CN115873348A - Impact-resistant polypropylene material and preparation method and application thereof - Google Patents
Impact-resistant polypropylene material and preparation method and application thereof Download PDFInfo
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- CN115873348A CN115873348A CN202211694430.9A CN202211694430A CN115873348A CN 115873348 A CN115873348 A CN 115873348A CN 202211694430 A CN202211694430 A CN 202211694430A CN 115873348 A CN115873348 A CN 115873348A
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 70
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- 238000000034 method Methods 0.000 claims abstract description 40
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 40
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
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- IBUKRVCWZGCWPB-UHFFFAOYSA-N cyclohexylmethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1CCCCC1 IBUKRVCWZGCWPB-UHFFFAOYSA-N 0.000 description 1
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- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
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- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
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- 235000011147 magnesium chloride Nutrition 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Graft Or Block Polymers (AREA)
Abstract
The invention provides an impact-resistant polypropylene alloy material and a preparation method thereof, wherein the impact-resistant polypropylene alloy material is prepared by a method of monomer composition periodic switching, firstly, a Ziegler-Natta catalyst is adopted to catalyze propylene to homopolymerize, and then, propylene and butylene are copolymerized under the condition of monomer composition periodic switching to prepare a polypropylene alloy, wherein the mass content of polypropylene is 50-98%, the mass content of a propane-butadiene block copolymer is 1-40%, and the mass content of a propane-butadiene random copolymer is 1-10%. The impact strength of the polypropylene alloy provided by the invention is obviously higher than that of the butadiene-propylene alloy prepared by a two-stage polymerization method under the same condition. The method provided by the invention can adjust the contents of the propyl-butyl block copolymer and the propyl-butyl random copolymer in a larger range, and the prepared propyl-butyl alloy has good rubber phase distribution after hot processing, so that the mechanical property of the polypropylene material is more excellent.
Description
Technical Field
The invention belongs to the technical field of preparation of polyolefin materials, and particularly relates to an impact-resistant polypropylene material, a preparation method and application thereof, in particular to an impact-resistant polypropylene alloy material and a preparation method thereof.
Background
Polypropylene is a thermoplastic polyolefin material obtained by polymerizing propylene as a monomer. The polypropylene with high isotacticity has good thermal stability, chemical stability and excellent mechanical properties (such as tensile strength, compressive strength and shear strength), is nontoxic, light in weight and easy to process, and is widely applied to various fields of films, fibers, pipes, injection molding and the like. However, polypropylene has poor impact resistance at normal temperature or low temperature and high notch sensitivity, which greatly limits the application of polypropylene in the fields of automobile industry and the like.
Polybutene is a semi-crystalline polyolefin material polymerized from 1-butene (hereinafter, butene is 1-butene) as a monomer, has excellent creep resistance, high temperature resistance, environmental stress cracking resistance and good impact resistance, and is widely applied in the field of pipes, especially hot water pipes. However, the crystal form of polybutene from a metastable state to a stable state is very slowly transformed, long-time annealing is needed, and the polybutene has poor tensile strength and is limited in application in other fields.
The defects of polypropylene (PP) and Polybutylene (PB) are overcome, the advantages of the PP and PB are comprehensively utilized, and the polypropylene-based alloy material is expected to have good impact resistance and tensile strength. There are two common methods currently used to prepare impact polypropylene alloys using polybutene or butene: the simplest and easiest approach is physical blending, i.e. melting and blending two polymer materials of polypropylene and polybutylene into a polymer alloy (for short: blended alloy). Polypropylene and polybutene are thermodynamically incompatible and thus PB/PP blends are immiscible. In order to improve the compatibility of the polypropylene and the polybutylene, a compatilizer is required to be added additionally, and the polypropylene/polybutylene blend is added with the propane-butadiene block copolymer, so that the compatibility of the polypropylene/polybutylene blend is improved, and the crystallization speed of the blend is accelerated; the addition of a suitable amount of the trimethylene block copolymer can slightly improve the tensile modulus and tensile strength of the polypropylene/polybutene blend. However, the production process is more complicated because the propylene-butadiene block copolymer is additionally added as the compatilizer, and three polymers are required to be prepared respectively and then blended together; and the mechanical property of the blend is not obviously improved by adding the compatilizer, and the mechanical property is even reduced by adding excessive compatilizer.
Another method is to directly prepare the alloy in the polymerization stage, i.e. directly generate polypropylene/polybutylene alloy or polypropylene/polybutylene copolymer alloy in the reactor, and the common methods can be summarized into two methods: direct copolymerization, two-stage polymerization. The direct copolymerization method is to add two monomers of propylene and butylene into a reactor together for the copolymerization of the propylene and the butylene, and the propylene and the butylene monomers are mixed together in the polymerization stage, so the propylene and the butylene copolymer with higher content is obtained by direct copolymerization. However, the direct copolymerization method lacking the homopolymerization link cannot generate polypropylene with high isotacticity; and the lack of high isotacticity polypropylene as a matrix, the strength of the material is reduced, and the melting point is lowered. A series of propane-butadiene in-kettle alloys are prepared by the liquid-phase copolymerization of propylene and butylene, and the result shows that the propane-butadiene copolymerization has higher polymerization rate and the product has lower melting temperature. However, the random copolymer content in the product obtained by direct copolymerization of propylene and butylene is high, the overall strength of the material is low, and the material is only suitable for the fields of packaging, films and the like. Propylene and butylene are put into a reactor together to carry out liquid phase copolymerization, the proportion of the propylene in the monomer is larger than that of the butylene, and therefore the obtained copolymer product containsThere are polypropylenes and a large number of propylene-butadiene copolymers, of which the isotacticity is low, the melting point being only 140.7 c, much lower than that of polypropylene (about 160 c). After the product sample strip is etched and scanned by an electron microscope, dense small holes left after the copolymer is etched can be observed, and the particle size of the holes is 10-100 nm, which shows that the disperse phase mainly comprising the propylene-butadiene copolymer and the matrix phase mainly comprising the polypropylene have excellent compatibility. However, the compatibility is too good and the particle size of the dispersed phase is too small, so that the functional effect of the dispersed phase on terminating the development of crazes is weakened. Therefore, the in-kettle alloy obtained by directly copolymerizing propylene and butylene has lower impact resistance and the impact strength is only 11.32kJ/m 2 。
The two-stage polymerization method can be divided into two-stage homopolymerization (or called two-stage homopolymerization) and one-stage homopolymerization and one-stage copolymerization. Both of these methods can produce polypropylene with high isotacticity, but the product has a low content of the propylene-butadiene block copolymer. The two-stage homopolymerization is to firstly carry out one-stage propylene homopolymerization in a reactor to generate polypropylene particles, on the basis, a monomer is switched into butylene, and the butylene homopolymerization is continued to generate polybutylene on the polypropylene particles; or firstly carrying out butylene homopolymerization and then carrying out propylene homopolymerization to generate the polyolefin alloy in the reaction kettle. However, the products obtained by sequential homopolymerization of propylene and butylene have low copolymer content, and the impact resistance is difficult to be greatly improved. The polypropylene/polybutene in-kettle alloy is prepared by a two-stage polymerization method, propylene homopolymerization is firstly carried out in a reactor, and then butene homopolymerization is carried out, a small amount of a propane-butane copolymer is generated during homopolymerization, and the compatibility between polypropylene and polybutene is improved. Compared with the alloy prepared by mechanical melting and blending of the two, the alloy in the kettle prepared by sequential homopolymerization has higher impact strength and tensile strength, and the impact strength is from 15kJ/m 2 Increased to 23kJ/m 2 . But the products of propylene and butylene homopolymerization sequentially have low content of the propylene-butylene copolymer, and the improvement of the impact resistance is limited compared with the blended alloy.
The one-stage homopolymerization and one-stage copolymerization means that propylene or butylene homopolymerization is firstly carried out in a reactor to generate polypropylene or polybutylene particles, then a monomer is replaced by a mixed monomer of propylene and butylene, the copolymerization of the propylene and the butylene is carried out, and the propylene or the polybutylene is subjected toGenerating a propane-butadiene copolymer on the olefin particles to prepare the polyolefin in-kettle alloy. Compared with two-stage homopolymerization, the homopolymerization and copolymerization method has the advantages that a polymerization product keeps certain homopolymer content, a certain amount of copolymer is obtained, but the content of a block copolymer is low, and the structure of the copolymer is difficult to adjust. The method comprises the steps of introducing a butylene monomer into a reaction kettle for butylene homopolymerization, adding a propylene monomer or a mixed monomer of butylene and propylene after homopolymerization time reaches a certain degree to perform butylene propylene copolymerization, wherein a polymerization product has high crystallization cooling rate, good tensile strength and low flexural modulus. Introducing a liquid-phase propylene monomer into the reaction kettle firstly to perform homopolymerization of the propylene body to generate polypropylene particles, introducing the liquid-phase butylene monomer after polymerization is carried out for a certain time to perform copolymerization of propylene and butylene, wherein the product has better tensile strength, but the content of the butadiene-propylene block copolymer is lower, and the impact strength of the material is low and is only 12.02kJ/m 2 。
In summary, the physical blending method can cause incompatibility between polypropylene and polybutylene, and the addition of a compatibilizer makes the process more complicated and the mechanical properties of the material difficult to greatly improve. The direct copolymerization method obtains high-content propane-butadiene copolymer, lacks high isotacticity polypropylene as a matrix, and has the advantages of reduced material strength and low melting point. The product obtained by the two-stage polymerization method has low content of the butadiene-propylene copolymer, particularly the butadiene-propylene block copolymer, and the structure and the content of the butadiene-propylene block copolymer are difficult to control.
Disclosure of Invention
In view of the above, the present invention aims to provide an impact-resistant polypropylene material, and a preparation method and an application thereof.
The invention provides an impact-resistant polypropylene material, wherein the mass content of ether soluble substances of the impact-resistant polypropylene material is 1-10%; the mass content of the ether insoluble substance is 90-99%;
the mass content of heptane soluble matters of the impact-resistant polypropylene material is 1-40%; the mass content of the heptane insoluble substance is 50-98%.
Preferably, the heptane solubles component comprises a propane-butadiene block copolymer;
the mole content of the triacrylate monomer unit sequence in the molecular chain of the propane-butadiene block copolymer is more than 30%.
Preferably, the heptane insoluble component comprises polypropylene having an isotacticity greater than 70%.
Preferably, the impact polypropylene material comprises:
a matrix phase;
a dispersed phase dispersed in the matrix phase;
the matrix phase is polypropylene;
the dispersed phase comprises: a propane-butadiene block copolymer and/or a propane-butadiene random copolymer;
the particle size of the dispersed phase comprises: 10-300 nm and 1-50 μm.
Preferably, the impact polypropylene material has a molecular weight distribution of Mw/Mn = 2-10 and a weight average molecular weight Mw of 20-100 × 10 4 g/mol；
The melting point of the impact-resistant polypropylene material is 150-169 ℃, and the melt flow rate is 0.01-50 g/min.
The invention provides a preparation method of the impact-resistant polypropylene material in the technical scheme, which comprises the following steps:
carrying out homopolymerization reaction on a propylene monomer, a catalyst, a cocatalyst, an external electron donor and hydrogen to obtain a reaction product;
and carrying out copolymerization reaction on the reaction product, a butylene monomer and a propylene monomer to obtain the impact-resistant polypropylene material.
Preferably, the feeding mode of the propylene monomer is periodic feeding, the interval time of each feeding period is 1-100 min, and the times of the feeding periods are 1-50.
Preferably, the catalyst is selected from Ziegler-Natta catalysts;
the cocatalyst is selected from an aluminum alkyl cocatalyst;
the external electron donor is selected from silicon compounds and/or aromatic compounds.
Preferably, the temperature of the homopolymerization reaction is preferably 55-90 ℃, the pressure is 0.1-5 MPa, and the time is 0.1-10 hours;
the temperature of the polymerization reaction is 55-90 ℃, and the time is 0.1-10 hours.
The present invention provides a composite material comprising:
the impact-resistant polypropylene material in the technical scheme is prepared;
and (3) an additive.
The invention adopts the monomer composition switching method in the reactor to prepare the polypropylene alloy, can regulate and control the content and the structure of the propane-butadiene block copolymer in the polymer, obtains the propane-butadiene block copolymer with long polypropylene chain segment, improves the compatibility of a dispersed phase and a matrix phase in the alloy, ensures that the dispersed phase has proper phase morphology and phase distribution, greatly improves the shock resistance of the alloy material, and has the impact strength of 42.9kJ/m 2 And above, and the tensile strength can reach 22.1MPa. The impact-resistant polypropylene alloy material provided by the invention is a spherical product, has the advantages of excellent impact resistance, thermal stability, high elongation at break, high tensile strength, good fluidity and the like, can replace part of polypropylene and polybutylene, is a novel polyolefin material, can be used for manufacturing pipes and pipe fittings, and can be used as an injection molding material in the industries of automobiles and household appliances or used as a general polyolefin material. The polypropylene alloy prepared by the preparation method has the advantages of easily controlled polymer composition, relatively simple process flow, high monomer conversion rate, no kettle adhesion of a polymerization product, spherical polymer particles and uniform particle size distribution, and is beneficial to industrial production.
Drawings
FIG. 1 is an SEM image (magnification of 10.0 kSE) of a cross section of a polymer alloy sample prepared in comparative example 1, wherein (a 1) is the cross section before etching, (a 2) is the cross section after etching with a solvent of diethyl ether and heptane, and (a 2') is a partial magnification of (a 2), and pores formed after etching are formed after removing a dispersed phase;
FIG. 2 is an SEM image (magnification of 10.0 kSE) of a cross section of a polymer alloy strip prepared in comparative example 2, (b 1) is a cross section before etching, (b 2) is a cross section after etching with a solvent of diethyl ether and heptane, and pores formed after etching are formed after removing a dispersion phase;
FIG. 3 is an SEM image of a cross section of a polymer alloy sample prepared in example 1 (magnification: 10.0 kSE), (c 1) is a cross section before etching, (c 2) is a cross section after etching with a solvent of diethyl ether and heptane, and pores formed after etching are formed after removing a dispersion phase;
FIG. 4 is an SEM image of a cross section of a polymer alloy sample prepared in example 2 (magnification: 10.0 kSE), (d 1) is a cross section before etching, (d 2) is a cross section after etching with a solvent of diethyl ether and heptane, and pores formed after etching are formed after removing a dispersion phase;
FIG. 5 shows the ether-soluble, heptane-soluble, and heptane-insoluble fractions of example 3 13 C-NMR nuclear magnetic spectrum, wherein curve a is diethyl ether soluble substance nuclear magnetic spectrum, curve b is heptane soluble substance nuclear magnetic spectrum, and curve C is heptane insoluble substance nuclear magnetic spectrum;
FIG. 6 is a melting curve obtained by DSC measurement of example 3 and its ether solubles, heptane insolubles, a is the melting curve of ether solubles, b is the melting curve of heptane solubles, c is the melting curve of heptane insolubles;
FIG. 7 is a schematic diagram of the structure of the three-monomer unit sequence in the molecular chain of the polymer prepared in example 3, which shows the possible arrangement of the three monomer units in the molecular chain, wherein P represents a propylene unit, and B represents a butylene unit;
FIG. 8 is a schematic diagram of the sequence of two monomer units in the molecular chain of the polymer prepared in example 3, which shows the possible arrangement of two monomer units in the molecular chain, wherein P represents a propylene unit, and B represents a butylene unit.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an impact-resistant polypropylene material, wherein the mass content of ether soluble substances of the impact-resistant polypropylene material is 1-10%; the mass content of the ether insoluble substance is 90-99%;
the mass content of heptane soluble matters of the impact-resistant polypropylene material is 1-40%; the mass content of the heptane insoluble substance is 50-98%.
In the present invention, the ether solubles content of the impact polypropylene material is preferably 2 to 8% by mass, more preferably 3 to 6% by mass; the mass content of the ether-insoluble substance is preferably 92 to 98%, more preferably 94 to 96%.
In the present invention, the main component of the ether solubles is preferably a trimethylene random copolymer.
In the present invention, the ether-insoluble matter is divided into heptane-soluble matter and heptane-insoluble matter; the impact polypropylene material preferably has a heptane solubles mass content of from 5 to 30%, more preferably from 10 to 20%, most preferably 15%; the heptane insoluble content is preferably 60 to 90% by mass, more preferably 70 to 80% by mass, most preferably 75% by mass.
In the present invention, the main component of the heptane solubles is preferably a propane-butadiene block copolymer; the propylene-butadiene block copolymer is preferably a long propylene chain segment propylene-butadiene block copolymer, and the molecular chain of the long propylene chain segment propylene-butadiene block copolymer preferably has a molar content of a triacrylate monomer unit sequence of more than 30%.
In the present invention, the heptane-insoluble fraction is preferably polypropylene, and the isotacticity of the polypropylene is preferably greater than 70%.
In the invention, the impact polypropylene material preferably contains polypropylene as a matrix phase, and the propylene-butadiene block copolymer and/or the propylene-butadiene random copolymer are/is dispersed in the matrix phase as a dispersed phase, the particle size of the dispersed phase in the matrix phase preferably has bimodal distribution, and the particle size distribution of the dispersed phase is preferably concentrated in 10-300 nm and 1-50 μm; the particle size of the dispersed phase is preferably 50 to 250nm, more preferably 100 to 200nm, most preferably 150nm; the particle size of the dispersed phase is preferably 5 to 40 μm, more preferably 10 to 30 μm, most preferably 20 μm. In the invention, the part with larger size in the dispersed phase can well play the roles of stress concentration, silver streak induction and termination, and dissipate impact energy, so that the polypropylene alloy has excellent impact resistance; the preparation method of the polypropylene alloy takes propylene and butylene as main monomers to carry out propylene homopolymerization and propylene-butylene copolymerization, and the composition of copolymerization reaction monomers is changed by periodically feeding the monomers in the copolymerization stage, thereby adjusting the composition and the content of the propylene-butylene copolymer.
In the invention, the detection methods of the mass content of the polypropylene, the mass content of the propane-butadiene block copolymer and the mass content of the propane-butadiene random copolymer in the impact-resistant polypropylene material are preferably as follows:
extracting the impact-resistant polypropylene material with the mass of W by using an ether solvent to obtain the impact-resistant polypropylene material with the mass of W 1 And W 2 The ether soluble substance and the ether insoluble substance, the ether soluble substance has a mass content of (W) 1 The mass content of the propylene random copolymer is the mass content of the propylene random copolymer; the mass content of the ether insoluble substance is (W) 2 /W)％；
Extracting the ether insoluble substance with heptane solvent to obtain W 3 And W 4 The heptane-soluble substance and the heptane-insoluble substance, the heptane-soluble substance having a mass content of (W) 3 The mass content of the propyidine segmented copolymer is as follows,/W)%; the mass content of heptane-insoluble substances is (W) 4 and/W)%, namely the mass content of the polypropylene.
In the present invention, the method for detecting the particle size of the dispersed phase in the impact polypropylene material is preferably as follows:
a sample strip prepared by processing an anti-impact polypropylene material is quenched by liquid nitrogen at low temperature, the section is extracted by ether solvent for more than 1h, then extracted by n-heptane solvent for more than 1h, and the section is observed by a scanning electron microscope with the magnification of 1000-20000 times; the time for solvent extraction is preferably 10 to 12 hours.
In the present invention, the impact polypropylene material preferably has a molecular weight distribution Mw/Mn =2 to 10, more preferably 3 to 8, most preferably 4 to 6; the weight-average molecular weight Mw is preferably (20 to 100). Times.10 4 g/mol, more preferably (30 to 80). Times.10 4 g/mol, most preferably (40 to 60). Times.10 4 g/mol; the melting point is preferably 150 to 169 ℃, and more preferably 160 ℃; the melt flow rate is preferably from 0.01 to 50g/min, more preferably from 0.1 to 40g/min, more preferably from 1 to 30g/min, most preferably from 5 to 20g/min.
The invention provides a preparation method of the impact-resistant polypropylene material in the technical scheme, which comprises the following steps:
carrying out homopolymerization reaction on a propylene monomer, a catalyst, a cocatalyst, an external electron donor and hydrogen to obtain a reaction product;
and carrying out copolymerization reaction on the reaction product, a butylene monomer and a propylene monomer to obtain the impact-resistant polypropylene material.
In the present invention, it is preferable that the homopolymerization is preceded by "
And carrying out prepolymerization.
In the present invention, the temperature of the prepolymer is preferably 0 to 50 ℃, more preferably 10 to 40 ℃, and most preferably 20 to 30 ℃; the time for the prepolymerization is preferably 0.1 to 3 hours, more preferably 0.5 to 2 hours, and most preferably 1.0 to 1.5 hours.
In the present invention, the catalyst is preferably selected from Ziegler-Natta catalysts (Ziegler-Natta catalysts), more preferably from porous granular or spherical catalysts comprising a titanium compound supported on magnesium halide; the titanium compound is preferably selected from any one of titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; the magnesium halide compound is preferably selected from any one of magnesium dichloride, magnesium dibromide and magnesium diiodide.
In the present invention, the cocatalyst is preferably selected from alkylaluminum cocatalysts, more preferably an aluminum compound, most preferably any one or more selected from triisobutylaluminum, triethylaluminum, dimethylaluminum monochloride, diethylaluminum monochloride, and isobutylaluminum dichloride. In the present invention, the cocatalyst is preferably a cocatalyst solution; the solvent in the cocatalyst solution is preferably toluene; the concentration of the catalyst solution is preferably 0.1 to 5mol/L, more preferably 0.5 to 4mol/L, more preferably 1 to 3mol/L, and most preferably 2mol/L.
In the present invention, the external electron donor is preferably selected from silicon compounds and/or aromatic compounds; the silicon compound is preferably selected from any one or more of cyclohexylmethyldimethoxysilane, cyclohexylmethyltrimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane and phenyltrimethoxysilane; the aromatic compound is preferably selected from ethyl ethoxybenzoate. In the present invention, the solvent in the external electron donor solution is preferably toluene; the concentration of the external electron donor solution is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.4mol/L, and most preferably 0.2 to 0.3mol/L.
In the present invention, the mass ratio of the catalyst to the propylene monomer is preferably (1 × 10) -6 ～1×10 -4 ): 1, more preferably 1X 10 -5 :1; the mass ratio of the hydrogen gas to the propylene monomer is preferably (0 to 1X 10) -3 ): 1, more preferably 0.5X 10 -3 :1; the molar ratio of Al in the cocatalyst to the metal element in the catalyst is preferably (1 to 1000): 1, more preferably (5 to 900): 1, more preferably (10 to 800): 1, more preferably (50 to 700): 1, more preferably (100 to 600): 1, more preferably (200 to 500): 1, most preferably (300 to 400): 1; the molar ratio of the propylene monomer to the external electron donor is preferably (200 to 500): 1, more preferably (300 to 400): 1.
in the present invention, the temperature of the homopolymerization reaction is preferably 55 to 90 ℃, more preferably 60 to 80 ℃, and most preferably 70 ℃; the pressure of the homopolymerization is preferably 0.1 to 5MPa, more preferably 0.5 to 4MPa, and most preferably 1 to 3MPa; the time for the homopolymerization is preferably 0.1 to 10 hours, more preferably 0.5 to 8 hours, more preferably 1 to 6 hours, more preferably 2 to 5 hours, and most preferably 3 to 4 hours. In the present invention, the homopolymerization is preferably performed under the conditions of vacuum and inert gas.
In the present invention, the method of the homopolymerization preferably includes:
after the reactor is vacuumized and replaced by inert gas, adding a propylene monomer, a Ziegler-Natta catalyst, an alkyl aluminum cocatalyst, an external electron donor and hydrogen, controlling the temperature of the reactor at 55-90 ℃ and the pressure at 0.1-5 MPa, performing homopolymerization reaction on the propylene, wherein the homopolymerization reaction time is 0.1-10 hours, the sudden drop of the pressure in the reaction process represents complete consumption of the propylene monomer, and the homopolymerization reaction is finished.
In the present invention, the mass ratio of the propylene monomer to the butene monomer is preferably (0.1 to 100): 1, more preferably (0.5 to 80): 1, more preferably (1 to 60): 1, more preferably (5 to 50): 1, more preferably (10 to 40): 1, most preferably (20 to 30): 1.
in the present invention, the feeding manner of the propylene monomer in the copolymerization reaction process is preferably periodic feeding, and the interval time of each feeding period is preferably 1 to 100min, more preferably 5 to 90min, more preferably 10 to 80min, more preferably 20 to 60min, more preferably 30 to 50min, and most preferably 40min; the number of feeding cycles is preferably 1 to 50, more preferably 5 to 40, more preferably 10 to 30, and most preferably 20.
In the present invention, the temperature of the copolymerization reaction is preferably 55 to 90 ℃, more preferably 60 to 80 ℃, and most preferably 70 ℃; the time for the copolymerization reaction is preferably 0.1 to 10 hours, more preferably 1 to 8 hours, more preferably 2 to 6 hours, and most preferably 3 to 5 hours.
In the present invention, it is preferable that the copolymerization reaction further comprises:
and removing unreacted butylene monomer or propylene monomer and hydrogen under reduced pressure to obtain the impact-resistant polypropylene material (polypropylene alloy material).
In the present invention, the method of polymerization preferably includes:
adding a butylene monomer and a propylene monomer into a polymerization system of homopolymerization reaction to perform propane-butadiene copolymerization reaction, wherein the temperature of the polymerization reaction is 55-90 ℃, the time of the polymerization reaction is 0.1-10 hours, and after the reaction is finished, removing the unreacted butylene monomer or the propylene monomer and hydrogen under reduced pressure to obtain the polypropylene alloy material.
In the present invention, the impact polypropylene material (polypropylene alloy material) is preferably in the form of a granular sphere.
In the present invention, the reaction apparatus for the homopolymerization and copolymerization reactions preferably consists of one reactor; the prepolymerization reaction is preferably carried out in the same reactor with homopolymerization reaction and copolymerization reaction; the reactor is preferably any one of a stainless steel pressure-resistant reaction kettle, a tubular reactor or a stirred tank reactor with a temperature control jacket and a mechanical stirring device; the reactor is preferably a tank reactor. The invention provides a method for preparing a polypropylene/propylene-butylene copolymer alloy in situ by adopting monomer composition switching in a reactor, which can effectively adjust the composition and structure of a propylene-butylene block copolymer.
The present invention provides a composite material comprising:
the impact-resistant polypropylene material in the technical scheme is prepared;
and (3) an additive.
In the present invention, the additive is preferably selected from any one or more of fillers, nucleating agents, color concentrates, plasticizers, antioxidants, light stabilizers, scratch resistance aids; the filler is preferably selected from any one or more of inorganic fillers, flame retardants, impact modifying materials, elastomers, electrically conductive fillers, thermally conductive fillers, reinforcing fibers.
The invention adopts one-section propylene homopolymerization to obtain a polypropylene homopolymer, then adds a butylene monomer to carry out copolymerization of propylene and butylene, in the propylene-butylene copolymerization stage after the butylene is added, propylene is periodically fed, the monomer composition in a reactor is controlled to be periodically switched, the product is adjusted to have proper contents of a propylene-butylene block copolymer and a propylene-butylene random copolymer, and the polypropylene with higher content is used as a continuous phase matrix in the hot processing process to provide rigidity for an alloy material, so that the material has higher tensile strength; the propylene periodic feeding controls the mode of periodic switching of monomer composition in the reaction kettle, so that the propylene segmented copolymer prepared at the copolymerization stage contains a longer polypropylene chain segment, can be embedded into a polypropylene lattice of a matrix phase to be crystallized in the crystallization process, and improves the compatibility between the dispersed phase and the matrix phase, thereby obtaining the polypropylene alloy material with good compatibility, high impact strength and balanced rigidity and toughness.
The tensile strength of the products is tested in the following examples according to the method specified in the national standard GB/T1040.1-2018 determination of tensile Properties of plastics. The impact strength of the product is tested according to the method specified in the national standard GB/T1843-2008 determination of Plastic Izod impact Strength. The polypropylene content, the content of the propane-butadiene block copolymer and the content of the propane-butadiene random copolymer in the impact-resistant polypropylene alloy material are measured by adopting a method of fractional extraction of diethyl ether and heptane, firstly, diethyl ether solvent is used for extraction to divide polymer particles into diethyl ether soluble substances and diethyl ether insoluble substances, and the diethyl ether insoluble substances are extracted by heptane solvent and are divided into heptane soluble substances and heptane insoluble substances. The nuclear magnetic spectrum of the polymer is measured by 13C-NMR nuclear magnetic (example 3), and the distribution of propylene and butylene monomer unit sequences of the molecular chain of the polymer is calculated according to the spectrum, such as the three-monomer unit sequence and the two-monomer unit sequence shown in figures 7 and 8, and the molar contents of propylene and butylene monomer units in the polymer, so as to determine the structure of the polymer. Observing the phase morphology and phase distribution of the dispersed phase of the polymer by adopting a scanning electron microscope SEM, quenching the alloy sample strip by using liquid nitrogen at low temperature, then placing the section in a Soxhlet extractor, extracting by using an ether solvent, extracting and etching by using an n-heptane solvent for more than 10 hours, and observing the section before and after etching by using the scanning electron microscope. The melting curve and melting temperature Tm of the alloy were measured by Differential Scanning Calorimetry (DSC).
Example 1
A10L stainless steel pressure polymerization kettle with a mechanical stirring device and a jacket is heated to 60 ℃, vacuumized for 30min, replaced by high-purity nitrogen for several times, and the temperature of circulating water is adjusted to reduce the temperature of the kettle to room temperature (25 ℃). 1.2kg of liquid-phase propylene monomer, 10mL (1 mol/L) of triethylaluminum TEA toluene solution, 0.42mL (0.1 mol/L) of external electron Donor Donor-C (methylcyclohexyldimethoxysilane) toluene solution and a catalyst (Ti content is 2.7 wt%) (commercially available product, main component is TiCl) 4 /MgCl 2 ) 0.1547g and 1L hydrogen, adjusting the temperature of the kettle to 60 ℃, polymerizing for 30min (rotating speed of 250 rpm) under stirring, and adding 0.6kg liquid phase butylene and the liquid phase into the reaction kettle0.5kg of propylene, reacting for 26.6min, adding 0.15kg of liquid-phase propylene into the reaction kettle, continuing to react for 26.6min, and after the reaction is finished, emptying residual monomers in the kettle, adding a proper amount of nitrogen for replacement to obtain 2.24kg of granular polymer; the product was extruded, pelletized, injection molded into specimens for mechanical testing, and the test results are shown in Table 1.
And (4) SEM test: after the polymer alloy sample strip prepared in the embodiment 1 is quenched by liquid nitrogen at low temperature, the section is placed in a soxhlet extractor and is extracted and etched by an ether solvent for 10 hours, then an n-heptane solvent is used for extraction and etching for 10 hours, the section shapes before etching and after etching are observed by a field emission scanning electron microscope, as shown in fig. 3, the section of the sample strip before etching is smooth and flat, the surface after etching is rough, holes with different sizes are generated, the holes are the etched dispersion phase, and the particle size of the dispersion phase is as large as 1-10 mu m, and the particle size of the dispersion phase is as small as 10-300 nm.
Example 2
A10L stainless steel pressure polymerization kettle with a mechanical stirring device and a jacket is heated to 60 ℃, vacuumized for 30min, replaced by high-purity nitrogen for several times, and the temperature of circulating water is adjusted to reduce the temperature of the kettle to room temperature (25 ℃). Sequentially metering 1.2kg of liquid-phase propylene monomer, 10mL (1 mol/L) of triethyl aluminum TEA toluene solution, 0.42mL (0.1 mol/L) of external electron Donor Donor-C toluene solution, 0.1567g of catalyst (with the Ti content of 2.7wt% in the same way as in example 1) and 1L of hydrogen into a reaction kettle, adjusting the kettle temperature to 60 ℃, polymerizing for 30min (rotating speed of 250 rpm) under stirring, adding 0.6kg of liquid-phase butene and 0.4kg of liquid-phase propylene into the reaction kettle, reacting for 16min, adding 0.1kg of liquid-phase propylene into the reaction kettle, continuing to react for 16min, emptying residual monomers in the kettle, and adding a proper amount of nitrogen to replace 2.13kg of granular polymer; the product was extruded, pelletized, injection molded into specimens for mechanical testing, and the test results are shown in Table 1.
And (4) SEM test: the alloy sample bar prepared in the embodiment 2 is quenched by liquid nitrogen at low temperature, the cross section of the sample bar is placed in a soxhlet extractor and is extracted and etched by ether solvent for 10 hours, then n-heptane solvent is used for extraction and etching for 10 hours, the cross section shapes before etching and after etching are observed by a field emission scanning electron microscope, as shown in fig. 4, the cross section of the sample bar before etching is smooth and flat, the surface after etching is rough, holes with different sizes are generated, the holes are the etched dispersion phase, and the particle size of the dispersion phase is as large as 1-10 microns, and the particle size of the dispersion phase is as small as 10-300 nm.
Example 3
A10L stainless steel pressure polymerization kettle with a mechanical stirring device and a jacket is heated to 60 ℃, vacuumized for 30min, replaced by high-purity nitrogen for several times, and the temperature of circulating water is adjusted to reduce the temperature of the kettle to room temperature (25 ℃). Sequentially metering 1.2kg of liquid-phase propylene monomer, 10mL (1 mol/L) of triethyl aluminum TEA toluene solution, 0.42mL (0.1 mol/L) of external electron Donor Donor-C toluene solution, 0.1547g of catalyst (with the Ti content of 2.7wt% in the same way as in example 1) and 1L of hydrogen into a reaction kettle, adjusting the temperature of the kettle to 20 ℃, carrying out low-temperature prepolymerization for 30min (the rotating speed is 250 rpm) under stirring, raising the temperature in the kettle to 60 ℃, carrying out reaction for 30min, adding 0.6kg of liquid-phase butylene and 0.5kg of liquid-phase propylene into the reaction kettle, carrying out reaction for 26.6min, then adding 0.15kg of liquid-phase propylene into the reaction kettle after the reaction for 26.6min, continuing the reaction for 26.6min, and emptying the residual monomer in the kettle and adding a proper amount of nitrogen for replacement to obtain 2.40kg of granular polymer; the product was extruded, pelletized, injection molded into bars and tested for mechanical properties, the results are shown in Table 1.
Comparative example 1
A10L stainless steel pressure polymerization kettle with a mechanical stirring device and a jacket is heated to 60 ℃, vacuumized for 30min, replaced by high-purity nitrogen for several times, and the temperature of circulating water is adjusted to cool the kettle to room temperature (25 ℃). 2.0kg of liquid-phase propylene, 0.6kg of liquid-phase butylene, 10mL (1 mol/L) of triethylaluminum TEA toluene solution, 0.41mL (0.1 mol/L) of external electron Donor Donor-C toluene solution, 0.1578g of catalyst (with the Ti content of 2.7wt% in the same example 1) and 1L of hydrogen are sequentially metered into a reaction kettle, the kettle temperature is adjusted to 60 ℃, polymerization is carried out for 110min (the rotating speed is 250 rpm) under stirring, after the reaction is finished, a proper amount of nitrogen is added into the emptied kettle for replacement, and 2.18kg of granular polymer is obtained; the product was extruded, pelletized, injection molded into specimens for mechanical testing, and the test results are shown in Table 1.
And (4) SEM test: the alloy sample strip prepared in the comparative example 1 is quenched by liquid nitrogen at low temperature, the section is placed in a soxhlet extractor and is extracted and etched by an ether solvent for 10 hours, then an n-heptane solvent is used for extraction and etching for 10 hours, the section shapes before etching and after etching are observed by a field emission scanning electron microscope, and the result is shown in figure 1, the section of the sample strip before etching is smooth and flat, the surface after etching is rough, dense tiny holes are formed, the holes are etched dispersion phase, and the particle size of the dispersion phase is 10-100 nm.
Comparative example 2
A10L stainless steel pressure polymerization kettle with a mechanical stirring device and a jacket is heated to 60 ℃, vacuumized for 30min, replaced by high-purity nitrogen for several times, and the temperature of circulating water is adjusted to cool the kettle to room temperature (25 ℃). 2.0kg of liquid-phase propylene monomer, 10mL (1 mol/L) of triethylaluminum TEA toluene solution, 0.42mL (0.1 mol/L) of external electron Donor Donor-C toluene solution, 0.1580g of catalyst (Ti content 2.7wt%, same as example 1) and 1L of hydrogen were sequentially metered into the reaction kettle, the kettle temperature was adjusted to 60 ℃, and polymerization was carried out for 50min (rotation speed 250 rpm) with stirring. Adding 0.6kg of liquid-phase butene into the reaction kettle, reacting for 60min, emptying residual monomers in the kettle, and adding a proper amount of nitrogen for replacement to obtain 1.96kg of granular polymer after the reaction is finished; the product was extruded, pelletized, injection molded into bars and tested for mechanical properties, the results are shown in Table 1.
And (4) SEM test: after the alloy sample strip is quenched by liquid nitrogen at low temperature, the section is placed in a rope extractor and is extracted and etched by ether solvent for 10 hours, then n-heptane solvent is used for extraction and etching for 10 hours, the section shapes before etching and after etching are observed by a field emission scanning electron microscope, as shown in figure 2, the section of the sample strip before etching is smooth and flat, a small number of holes are formed after etching, the holes are the etched disperse phase, and the particle size of the disperse phase is about 10-500 nm.
Performance detection
Using diethyl ether and n-heptane as solvents, carrying out extraction classification of the solvents on the polymer particles prepared in the examples; placing about 3g of polymer particles in a sand core glass tube, heating and refluxing the polymer particles by diethyl ether in a Soxhlet extractor for 10 hours to obtain diethyl ether soluble substances a and diethyl ether insoluble substances, drying the diethyl ether soluble substances a and the diethyl ether insoluble substances in a vacuum oven at 60 ℃, and weighing the diethyl ether insoluble substances; the dried ether insoluble matter was extracted with n-heptane for 10 hours, and after separation, it was dried to obtain heptane soluble matter b and n-heptane insoluble matter c. Nuclear magnetic testing: the polymer particles prepared in example 3 were added to a deuterated o-dichlorobenzene solvent to prepare a 0.1g/mL solution, and a nuclear magnetic scan was performed at 120 ℃ for 0.8s of collection time, 3s of pulse delay time, 90 ° of pulse angle, reverse proton decoupling, and 3000 scans to obtain a nuclear magnetic spectrum, as shown in fig. 5.
