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CN119081029B - Propylene-based olefin block copolymer with flame retardant function, preparation method thereof and composition containing recycled plastic - Google Patents

Propylene-based olefin block copolymer with flame retardant function, preparation method thereof and composition containing recycled plastic Download PDF

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Publication number
CN119081029B
CN119081029B CN202411497993.8A CN202411497993A CN119081029B CN 119081029 B CN119081029 B CN 119081029B CN 202411497993 A CN202411497993 A CN 202411497993A CN 119081029 B CN119081029 B CN 119081029B
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propylene
flame retardant
block
block copolymer
retardant function
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CN119081029A (en
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王瀚霖
吴利平
黄旭东
李新乐
孟繁茂
肖越
刘恒之
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China Petroleum Shanghai New Materials Research Institute Co ltd
Petrochina Co Ltd
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China Petroleum Shanghai New Materials Research Institute Co ltd
Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a propenyl olefin block copolymer with a flame retardant function, a preparation method thereof and a composition containing recycled plastics. The propylene-based olefin block copolymer with flame retardant function comprises a first block and a second block, wherein the first block comprises a polypropylene block, and the second block comprises a copolymer block of propylene, ethylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds. The composition containing the recycled plastic comprises polyethylene recycled plastic, polypropylene recycled plastic and the propenyl olefin block copolymer with flame retardant function. The propenyl olefin block copolymer with flame retardant function can be used as a compatilizer in ethylene-propylene reclaimed plastics, so that the ethylene-propylene reclaimed plastics have excellent mechanical property and flame retardant property.

Description

Propenyl olefin block copolymer with flame-retardant function, preparation method thereof and composition containing recycled plastic
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a propenyl olefin block copolymer with a flame retardant function, a preparation method thereof and a composition containing recycled plastics.
Background
Polyethylene and polypropylene plastics are the most widely used synthetic plastics in the current society due to simple structure, excellent performance and lower cost, and the two plastics account for nearly 60% of the global plastic yield. However, both plastics are polymer materials which are difficult to degrade and cause continuous environmental pollution after being discarded, so that in recent years, attention has been paid to efficient recovery and high-value reuse of polyethylene and polypropylene.
It is worth pointing out that two kinds of plastics of polyethylene and polypropylene can be mixed in same scene commonly and used, for example polyethylene for body, polypropylene for bottle lid are difficult to realize thorough sorting when retrieving, but two thermodynamics incompatibility, and the recovery blending can cause serious phase separation, makes the mechanical properties of recovery plastics very poor, is difficult to high value recycle.
In the prior art, an olefin block copolymer is used as a compatilizer for recycling ethylene-propylene plastics, so that the interfacial tension of the olefin block copolymer and the ethylene-propylene plastics is reduced, the compatibility of the olefin block copolymer and the ethylene-propylene plastics can be improved, and the mechanical properties such as impact strength of the recycled plastics can be improved. However, because the constituent elements of the polyethylene, the polypropylene and the olefin block copolymer are only two of carbon and hydrogen, the oxygen index is very low, the polyethylene, the polypropylene and the olefin block copolymer are very easy to burn, and a great amount of heat is released by burning, molten drops are generated in the process, flame propagation is accelerated, and even explosion accidents are caused, the application prospect of the ethylene-propylene recycled plastic taking the olefin block copolymer as a compatilizer is severely limited.
Flame retardant materials are generally prepared from polyethylene and polypropylene by adding flame retardants, which are generally classified into reactive type and additive type, with additive type flame retardants being most commonly used. The phosphorus flame retardant is an important one in the additive flame retardants, but it can be seen from the report of CN104693604A that the introduction of phosphorus flame retardant particles in the matrix can destroy interface bonding, so that the mechanical property is obviously reduced. Therefore, as reported in CN109679203a and CN117866336a, reinforcements are often added to enhance the mechanical properties of the flame retardant materials when such additive flame retardants are used. In addition, if red phosphorus is directly used as a flame retardant, the flame retardant efficiency is high, but the red phosphorus is easy to absorb moisture, and a coating technology is generally used for preventing the red phosphorus from losing efficacy. The use of the cladding technology makes the production cost higher and the process more complex.
Therefore, developing a compatilizer for ethylene-propylene reclaimed plastic, which enables the ethylene-propylene reclaimed plastic to have excellent mechanical property and flame retardant property at the same time, becomes one of the problems to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a propenyl olefin block copolymer with a flame retardant function, a preparation method thereof and a composition containing recycled plastics. The propenyl olefin block copolymer with flame retardant function can be used as a compatilizer in ethylene-propylene reclaimed plastics, so that the ethylene-propylene reclaimed plastics have excellent mechanical property and flame retardant property.
In order to achieve the above object, the first aspect of the present invention provides a propylene-based olefin block copolymer having a flame retardant function, which comprises a first block comprising a polypropylene block and a second block comprising a copolymer block of propylene, ethylene and a monomer comprising a phosphonic acid group and a carbon-carbon double bond, wherein the content of the first block is 20 to 30% and the content of the second block is 70 to 80% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function.
According to an embodiment of the present invention, it is preferable that the ratio of the number average molecular weight of the first block and the second block is 1 (3 to 4).
According to a specific embodiment of the present invention, preferably, the first block contains an isotactic polypropylene block, and the isotacticity of the isotactic polypropylene block is 85-95%.
According to a specific embodiment of the present invention, preferably, the number average molecular weight of the first block is 15 to 30 kDa.
According to a specific embodiment of the present invention, preferably, the molar ratio of the structural units derived from propylene, the structural units derived from ethylene and the structural units derived from the monomer containing a phosphonic acid group and a carbon-carbon double bond in the second block is (4 to 5): 1 to 2): 0.6 to 3.5.
According to a specific embodiment of the present invention, preferably, the monomer containing a phosphonic acid group and a carbon-carbon double bond includes one or more of vinyl phosphonic acid, methyl vinyl phosphonate, dimethyl vinyl phosphonate, ethyl vinyl phosphonate, diethyl vinyl phosphonate, and the like.
According to a specific embodiment of the present invention, preferably, the number average molecular weight of the second block is 60 to 90 kDa.
According to the specific embodiment of the invention, preferably, the number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 75-120 kDa, and the molecular weight distribution is 1.9-3.0.
According to the specific embodiment of the invention, preferably, the limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 30-40%, and the flame retardant grade of the propenyl olefin block copolymer with the flame retardant function is V-0 grade of UL 94.
The second aspect of the present invention provides a method for preparing the above propylene-based olefin block copolymer having a flame retardant function, comprising the steps of:
(1) Under the anhydrous and anaerobic condition, propylene is subjected to a first polymerization reaction in an organic solvent and in the presence of a main catalyst, a cocatalyst and a chain transfer agent to obtain a mixed system after the first polymerization reaction;
(2) Under the anhydrous and anaerobic condition, adding ethylene, propylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds into the mixed system after the first polymerization reaction, and carrying out a second polymerization reaction to obtain a mixed system after the second polymerization reaction;
(3) At least precipitating and carrying out solid-liquid separation on the mixed system after the second polymerization reaction to obtain the propenyl olefin block copolymer with the flame retardant function;
wherein the main catalyst comprises a complex of a ligand containing pyridyl and imine and a group IVB transition metal, the cocatalyst comprises an organoboron compound, and the chain transfer agent comprises an alkyl aluminum compound and/or an alkyl zinc compound.
According to a specific embodiment of the present invention, preferably, the temperature of the first polymerization reaction is 25 to 70 ℃ and the pressure is 0.1 to 0.5 MPa.
According to a specific embodiment of the present invention, preferably, the procatalyst comprises a complex having a structure as shown in formula I and/or formula II:
I is a kind of
II (II)
Wherein M is selected from one of IVB group transition metals;
Each R 1、R2 is independently selected from one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted polycyclic aryl.
According to a specific embodiment of the present invention, preferably, the cocatalyst includes one or more of trityl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetra-N-butyltetraphenylammonium borate, and the like.
According to a specific embodiment of the present invention, preferably, the chain transfer agent includes one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylzinc, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.
According to a specific embodiment of the present invention, preferably, the molar ratio of the main catalyst to the chain transfer agent is 1 (150 to 200).
According to a specific embodiment of the present invention, preferably, the temperature of the second polymerization reaction is 25 to 70 ℃ and the pressure is 0.1 to 0.5 MPa.
The third aspect of the invention provides a composition containing recycled plastics, which comprises the recycled plastics, the recycled plastics and a compatilizer, wherein the compatilizer comprises the propenyl olefin block copolymer with a flame retardant function, and the mass ratio of the total amount of the recycled plastics to the compatilizer is 8 (1-2).
The invention has at least the following beneficial effects:
The propylene-based olefin block copolymer having a flame retardant function of the present invention comprises a first block comprising a polypropylene block which is a hard block and a second block comprising a copolymer block of propylene, ethylene and a monomer containing a phosphonic acid group and a carbon-carbon double bond which is a soft block. The propylene-based olefin block copolymer simultaneously contains a polypropylene chain segment and a copolymer chain segment containing ethylene structural units, and the propylene-based olefin block copolymer is used as a compatilizer in ethylene-propylene reclaimed plastics, and polyethylene and polypropylene in the reclaimed plastics are combined with similar chain segments in the propylene-based olefin block copolymer, so that the compatibility of the polyethylene and the polypropylene is increased, and the reclaimed plastics have excellent mechanical properties. Meanwhile, compared with a random copolymer or a graft copolymer formed by propylene, ethylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds, the segmented copolymer of the invention has the advantages that the structure height of the segmented copolymer is adjustable, the compatibility can be improved by adjusting the content or the proportion of soft segments and hard segments according to the proportion of polyethylene and polypropylene in recycled plastics, and the universality of the segmented copolymer of the invention as the compatilizer is obviously improved. In addition, the second block of the propenyl olefin block copolymer contains structural units from monomers containing phosphonic acid groups and carbon-carbon double bonds, so that the propenyl olefin block copolymer has a flame retardant function, is used as a compatilizer in ethylene-propylene reclaimed plastics, has excellent flame retardant property and widens the application scene of the reclaimed plastics. In addition, the material with flame retardant function is not introduced into the recycled plastic in the prior art in a blending way, but the monomer containing phosphonic acid groups and carbon-carbon double bonds is introduced in a copolymerization way, and the propenyl olefin segmented copolymer is prepared as a compatilizer, so that the adverse effect of the flame retardant material introduced in the blending way on the mechanical property of the recycled plastic is avoided, the recycled plastic has excellent flame retardant property and mechanical property, and the preparation process complexity of the recycled plastic with flame retardant property is not increased.
Drawings
FIG. 1 is a scanning electron microscope image of the recycled plastic of example 1.
FIG. 2 is a scanning electron microscope image of the recycled plastic of example 2.
FIG. 3 is a scanning electron microscope image of the recycled plastic of example 3.
FIG. 4 is a scanning electron microscope image of the recycled plastic of example 4.
FIG. 5 is a scanning electron microscope image of the recycled plastic of example 6.
FIG. 6 is a scanning electron microscope image of the recycled plastic of comparative example 1.
FIG. 7 is a scanning electron microscope image of the recycled plastic of comparative example 2.
Detailed Description
The following detailed description of the present invention will be presented for a clearer understanding of the technical features, objects and advantages of the present invention, but should not be construed as limiting the scope of the invention.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
It is noted that all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless otherwise indicated.
The various raw materials, reagents, instruments, equipment, etc., used in the present invention are commercially available or may be prepared by existing methods unless otherwise specifically indicated.
According to a specific embodiment of the first aspect of the present invention, there is provided a propylene-based olefin block copolymer having a flame retardant function, which comprises a first block comprising a polypropylene block and a second block comprising a copolymer block of propylene, ethylene and a monomer having a phosphonic acid group and a carbon-carbon double bond, wherein the content of the first block is 20 to 30%, for example 20%, 25% or 30% or the like, and the content of the second block is 70 to 80%, for example 70%, 75% or 80% or the like, based on 100% of the total average molecular weight of the propylene-based olefin block copolymer having a flame retardant function.
In some embodiments, the ratio of the number average molecular weights of the first block and the second block is 1 (3-4).
In some embodiments, the first block comprises an isotactic polypropylene block having an isotacticity of 85 to 95%, such as 85%, 86%, 88%, 90%, 92%, 94%, or 95%, etc., preferably 90 to 95%.
In some embodiments, the first block has a number average molecular weight of 15 to 30 kDa, preferably 20 to 25 kDa, and a molecular weight distribution of 1.9 to 2.1.
In some embodiments, the molar ratio of structural units derived from propylene, structural units derived from ethylene, and structural units derived from a monomer containing a phosphonic acid group and a carbon-carbon double bond in the second block is (4-5): 1-2): 0.6-3.5, preferably 5:1 (1-2).
In some embodiments, the monomer containing a phosphonic acid group and a carbon-carbon double bond includes one or more of vinyl phosphonic acid, methyl vinyl phosphonate, dimethyl vinyl phosphonate, ethyl vinyl phosphonate, diethyl vinyl phosphonate, and the like.
In some embodiments, the number average molecular weight of the second block is 60-90 kDa, preferably 70-85 kDa, and the molecular weight distribution of the second block is 1.9-3.0.
In some embodiments, the number average molecular weight of the propenyl olefin block copolymer with flame retardant function is 75-120 kDa, preferably 90-110 kDa, and the molecular weight distribution of the propenyl olefin block copolymer with flame retardant function is 1.9-3.0.
In some embodiments, the limiting oxygen index of the propenyl olefin block copolymer with flame retardant function is 30-40%, and the flame retardant grade of the propenyl olefin block copolymer with flame retardant function is V-0 grade of UL 94.
According to a second aspect of the present invention, there is provided a method for producing the above propylene-based olefin block copolymer having a flame retardant function, comprising the steps of:
(1) Under the anhydrous and anaerobic condition, propylene is subjected to a first polymerization reaction in an organic solvent and in the presence of a main catalyst, a cocatalyst and a chain transfer agent to obtain a mixed system after the first polymerization reaction;
(2) Under the anhydrous and anaerobic condition, adding ethylene, propylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds into the mixed system after the first polymerization reaction, and carrying out a second polymerization reaction to obtain a mixed system after the second polymerization reaction;
(3) At least precipitating and carrying out solid-liquid separation on the mixed system after the second polymerization reaction to obtain the propenyl olefin block copolymer with the flame retardant function;
wherein the main catalyst comprises a complex of a ligand containing pyridyl and imine and a group IVB transition metal, the cocatalyst comprises an organoboron compound, and the chain transfer agent comprises an alkyl aluminum compound and/or an alkyl zinc compound.
In some embodiments, the temperature of the first polymerization reaction is 25-70 ℃ and the pressure is 0.1-0.5 MPa.
In some embodiments, the procatalyst includes a complex having a structure as shown in formula I and/or formula II:
I is a kind of
II (II)
Wherein M is selected from one of IVB group transition metals, specifically, M is selected from one of titanium (Ti), zirconium (Zr) and hafnium (Hf);
Me represents methyl;
Each R 1、R2 is independently selected from one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted polycyclic aryl. Specifically, R 1、R2 is independently selected from C1-C10 substituted or unsubstituted alkyl, C3-C10 substituted or unsubstituted cycloalkyl, C6-C20 substituted or unsubstituted aryl and C10 or more substituted or unsubstituted polycyclic aryl. Among the polycyclic aryl groups include non-condensed ring type polycyclic aryl groups (e.g., biphenyl and biphenylyl, etc.) and condensed ring type aryl groups (e.g., naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl, acenaphthylenyl, pyrenyl, coronenyl, etc.). Preferably, each R 1、R2 is independently selected from one of phenyl and isopropyl substituted phenyl (e.g., 2, 6-diisopropylphenyl) and the like.
The procatalyst employed in the present invention may be prepared by methods disclosed in the prior art, for example in the 2.2.4 paper reported by Yin Xiao (Yin Xiao. Chain shuttling polymerization to stereoblock polypropylene [ D ]. Tianjin university, 2020.).
In some embodiments, the cocatalyst includes one or more of trityl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetra-N-butyltetraphenylammonium borate, and the like.
In some embodiments, the chain transfer agent comprises one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylzinc, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.
In some embodiments, the molar ratio of the procatalyst to the chain transfer agent is 1 (150-200), such as 1:150, 1:160, 1:170, 1:180, 1:190, or 1:200, etc.
In some embodiments, the molar ratio of the procatalyst to the cocatalyst is 1 (1-5). Generally, the amount of the cocatalyst may be slightly higher than that of the main catalyst, and the molar ratio of the main catalyst to the cocatalyst is, for example, 1 (1.5-2).
In some embodiments, the organic solvent is an inert organic solvent conventional in the art, such as one or more of n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, toluene, xylene, and the like. The amount of the organic solvent may be adjusted conventionally by those skilled in the art.
In some embodiments, the second polymerization reaction is at a temperature of 25 to 70 ℃ and a pressure of 0.1 to 0.5 MPa.
In some embodiments, in step (1) and step (2), propylene and ethylene are introduced into the reaction system in gaseous form, and the monomer containing the phosphonic acid group and the carbon-carbon double bond is added to the reaction system by dropwise addition. The molar ratio of propylene and ethylene introduced in the step (2) and the monomer containing phosphonic acid groups and carbon-carbon double bonds added dropwise is not particularly limited and can be adjusted by one skilled in the art based on the molar ratio of the structural units derived from the three monomers in the second block described hereinabove.
In some embodiments, in step (3), the block copolymer may be precipitated using solvents conventional in the art, such as alcohols and the like. The solid-liquid separation can be carried out by conventional filtration or the like. And, washing and drying may be performed to obtain the propylene-based olefin block copolymer having a flame retardant function.
According to a specific embodiment of the third aspect of the invention, the invention provides a composition containing recycled plastics, which comprises the recycled plastics, the recycled plastics and a compatilizer, wherein the compatilizer comprises the propenyl olefin block copolymer with a flame retardant function, and the mass ratio of the total amount of the recycled plastics to the compatilizer is 8 (1-2). The mass ratio of the polyethylene recycled plastic to the polypropylene recycled plastic can be adjusted according to actual needs, for example, can be 1:1.
The propylene-based olefin block copolymer having a flame retardant function of the present invention comprises a first block comprising a polypropylene block (preferably an isotactic polypropylene block) which is a hard block and a second block comprising a copolymer block of propylene, ethylene and a monomer containing a phosphonic acid group and a carbon-carbon double bond, the copolymer block being a random copolymer block which is a soft block. The invention controls the content and proportion of the first block and the second block, and the proportion of the structural unit from propylene, the structural unit from ethylene and the structural unit from the monomer containing phosphonic acid groups and carbon-carbon double bonds in the second block, so that when the block copolymer is used as a compatilizer in ethylene-propylene recycled plastics, the recycled plastics not only have excellent mechanical properties, but also have obvious flame retardant effect, and the condition of high flammability after the polyethylene and polypropylene recycled plastics are blended in the prior art is avoided. In addition, the preparation process of the segmented copolymer is simple and easy to realize, and the propenyl olefin segmented copolymer with the flame-retardant function has high purity. In addition, the composition containing the recycled plastic can reduce or even avoid adding other flame retardant materials during blending due to the adoption of the segmented copolymer, so that the problems of uneven blending, reduced mechanical property and the like caused by introducing the flame retardant materials in a blending manner are avoided, and the preparation process complexity of the recycled plastic with the flame retardant property is not increased. Therefore, the ethylene-propylene reclaimed plastic containing the block copolymer has excellent mechanical property and flame retardant property, and breaks through the application scene of serious limitation for a long time.
The following will specifically explain the technical aspects of the present invention by way of examples, but the present invention is not limited to these examples, and can be carried out by varying the scope of the gist of the present invention.
The testing method comprises the following steps:
(1) Purity of the propylene-based olefin block copolymer having flame retardant function:
Testing was performed using a cross-fractionation chromatograph (CFC) that combines Temperature Rising Elution Fractionation (TREF) and Gel Permeation Chromatography (GPC). A sample (10 mg) of the polymer (i.e., the product in the following example) was placed in a disposable sample bottle and 1,2, 4-trichlorobenzene containing 0.1 ppm 2, 6-di-tert-butyl-4-methylphenol (BHT) was automatically injected by an autosampler at 150 ℃. After 1.5 hours, the polymer solution was eluted through a TREF column, crystallized from 140℃to 25℃at a cooling rate of 0.5℃per minute, and then eluted the fraction at progressively increasing temperatures. From the 2D (molecular weight-temperature) and 3D (molecular weight-temperature-content percent) maps of CFCs, it is apparent that the two components are distributed in the high temperature region (80-130 ℃) and in the low temperature region (0-40 ℃) where the low temperature region component is an impurity, the high temperature region component is a block copolymer, and the content of the high region component is the content (purity) of the block copolymer in the product.
(2) Molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from a monomer containing a phosphonic acid group and a carbon-carbon double bond in the second block:
High temperature 13C {1 H } NMR spectra were measured using BrukerAVANCE IIITM HD 400,400, 400 MHz NMR spectrometer. The test was performed at 120℃with 1, 2-tetrachloroethane-d 2 (1, 2-TCE-d 2) as deuterating agent. The test sample was the high temperature component obtained after elution with a cross-fractionation chromatograph (CFC) in test (1) above.
The peak at about 21.94 ppm is considered to be a pentad isotactic polypropylene signal PPPPP, the peak at about 46.6 ppm is considered to be a tetrad isotactic polypropylene signal PPPP, the peak at about 28.97 ppm is considered to be a tri-link isotactic polypropylene signal PPP, all three signals are the signals of the first block by default, all the remaining signals are the signals of the second block, and the sum of the peak area integral of the remaining signals is calculated and recorded as S. The peak at about 11.98 ppm is considered to be a hydroxyl signal in the phosphonic acid group, and the area integral of the peak is calculated and designated as S 1. The molar ratio of structural units derived from ethylene and propylene in the second block was calculated according to the method described in J.Polym.Sci., part C: polym.Rev.1989, 29, pages 237-256 of 201-317, and peaks at positions 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm are considered to be signals of random copolymerization of ethylene and propylene such as EPEPE +EPE, EPEE+EEPE, PPEE+ EEPP, PEEP, PEEE +EEEP, EEE, respectively. The sum of the area integrals of the signal peaks corresponding to the structural units from ethylene and propylene is S-S 1, the area integral of the signal peak of the structural unit from ethylene is calculated to be S 2 according to the mole ratio and S-S 1, and the area integral of the signal peak of the structural unit from propylene is S 3.S3：S2：S1, namely the mole ratio of the structural unit from propylene, the structural unit from ethylene and the structural unit from the monomer containing phosphonic acid groups and carbon-carbon double bonds.
(3) Number average molecular weight and molecular weight distribution of the first block, the second block, and the propylene-based olefin block copolymer having a flame retardant function:
The number average molecular weight and molecular weight distribution (PDI) were determined by high temperature gel permeation chromatography (high temperature GPC). The column was PLgel Olexis, mm X7.5, mm X13 μm (3 in series). The mobile phase was 1,2, 4-trichlorobenzene (1, 2, 4-TCB) containing 2, 6-di-tert-butyl-4-methylphenol (BHT, 200 mg/L) as stabilizer at a flow rate of 1.0 mL/min. The test temperature was 150 ℃. The test sample is a polymer solution with the mass concentration of 50 mg/ml prepared by using a mobile phase as a solvent, and the sample injection amount is 10 mu L. The polymer tested was the high temperature component obtained after elution with a cross-fractionation chromatograph (CFC) in test (1) above. The molecular weight obtained was calibrated against polystyrene standard Easi-Cal PS-1 (PL).
Wherein the number average molecular weight of the first block is determined by the above method for the product obtained by performing only the first polymerization reaction, and the number average molecular weight of the second block is obtained by subtracting the number average molecular weight of the first block from the number average molecular weight of the finally obtained block copolymer. The product obtained by the first polymerization reaction is obtained by carrying out precipitation, solid-liquid separation, washing and drying on the mixed system after the first polymerization reaction.
(4) Content of the first block and the second block:
The content of the first block and the second block is the number average molecular weight of the first block and the number average molecular weight of the second block, respectively, as a percentage of the number average molecular weight of the block copolymer.
(5) Isotacticity of isotactic polypropylene blocks:
The isotacticity was determined by 13 C nuclear magnetic resonance method. A Bruker 600 MHz high temperature nmr spectrometer was used. 50mg of the sample is taken and added into a nuclear magnetic tube, 0.6mL of deuterated o-dichlorobenzene is added, the mixture is heated and dissolved by a hot air gun, and the mixture is uniformly mixed and then tested at 120 ℃. The sample was the product of the first polymerization reaction.
(6) Limiting oxygen index:
Limiting oxygen index was tested according to the method described in GB 2406.2-2009. Limiting oxygen index refers to the minimum oxygen concentration required to maintain stable combustion of a sample in a mixed stream of oxygen and nitrogen under specified test conditions. The testing method comprises the steps of vertically fixing a sample in a glass combustion cylinder, wherein the base of the sample is connected with a device capable of generating a nitrogen-oxygen mixed gas flow, igniting the top end of the sample, continuously reducing the oxygen concentration in the mixed gas flow until the flame is extinguished, and enabling the oxygen concentration when the flame is just extinguished to be the limiting oxygen index. 5 samples were tested for each material and averaged. Each sample was required to be smooth and bubble free. The sample has dimensions of 120mm in length, 10.0mm in width and 4mm in thickness.
(7) Flame retardant rating:
Flame retardant rating was tested according to the method described in the vertical burn test in UL 94-2018. Specifically, the testing steps include test sample preparation, sample pretreatment, flame rating and test equipment. The test classifies the material into V-0, V-1, V-2, NR grades, where V-0 has the highest flame retardant grade and NR represents the non-flame retardant grade.
(8) Tensile strength and elongation at break:
Tensile strength and elongation at break were tested using an Instron 3367 universal tester. The test was performed according to the method described in ASTM D1708-13. Dumbbell-shaped samples with a width of 5 mm and a thickness of 0.5 mm were used. At least five tensile tests were repeated for each sample and an average was taken. The tensile speed in the tensile test was 10 mm/min.
Example 1
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a rate of 0.6 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
The hafnium picolinate can be prepared using methods disclosed in the prior art, for example, the preparation method disclosed in the paper reported by Yin Xiao (Yin Xiao. Chain shuttling polymerization to stereoblock polypropylene [ D ]. Tianjin university, 2020.) 2.2.4.
The product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.8% and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, and the total mass of the product obtained was 12.2 g, and the content of the first block was 24.1% and the content of the second block was 75.9% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from a monomer of vinylphosphonic acid in the second block is 5:1.8:0.6. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 69.3 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 91.3 kDa, and the molecular weight distribution is 2.65.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content (purity) in the product of 91.4%. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 32%, and the flame retardant grade is V-0 grade of UL 94. It is to be noted that the limiting oxygen index and the flame retardant rating are tested here on the products (not purified) obtained in the examples, as are the following examples and comparative examples.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added. The propylene-based olefin block copolymer having a flame retardant function added here was the product (not purified) obtained in the examples, as was the case with the following examples and comparative examples.
The scanning electron microscope of the recycled plastic is shown in figure 1.
Example 2
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a rate of 0.7 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
The product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.5% and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, and the total mass of the product obtained was 12.4 g, and the content of the first block was 23.7% and the content of the second block was 76.3% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid in the second block was 5:1.5:0.88. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 70.8 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 92.8 kDa, and the molecular weight distribution is 2.8.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 90.2% in the product. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 33%, and the flame retardant grade is V-0 grade of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added.
The sem image of the recycled plastic is shown in fig. 2.
Example 3
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a rate of 0.8 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
the product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.8% and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, and the total mass of the product obtained was 12.8 g, and the content of the first block was 23.0% and the content of the second block was 77.0% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid in the second block was 5:1:1.06. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 73.7 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 95.7 kDa, and the molecular weight distribution is 2.74.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 88.6% in the product. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 34.5%, and the flame retardant grade is V-0 grade of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added.
The sem image of the recycled plastic is shown in fig. 3.
Example 4
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a speed of 1.0 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
The product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.5% and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, and the total mass of the product obtained was 13.6 g, and the content of the first block was 21.6% and the content of the second block was 78.4% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid in the second block was 5:1:1.98. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 79.9 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 101.9 kDa, and the molecular weight distribution is 2.91.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 85.7% in the product. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 37%, and the flame retardant grade is V-0 grade of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added.
The sem image of the recycled plastic is shown in fig. 4.
Example 5
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 2.0 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a speed of 1.0 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
The product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.8% and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, and the total mass of the product obtained was 13.8 g, and the content of the first block was 21.7% and the content of the second block was 78.3% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid in the second block was 5:1:1.86. The number average molecular weight of the first block was 17.3 kDa. The number average molecular weight of the second block was 62.6 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 79.9 kDa, and the molecular weight distribution is 2.5.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 86.0% in the product. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 36.5 percent, and the flame retardant grade is V-0 grade of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added.
Example 6
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol of hafnium picolinamide, and 20. Mu. Mol of trityl tetrakis (pentafluorophenyl) borate; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2 MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of the reaction kettle to be 0.2 MPa, simultaneously dropwise adding vinyl phosphonic acid at a speed of 1.2 g/min, carrying out polymerization reaction at 50 ℃ and 0.2 MPa for 10 minutes, stopping dropwise adding vinyl phosphonic acid, and simultaneously stopping introducing ethylene gas and propylene gas;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
The structure of the hafnium picolinate is as follows:
。
The product of this example contained a propylene-based olefin block copolymer having a flame retardant function, which contained a first block containing an isotactic polypropylene block having an isotacticity of 94.8%, the total mass of the product obtained was 14.4 g, and a second block containing a random copolymer block of propylene, ethylene and vinylphosphonic acid, the content of the first block being 20.4% and the content of the second block being 79.6% based on 100% of the total number average molecular weight of the propylene-based olefin block copolymer having a flame retardant function. The molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid in the second block was 4:1:3.12. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 85.8 kDa. The number average molecular weight of the propenyl olefin block copolymer with the flame retardant function is 107.8 kDa, and the molecular weight distribution is 2.82.
The propylene-based olefin block copolymer having a flame retardant function of this example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 85.0% in the product. The propylene-based olefin block copolymer having a flame retardant function of the present example was confirmed to contain the first block and the second block described above by the nuclear magnetic resonance spectrometer described in the above test method (2) and observed to show peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 11.98 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm and the like.
The limiting oxygen index of the propenyl olefin block copolymer with the flame retardant function is 39%, and the flame retardant grade is V-0 grade of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer with flame retardant function of this example were added to an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer with flame retardant effect was added.
The sem image of the recycled plastic is shown in fig. 5.
Comparative example 1
This comparative example is essentially the same as example 1, except that no vinylphosphonic acid was added.
(1) 250Ml of toluene was added to the reaction vessel under anhydrous and anaerobic conditions, followed by 1.5 mmol triisobutylaluminum, 10. Mu. Mol hafnium picolinamide, and 20. Mu. Mol tris (pentafluorophenyl) borate to the toluene; introducing propylene gas into a reaction kettle, and carrying out polymerization reaction at 50 ℃ and 0.2MPa, wherein after 5 minutes of reaction, the propylene gas is rapidly discharged to obtain a mixed system after the first polymerization reaction;
(2) Introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the mixed system obtained in the step (1) under the anhydrous and anaerobic condition, maintaining the pressure of a reaction kettle to be 0.2 MPa, carrying out polymerization reaction under the conditions of 50 ℃ and 0.2 MPa, and stopping introducing the ethylene gas and the propylene gas after reacting for 10 minutes;
(3) Transferring the mixed system obtained in the step (2) after the second polymerization reaction from the reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitate to obtain a product;
Wherein the structure of the hafnium picolinate was the same as in example 1.
The product of this comparative example contained a propylene-based olefin block copolymer comprising a first block and a second block, the first block comprising an isotactic polypropylene block having an isotacticity of 94.8% and the second block comprising a copolymer block of propylene and ethylene, the total mass of the product produced was 11.9 g, the content of the first block was 24.7% and the content of the second block was 75.3% based on 100% of the total average molecular weight of the propylene-based olefin block copolymer. The molar ratio of structural units derived from propylene to structural units derived from ethylene in the second block was 5:2. The number average molecular weight of the first block was 22 kDa. The number average molecular weight of the second block was 67 kDa. The number average molecular weight of the propylene-based olefin block copolymer was 89 kDa.
The propylene-based olefin block copolymer of this comparative example was obtained by the cross-fractionation chromatograph (CFC) described in the above test method (1) to have a mass content of 95.1% in the product. Peaks at positions 21.94 ppm, 46.6 ppm, 28.97 ppm, 37.94 ppm, 37.58 ppm, 37.50 ppm, 30.76 ppm, 30.38 ppm, 29.98 ppm, etc. were observed by the nuclear magnetic resonance spectrometer described in test method (2) above, confirming that the propylene-based olefin block copolymer of this comparative example contains the first block and the second block described above.
The propylene-based olefin block copolymer has a limiting oxygen index of 15% and a flame retardant rating of NR rating of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the propylene-based olefin block copolymer of the present comparative example were fed into an extruder in a mass ratio of 40:40:20, and after mixing at 200 ℃ and 100rpm for 7 minutes, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene reclaimed plastic to which a compatibilizer was added.
The sem image of the recycled plastic is shown in fig. 6.
Comparative example 2
The recycled plastic of this comparative example was free of compatibilizing agent.
High density polyethylene (Sabic B4660) and isotactic polypropylene (Dow CHEMICAL H314-02Z) were added to an extruder in a mass ratio of 40:40, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to give an ethylene propylene reclaimed plastic.
The sem image of the recycled plastic is shown in fig. 7.
Comparative example 3
The present comparative example uses a random copolymer of propylene, ethylene and vinyl phosphonic acid as the compatibilizer.
(1) Adding 250ml of toluene into a reaction kettle under anhydrous and anaerobic conditions, then adding 1.5 mmol triisobutylaluminum, 10 mu mol of pyridine imine hafnium and 20 mu mol of trityl tetra (pentafluorophenyl) borate into the toluene, introducing ethylene gas and propylene gas with a molar ratio of 1:1 into the reaction kettle, simultaneously dropwise adding vinyl phosphonic acid at a rate of 0.67: 0.67 g/min, carrying out polymerization reaction at 50 ℃ and 0.2: 0.2 MPa for 15 minutes, stopping dropwise adding vinyl phosphonic acid, simultaneously stopping introducing ethylene gas and propylene gas, and then reducing the pressure of the reaction kettle to normal pressure to obtain a mixed system after polymerization reaction;
(2) Transferring the mixed system obtained in the step (1) after polymerization reaction from a reaction kettle, adding ethanol for precipitation, and filtering, washing and drying the precipitation to obtain a product;
Wherein the structure of the hafnium picolinate was the same as in example 1.
The product of this comparative example contains a random copolymer of propylene, ethylene and vinylphosphonic acid having a molar ratio of structural units derived from propylene, structural units derived from ethylene and structural units derived from vinylphosphonic acid of 5:1:2.05. The random copolymer of propylene, ethylene and vinylphosphonic acid has a number average molecular weight of 103 kDa.
The random copolymer of propylene, ethylene and vinyl phosphonic acid has a limiting oxygen index of 37% and a flame retardant rating of V-0 of UL 94.
The high-density polyethylene (Sabic B4660), the isotactic polypropylene (Dow CHEMICAL H314-02Z) and the random copolymer of propylene, ethylene and vinyl phosphonic acid of the present comparative example were fed into an extruder in a mass ratio of 40:40:20, and after mixing for 7 minutes at 200 ℃ and 100rpm, the mixed blend was extruded and cooled in air to obtain an ethylene-propylene recycled plastic to which a compatibilizer having a flame retardant effect was added.
Comparative example 4
This comparative example is essentially the same as example 1 except that the hafnium picolinate catalyst used as the main catalyst in example 1 is replaced with a metallocene catalyst in the same amount as example 1. The metallocene catalyst is dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride, and the structure is shown as follows:
。
the product prepared in this comparative example was different from example 1 in that only the first block, i.e., the polypropylene block, having a mass of 2 g and a number average molecular weight of 15 kDa could be prepared, and the propylene-based olefin block copolymer having a flame retardant function of example 1 could not be prepared.
The samples of the recycled plastics prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to mechanical properties, vertical combustion and limiting oxygen index tests, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the propylene-based olefin block copolymer with flame retardant function of each embodiment of the invention is used as a compatilizer in ethylene-propylene reclaimed plastics, the reclaimed plastics have excellent mechanical properties and flame retardant properties.
It should be understood that the foregoing examples of the present invention are provided merely for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (15)

1. A propylene-based olefin block copolymer with a flame-retardant function is characterized by comprising a first block and a second block, wherein the first block comprises a polypropylene block, the second block comprises a copolymer block of propylene, ethylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds, the content of the first block is 20-30% and the content of the second block is 70-80% based on 100% of the total average molecular weight of the propylene-based olefin block copolymer with the flame-retardant function;
Wherein the molar ratio of the structural unit from propylene to the structural unit from ethylene to the structural unit from the monomer containing phosphonic acid groups and carbon-carbon double bonds in the second block is (4-5): 1-2): 0.6-3.5;
The monomer containing phosphonic acid groups and carbon-carbon double bonds comprises one or more than two of vinyl phosphonic acid, methyl vinyl phosphonate, dimethyl vinyl phosphonate, ethyl vinyl phosphonate and diethyl vinyl phosphonate.
2. The propylene-based olefin block copolymer having a flame retardant function according to claim 1, wherein the ratio of the number average molecular weights of the first block and the second block is 1 (3 to 4).
3. The propylene-based olefin block copolymer with flame retardant function according to claim 1, wherein the first block contains an isotactic polypropylene block having an isotacticity of 85 to 95%.
4. The propylene-based olefin block copolymer with flame retardant function according to claim 1, wherein the number average molecular weight of the first block is 15-30 kDa.
5. The propylene-based olefin block copolymer with flame retardant function according to claim 1, wherein the number average molecular weight of the second block is 60 to 90 kDa.
6. The propylene-based olefin block copolymer with a flame retardant function according to claim 1, wherein the propylene-based olefin block copolymer with a flame retardant function has a number average molecular weight of 75-120 kDa and a molecular weight distribution of 1.9-3.0.
7. The propylene-based olefin block copolymer with flame retardant function according to claim 1, wherein the limiting oxygen index of the propylene-based olefin block copolymer with flame retardant function is 30-40%, and the flame retardant rating of the propylene-based olefin block copolymer with flame retardant function is V-0 rating of UL 94.
8. A method for producing the propylene-based olefin block copolymer having a flame retardant function according to any one of claims 1 to 7, comprising the steps of:
(1) Under the anhydrous and anaerobic condition, propylene is subjected to a first polymerization reaction in an organic solvent and in the presence of a main catalyst, a cocatalyst and a chain transfer agent to obtain a mixed system after the first polymerization reaction;
(2) Under the anhydrous and anaerobic condition, adding ethylene, propylene and a monomer containing phosphonic acid groups and carbon-carbon double bonds into the mixed system after the first polymerization reaction, and carrying out a second polymerization reaction to obtain a mixed system after the second polymerization reaction;
(3) At least precipitating and carrying out solid-liquid separation on the mixed system after the second polymerization reaction to obtain the propenyl olefin block copolymer with the flame retardant function;
wherein the main catalyst comprises a complex of a ligand containing pyridyl and imine and a group IVB transition metal, the cocatalyst comprises an organoboron compound, and the chain transfer agent comprises an alkyl aluminum compound and/or an alkyl zinc compound.
9. The method according to claim 8, wherein the temperature of the first polymerization reaction is 25 to 70 ℃ and the pressure is 0.1 to 0.5 MPa.
10. The process of claim 8, wherein the procatalyst comprises a complex having a structure according to formula I and/or formula II:
I is a kind of
II (II)
Wherein M is selected from one of IVB group transition metals;
Each R 1、R2 is independently selected from one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted polycyclic aryl.
11. The method according to claim 8, wherein the cocatalyst comprises one or more of trityl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and tetra-N-butyltetraphenylammonium borate.
12. The production method according to claim 8, wherein the chain transfer agent comprises one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylzinc, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
13. The process according to claim 8, wherein the molar ratio of the main catalyst to the chain transfer agent is 1 (150 to 200).
14. The method according to claim 8, wherein the second polymerization reaction is carried out at a temperature of 25 to 70 ℃ and a pressure of 0.1 to 0.5 MPa.
15. A composition comprising recycled plastic, which is characterized by comprising a polyethylene recycled plastic, a polypropylene recycled plastic and a compatibilizer, wherein the compatibilizer comprises the propylene-based olefin block copolymer having a flame retardant function as defined in any one of claims 1 to 7, and the mass ratio of the total amount of the polyethylene recycled plastic and the polypropylene recycled plastic to the compatibilizer is 8 (1 to 2).
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