CN112143113B - Long-chain branched polypropylene impact copolymer and preparation method thereof - Google Patents

Long-chain branched polypropylene impact copolymer and preparation method thereof Download PDF

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CN112143113B
CN112143113B CN202010344231.XA CN202010344231A CN112143113B CN 112143113 B CN112143113 B CN 112143113B CN 202010344231 A CN202010344231 A CN 202010344231A CN 112143113 B CN112143113 B CN 112143113B
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董金勇
张志箭
秦亚伟
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Abstract

The invention provides a long-chain branched polypropylene impact copolymer and a preparation method thereof. The copolymer consists of random copolymerization polypropylene and a copolymer of propylene and alpha-olefin, wherein the polypropylene impact copolymer contains a long-chain branched structure, and the long-chain branched structure has a structure of bridging olefin polymer molecules by-Si-O-Si-. The preparation method comprises the steps of carrying out first copolymerization reaction of propylene and a small amount of first alpha-olefin in the presence of a catalyst, then introducing second alpha-olefin into a polymerization reaction system, and carrying out second copolymerization reaction of the propylene and the second alpha-olefin, wherein the general formula of the first copolymerization reaction and the second copolymerization reaction is R1SiX2R2Is carried out in the presence of 0.001 to 20 parts by weight of an organosilane relative to 100 parts by weight of the total amount of monomers to be polymerized. The long-chain branched polypropylene impact copolymer obtained by the method has a long-chain branched structure, and has high melt strength and impact toughness.

Description

Long-chain branched polypropylene impact copolymer and preparation method thereof
Technical Field
The invention relates to the field of olefin multiphase copolymerization, in particular to a preparation method of a long-chain branched high-melt-strength polypropylene impact copolymer and the long-chain branched high-melt-strength polypropylene impact copolymer prepared by the method.
Background
The high impact polypropylene (hiPP) or Impact Polypropylene Copolymer (IPC) accounts for nearly 50% of all polypropylene resin products because the low-temperature toughness of polypropylene is effectively compensated, and the high impact polypropylene (hiPP) or Impact Polypropylene Copolymer (IPC) becomes a main raw material of automobile plastics, household article plastics and electronic and electrical plastics, and has wide application prospects in the fields of building insulation, cables, aerospace and the like.
The preparation method of the impact-resistant polypropylene copolymer mainly comprises a mechanical blending technology and a polypropylene in-kettle alloy technology. The polypropylene in-tank alloy technology is generally formed by polymerizing propylene in the presence of an olefin polymerization catalyst to form porous polypropylene particles, then introducing ethylene and an alpha-olefin comonomer into a polymerization system to perform copolymerization reaction in the porous polypropylene particles, and filling gaps of the porous polypropylene particles with the generated elastic copolymer. Compared with the traditional mechanical blending technology, the method not only saves the complex process of post-modification and reduces the production cost, but also has the characteristics of controllable crosslinking degree and more diversified products in the in-kettle alloy technology, can realize controllable preparation of the series of in-kettle polypropylene alloys by adjusting the types and the addition of crosslinking monomers, and has lower dependence on a polymerization catalyst and a polymerization process.
In recent years, some functional modifiers with new structures and new properties are discovered and applied to polypropylene in-kettle alloy technology, but the molecular structure of the prepared polypropylene impact copolymer is still linear, so that the processing window is narrow, the melt strength is low, and the tensile strain hardening phenomenon is avoided in the molten state.
Disclosure of Invention
The invention aims to provide a preparation method of a long-chain branched polypropylene impact copolymer and the long-chain branched polypropylene impact copolymer prepared by the method.
Specifically, according to the first aspect of the invention, a long-chain branched polypropylene impact copolymer is provided, wherein the polypropylene impact copolymer comprises random copolymerization polypropylene and a propylene and alpha-olefin copolymer, and the polypropylene impact copolymer contains a long-chain branched structure, and the long-chain branched structure has a structure of-Si-O-Si-as a bridging olefin polymer molecule.
Preferably, the weight ratio of the propylene to alpha-olefin copolymer to the random copolymerized polypropylene is 1 to 100: 100.
preferably, the weight ratio of the alpha-olefin to the propylene in the propylene/alpha-olefin copolymer is from 10 to 150: 100.
preferably, the polypropylene impact copolymer consists of random copolymerized polypropylene and propylene and alpha-olefin copolymer.
Preferably, the random copolymer polypropylene has a melt index of 0.1 to 100g/10min, measured at 230 ℃ under a load of 2.16 kg.
Preferably, the long chain branched polypropylene impact copolymer has a melt index of 0.1 to 30g/10min measured at 230 ℃ under a load of 2.16 kg.
Preferably, the long chain branched polypropylene impact copolymer has a melt strength of from 1 to 200 cN.
