CN111138569A - Organosilane compound, polyolefin resin, and preparation method and application thereof - Google Patents
Organosilane compound, polyolefin resin, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of olefin polymerization, and discloses an organosilane compound, a polyolefin resin, and preparation methods and applications thereof. The organosilane compounds of the invention have the formula R1R2R3SiX, wherein R1And R2Is a linear, branched or isomerized alkenyl group with 2-20 carbon atoms and contains α -olefinic double bond at the terminal, R3Is a straight chain, branched chain or isomerized alkane group with 1-20 carbon atoms, and X is halogen. The organosilane compound can be used for preparing polyolefin resin, and improves the melt processability and mechanical property of the polyolefin resin.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to an organic silane compound, a polyolefin resin, and preparation methods and applications thereof.
Background
For thousands of years, carbon-based materials play an important role in daily life and social progress through the history of material development, and play a significant role in promoting the development of human society. With the development of organic carbon chemistry and the appearance of silicon-based compounds belonging to the same main group as carbon in the periodic table of elements, organic silicon compounds with new structures and new performances are continuously emerging, so that the performances of known materials are improved, the application field is expanded, a large number of new functional materials are promoted, the rapid development of scientific technology is greatly promoted, and the life quality and the social development of people are improved. At present, the 'shadow' of the organosilicon compound can be seen in various fields of aerospace, electronic components, household appliances, packaging, buildings, automobiles, automatic control and daily life.
Different from carbon-carbon bonds in carbon-based materials, carbon-silicon bonds in the organic silicon compounds have longer bond lengths and larger bond angles, and the bonding property of the organic silicon compounds is between that of covalent bonds and ionic bonds, so the organic silicon compounds have the outstanding advantages of strong designability of molecular structures, multiple synthesis methods, strong application specificity and the like. Based on the above characteristics, the research on the structural design, preparation and application of organosilicon compounds has been the focus of attention of researchers and industry. The synthetic method of the organic silicon compound is also subjected to continuous method improvements such as a direct synthesis method, an organic metal compound method (Grignard method and the like), a thermal condensation method, a hydrosilylation method and the like (synthesis process and application (second edition) of organic silicon products, Chinese bridges, Happy pine people and the like, chemical industry publishers, 2009, organic silicon physical and chemical parameters and design data, Liao torrent, Zhaokkai, Ouyangjiasong and the like, chemical industry publishers, 2010, US 5206402), the organic silicon compound with a new structure is continuously developed, the application performance is continuously developed, the application field is also continuously expanded, and finally the vigorous development of organic silicon chemistry is promoted.
Disclosure of Invention
The invention aims to provide an organic silane compound with a novel structure, which can be used for preparing polyolefin resin and improving the melt processability and mechanical property of the polyolefin resin.
In order to achieve the above object, the present invention provides an organosilane compound, wherein the organosilane compound has the general formula R1R2R3SiX, wherein R1And R2Is a linear, branched or isomerized alkenyl group with 2-20 carbon atoms and contains α -olefinic double bond at the terminal, R3Is a linear, branched or isomerized alkyl hydrocarbon group with 1-20 carbon atomsAnd X is halogen.
Preferably, X is F, Cl, Br or I.
Preferably, the organosilane compound is bis (3-butenyl) methylchlorosilane, bis (3-butenyl) ethylchlorosilane, bis (3-butenyl) propylchlorosilane, bis (3-butenyl) isopropylchlorosilane, bis (4-pentenyl) methylchlorosilane, bis (4-pentenyl) ethylchlorosilane, bis (4-pentenyl) propylchlorosilane, bis (4-pentenyl) isopropylchlorosilane, bis (5-hexenyl) methylchlorosilane, bis (5-hexenyl) ethylchlorosilane, bis (5-hexenyl) propylchlorosilane, bis (5-hexenyl) isopropylchlorosilane, bis (6-heptenyl) methylchlorosilane, bis (6-heptenyl) ethylchlorosilane, bis (6-heptenyl) propylchlorosilane, di (3-butenyl) ethylchlorosilane, bis (4-pentenyl) propylchlorosilane, bis (4-pentenyl, Bis (6-heptenyl) isopropylchlorosilane, bis (7-octenyl) methylchlorosilane, bis (7-octenyl) ethylchlorosilane, bis (7-octenyl) propylchlorosilane, bis (7-octenyl) isopropylchlorosilane, bis (8-nonenyl) methylchlorosilane, bis (8-nonenyl) ethylchlorosilane, bis (8-nonenyl) propylchlorosilane, bis (8-nonenyl) isopropylchlorosilane, bis (9-decenyl) methylchlorosilicon, bis (9-decenyl) ethylchlorosilane, bis (9-decenyl) propylchlorosilane, bis (9-decenyl) isopropylchlorosilane, (5-hexenyl) (7-octenyl) methylchlorosilane, (5-hexenyl) (7-octenyl) ethylchlorosilane, bis (8-nonenyl) propylchlorosilane, bis (8-nonenyl) isopropylchlorosilane, One or more of (5-hexenyl) (7-octenyl) propylchlorosilane and (5-hexenyl) (7-octenyl) isopropylchlorosilane.