DSC test: 8mg of the polymer particles prepared in example 3 were heated to 200 ℃ at 20 ℃/min in a differential scanning calorimeter under a nitrogen atmosphere, and the temperature was maintained for 5min to remove the thermal history, then cooled to-60 ℃ at a cooling rate set at 10 ℃/min and maintained for 5min, and finally heated to 200 ℃ at 10 ℃/min to obtain a melting curve, as shown in FIG. 6.
The combined nuclear magnetism and DSC test result can confirm that the ether solubles are mainly the propane-butadiene random copolymer, the heptane solubles are mainly the propane-butadiene block copolymer and a small amount of polybutene, the propane-butadiene block copolymer contains longer polypropylene segments, and the heptane insoluble is mainly polypropylene and a small amount of propane-butadiene block copolymer, as shown in figure 7 and figure 8.
Table 1 physical property parameters and mechanical property detection results of polymer alloys prepared in comparative example and example
TABLE 2 distribution of sequences of units of ether solubles a, heptane solubles b, heptane insoluble c of the polymer prepared in example 3
The invention adopts the method of monomer composition switching in the reactor to prepare the polypropylene alloy, can regulate and control the content and the structure of the propane-butadiene block copolymer in the polymer and obtain the long polypropylene alloyThe polypropylene segmented propane-butadiene block copolymer improves the compatibility of a dispersed phase and a matrix phase in the alloy, enables the dispersed phase to have proper phase morphology and phase distribution, greatly improves the impact resistance of the alloy material, and can achieve the impact strength of 42.9kJ/m 2 And above, and the tensile strength can reach 22.1MPa. The impact-resistant polypropylene alloy material provided by the invention is a spherical product, has the advantages of excellent impact resistance, thermal stability, high elongation at break, high tensile strength, good fluidity and the like, can replace part of polypropylene and polybutylene, is a novel polyolefin material, can be used for manufacturing pipes and pipe fittings, and can be used as an injection molding material in the industries of automobiles and household appliances or used as a general polyolefin material. The polypropylene alloy prepared by the preparation method has the advantages of easily controlled polymer composition, relatively simple process flow, high monomer conversion rate, no kettle adhesion of a polymerization product, spherical polymer particles and uniform particle size distribution, and is beneficial to industrial production.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes may be made to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application without departing from the true spirit and scope of the invention as defined by the appended claims. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. An anti-impact polypropylene material, wherein the mass content of ether soluble substances of the anti-impact polypropylene material is 1-10%; the mass content of the ether insoluble substance is 90-99%;
the mass content of heptane soluble matters of the impact-resistant polypropylene material is 1-40%; the mass content of the heptane insoluble substance is 50-98%.
2. The impact polypropylene material of claim 1, wherein the heptane solubles component comprises a propane-butadiene block copolymer;
the mole content of the triacrylate monomer unit sequence in the molecular chain of the propane-butadiene block copolymer is more than 30%.
3. The impact polypropylene material of claim 1, wherein the heptane-insoluble content comprises polypropylene having an isotacticity greater than 70%.
4. The impact polypropylene material of claim 1, wherein the impact polypropylene material comprises:
a matrix phase;
a dispersed phase dispersed in the matrix phase;
the matrix phase is polypropylene;
the dispersed phase comprises: a propane-butadiene block copolymer and/or a propane-butadiene random copolymer;
the particle size of the dispersed phase comprises: 10-300 nm and 1-50 μm.
5. The impact polypropylene material according to claim 1, wherein the impact polypropylene material has a molecular weight distribution Mw/Mn = 2-10 and a weight average molecular weight Mw of 20-100 x 10 4 g/mol；
The melting point of the impact-resistant polypropylene material is 150-169 ℃, and the melt flow rate is 0.01-50 g/min.
6. A method of making the impact polypropylene material of claim 1, comprising:
carrying out homopolymerization reaction on a propylene monomer, a catalyst, a cocatalyst, an external electron donor and hydrogen to obtain a reaction product;
and carrying out copolymerization reaction on the reaction product, a butylene monomer and a propylene monomer to obtain the impact-resistant polypropylene material.
7. The method according to claim 6, characterized in that the feeding mode of the propylene monomer is periodic feeding, the interval time of each feeding period is 1-100 min, and the number of feeding periods is 1-50.
8. The process according to claim 6, characterized in that the catalyst is selected from Ziegler-Natta catalysts;
the cocatalyst is selected from an aluminum alkyl cocatalyst;
the external electron donor is selected from silicon compounds and/or aromatic compounds.
9. The process according to claim 6, characterized in that the temperature of the homopolymerization is preferably 55-90 ℃, the pressure is 0.1-5 MPa, and the time is 0.1-10 hours;
the temperature of the polymerization reaction is 55-90 ℃, and the time is 0.1-10 hours.
10. A composite material, comprising:
the impact polypropylene material of claim 1;
and (3) an additive.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
| WO2019141462A1 (en) * | 2018-01-22 | 2019-07-25 | Borealis Ag | Nucleated c3c4 copolymers |
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- 2022-12-28 CN CN202211694430.9A patent/CN115873348A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
| WO2019141462A1 (en) * | 2018-01-22 | 2019-07-25 | Borealis Ag | Nucleated c3c4 copolymers |
Non-Patent Citations (2)
| Title |
|---|
| 任合刚等: "球形聚丙烯/聚丁烯-1合金粒子制备和性能", 材料研究学报, no. 07, pages 518 - 524 * |
| 黄凯等: "丙烯/1-丁烯聚合物合金的单体组成切换法制备：动力学及聚合器模型", 化工学报, vol. 69, no. 11, pages 4693 - 4701 * |
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