According to a second aspect of the present invention, there is provided a process for preparing a long chain branched polypropylene impact copolymer, comprising a first copolymerization of propylene and a first α -olefin in the presence of a catalyst, followed by a second copolymerization of propylene and a second α -olefin by feeding the second α -olefin into the polymerization system, wherein the first and second copolymerization reactions are of the formula R1SiX2R2In the presence of 0.001 to 20 parts by weight of an organosilane per 100 parts by weight of the total amount of the first and second comonomers, wherein R is1Is C2-C20Is a-olefin of (A), X is halogen, R2Is C1-C20Linear, branched or isomerized alkyl groups.
Preferably, the organosilane is not contained in the catalyst component.
Preferably, R1Is C2-C20Is a-olefin of (A), X is halogen, R2Is C1-C20Linear, branched or isomerized alkyl groups.
Preferably, the organosilane is at least one of 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane; more preferably, the organosilane is at least one of 3-butenylmethyl dichlorosilane, 4-pentenyl methyl dichlorosilane, 5-hexenylmethyl dichlorosilane, 6-heptenylmethyl dichlorosilane and 7-octenylmethyl dichlorosilane.
Preferably, the organosilane is used in a total amount of 0.04 to 2.6 parts by weight with respect to 100 parts by weight of the total amount of the first and second comonomers.
Preferably, the catalyst is a Ziegler-Natta catalyst.
Preferably, the molar ratio of the organoaluminium compound to the external electron donor in the Ziegler-Natta catalyst is 1: 1-100: 1, more preferably 10: 1-50: 1.
preferably, the first alpha-olefin may be one or more of ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and the like.
Preferably, the second alpha-olefin may be one or more of ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and the like.
Preferably, the first alpha-olefin is added in an amount of 1 to 10 wt% based on the total weight of the propylene and the first alpha-olefin in the first copolymerization reaction.
Preferably, in the second copolymerization, the second α -olefin is added in an amount of 1 to 99% by weight, based on the total weight of the propylene and the second α -olefin.
Preferably, the hydrogen is used in an amount of 0 to 10 parts by weight, relative to 100 parts by weight of the first copolymerization monomer, in the first copolymerization.
Preferably, in the second copolymerization, the hydrogen is used in an amount of 0 to 1 part by weight, relative to 100 parts by weight of the second copolymerization monomer.
Preferably, the conditions of the first copolymerization reaction include a reaction temperature of 30 to 90 ℃ and a reaction time of 0.05 to 10 hours.
Preferably, the second copolymerization reaction conditions include a reaction temperature of 60 to 120 ℃ and a reaction time of 0.1 to 10 hours.
Preferably, the first copolymerization pressure is from 0 to 40 atmospheres.
Preferably, the second copolymerization reaction pressure is 0.1 to 15 atmospheres.
According to a third aspect of the present invention there is provided a long chain branched polypropylene impact copolymer prepared by the process of the present invention.
After a great deal of experiments and intensive researches, the inventor of the invention finds that the structural general formula is R1SiX2R2Is prepared from organosilane and has a structural general formula of SiR'4(wherein R' is C1-C20Linear, branched or isomerized alkyl) and the general structural formula SiX'4(wherein X' is a halogen) shows a completely different behavior during the preparation of polypropylene impact copolymers, and in the present invention, the organosilicon compounds of the above general structural formula are used as starting materials and crosslinkers in polymerization reactions, since the organosilicon compound of the above general structural formula has an olefin structure as a raw material to participate in polymerization reaction to form a polymer chain and has a dihalosilane group on a side chain of the polymer chain, the group forms a structure with-Si-O-Si-as a bridging olefin polymer molecule through hydrolytic condensation, on the other hand, the organic silicon compound with the structural general formula can be used as a cross-linking agent to connect a first-stage polymer and a second-stage polymer together, thus, the present invention is achieved by placing the first copolymerization and the second copolymerization in the general formula R.1SiX2R2In the presence of organosilane(s), the obtained polypropylene impact copolymer has a long-chain branched structure, and has higher melt strength and impact toughness.
And has a general structural formula of R1SiX2R2The organosilane compound of (A) is a simple monoene structureThe meta-resistance is small, the efficiency of the copolymer in the first copolymerization reaction and the second copolymerization reaction is high, the interface combination of two phases is improved, and the polypropylene impact copolymer prepared by the organosilane has high melt strength and impact toughness. Meanwhile, a large amount of double bond residues do not exist in the polypropylene impact copolymer, so that the ultraviolet resistance, ageing resistance and long-term use stability of the polypropylene impact copolymer are improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a plot of viscosity versus time for the polypropylene impact copolymer of example 1 at various draw down rates.
FIG. 2 is a plot of viscosity versus time for the polypropylene impact copolymer of comparative example 1 at various draw down rates.
FIG. 3 is an infrared spectrum of a long chain branched polypropylene impact copolymer of example 1 and a polypropylene impact copolymer of comparative example 1.
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 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.