The present invention also provides a method for preparing the above organosilane compound, wherein the method for preparing the organosilane compound comprises the following steps:
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX products with dichloroorganosilanes R2R3SiCl2And contacting to obtain the organosilane compound.
Preferably, in step 1), the molar ratio of the halogenated olefin to the metal is 10 to 1: 1.
preferably, in step 1), the metal M is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum, and the like.
Preferably, X is F, Cl, Br or I.
Preferably, in step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane.
Preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1The molar ratio of MX product to dichloroorganosilane is 10-1: 1.
preferably, in step 2), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours.
The present invention also provides a method for preparing the above organosilane compound, wherein the method for preparing the organosilane compound comprises the following steps:
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX products with trichloroorganosilanes R3SiCl3And contacting to obtain the organosilane compound.
Preferably, in step 1), the halogenated olefin R1The feeding molar ratio of the X to the metal M is 10-1: 1;
preferably, in step 1), the metal M is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum, and the like.
Preferably, X is F, Cl, Br or I.
Preferably, in step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane.
Preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1Product R of MX1MX and trichloroorganosilane R3SiCl3In a molar ratio of 20-2: 1.
preferably, in step 2), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours.
The present invention also provides a method for preparing the above organosilane compound, wherein the method for preparing the organosilane compound comprises: reacting an organochlorosilane R in the presence of a catalyst2R3A step of carrying out a first hydrosilylation reaction of SiHCl with α, omega-diolefin represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
Preferably, the first catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of (a).
Preferably, the first catalyst is reacted with α, omega-diolefin and organochlorosilane R represented by the formula (1)2R3The molar ratio of the total SiHCl is 0.005-0.5: 1.
preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R2R3The molar ratio of SiHCl is 100-1: 1.
preferably, the conditions of the first hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours.
The present invention also provides a method for preparing the above organosilane compound, wherein the method for preparing the organosilane compound comprises: reacting an organochlorosilane R in the presence of a second catalyst3SiH2A second hydrosilylation reaction of Cl with α, omega-diene represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
Preferably, the second catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of (a).
Preferably, the second catalyst is reacted with the organochlorosilane R3SiH2The molar ratio of Cl to the total amount of α, omega-diolefin of formula (1) is 0.005-0.5: 1.
Preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R3SiH2The mol ratio of Cl is 100-2: 1.
preferably, the conditions of the second hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours.
The present invention also provides a method for preparing a polyolefin resin, which comprises subjecting an olefin monomer to olefin polymerization in the presence of a catalyst, wherein the method further comprises adding an organosilane compound to a polymerization reaction system before and/or during the olefin polymerization, wherein the organosilane compound is the organosilane compound according to the present invention.
Preferably, the organosilane is used in an amount of 0.0001 to 20 parts by weight, relative to 100 parts by weight of the olefin monomer.
Preferably, the catalyst is one or more of a Ziegler-Natta catalyst, a metallocene catalyst and a non-metallocene catalyst.
Preferably, the olefin monomer is ethylene and/or α -olefin.
Preferably, the α -olefin is one or more of propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
The present invention also provides a polyolefin resin prepared by the method for preparing a polyolefin resin of the present invention.
The present invention also provides the use of the organosilane compound of the invention for the preparation of polyolefin resins.
The organosilane compound according to the present invention can be used for preparing a polyolefin resin and can improve melt processability and mechanical properties of the polyolefin resin.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The organosilane compound provided by the invention has the general formula R1R2R3SiX, wherein R1And R2Is a linear, branched or isomerized alkenyl group with 2-20 carbon atoms and contains α -olefinic double bond at the terminal, R3Is a straight chain, branched chain or isomerized alkane group with 1-20 carbon atoms, and X is halogen.
According to the invention, R in the same general formula1And R2May be the same or different. Similarly, a plurality of X in the same general formula may be the same or different, and may be each independently halogen (including fluorine, chlorine, bromine, iodine).
According to the invention, R is1Or R2Has α -olefinic double bond (CH) at the end2CH-) except for α -olefinic double bond, R1The structure of the intermediate portion is not limited, and includes straight-chain hydrocarbon groups (containing double bonds, triple bonds, etc.) or isomers thereof. Preferably, R1And R2Is a linear, branched or isomerized alkenyl group having 2-10 carbon atoms and containing α -olefinic double bond at the terminal, more preferably R1And R2Is a linear alkylene group having 4 to 10 carbon atoms and has α -olefinic double bond at the terminal, and more preferably R1And R2Examples of such a group include a 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, and 9-decenyl group.
According to the invention, preferably R3Is a linear, branched or isomerized alkyl group with 1-10 carbon atoms; more preferably, R3Is a linear, branched or isomerized alkyl hydrocarbon group with 1-6 carbon atoms; further preferably, R3Is a straight-chain, branched or isomerized alkane group with 1-3 carbon atoms. Examples of such groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl and the like.
In the present invention, specific examples of the organosilane include, but are not limited to: bis (3-butenyl) methylchlorosilane, bis (3-butenyl) ethylchlorosilane, bis (3-butenyl) propylchlorosilane, bis (3-butenyl) isopropylchlorosilane, bis (4-pentenyl) methylchlorosilane, bis (4-pentenyl) ethylchlorosilane, bis (4-pentenyl) propylchlorosilane, bis (4-pentenyl) isopropylchlorosilane, bis (5-hexenyl) methylchlorosilane, bis (5-hexenyl) ethylchlorosilane, bis (5-hexenyl) propylchlorosilane, bis (5-hexenyl) isopropylchlorosilane, bis (6-heptenyl) methylchlorosilane, bis (6-heptenyl) ethylchlorosilane, bis (6-heptenyl) propylchlorosilane, bis (6-heptenyl) isopropylchlorosilane, bis (3-butenyl) ethylchlorosilane, bis (4-pentenyl) propylchlorosilane, bis (4-pentenyl) isopropylchlorosilane, bis (, Bis (7-octenyl) methylchlorosilane, bis (7-octenyl) ethylchlorosilane, bis (7-octenyl) propylchlorosilane, bis (7-octenyl) isopropylchlorosilane, bis (8-nonenyl) methylchlorosilane, bis (8-nonenyl) ethylchlorosilane, bis (8-nonenyl) propylchlorosilane, bis (8-nonenyl) isopropylchlorosilane, bis (9-decenyl) methylchlorosilane, bis (9-decenyl) ethylchlorosilane, bis (9-decenyl) propylchlorosilane, bis (9-decenyl) isopropylchlorosilane, (5-hexenyl) (7-octenyl) methylchlorosilane, (5-hexenyl) (7-octenyl) ethylchlorosilane, (5-hexenyl) (7-octenyl) propyl and (5-hexenyl) (7-octenyl) isopropylchlorosilicon One or more of alkanes.
The organosilane compound can be produced by the following methods A to C.
The method A comprises the following steps: the method for preparing the organosilane compound comprises the following steps,
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX product with dichlorosilane R2R3SiCl2And contacting to obtain the organosilane compound.
Preferably, in step 1), the molar ratio of the halogenated olefin to the metal is 10 to 1: 1, more preferably 5-1: 1.
preferably, in step 1), the metal is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum, and the like.
Preferably, X is F, Cl, Br or I.
Preferably, in step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane.
Preferably, in step 1), the haloalkene R1The conditions under which X reacts with metal M include: the reaction temperature is 0-140 ℃, and the reaction time is 0.5-120 hours; more preferably, a haloalkene R1The conditions under which X reacts with metal M include: the reaction temperature is 10-120 ℃, and the reaction time is 1-48 hours.
Preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1The molar ratio of MX product to dichloroorganosilane is 10-1: 1, more preferably 5-1: 1.
preferably, in step 2), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours; more preferably, the conditions of the contacting include: the contact temperature is 10-80 ℃, and the contact time is 2-48 hours.
In the process A, R1、R2And R3Are each as defined above for formula R1R2R3SiX2In R1、R2And R3The same definition is applied.
The method B comprises the following steps: the method for preparing the organosilane compound comprises the following steps,
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX products with trichloroorganosilanes R3SiCl3And contacting to obtain the organosilane compound.
Preferably, in step 1), the halogenated olefin R1The feeding molar ratio of X to the metal is 10-1: 1, more preferably 5-1: 1.
preferably, in step 1), the metal is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum, and the like.
Preferably, X is F, Cl, Br or I.
Preferably, in step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane.
Preferably, in step 1), the haloalkene R1The conditions under which X reacts with metal M include: the reaction temperature is 0-140 ℃, and the reaction time is 0.5-120 hours; more preferably, a haloalkene R1The conditions under which X reacts with metal M include: the reaction temperature is 10-120 ℃, and the reaction time is 1-48 hours.
Preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1MX products with trichloroorganosilanes R3SiCl3In a molar ratio of 20-2: 1, more preferably 10-2: 1.
preferably, in step 2), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours; more preferably, the conditions of the contacting include: the contact temperature is 10-80 ℃, and the contact time is 2-48 hours.
In the process B, R1And R3Are each as defined above for formula R1R2R3SiX2In R1And R3The same definition is applied.
