butylene copolymer of the hexene of ethene with excellent workability and environmental stress crack resistance/1 or ethene/1 | |
| KR101715435B1 (en) | Polymers comprising units derived from ethylene and siloxane | |
| CN106565883B (en) | A kind of application of organosilan and polyolefin resin and preparation method thereof | |
| EP3372620B1 (en) | Catalyst composition for synthesizing olefin copolymer, and method for preparing olefin copolymer | |
| CN102597022A (en) | Process for the preparation of impact resistant propylene polymer compositions | |
| CN108659151A (en) | A kind of application of organosilan and polypropylene and preparation method thereof | |
| CN108659150A (en) | A kind of application of organosilan and polypropylene and preparation method thereof | |
| CN106565870A (en) | Olefin polymerization catalyst and preparation method thereof, olefin polymerization catalyst system and applications thereof, and polyolefin resin preparation method | |
| CN110678937A (en) | Cable sheathing composition | |
| EP3290450B1 (en) | Composition comprising at least one ethylene-based polymer, prepared from a free-radical polymerization | |
| CN110248968A (en) | The method for manufacturing low emission homopolymer or random polypropylene | |
| CN104558300B (en) | A kind of polyacrylic method of production and thus obtained polypropylene | |
| EP3363822B1 (en) | Use of organic siloxane, and polyolefin resin and preparation method thereof | |
| EP3363825B1 (en) | Use of organic siloxane, and polyolefin in-reactor alloy and preparation method thereof | |
| JP2020510583A (en) | Caps and closures | |
| CN112142896B (en) | Application of organosilane, polypropylene in-kettle alloy and preparation method thereof | |
| KR20210149083A (en) | Trifunctional Long Chain Branched Polyolefin | |
| CN114555655A (en) | Ethylene-based polymer compositions with branching | |
| CN105585772B (en) | A kind of acrylic resin and its preparation method and application and automobile instrument plate material | |
| CN111138575B (en) | Organosilane compound, polyolefin resin, and preparation method and application thereof | |
| WO2023115026A2 (en) | Crosslinkable olefin/silane interpolymer compositions | |
| KR20210148207A (en) | Method for Polymerization of Trifunctional Long Chain Branched Olefins | |
| KR20210148208A (en) | Method for Polymerization of Trifunctional Long Chain Branched Olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180329 Address after: 100190 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Applicant after: Institute of Chemistry, Chinese Academy of Sciences Applicant after: University of Chinese Academy of Sciences Address before: 100190 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Applicant before: Institute of Chemistry, Chinese Academy of Sciences |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |