CN111944234B - Method for preparing polyolefin in-kettle alloy and polyolefin in-kettle alloy prepared by method - Google Patents
Method for preparing polyolefin in-kettle alloy and polyolefin in-kettle alloy prepared by method Download PDFInfo
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- CN111944234B CN111944234B CN201910414453.1A CN201910414453A CN111944234B CN 111944234 B CN111944234 B CN 111944234B CN 201910414453 A CN201910414453 A CN 201910414453A CN 111944234 B CN111944234 B CN 111944234B
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- 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
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Abstract
The invention relates to the field of olefin polymerization, and discloses a method for preparing polyolefin in-kettle alloy and the polyolefin in-kettle alloy prepared by the method. The preparation method of the polyolefin in-kettle alloy comprises the following steps: 1) carrying out a first polymerization reaction by using a first olefin monomer in the presence of a catalyst, and then introducing a second olefin monomer into a polymerization reaction system to carry out a second polymerization reaction, wherein the first olefin monomer is different from the second olefin monomer, and the first polymerization reaction and/or the second polymerization reaction are/is carried out in the presence of organosilane; 2) contacting water and/or an alcohol with the product obtained in step 1), wherein the organosilane has the general formula R1 mSiXnR2 kWherein R is1Is C7‑C201-alkenyl of (2), R2Is C2‑C20X is halogen, m, n and k are each 1 or 2, respectively, and m + n + k is 4. The alloy rubber in the polyolefin kettle has high crosslinking degree, and has higher impact toughness and flexural modulus.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a preparation method of a polyolefin in-kettle alloy and the polyolefin in-kettle alloy prepared by the method.
Background
The polypropylene is indispensable in our life, is one of the most widely used synthetic resins with the fastest yield increase at present, has the characteristics of low density, high melting point, easy processing, excellent comprehensive performance and the like, and is widely applied to the fields of automobiles, home decoration, buildings, packaging, agriculture and the like.
The polyolefin in-kettle alloy is obtained directly from reaction monomers by an in-kettle polymerization mode, so that the traditional blending method for melting and blending polymers is replaced. The most common of polyolefin tank alloys is polypropylene tank alloy. The alloy in the polypropylene kettle is based on a particle reactor technology, polypropylene primary particles are used as a particle reactor, ethylene/propylene copolymerization is catalyzed in the particle reactor to generate ethylene-propylene random copolymer, and the generated ethylene-propylene random copolymer is filled in gaps of porous polypropylene.
In recent years, olefin polymerization modifiers having new structures and new properties have been discovered and used in the research of high performance of polyolefins. At present, the normal impact copolymer polypropylene medium-sized polypropylene and the ethylene-propylene random copolymer are two thermodynamically incompatible components in the melting process, and are easy to generate phase separation, so that the ethylene-propylene random copolymer is finally dispersed in the medium-sized polypropylene in an aggregation state, and the toughening effect of the ethylene-propylene random copolymer on the polypropylene matrix resin is obviously reduced. Some researchers introduce diene monomers during the polymerization process, and the two double bonds participate in the reaction, so that the mutual fusion of the ethylene-propylene random copolymer is inhibited. For example, 1, 9-decadiene can realize the synthesis of the multiphase copolymerization polypropylene with the ethylene propylene rubber phase having a cross-linked structure by a reactor method, but the 1, 9-decadiene can reduce the activity of polymerization reaction, and the monomer consumption is large, the efficiency is low, and both the low-temperature impact property and the flexural modulus of the polypropylene alloy are not reported.
Disclosure of Invention
The invention aims to provide a polyolefin in-kettle alloy and a preparation method thereof.
According to a first aspect of the present invention, there is provided a process for preparing a polyolefin in-kettle alloy, the process comprising the steps of:
1) carrying out a first polymerization reaction by using a first olefin monomer in the presence of a catalyst, and then introducing a second olefin monomer into a polymerization reaction system to carry out a second polymerization reaction, wherein the first olefin monomer is different from the second olefin monomer, and the first polymerization reaction and/or the second polymerization reaction are/is carried out in the presence of organosilane;
2) contacting water and/or alcohol with the product obtained in step 1),
wherein the organosilane has the general formula R1 mSiXnR2 kWherein R is1Is C7-C201-alkenyl of (2), R2Is C2-C20X is halogen, m, n and k are each 1 or 2, respectively, and m + n + k is 4.
Preferably, R1Is C7-C201-alkenyl of (2), R2Is C2-C10X is halogen, m is 1 or 2, n is 1 or 2, k is 1, and m + n is 3.
Preferably, the organosilane is one of tris (9-decenyl) chlorosilane, tris (7-octenyl) chlorosilane, bis (9-decenyl) dichlorosilane, bis (7-octenyl) allylchlorosilane, bis (9-decenyl) - (4-pentenyl) chlorosilane, 9-decenyl allyldichlorosilane, 7-octenyl allyldichlorosilane, 9-decenyl- (4-pentenyl) dichlorosilane, 7-octenyl- (4-pentenyl) dichlorosilane, 9-decenyl- (5-hexenyl) dichlorosilane, 7-octenyl- (3-butenyl) dichlorosilane and 9-decenyl- (3-butenyl) dichlorosilane Or a plurality thereof; more preferably, the organosilane is bis (7-octenyl) dichlorosilane and/or 7-octenyl- (5-hexenyl) dichlorosilane.
Preferably, the water is deionized water.
Preferably, the alcohol is one or more of methanol, ethanol, n-propanol, isopropanol and n-butanol; more preferably, the alcohol is methanol and/or ethanol.
Preferably, the conditions of the contacting include: the contact temperature is 50-130 deg.C, and the contact time is 5-60 min.
Preferably, the catalyst is a Ziegler-Natta catalyst.
Preferably, the conditions of the first polymerization reaction include: the reaction temperature is 50-80 ℃ and the reaction time is 0.2-2 hours.
Preferably, the conditions of the second polymerization reaction include: the reaction temperature is 60-120 ℃, and the reaction time is 0.1-3 hours.
Preferably, the polyolefin in-pot alloy is a polypropylene in-pot alloy.
Preferably, the first olefin monomer is propylene and the second olefin monomer is a mixture of ethylene and an alpha-olefin.
Preferably, the organosilane is used in a total amount of 0.001 to 20 parts by weight, relative to 100 parts by weight of the total amount of the first and second olefin monomers.
According to a second aspect of the present invention, there is also provided a polyolefin in-kettle alloy prepared by the above-described process of the present invention.
Through extensive use research, the inventor of the invention finds that the gel content of the polyolefin kettle alloy prepared by the method is increased, and the impact toughness and the bending strength of the polyolefin kettle alloy are further improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The preparation method of the polyolefin in-kettle alloy provided by the invention comprises the following steps:
1) carrying out a first polymerization reaction by using a first olefin monomer in the presence of a catalyst, and then introducing a second olefin monomer into a polymerization reaction system to carry out a second polymerization reaction, wherein the first olefin monomer is different from the second olefin monomer, and the first polymerization reaction and/or the second polymerization reaction are/is carried out in the presence of organosilane;
2) contacting water and/or alcohol with the product obtained in step 1),
wherein the organosilane has the general formula R1 mSiXnR2 kWherein R is1Is C7-C201-alkenyl of (2), R2Is C2-C20X is halogen, m, n and k are each 1 or 2, respectively, and m + n + k is 4.
According to the invention, preferably, the organosilane has the formula R1 mSiXnR2 kPlural R in the same general formula1May be the same or different and may each independently be C7-C201-alkenyl of (A); 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); multiple R in the same formula2May be the same or different and may each independently be C2-C10M and n are each 1 or 2, k is 1, and m + n is 3. The preferable organosilane is added into the polymerization reaction, and the prepared polymer is subjected to water/alcohol treatment, so that the crosslinking degree of a rubber phase in the alloy in the polyolefin kettle is improved, and the impact toughness of the alloy in the polyolefin kettle is further improved.
Specific examples of organosilanes according to the invention include, but are not limited to: tris (9-decenyl) chlorosilane, tris (7-octenyl) chlorosilane, bis (9-decenyl) dichlorosilane, bis (7-octenyl) allylchlorosilane, bis (9-decenyl) - (4-pentenyl) chlorosilane, 9-decenyl allyldichlorosilane, one or more of 7-octenylallyldichlorosilane, 9-decenyl- (4-pentenyl) dichlorosilane, 7-octenyl- (4-pentenyl) dichlorosilane, 9-decenyl- (5-hexenyl) dichlorosilane, 7-octenyl- (3-butenyl) dichlorosilane, and 9-decenyl- (3-butenyl) dichlorosilane; preferably, the organosilane is bis (7-octenyl) dichlorosilane and/or 7-octenyl- (5-hexenyl) dichlorosilane.
In the present invention, the organosilane, which is not supported on the catalyst, is introduced as a comonomer during polymerization, functioning as a crosslinking agent, whereby the content of crosslinking can be adjusted by the amount added.
According to the invention, the more the amount of the organic silane is, the more the branching and crosslinking contents of the obtained polypropylene kettle alloy are, therefore, the amount of the organic silane can be selected according to the specific requirements to obtain the impact toughness and the bending strength of the polypropylene kettle alloy. Preferably, the organosilane is used in a total amount of 0.002 to 20 parts by weight, more preferably 0.005 to 10 parts by weight, still more preferably 0.02 to 5 parts by weight, and most preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total amount of the first olefin monomer and the second olefin monomer, so that the impact toughness and the flexural modulus of the alloy in the polypropylene tank can be further improved.
The main improvement of the preparation method of the polyolefin in-kettle alloy provided by the invention is that after the second polymerization reaction is finished, the product obtained by polymerization is treated by water and/or alcohol (namely, the water and/or alcohol is contacted with the product obtained in the step 1). Preferably, the conditions of the contacting include: the contact temperature is 0-140 deg.C, and the contact time is 5-80 min; more preferably, the conditions of the contacting include: the contact temperature is 50-130 ℃, and the contact time is 5-60 min; particularly preferably, the contact temperature is 70-105 ℃ and the contact time is 5-50 min. The contact is preferably performed at a temperature not higher than the boiling point of the solvent used.
The mode of the contact is not particularly limited, and for example, the product obtained in step 1) may be mixed with water and/or alcohol and then contacted under the above-mentioned contact conditions. In addition, stirring is preferably performed during the contact.
According to the invention, the water is deionized water.
Preferably, the alcohol is one or more of methanol, ethanol, n-propanol, isopropanol and n-butanol; more preferably, the alcohol is methanol and/or ethanol.
According to the present invention, the first olefin monomer and the second olefin monomer may be any of various existing monomers capable of olefin polymerization, and specifically may be ethylene and/or α -olefin. The alpha-olefin may be any mono-olefin having various double bonds at the end of the molecular chain, and may be at least one of propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, for example. Particularly preferably, the first olefin monomer is propylene and the second olefin monomer is a mixture of ethylene and an alpha-olefin, and the polyolefin in-pot alloy obtained at this time is a polypropylene in-pot alloy. In this case, the ethylene may be used in an amount of 1 to 99% by weight, preferably 20 to 50% by weight, based on the total weight of the ethylene and α -olefin, in the second polymerization process; the alpha-olefin may be used in an amount of 1 to 99% by weight, preferably 50 to 80% by weight. The weight ratio of the amount of propylene used in the first polymerization process to the total amount of ethylene and alpha-olefins used in the second polymerization process may be from 0.2 to 100: 1, preferably 1 to 10: 1. in addition, it should be noted that the first olefin monomer is different from the second olefin monomer, which means that the kind of the first olefin monomer is not completely the same as that of the second olefin monomer, and may be completely different or partially different.
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: at least one of a Ziegler-Natta catalyst, a metallocene catalyst, and a non-metallocene catalyst.
According to the invention, the catalyst is preferably a Ziegler-Natta catalyst, preferably MgCl2Supported catalytic systems, in particular MgCl2MgCl is usually contained in supported catalyst systems2、TiCl4An alkyl aluminum and/or an alkoxy aluminum and optionally an internal electron donor and/or an external electron donor, preferably the Ziegler-Natta catalyst contains the internal electron donor, more preferably the internal electron donor of the Ziegler-Natta catalyst can be at least one of monoester, diester and diether; further preferably, the internal electron donor of the Ziegler-Natta catalyst is 9, 9-bis (methoxymethyl) fluorene.
The conditions of the first polymerization reaction and the second polymerization reaction are not particularly limited in the present invention. For example, the conditions of the first polymerization reaction generally include that the reaction temperature may be 50 to 80 ℃, preferably 60 to 70 ℃; the reaction time may be 0.2 to 2 hours, preferably 0.5 to 1 hour. The conditions of the second polymerization reaction generally include that the reaction temperature may be 60 to 120 ℃, preferably 75 to 95 ℃; the reaction time may be 0.1 to 3 hours, preferably 0.1 to 0.5 hour. In the present invention, the pressures are gauge pressures. Further, the first polymerization reaction and/or the second polymerization reaction is preferably carried out in the presence of hydrogen. Preferably, the hydrogen may be used in an amount of 0.001 to 0.5 parts by weight, preferably 0.005 to 0.1 parts by weight, relative to 100 parts by weight of the first olefin monomer in the first polymerization process.
The invention also provides the polyolefin in-kettle alloy obtained by the preparation method.
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 alloy in the polyolefin pot was determined as follows: drying the alloy in the polypropylene kettle in a vacuum drying oven at 50 ℃ to constant weight, weighing and recording as W1Dissolving the dried polypropylene alloy in xylene, oscillating at 135 deg.C to dissolve completely, filtering with 200 mesh stainless steel net, collecting insoluble polymer remained on the stainless steel net, drying the insoluble polymer on the stainless steel net in a vacuum drying oven at 100 deg.C for 4 hr, weighing, and recording as W2The gel content of the alloy in the polyolefin kettle is calculated as follows:
gel content (% by weight) is (W)2/W1) X 100 (wt%).
Example 1
(1) Homopolymerization of propylene in a 500ml dry autoclave, 50ml dry n-hexane was added first, 1ml triethylaluminum with a concentration of 1.8mol/L, and a diether type olefin catalyst (MgCl)2/TiCl4/BMMF, wherein BMMF is internal electron donor 9, 9-di (methoxymethyl) fluorene, MgCl2、TiCl4Nature of BMMFThe weight ratio is 73.6:15.2:11.2)20.0mg, 0.2g of bis- (7-octenyl) dichlorosilane is added, 0.06g of hydrogen is introduced, then propylene gas is introduced, and polymerization reaction is carried out for 30min at 60 ℃ and under the pressure of 0.4MPa to obtain polypropylene particles, and the next reaction is directly carried out.
(2) Ethylene-propylene copolymerization
The propylene gas in the above step (1) was vented, and the hexane solvent in the polymerization system was evacuated by a vacuum pump under a degree of vacuum of about 5mmHg for about 5 min. And then introducing ethylene-propylene mixed gas with the gas molar ratio of 1: 1, controlling the polymerization temperature at 70-90 ℃, controlling the polymerization pressure at 0.4MPa, carrying out polymerization reaction for 100min, finishing the polymerization reaction, releasing the gas pressure in the high-pressure kettle, transferring the polymer into deionized water at 100 ℃, continuing the reaction for 10min, and then carrying out vacuum drying at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 2
According to the method of example 1, except that after the polymerization reaction is completed, the gas in the reaction kettle is emptied, then the polymer is transferred to deionized water at 100 ℃ to continue the reaction for 30min, and then vacuum drying is carried out at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 3
According to the method of example 1, except that after the polymerization reaction is completed, the gas in the reaction kettle is vented, then the polymer is transferred to deionized water at 100 ℃ to continue the reaction for 50min, and then vacuum drying is carried out at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 4
According to the method of example 1, except that after the polymerization reaction is completed, the gas in the reaction kettle is emptied, then the polymer is transferred to the absolute ethyl alcohol with the temperature of 80 ℃ to continue the reaction for 10min, and then the polymer is dried in vacuum at the temperature of 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 5
According to the method of example 1, except that after the polymerization reaction is completed, the gas in the reaction kettle is emptied, then the polymer is transferred to the absolute ethyl alcohol with the temperature of 80 ℃ to continue the reaction for 30min, and then the polymer is dried in vacuum at the temperature of 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 6
According to the method of example 1, except that after the polymerization reaction is completed, the gas in the reaction kettle is emptied, then the polymer is transferred to 80 ℃ absolute ethyl alcohol to continue the reaction for 50min, and then vacuum drying is carried out at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 7
The procedure is as in example 1, except that bis- (7-octenyl) dichlorosilane is replaced with the same volume of 7-octenyl-5-hexenyldichlorosilane. After the polymerization reaction is finished, the gas pressure in the autoclave is released, then the polymer is transferred to deionized water at 100 ℃ for continuous reaction for 30min, and then vacuum drying is carried out at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 8
The procedure is as in example 1, except that bis- (7-octenyl) dichlorosilane is replaced with the same volume of 7-octenyl-5-hexenyldichlorosilane. And after the polymerization reaction is finished, releasing the gas pressure in the high-pressure kettle, transferring the polymer into anhydrous ethanol at the temperature of 80 ℃ to continue reacting for 30min, and then performing vacuum drying at the temperature of 60 ℃ to obtain a solid particle product polypropylene in-kettle alloy.
Example 9
The procedure is as in example 1, except that bis- (7-octenyl) dichlorosilane is replaced with the same volume of 7-octenylallyldichlorosilane. After the polymerization reaction is finished, the gas in the reaction kettle is discharged, then the polymer is transferred to deionized water at 100 ℃ to continue the reaction for 30min, and then the vacuum drying is carried out at 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Example 10
The procedure is as in example 1, except that bis- (7-octenyl) dichlorosilane is replaced with the same volume of 7-octenylallyldichlorosilane. And after the polymerization reaction is finished, the gas in the reaction kettle is discharged, then the polymer is transferred into absolute ethyl alcohol at the temperature of 80 ℃ to continue to react for 30min, and then the polymer is dried in vacuum at the temperature of 60 ℃ to obtain the solid particle product polypropylene in-kettle alloy.
Comparative example 1
The procedure of example 1 was followed except that after the polymerization reaction was completed, the gas in the reactor was vented and the polymer was not treated to obtain a solid particulate product, polypropylene in-tank alloy.
Comparative example 2
Following the procedure of example 1, except that bis- (7-octenyl) dichlorosilane was not added, a solid particulate product polypropylene in-pot alloy was obtained.
Comparative example 3
The procedure of example 1 was followed except that bis- (7-octenyl) dichlorosilane was replaced with the same volume of tetrachlorosilane, and after completion of the polymerization reaction, the gas in the reactor was vented, and then the polymer was transferred to 100 ℃ deionized water to continue the reaction for 30min, followed by vacuum drying at 60 ℃ to obtain a solid particulate product polypropylene in-kettle alloy.
Comparative example 4
The procedure of example 1 was followed except that bis- (7-octenyl) dichlorosilane was replaced with the same volume of tetrachlorosilane, and after completion of the polymerization reaction, the gas in the reaction vessel was vented, and then the polymer was transferred to 80 ℃ absolute ethanol to continue the reaction for 30min, followed by vacuum drying at 60 ℃ to obtain a solid particulate product polypropylene in-vessel alloy.
Test example 1
Test examples are used to illustrate the testing of the mechanical properties of the alloy in a polyolefin kettle.
The impact strength was measured according to the method specified in ASTM D256A, and the results are shown in table 1.
The flexural modulus was measured according to the method specified in GB/T9341-2000, and the results are shown in Table 1.
TABLE 1
From the results, the crosslinking degree of the rubber phase in the polyolefin in-kettle alloy prepared by the method provided by the invention is higher, and the polyolefin in-kettle alloy resin has higher impact toughness and flexural modulus. Comparing the results of examples 2 and 4 with those of comparative example 1, it can be seen that the degree of crosslinking of the rubber phase in the polyolefin in-pot alloy is higher after the polymer is reacted in deionized water or alcohol, and thus the polyolefin in-pot alloy has higher impact toughness and flexural modulus. From the results of example 2 and comparative example 3, it can be seen that the organosilane provided by the invention and the silicon tetrahalide show different behaviors in the olefin polymerization process, and the polyolefin in-kettle alloy obtained by using the organosilane provided by the invention has higher impact toughness and flexural modulus.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method for preparing polyolefin in-kettle alloy is characterized by comprising the following steps:
1) carrying out a first polymerization reaction by using a first olefin monomer in the presence of a catalyst, and then introducing a second olefin monomer into a polymerization reaction system to carry out a second polymerization reaction, wherein the first olefin monomer is different from the second olefin monomer, and the first polymerization reaction and/or the second polymerization reaction are/is carried out in the presence of organosilane;
2) contacting water and/or alcohol with the product obtained in step 1),
wherein the organosilane has the general formula R1 mSiXnR2 kWherein R is1
Is C7-C201-alkenyl of (2), R2Is C2-C20Is 1-alkenyl, X is halogen, m, n and k are each1 or 2, respectively, and m + n + k is 4,
the conditions of the contacting include: the contact temperature is 50-130 deg.C, and the contact time is 30-60 min.
2. The method of claim 1, wherein R1Is C7-C201-alkenyl of (2), R2Is C2-C10X is halogen, m is 1 or 2, n is 1 or 2, k is 1, and m + n is 3.
3. The method of claim 2, wherein the organosilane is tris (9-decenyl) chlorosilane, tris (7-octenyl) chlorosilane, bis (9-decenyl) dichlorosilane, bis (7-octenyl) allylchlorosilane, bis (9-decenyl) - (4-pentenyl) chlorosilane, 9-decenyl allyldichlorosilane, 7-octenyl allyldichlorosilane, 9-decenyl- (4-pentenyl) dichlorosilane, 7-octenyl- (4-pentenyl) dichlorosilane, 9-decenyl- (5-hexenyl) dichlorosilane, 7-octenyl- (3-butenyl) dichlorosilane, and 9-decenyl- (3-butenyl) dichlorosilane -butenyl) dichlorosilane.
4. A process according to claim 3, wherein the organosilane is bis (7-octenyl) dichlorosilane and/or 7-octenyl- (5-hexenyl) dichlorosilane.
5. The method of any of claims 1-4, wherein the water is deionized water.
6. The process of any one of claims 1-4, wherein the alcohol is one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol.
7. The process according to claim 5, wherein the alcohol is methanol and/or ethanol.
8. The process according to any one of claims 1-4, wherein the catalyst is a Ziegler-Natta catalyst.
9. The method of any of claims 1-4, wherein the conditions of the first polymerization reaction comprise: the reaction temperature is 50-80 ℃ and the reaction time is 0.2-2 hours.
10. The method of claim 9, wherein the conditions of the second polymerization reaction comprise: the reaction temperature is 60-120 ℃, and the reaction time is 0.1-3 hours.
11. The method of any of claims 1-4, wherein the polyolefin tank alloy is a polypropylene tank alloy.
12. The process of claim 11 wherein the first olefin monomer is propylene and the second olefin monomer is a mixture of ethylene and an alpha-olefin.
13. The process according to any one of claims 1 to 4, wherein the organosilane is used in a total amount of 0.001 to 20 parts by weight relative to 100 parts by weight of the total amount of the first and second olefin monomers.
14. A polyolefin in-tank alloy prepared by the process of any one of claims 1-13.
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