The method C comprises the following steps: the method for preparing the organosilane compound comprises the following steps: reacting an organochlorosilane R in the presence of a first catalyst2R3A step of carrying out a first hydrosilylation reaction of SiHCl with α, omega-diolefin represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
Preferably, the first catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of (a) or (b),
preferably, the first catalyst is reacted with α, omega-diolefin and organochlorosilane R represented by the formula (1)2R3The molar ratio of the total SiHCl is 0.005-0.5: 1, more preferably 0.005 to 0.1: 1.
preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R2R3The molar ratio of SiHCl is 100-1: 1, more preferably 20-1: 1.
preferably, the conditions of the first hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours; more preferably, the conditions of the first hydrosilylation reaction include: the reaction temperature is 0-80 ℃, and the reaction time is 0.5-48 hours.
The method D comprises the following steps: the method for preparing the organosilane compound comprises the following steps: reacting an organochlorosilane R in the presence of a second catalyst3SiH2A second hydrosilylation reaction of Cl with α, omega-diene represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
Preferably, the second catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of (a).
Preferably, the second catalyst is reacted with the organochlorosilane R3SiH2The molar ratio of Cl to the total amount of α, omega-diolefin of formula (1) is 0.005-0.5: 1, more preferably 0.005-0.1: 1.
Preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R3SiH2The mol ratio of Cl is 100-2: 1, more preferably 50-2: 1.
preferably, the conditions of the second hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours; more preferably, the conditions of the second hydrosilylation reaction include: the reaction temperature is 0-80 ℃, and the reaction time is 0.5-72 hours.
In the process C, R2And R3Are each as defined above for formula R1R2R3SiX2In R2And R3The same definition is applied.
The synthesis of the organic silane compound according to the present invention can be carried out by the above-mentioned method, but is not limited thereto.
The present invention also provides a method for preparing a polyolefin resin, which comprises subjecting an olefin monomer to olefin polymerization in the presence of a catalyst, wherein the method further comprises adding an organosilane compound to a polymerization reaction system before and/or during the olefin polymerization, wherein the organosilane compound is the organosilane compound according to the present invention.
The organosilane compound has been described above and will not be described in further detail herein.
The amount of the organic silane compound used in the present invention is not particularly limited, and preferably, the organic silane compound is used in an amount of 0.0001 to 20 parts by weight, more preferably 0.0001 to 5 parts by weight, even more preferably 0.0005 to 1 part by weight, and most preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the olefin monomer, so that the melt processability and mechanical properties of the resulting polyolefin resin can be further improved.
The main improvement of the process for preparing polyolefin resin provided by the present invention is that the organosilane compound described in the present invention is added to the polymerization reaction system before and/or during the olefin polymerization reaction, and the kinds of olefin monomers and catalysts and the process and conditions for olefin polymerization reaction can be conventionally selected in the art.
For example, the olefin monomer may be any of various existing monomers capable of performing olefin polymerization, and specifically may be ethylene and/or α -olefin, wherein the α -olefin may be any of various existing monoolefins having double bonds at the molecular chain end, such as one or more of propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.
The catalyst may be any of various materials that can be used to catalyze the polymerization of olefin monomers, and specific examples thereof include, but are not limited to: one or more of a Ziegler-Natta catalyst, a metallocene catalyst, and a non-metallocene catalyst. The specific composition of these catalysts is well known to those skilled in the art, and for example, the Ziegler-Natta catalyst may be MgCl2Supported catalytic system, VOCl3-AlEt2Cl catalytic systems, and the like. Specifically, MgCl2MgCl is usually contained in supported catalyst systems2、TiCl4Alkyl, alkylThe aluminum base and/or the aluminum alkoxide and optionally the internal electron donor and/or the external electron donor are known to those skilled in the art and will not be described herein.
The conditions for the olefin polymerization reaction in the present invention are not particularly limited, and generally include that the polymerization temperature may be 30 to 90 ℃, preferably 40 to 80 ℃; the polymerization pressure may be from 1 to 10 atmospheres, preferably from 1 to 7 atmospheres; the polymerization time may be from 0.05 to 10 hours, preferably from 0.05 to 2 hours. In the present invention, the polymerization pressure means a gauge pressure. The polymerization reaction may be a slurry polymerization reaction or a bulk polymerization reaction. When the polymerization is a slurry polymerization, the polymerization should also be carried out in the presence of an organic solvent. The organic solvent may be C5-C10Alkane or C6-C8Wherein said C is5-C10Preferably one or more of heptane, n-hexane and cyclohexane, C6-C8The aromatic hydrocarbon of (a) is preferably toluene. In addition, the amount of the organic solvent may be selected conventionally in the art, and is not described herein.
In addition, in order to adjust the melt index of the polyolefin resin, it is also possible to generally introduce hydrogen into the polymerization reaction system during the production of the polyolefin resin. The hydrogen may be used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, relative to 100 parts by weight of the olefin monomer.
According to the preparation method of the polyolefin resin provided by the invention, preferably, the method further comprises washing the obtained olefin polymerization reaction product at 20-120 ℃ by using water and/or alcohol after the olefin polymerization reaction is completed, so that the obtained olefin polymerization reaction product has a certain branched or crosslinked structure, and the melt strength and the mechanical strength of the olefin polymerization reaction product are improved. Wherein the kind of the alcohol may be conventionally selected in the art, and specific examples thereof include, but are not limited to: one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, etc.
In addition, the invention also provides the polyolefin resin prepared by the method.
The present invention also provides the use of the organosilane compound of the invention for the preparation of polyolefin resins.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the gel content of the polyolefin resin was measured according to the following method:
the polyolefin resin was dried in a vacuum oven at 50 ℃ to constant weight, weighed and recorded as W1Then, the dried polyolefin resin was dissolved in xylene, sufficiently dissolved by shaking at 135 ℃ and filtered through a 200-mesh stainless steel net, the insoluble polymer remaining on the stainless steel net was collected, dried in a vacuum drying oven at 100 ℃ for 4 hours, and weighed as W2The calculation formula of the gel content of the polyolefin resin is as follows:
gel content (% by weight) is (W)2/W1) X 100 (wt%).
Preparation example 1
Under the protection of nitrogen, 0.22 mol of magnesium powder and a plurality of iodine particles are added into 200ml of anhydrous ether, magnetic stirring is carried out, then a small amount of 6-chloro-1-hexene is slowly dripped into the solution, the reaction temperature is 10 ℃, when the purple red color of the solution fades, 0.25 mol of 6-chloro-1-hexene is slowly dripped, the reaction temperature is controlled to be 10 +/-1 ℃, after the dripping is finished, reflux reaction is carried out for 8 hours, and then the unreacted magnesium powder is removed by filtration, thus obtaining the ether solution of the metal organic compound (5-hexenyl magnesium chloride); the metal organic compound solution is added into 0.10 mol of methyl trichlorosilane, the reaction temperature is 10 ℃, and after the dropwise addition is finished, the reflux reaction is carried out for 24 hours. After completion of the reaction, distillation was carried out under reduced pressure to obtain a 67 ℃ C. (10mmHg) fraction, thereby obtaining 0.08 mol of bis (5-hexenyl) methylchlorosilane.1H NMR(CDCl3)：δ0.94(s,3H),δ1.05(d,4H),δ1.45-1.55(m,8H),δ2.10(s,4H),δ5.01-5.20(m,4H),δ5.75-5.85(m,2H).13C NMR(CDCl3):δ13.1,20.1,22.5,31.3,33.5,115.0,138.8.29Si NMR(CDCl3):δ23.4.
Preparation example 2
1 mol of 1, 7-octadiene and 0.02 mol of H are taken2PtCl6Under magnetic stirring, slowly dripping 0.45 mol of ethylchlorosilane into 1, 7-octadiene at room temperature, reacting at 50 ℃ for 24 hours after finishing dripping, and distilling under reduced pressure after finishing the reaction to obtain 168 ℃ (10mmHg) fraction to obtain 0.4 mol of bis (7-octenyl) ethylchlorosilane.1H NMR(C6D6):δ5.75-5.85(m,2H),4.92-5.04(m,4H),2.01-2.08(m,4H),135-1.53(m,16H),1.06-1.11(m,8H),0.94(s,3H).13C NMR(C6D6):δ138.99,114.32,33.76,32.31,28.71,28.60,22.35,20.34,13.1.29SiNMR(C6D6):δ19.1.
Preparation example 3
Under the protection of nitrogen, 0.22 mol of magnesium powder and a few iodine particles are added into 200ml of anhydrous tetrahydrofuran, magnetic stirring is carried out, then a small amount of 3-chloro-1-butene is slowly dripped into the solution, the reaction temperature is 0 ℃, when the purple red of the solution fades, 0.25 mol of 3-chloro-1-butene is slowly dripped, the reaction temperature is controlled to be 0 +/-1 ℃, after the dripping is finished, reflux reaction is carried out for 4 hours, and then the unreacted magnesium powder is removed by filtration, thus obtaining the tetrahydrofuran solution of the metal organic compound (3-butenyl magnesium chloride); the metal organic compound solution is added into 0.10 mol of 3-butenyl methyl chlorosilane, the reaction temperature is 10 ℃, and after the dropwise addition is finished, the reflux reaction is carried out for 48 hours. After completion of the reaction, distillation was carried out under reduced pressure to obtain a 50 ℃ C. (10mmHg) fraction, thereby obtaining 0.09 mol of bis (3-butenyl) methylchlorosilane.1H NMR(CDCl3)：δ0.50(s,3H),δ1.10(d,4H),δ1.8-2.0(m,4H),δ5.01-5.20(m,4H),δ5.75-5.85(m,2H).13C NMR(CDCl3):δ0.4,14.1,25.9,115.0,138.8.29Si NMR(CDCl3):δ20.1.
Preparation example 4
1 mol of 1, 6-heptadiene and 0.05 mol of H are taken2PtCl6Slowly dropwise adding 0.90 mol of 6-heptenyl isopropyl chlorosilane into 1, 6-heptadiene at room temperature under magnetic stirring, reacting at 80 deg.C for 24 hr after dropwise adding, distilling under reduced pressure to obtain 110 deg.C (10mmHg) fraction to obtain 0.75 mol of di (6-heptenyl) isopropyl chlorosilaneA chlorosilane group.1H NMR(C6D6):δ5.75-5.85(m,2H),4.92-5.04(m,4H),2.01-2.08(m,4H),1.7-1.8(m,2H),1.15-1.30(m,16H),0.94(s,6H).13C NMR(C6D6):δ137.7,115.7,33.9,32.2,29.4,22.2,18.1,10.3,9.6.29Si NMR(C6D6):δ20.8
Preparation example 5
1 mol of 1, 9-decadiene and 0.1 mol of K { Pt (CH)2＝CH2)Cl3}H2And O, slowly dripping 0.90 mol of 9-decenyl propyl chlorosilane into 1, 9-decadiene at room temperature under the magnetic stirring, reacting for 72 hours at 80 ℃ after finishing dripping, and distilling under reduced pressure after the reaction is finished to obtain 180 ℃ (10mmHg) fraction to obtain 0.30 mol of bis (9-decenyl) propyl chlorosilane.1H NMR(C6D6):δ5.75-5.85(m,2H),4.92-5.04(m,4H),1.8-2.08(m,4H),1.22-1.36(m,32H),0.94(m,3H).13C NMR(C6D6):δ137.7,115.7,33.9,32.1,29.8,29.7,29.6,29.4,26.6,21.8,16.5,14.6,12.4.29Si NMR(C6D6):δ24.5
Preparation example 6
Under the protection of nitrogen, 0.22 mol of magnesium powder and a plurality of iodine particles are added into 200ml of anhydrous butyl ether, magnetic stirring is carried out, then a small amount of 6-chloro-1-hexene is slowly dripped into the solution, the reaction temperature is 10 ℃, when the purple red color of the solution fades, 0.25 mol of 6-chloro-1-hexene is slowly dripped, the reaction temperature is controlled to be 40 +/-1 ℃, after the dripping is finished, reflux reaction is carried out for 12 hours, and then the unreacted magnesium powder is removed by filtration, thus obtaining the butyl ether solution of the metal organic compound (5-hexenyl magnesium chloride); the organometallic compound solution was added to 0.20 mol of 7-octenylmethyldichlorosilane at room temperature (20 ℃ C.), and after completion of the dropwise addition, the reaction was refluxed for 48 hours. After completion of the reaction, distillation was carried out under reduced pressure to obtain a 140 ℃ C. (10mmHg) fraction, and 0.10 mol of (5-hexenyl) (7-octenyl) methylchlorosilane was obtained.1H NMR(CDCl3)：δ0.45(s,3H),δ1.25-1.35(m,12H),δ2.10(m,4H),δ5.01-5.20(m,4H),δ5.75-5.85(m,2H).13C NMR(CDCl3):δ0.5,14.6,14.7,21.5,21.6,29.5,29.7,32.1,32.2,33.6,33.9,115.0,138.8.29Si NMR(CDCl3):δ22.2.
Example 1
200mL of n-hexane were taken and charged with 0.01 mol of triethylaluminum, 1.0g of bis (5-hexenyl) methylchlorosilane and 20mg of Ziegler-Natta catalyst (TiCl)4/BMMF/MgCl2Wherein BMMF is 9, 9-dimethoxyfluorene, Ti% ═ 3.5 wt%, BMMF% ═ 18.0 wt%, Mg% ═ 17.1 wt%, then propylene gas was introduced and the propylene pressure was maintained at 0.7MPa, 60 ℃, 1 hour, after completion of the reaction, the reaction was terminated with acid alcohol (ethanol solution containing 10% hydrochloric acid) and washed repeatedly three times with deionized water and ethanol, respectively, and finally vacuum-dried at 70 ℃ for 24 hours to obtain 72g of polypropylene having a branched and crosslinked structure and a gel content of 5 wt%.
Example 2
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of bis (3-butenyl) methylchlorosilane to give 66g of polypropylene having a branched and crosslinked structure and a gel content of 8% by weight.
Example 3
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of bis (6-heptenyl) isopropylchlorosilane to give 70g of polypropylene having a branched and crosslinked structure and a gel content of 8% by weight.
Example 4
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of bis (9-decenyl) propylchlorosilane to obtain 60g of polypropylene having a branched and crosslinked structure and a gel content of 1% by weight.
Example 5
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of (5-hexenyl) (7-octenyl) methylchlorosilane, to give 65g of polypropylene having a branched and crosslinked structure and a gel content of 1% by weight.
Example 6
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of bis (7-octenyl) ethylchlorosilane to obtain 68g of polypropylene having a branched and crosslinked structure and a gel content of 1% by weight.
Comparative example 1
A polyolefin resin was prepared by following the procedure of example 1 except that bis (5-hexenyl) methylchlorosilane was not added to give a reference polypropylene.
Comparative example 2
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of silicon tetrachloride to obtain a reference polypropylene.
Comparative example 3
A polyolefin resin was prepared by following the procedure of example 1, except that bis (5-hexenyl) methylchlorosilane was replaced with the same molar amount of tetramethoxysilane to obtain a reference polypropylene.
Test example
The polyolefin resins obtained in examples and comparative examples were subjected to the following property tests.
(1) Testing of melt Strength:
the experimental setup for determining melt strength consisted of a single screw extruder equipped with a capillary and a Gottfert Rheotens melt strength tester. Firstly, extruding the polyolefin resin melt with the melt strength to be measured from a mouth die of an extruder, and then drawing the obtained extruded melt beam sample strip by using two rollers which are arranged on a balance beam and have opposite moving directions. The force experienced by the melt beam as it is stretched is a function of the roller speed and time. The rolls are uniformly accelerated until the melt strand breaks, and the force to which the melt strand breaks is defined as the melt strength. The results obtained are shown in table 1.
(2) And (3) testing mechanical properties:
the impact strength was measured according to the method specified in ASTM D256A, and the results are shown in table 1.
TABLE 1
| Numbering | Melt strength, cN | Impact strength, kJ/m2 |
| Example 1 | 25 | 5.0 |
| Example 2 | 32 | 4.6 |
| Example 3 | 26 | 5.1 |
| Example 4 | 28 | 6.1 |
| Example 5 | 21 | 5.4 |
| Example 6 | 28 | 5.0 |
| Comparative example 1 | 6 | 2.0 |
| Comparative example 2 | 6.1 | 2.1 |
| Comparative example 3 | 6.0 | 2.2 |
From the above results, it can be seen that the polyolefin resin provided by the present invention has high melt strength and impact strength. As can be seen from the comparison of the examples with the comparative examples, when the organosilane was added to the olefin polymerization process, both the melt properties (melt strength) and the impact toughness (impact strength) of the resulting polymer were greatly improved, and in combination with the measurement of the gel content, it was revealed that a branched or crosslinked structure was formed in the molecular chain.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (16)
1. An organosilane compound having the formula R1R2R3SiX, wherein R1And R2Is a straight chain, branched chain or isomeric form having 2 to 20 carbon atomsAn alkenylated radical having at the end an α -olefinic double bond, R3Is a straight chain, branched chain or isomerized alkane group with 1-20 carbon atoms, and X is halogen.
2. The organosilane compound of claim 1, wherein X is F, Cl, Br or I.
3. The organosilane compound of claim 1, wherein the organosilane compound is bis (3-butenyl) methylchlorosilane, bis (3-butenyl) ethylchlorosilane, bis (3-butenyl) propylchlorosilane, bis (3-butenyl) isopropylchlorosilane, bis (4-pentenyl) methylchlorosilane, bis (4-pentenyl) ethylchlorosilane, bis (4-pentenyl) propylchlorosilane, bis (4-pentenyl) isopropylchlorosilane, bis (5-hexenyl) methylchlorosilane, bis (5-hexenyl) ethylchlorosilane, bis (5-hexenyl) propylchlorosilane, bis (5-hexenyl) isopropylchlorosilane, bis (6-heptenyl) methylchlorosilane, bis (6-heptenyl) ethylchlorosilane, Bis (6-heptenyl) propylchlorosilane, bis (6-heptenyl) isopropylchlorosilane, bis (7-octenyl) methylchlorosilane, bis (7-octenyl) ethylchlorosilane, bis (7-octenyl) propylchlorosilane, bis (7-octenyl) isopropylchlorosilane, bis (8-nonenyl) methylchlorosilane, bis (8-nonenyl) ethylchlorosilane, bis (8-nonenyl) propylchlorosilane, bis (8-nonenyl) isopropylchlorosilane, bis (9-decenyl) methylchlorosilane, bis (9-decenyl) ethylchlorosilane, bis (9-decenyl) propylchlorosilane, bis (9-decenyl) isopropylchlorosilane, (5-hexenyl) (7-octenyl) methylchlorosilane, (5-hexenyl) (7-octenyl) ethylchlorosilane, bis (9-decenyl) propylchlorosilane, One or more of (5-hexenyl) (7-octenyl) propylchlorosilane and (5-hexenyl) (7-octenyl) isopropylchlorosilane.
4. A method for producing an organosilane compound as claimed in any one of claims 1 to 3, characterized in that the method for producing an organosilane compound comprises the steps of:
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX products with dichloroorganosilanes R2R3SiCl2And contacting to obtain the organosilane compound.
5. The process of claim 4, wherein in step 1), the molar ratio of the halo-olefin to the metal charge is from 10 to 1: 1;
preferably, in the step 1), the metal M is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum and the like;
preferably, X is F, Cl, Br or I;
preferably, in the step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane;
preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1The molar ratio of MX product to dichloroorganosilane is 10-1: 1;
preferably, in step 1), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours.
6. A method for producing an organosilane compound as claimed in any one of claims 1 to 3, characterized in that the method for producing an organosilane compound comprises the steps of:
1) reacting a halogenated olefin R in a reaction solvent1X reacts with metal M to obtain a metal-containing organic compound R1The product of MX;
2) the metal-containing organic compound R obtained in the step 1) is1MX products with trichloroorganosilanes R3SiCl3And contacting to obtain the organosilane compound.
7. The process of claim 6, wherein in step 1), the haloalkene R1X and the metal MThe feeding molar ratio of (A) to (B) is 10-1: 1;
preferably, in the step 1), the metal M is one or more of lithium, magnesium, samarium, sodium, zinc, potassium, aluminum and the like;
preferably, X is F, Cl, Br or I;
preferably, in the step 1), the reaction solvent is one or more of diethyl ether, dibutyl ether, tetrahydrofuran and n-hexane;
preferably, in step 2), the metal-containing organic compound R1Organometallic compounds R in MX products1MX meter, said metal-containing organic compound R1MX products with trichloroorganosilanes R3SiCl3In a molar ratio of 20-2: 1;
preferably, in step 2), the contacting conditions include: the contact temperature is 0-120 ℃, and the contact time is 0.5-100 hours.
8. A method for producing an organosilane compound as claimed in any one of claims 1 to 3, characterized in that the method for producing an organosilane compound comprises: reacting an organochlorosilane R in the presence of a catalyst2R3A step of carrying out a first hydrosilylation reaction of SiHCl with α, omega-diolefin represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
9. The method of claim 8, wherein the first catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of;
preferably, said first catalyst is reacted with α, omega-diolefin of said formula (1) andorganochlorosilanes R2R3The molar ratio of the total SiHCl is 0.005-0.5: 1;
preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R2R3The molar ratio of SiHCl is 100-1: 1;
preferably, the conditions of the first hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours.
10. A method for producing an organosilane compound as claimed in any one of claims 1 to 3, characterized in that the method for producing an organosilane compound comprises: reacting an organochlorosilane R in the presence of a second catalyst3SiH2A second hydrosilylation reaction of Cl with α, omega-diene represented by formula (1),
in the formula (1), R5Is a straight-chain or isomerized alkane group with 1-16 carbon atoms.
11. The method of claim 10, wherein the second catalyst is platinum, palladium, PtCl2、H2PtCl6、Na2PtCl4·4H2O、K{Pt(CH2＝CH2)Cl3}H2O and Pt2(CH2＝CH2)Cl4One or more of;
preferably, the second catalyst is reacted with the organochlorosilane R3SiH2The molar ratio of Cl to the total amount of α, omega-diolefin represented by formula (1) is 0.005-0.5: 1;
preferably, said α, omega-diene represented by formula (1) and said organochlorosilane R3SiH2The mol ratio of Cl is 100-2: 1;
preferably, the conditions of the second hydrosilylation reaction include: the reaction temperature is 0-120 ℃, and the reaction time is 0.5-100 hours.
12. A process for producing a polyolefin resin, which comprises polymerizing an olefin monomer in the presence of a catalyst, characterized by further comprising adding an organic silane compound according to any one of claims 1 to 3 to the polymerization reaction system before and/or during the olefin polymerization reaction.
13. The method of claim 12, wherein the organosilane is used in an amount of 0.0001 to 20 parts by weight relative to 100 parts by weight of the olefin monomer.
14. The method of claim 12, wherein the catalyst is one or more of a Ziegler-Natta catalyst, a metallocene catalyst, and a non-metallocene catalyst;
preferably, the olefin monomer is ethylene and/or α -olefin;
preferably, the α -olefin is one or more of propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
15. A polyolefin resin produced by the process of any one of claims 12 to 14.
16. Use of the organosilane compound as claimed in any of claims 1 to 3 for the preparation of a polyolefin resin.
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| CN108659151A (en) * | 2017-03-30 | 2018-10-16 | 中国科学院化学研究所 | A kind of application of organosilan and polypropylene and preparation method thereof |
| US20180305477A1 (en) * | 2015-10-12 | 2018-10-25 | Institute Of Chemistry, Chinese Academy Of Sciences | Olefin polymerization catalyst, preparation method therefor, olefin polymerization catalyst system, application thereof, and preparation method for polyolefin resin |
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| JPS56155213A (en) * | 1979-12-26 | 1981-12-01 | Chisso Corp | Silane-modified propylene polymer |
| EP0360297A1 (en) * | 1986-06-17 | 1990-03-28 | Amoco Corporation | Olefin polymerization catalyst |
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