According to a first aspect of the present invention, there is provided a long chain branched polypropylene impact copolymer, wherein the polypropylene impact copolymer comprises a random copolymer polypropylene and a propylene and alpha-olefin copolymer, and the polypropylene impact copolymer contains a long chain branched structure having a structure of-Si-O-Si-as a bridged olefin polymer molecule.
The long-chain branched structure is formed by hydrolyzing and condensing organosilane, and is a structure which takes-Si-O-Si-as a bridging olefin polymer molecule and is formed by hydrolyzing and condensing dihalosilane groups after a molecular chain with dihalosilane groups on side chains is treated with water. Preferably, the long-chain branched structure is formed as an "H" -type long-chain branched structure.
According to the present invention, preferably, the weight ratio of the propylene/α -olefin copolymer to the random copolymerized polypropylene is 1 to 100: 100, preferably 10 to 60: 100. by having the advantage of high impact toughness in the above range.
According to the present invention, preferably, the weight ratio of the alpha-olefin to propylene in the propylene/alpha-olefin copolymer is from 10 to 150: 100, more preferably 50 to 100: 100. by having the advantage of high impact toughness in the above range.
According to the present invention, preferably, the polypropylene impact copolymer consists of random copolymerized polypropylene and a copolymer of propylene and alpha-olefin.
According to the present invention, preferably, the random copolymerized polypropylene has a melt index of 0.1 to 100g/10min, more preferably 5 to 10g/10min, measured at 230 ℃ under a load of 2.16 kg. By having the advantage of high melt strength in the above range.
According to the present invention, preferably the long chain branched polypropylene impact copolymer has a melt index of 0.1 to 30g/10min, more preferably 1 to 5g/10min, measured at 230 ℃ under a load of 2.16 kg. By having the advantage of high melt strength in the above range.
The long chain branched polypropylene impact copolymer has a melt strength of from 1 to 200cN, more preferably from 10 to 40 cN.
According to a second aspect of the present invention, there is provided a process for preparing a long chain branched polypropylene impact copolymer comprising a first copolymerization of propylene with a small amount of a first α -olefin in the presence of a catalyst followed by a second copolymerization of propylene with a second α -olefin by feeding the second α -olefin to the polymerization system, wherein the first copolymerization and the second copolymerization are carried out in the presence of a catalystA second copolymerization of the general formula R1SiX2R2In the presence of 0.001 to 20 parts by weight of an organosilane per 100 parts by weight of the total amount of the first and second comonomers, wherein R is1Is C2-C20Is a-olefin of (A), X is halogen, R2Is C1-C20Linear, branched or isomerized alkyl groups.
Preferably, R1Is C4-C20More preferably C4-C15Is more preferably C4-C12Of alpha-olefins.
Preferably, X is halogen, and a plurality of X in the same general formula may be the same or different, and may each independently be halogen (including fluorine, chlorine, bromine, iodine); more preferably, X is chlorine.
Preferably, R2Is C1-C10More preferably C1-C6Linear, branched or isomerized alkyl; more preferably C1-C3Is particularly preferably C1-C2Alkyl group of (1).
Specific examples of organosilanes according to the invention include, but are not limited to: 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane; preferably, the organosilane is at least one of 3-butenylmethyl dichlorosilane, 4-pentenyl methyl dichlorosilane, 5-hexenylmethyl dichlorosilane, 6-heptenylmethyl dichlorosilane and 7-octenylmethyl dichlorosilane. The preferable organosilane is used as a modifier in the preparation process of the long-chain branched polypropylene impact copolymer, so that the melt strength and the impact toughness of the long-chain branched polypropylene impact copolymer are improved.
According to the invention, the melt strength of the long-chain branched polypropylene impact copolymer is enhanced differently by different organosilanes, according to the general formula R1SiX2R2In organosilane (II) of (III)1Appropriate variation of the number of carbon atoms in the group and R2A reduction in the number of carbon atoms in the group, said general structural formula being R1SiX2R2The melt strength enhancing effect of the organosilane on the long-chain branched polypropylene impact copolymer is gradually enhanced. Preferably, the general structural formula is R1SiX2R2In the organosilane of (2), R1Is C2-C20The 2X in the same general structural formula may be the same or different, and may be each independently halogen (including fluorine, chlorine, bromine, iodine), R2Is C1-C10Linear, branched or isomerized alkyl groups. More preferably, the general structural formula is R1SiX2R2In the organosilane of (2), R1Is C2-C20The 2X in the same general structural formula may be the same or different, and may be each independently halogen (including fluorine, chlorine, bromine, iodine), R2Is C1-C5Linear, branched or isomerized alkyl groups. The preferable organosilane is used as a modifier in the preparation process of the long-chain branched polypropylene impact copolymer, so that the melt strength of the long-chain branched polypropylene impact copolymer is improved.
According to the present invention, the organosilane is preferably used in a total amount of 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.03 to 3 parts by weight, still more preferably 0.04 to 2.6 parts by weight, still more preferably 0.04 to 1.0 part by weight, and particularly preferably 0.04 to 0.05 part by weight, based on 100 parts by weight of the total amount of the first and second comonomers. By using the organic silane within the above range, the melt strength of the resulting long chain branched polypropylene impact copolymer can be further improved.
According to the preparation method of the long-chain branched polypropylene impact copolymer provided by the invention, the first copolymerization reaction and the second copolymerization reaction are carried out in the presence of the organosilane, so that the melt strength and the impact toughness of the long-chain branched polypropylene impact copolymer are improved.
According to the preparation method of the long-chain branched polypropylene impact copolymer provided by the invention, the first copolymerization reaction monomer is propylene and first alpha-olefin, and the second copolymerization reaction monomer is propylene and second alpha-olefin. According to a preferred embodiment of the present invention, the first copolymerization monomer is propylene and ethylene, and the second copolymerization monomer is propylene and ethylene. In the first copolymerization, the first α -olefin may be added in an amount of 1 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 2% by weight, based on the total weight of the propylene and the first α -olefin; in the second copolymerization, the second α -olefin may be added in an amount of 1 to 99% by weight, preferably 10 to 70% by weight, more preferably 20 to 50% by weight, based on the total weight of the propylene and the second α -olefin, which is advantageous in improving the melt strength of the long-chain branched polypropylene impact copolymer.
The main improvement of the preparation method of the long-chain branched polypropylene impact copolymer provided by the invention is that the general structural formula R is added in the preparation process of the polypropylene impact copolymer1SiX2R2The catalyst is selected from Ziegler-Natta catalyst, and the type of Ziegler-Natta catalyst and the conditions of the first copolymerization reaction and the second copolymerization reaction can be selected conventionally in the field.
According to the invention, the catalyst is a Ziegler-Natta catalyst, preferably MgCl2Supported catalytic system, said MgCl2MgCl is contained in the supported catalyst system2、TiCl4An alkylaluminium and/or an aluminium alkoxide and optionally an internal and/or external electron donor.Preferably, the cocatalyst of the Ziegler-Natta catalyst is at least one of aluminum alkyl and aluminum alkoxide, more preferably, the cocatalyst of the Ziegler-Natta catalyst is triethylaluminum; the internal electron donor of the Ziegler-Natta catalyst is at least one of a monoester, a diester and a diether, more preferably the internal electron donor of the Ziegler-Natta catalyst is diisobutylphthalate and/or 9, 9-bis (methoxymethyl) fluorene, most preferably the Ziegler-Natta catalyst is 9, 9-bis (methoxymethyl) fluorene; the external electron donor of the Ziegler-Natta catalyst is at least one of alkoxy silane compounds, more preferably, the external electron donor of the Ziegler-Natta catalyst is diisopropyl diethoxy silane, and the preferable Ziegler-Natta catalyst is adopted, so that the melt strength of the long-chain branched polypropylene impact copolymer can be improved.
In the present invention, the organosilane is not contained in the catalyst component. Also, the organosilane of the present invention does not include an organosilane supported on a catalyst carrier, nor an organosilane added as a catalyst component.
The conditions of the first copolymerization and the second copolymerization are not particularly limited in the present invention. For example, the conditions of the first copolymerization reaction generally include that the reaction temperature may be from 30 to 90 ℃, preferably from 40 to 80 ℃, more preferably from 60 to 75 ℃; the reaction time may be 0.05 to 10 hours, preferably 0.1 to 2 hours, more preferably 0.1 to 0.5 hours. In addition, when the propylene monomer introduced in the first copolymerization reaction is in a gaseous state, the conditions of the first copolymerization reaction further include that the reaction pressure may be from 0 to 40 atmospheres, preferably from 1 to 35 atmospheres, and more preferably from 5 to 10 atmospheres. The conditions of the second copolymerization reaction generally include that the reaction temperature may be 60 to 120 ℃, preferably 75 to 95 ℃, more preferably 80 to 90 ℃; the reaction time may be 0.1 to 10 hours, preferably 0.1 to 2 hours, more preferably 0.2 to 0.5 hours. In addition, when the comonomer introduced in the second copolymerization is in a gaseous state, the conditions for the second copolymerization further include that the reaction pressure may be in the range of 0.1 to 15 atmospheres, preferably 0.2 to 10 atmospheres, and more preferably 4 to 6 atmospheres. In the present invention, the pressures are gauge pressures.
In addition, in order to adjust the melt index of the long-chain branched polypropylene impact copolymer and provide the long-chain branched polypropylene impact copolymer with better processability, the first copolymerization and/or the second copolymerization is preferably carried out in the presence of hydrogen, and the addition amount of the hydrogen can be selected according to the function of the long-chain branched polypropylene impact copolymer obtained in actual need, for example, the hydrogen can 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 copolymerization monomer during the first copolymerization; in the second copolymerization process, the hydrogen may be used in an amount of 0 to 1 part by weight, preferably 0.02 to 0.15 part by weight, with respect to 100 parts by weight of the first copolymerization monomer.
According to the preparation method of the long-chain branched polypropylene impact copolymer provided by the invention, preferably, the method further comprises the step of performing water or alcohol treatment on the obtained polypropylene impact copolymer at the temperature of 20-120 ℃ after the second copolymerization reaction is completed, wherein the treatment time is 5-200 minutes, preferably 10-100 minutes, so that the branching degree of the polypropylene impact copolymer can be further improved, and the melt strength is improved. Wherein the kind of the alcohol may be conventionally selected in the art, and specific examples thereof include, but are not limited to: at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, etc.
The invention also provides the long-chain branched polypropylene impact copolymer prepared by the method.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the rubber phase content in a long chain branched polypropylene impact copolymer was determined as follows: the polypropylene impact copolymer was dried to constant weight in a vacuum oven at 60 ℃ and weighed as W1Dissolving in xylene (145 deg.C under nitrogen protection) for 1 hr, slowly cooling to 20 deg.C (controlled by water bath), maintaining the temperature for 2 hr, filtering with 250 mesh filter cloth, and rotary steaming the filtrate to obtain the final productThe solid was Xylene soluble (Xs) as a rubber phase, and the Xylene soluble obtained was dried in a vacuum oven at 80 ℃ for 4 hours and weighed as Wxs. The formula for calculating the rubber phase content in the long chain branched polypropylene impact copolymer is as follows:
rubber phase content (% by weight) — (Wx)s/W1) X 100 (wt%).
The weight ratio of the propylene-ethylene copolymer to the random copolymerization polypropylene is as follows: wxs：(W1-Wxs)。
The method for measuring the content of the ethylene in the propylene and ethylene copolymer comprises the following steps: the polymer was extracted with boiling heptane and its spectra were measured by FTIR at 1379 and 1460cm-1The absorption peaks of (a) are respectively a C-H characteristic absorption peak of a methyl group and a C-H characteristic absorption peak of a methylene group, and the relative molar amounts of ethylene and propylene are as follows: eIR％＝1.263-1.575*A1379cm-1/A1460cm-1。
The melt strength of the long-chain branched polypropylene impact copolymer is tested by adopting a Rheotens melt strength tester with the model number of 71.97 of Goettfert company, the outlet temperature is 200 ℃, and the testing acceleration is 2-150 mm/s2。
The melt index of the long chain branched polypropylene impact copolymer was measured using a Haake-SWO melt index apparatus, model 556-0031, from Haake, Germany.
When the internal electron donor in the Ziegler-Natta catalyst is 9, 9-bis (methoxymethyl) fluorene, the content of Ti in the composition of the catalyst is 3.44 wt%, and the content of 9, 9-bis (methoxymethyl) fluorene is 12.12 wt%, based on the total weight of the catalyst, which will be referred to as a diether-type catalyst hereinafter.
When the internal electron donor in the Ziegler-Natta catalyst is diisobutyl phthalate, the content of Ti in the composition of the catalyst is 2.78 wt% and the content of diisobutyl phthalate is 6.91 wt%, based on the total weight of the catalyst, and the catalyst is hereinafter referred to as diester catalyst.
When the internal electron donor in the Ziegler-Natta catalyst is a mixture of 9, 9-bis (methoxymethyl) fluorene and diisobutyl phthalate, the content of Ti in the composition of the catalyst is 2.52 wt%, the content of diisobutyl phthalate is 1.86 wt%, and the content of 9, 9-bis (methoxymethyl) fluorene is 5.33 wt%, based on the total weight of the catalyst, which will be referred to as a composite catalyst hereinafter.
Example 1
Under vacuum, 1000 g of liquid propylene monomer was charged into a reaction vessel, followed by sequentially adding 15g of ethylene, 0.4g of hydrogen, 0.25mol of triethylaluminum, 0.5g of 5-hexenylmethyldichlorosilane and 10mg of a diether-type catalyst at 30 ℃ and then raising the reaction temperature to 70 ℃ for 1 hour. Then evacuating the residual propylene monomer in the reaction kettle, reducing the temperature to 50 ℃, introducing a mixed gas of 40g of ethylene and 60g of propylene into the reaction kettle, controlling the reaction temperature at 80 ℃ to continue to react for 0.5 hour, treating with deionized water at 50 ℃ for 20 minutes after the reaction is finished, and finally carrying out vacuum drying at 70 ℃ to obtain 502g of long-chain branched polypropylene impact copolymer.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the resulting long chain branched polypropylene impact copolymer had a weight ratio of propylene to ethylene copolymer to random copolymerized polypropylene of 25: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 67: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.3g/10 min.
Example 2
Under vacuum, 1000 g of liquid propylene monomer was charged into a reaction vessel, followed by sequentially adding 15g of ethylene, 0.4g of hydrogen, 0.25mol of triethylaluminum, 0.5g of 3-butenylmethyldichlorosilane and 10mg of a diether type catalyst at 30 ℃ and then raising the reaction temperature to 70 ℃ for 1 hour. Then evacuating the residual propylene monomer in the reaction kettle, reducing the temperature to 50 ℃, introducing a mixed gas of 40g of ethylene and 60g of propylene into the reaction kettle, controlling the reaction temperature at 80 ℃ to continue to react for 0.5 hour, treating the mixture for 20 minutes by using deionized water at 50 ℃ after the reaction is finished, and finally drying the mixture in vacuum at 70 ℃ to obtain 498g of long-chain branched polypropylene impact copolymer.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene and ethylene copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 27: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 66: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.5/10 min.
Example 3
Under vacuum, 1000 g of liquid propylene monomer is added into a reaction kettle, then 15g of ethylene, 0.4g of hydrogen, 0.25mol of triethyl aluminum, 0.5g of 7-octenylmethyldichlorosilane and 10mg of diether type catalyst are added at 30 ℃ in sequence, and then the reaction temperature is raised to 70 ℃ for reaction for 1 hour; then evacuating the residual propylene monomer in the reaction kettle, reducing the temperature to 50 ℃, introducing a mixed gas of 40g of ethylene and 60g of propylene into the reaction kettle, controlling the reaction temperature at 80 ℃ to continue to react for 0.5 hour, treating the mixture for 20 minutes by using deionized water at 50 ℃ after the reaction is finished, and finally drying the mixture in vacuum at 70 ℃ to obtain 495g of long-chain branched polypropylene impact copolymer.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the resulting long chain branched polypropylene impact copolymer had a weight ratio of propylene to ethylene copolymer to random copolymerized polypropylene of 25: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 67: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 8.1g/10 min.
Example 4
Following the procedure of example 1, except that the catalyst added during the first copolymerization was the same amount of diester-type catalyst, 505g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene to ethylene copolymer to the random copolymerized polypropylene in the resulting long chain branched polypropylene impact copolymer was 28: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 66: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.9g/10 min.
Example 5
According to the method of example 1, with the difference that the catalyst added in the first copolymerization process is the composite catalyst with the same amount, 501g of long-chain branched polypropylene impact copolymer is finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene and ethylene copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 27: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 68: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.6g/10 min.
Example 6
According to the procedure of example 1, except that the organosilane added during the first copolymerization was 5-hexenylethyldichlorosilane in the same amount, 497g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the resulting long chain branched polypropylene impact copolymer had a weight ratio of propylene to ethylene copolymer to random copolymerized polypropylene of 25: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 66: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 8.1g/10 min.
Example 7
Following the procedure of example 1, except that 0.05g of hydrogen was added during the second copolymerization, 509g of a long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene to ethylene copolymer to the random copolymerized polypropylene in the resulting long chain branched polypropylene impact copolymer was 28: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 67: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.5g/10 min.
Example 8
Following the procedure of example 1, except that no hydrogen was added during the first copolymerization, 496g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the resulting long chain branched polypropylene impact copolymer had a weight ratio of propylene to ethylene copolymer to random copolymerized polypropylene of 25: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 66: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 3.1g/10 min.
Example 9
Following the procedure of example 1, except that 100g of ethylene was added during the first copolymerization, 550g of a long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene and ethylene copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer is 30: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 68: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.9g/10 min.
Example 10
Following the procedure of example 1, except that the first α -olefin was added during the first copolymerization in the same amount of butene-1, 508g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene-butene-1 copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 28: 100, the weight ratio of the butene-1 to the propylene in the propylene-butene-1 copolymer is 68: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.5g/10 min.
Example 11
Following the procedure of example 1, except that the co-polymerization was carried out with a gas mixture of 100g of ethylene and 100g of propylene, 591g of a long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene and ethylene copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 48: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 101: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.5g/10 min.
Example 12
Following the procedure of example 1, except that the gas mixture fed during the copolymerization was a gas mixture of 20g of butene-1 and 30g of propylene, 453g of a long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene-butene-1 copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 13: 100, the weight ratio of the butene-1 to the propylene in the propylene-butene-1 copolymer is 66: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 7.3g/10 min.
Example 13
Following the procedure of example 1, except that 30g of 5-hexenylmethyldichlorosilane was added during the first copolymerization of the propylene with a small amount of the first α -olefin, 506g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. Also, FIG. 3 is an infrared spectrum of the long-chain branched polypropylene impact copolymer obtained in the present example and the polypropylene impact copolymer obtained in comparative example 1, and as shown in FIG. 3, it can be seen from the results of the infrared spectrum test that a Si-O-Si structure exists in the polymer structure, indicating that the long-chain branched structure has a structure in which the-Si-O-Si-is a bridged chain olefin polymer molecule. In contrast, the polypropylene impact copolymer of comparative example 1, to which no organosilane was added in the reaction, did not have a Si-O-Si structure.
In addition, the weight ratio of the propylene and ethylene copolymer to the random copolymerized polypropylene in the prepared long chain branched polypropylene impact copolymer was 27: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 67: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 2.8g/10 min.
Example 14
Following the procedure of example 1, except that 4g of hydrogen was added during the first copolymerization of the propylene with a small amount of the first α -olefin, 508g of long chain branched polypropylene impact copolymer was finally obtained.
The melt strength, impact strength, melt index and rubber phase content of the long-chain branched polypropylene impact copolymer prepared as described above were measured, and the results are shown in table 1. And the result of infrared spectrum test shows that the Si-O-Si structure exists in the polymer structure, which shows that the long-chain branched structure has the structure of olefin polymer molecule with-Si-O-Si-as bridging link.
In addition, the weight ratio of the propylene to ethylene copolymer to the random copolymerized polypropylene in the resulting long chain branched polypropylene impact copolymer was 28: 100, the weight ratio of ethylene to propylene in the propylene-ethylene copolymer is 65: 100, respectively; the melt index of the random copolymerized polypropylene measured at 230 ℃ under a load of 2.16kg was 28.8g/10 min.
Comparative example 1
Following the procedure of example 1, except that no organosilane was added during the first copolymerization of the propylene with a small amount of the first α -olefin (and also neither during the second copolymerization), 505g of a polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
Comparative example 2
Following the procedure of example 1, except that no organosilane was added during the first copolymerization of the propylene with a small amount of the first α -olefin, and organosilane was added in the second copolymerization (after aeration of the gas mixture), 501g of polypropylene impact copolymer was finally obtained.
Comparative example 3
Following the procedure of example 1, except that after the first copolymerization was completed, the polymer was washed three times with anhydrous hexane in the kettle to remove unreacted 5-hexenylmethyl dichlorosilane, and then subjected to a second copolymerization to finally obtain 497g of polypropylene impact copolymer.
Comparative example 4
Following the procedure of example 1, except that the 5-hexenylmethyl dichlorosilane was added in an amount of 0.01g, 495g of polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
Comparative example 5
Following the procedure of example 1, except that the organosilane added during the first copolymerization of the propylene with a small amount of the first α -olefin was the same amount of bis- (5-hexenyl) dichlorosilane, 504g of polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
Comparative example 6
Following the procedure of example 1, except that the organosilane added during the first copolymerization of the propylene with a small amount of the first α -olefin was the same amount of bis- (5-hexenyl) dichlorosilane and the polymer was treated with anhydrous ethanol instead of deionized water, 504g of polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
Comparative example 7
Following the procedure of example 1, except that the organosilane added during the first copolymerization of propylene with a small amount of the first α -olefin was 5g of tetramethylsilane, 510g of a long chain branched polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
Comparative example 8
Following the procedure of example 1, except that the organosilane added during the first copolymerization of propylene with a small amount of the first α -olefin was the same amount of tetrachlorosilane, 493g of polypropylene impact copolymer was finally obtained.
The polypropylene impact copolymers prepared above were tested for melt strength, impact strength, melt index and rubber phase content, and the results are shown in table 1.
TABLE 1
Figure BDA0002469497980000211
Figure BDA0002469497980000221
Figure BDA0002469497980000231
As can be seen from the results in Table 1, the long-chain branched polypropylene impact copolymer prepared by the method provided by the invention has high melt strength and impact toughness. Specifically, as can be seen from a comparison of example 1 with examples 2-6, in the general structural formula R1SiX2R2In the organosilane of (2), R1Has 6 carbon atoms and R2Has a carbon number of 1, soThe organosilane has the most obvious effect on the melt strength enhancement and impact toughness of the long-chain branched polypropylene impact copolymer. Comparing examples 1-3 with comparative examples 2-3, it can be seen that the first copolymerization and the second copolymerization both prepared in the presence of organosilane gave long chain branched polypropylene impact copolymers having higher melt strength and impact toughness. Comparing examples 1-3 with comparative examples 5-6, it can be seen that the melt strength and impact toughness of the long-chain branched polypropylene impact copolymer prepared by using the organosilane provided by the invention are enhanced to a greater extent. Comparing the results of examples 1-14 and comparative examples 7-8, it can be seen that the organosilane provided in the present invention with silicon tetrahalide and tetraalkylsilane showed different behaviors during the preparation of long chain branched polypropylene impact copolymer, and the long chain branched polypropylene impact copolymer prepared by the method provided in the present invention has both high melt strength and high impact toughness.
Test example 1
The tensile rheological properties of the copolymers obtained in example 1 and comparative example 1 were tested. The test is carried out by adopting an ARES-G2 model rotational rheometer of TA company, UXF rotors are selected for the test, and the tensile rate of the test is set to be 1s-1、0.1s-1、0.01s-1The test specimen had a length of 22mm, a width of 10mm and a thickness of 0.5 mm. The viscosity of the copolymer was plotted against time at different draw down rates as shown in figures 1 and 2, respectively.
As can be seen from fig. 1 and 2, the long-chain branched polypropylene impact copolymer prepared by the method of the present invention has a significant tensile strain hardening phenomenon, because the copolymer obtained in example 1 has a structure in which-Si-O-Si-is a bridged olefin polymer molecule.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto, and various simple modifications including combination of various technical features in any other suitable manner can be made to the technical solution of the present invention within the scope of the technical idea of the present invention, and these simple modifications are included in the scope of the present invention. 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 (19)

1. A process for preparing long-chain branched impact copolymer of polypropylene includes the first copolymerization of propylene and the first alpha-olefin or ethylene in the presence of catalyst, and the second copolymerization of propylene and the second alpha-olefin or ethylene1SiX2R2In the presence of 0.001 to 20 parts by weight of an organosilane per 100 parts by weight of the total amount of the first and second comonomers, wherein R is1Is C2-C20A-olefin of (A), X is halogen, R2Is C1-C20Linear, branched or isomerized alkyl groups.
2. The method of claim 1, wherein the organosilane is not included in the catalyst component.
3. The method of claim 1, wherein R1Is C2-C20A-olefin of (A), X is halogen, R2Is C1-C20Linear, branched or isomerized alkyl groups.
4. The method of claim 3, wherein the organosilane is at least one of 9-decenylmethyldichlorosilane, 9-decenylethyldichlorosilane, 8-nonenylmethyldichlorosilane, 8-nonenylethyldichlorosilane, 7-octenylmethyldichlorosilane, 7-octenylethyldichlorosilane, 6-heptenylmethyldichlorosilane, 6-heptenylethyldichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenylethyldichlorosilane, 4-pentenylmethyldichlorosilane, 4-pentenylethyldichlorosilane, 3-butenylmethyldichlorosilane, 3-butenylethyldichlorosilane.
5. The method of claim 4, wherein the organosilane is at least one of 3-butenylmethyl dichlorosilane, 4-pentenyl methyl dichlorosilane, 5-hexenyl methyl dichlorosilane, 6-heptenylmethyl dichlorosilane, and 7-octenylmethyl dichlorosilane.
6. The process of any one of claims 1 to 5, wherein the organosilane is used in a total amount of 0.04 to 2.6 parts by weight relative to 100 parts by weight of the total amount of the first and second comonomers.
7. The process of any of claims 1-5, wherein the catalyst is a Ziegler-Natta catalyst.
8. The process according to claim 7, wherein the molar ratio of organoaluminium compound to external electron donor in the Ziegler-Natta catalyst is 1: 1-100: 1.
9. the process of any one of claims 1 to 5, wherein the first a-olefin is one or more of butene-1, pentene-1, hexene-1, heptene-1, octene-1.
10. The process of any one of claims 1 to 5, wherein the second a-olefin is one or more of butene-1, pentene-1, hexene-1, heptene-1, octene-1.
11. The process of any of claims 1-5, wherein the first a-olefin or ethylene is added in an amount of 1-10 wt% based on the total weight of the propylene and first a-olefin or ethylene in the first copolymerization.
12. The process according to any one of claims 1 to 5, wherein the second a-olefin or ethylene is added in an amount of 1 to 99% by weight based on the total weight of the propylene and the second a-olefin or ethylene in the second copolymerization.
13. The process according to any one of claims 1 to 5, wherein hydrogen is used in an amount of 0 to 10 parts by weight per 100 parts by weight of the first co-polymerized monomers in the first co-polymerization.
14. The method according to any one of claims 1 to 5, wherein hydrogen is used in an amount of 0 to 1 part by weight relative to 100 parts by weight of the second copolymerization monomer in the second copolymerization.
15. The process according to any one of claims 1 to 5, wherein the conditions of the first copolymerization reaction include a reaction temperature of 30 to 90 ℃ and a reaction time of 0.05 to 10 hours.
16. The process as claimed in any one of claims 1 to 5, wherein the conditions of the second copolymerization reaction include a reaction temperature of 60 to 120 ℃ and a reaction time of 0.1 to 10 hours.
17. The process of claim 15, wherein the first copolymerization pressure is from 0 to 40 atmospheres.
18. The process of claim 16, wherein the second copolymerization pressure is from 0.1 to 15 atmospheres.
19. A long chain branched polypropylene impact copolymer prepared by the process of any one of claims 1 to 18.
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WO2007137756A1 (en) * 2006-05-30 2007-12-06 Borealis Technology Oy A silicon containing compound as processing aid for polyolefin composition
CN105622819A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing impact-resistant polypropylene material with high melt strength
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WO2007137756A1 (en) * 2006-05-30 2007-12-06 Borealis Technology Oy A silicon containing compound as processing aid for polyolefin composition
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CN108659150A (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

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