CN109705247B - Flame-retardant polyolefin and preparation method thereof, and method for improving compatibility of polyolefin and flame retardant and simultaneously enhancing flame retardance of polyolefin - Google Patents
Flame-retardant polyolefin and preparation method thereof, and method for improving compatibility of polyolefin and flame retardant and simultaneously enhancing flame retardance of polyolefin Download PDFInfo
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Abstract
The invention relates to flame-retardant polyolefins of formula (I) or (II) in which m, n, q, R and R are1‑R5The flame retardant polyolefin of formula (I) or (II) is obtained by polymerizing ethylene monomers with the corresponding phosphorus-containing ethylene monomer and optionally silicon-containing ethylene monomer and/or boron-containing ethylene monomer in the presence of a palladium phosphine sulfonate catalyst, as defined herein. The flame-retardant polyolefin provided by the invention has excellent flame-retardant performance and thermal stability. The invention also relates to a method for improving the compatibility of a polyolefin with a flame retardant while enhancing the flame retardancy of the polyolefin using a compatibility modifier of formula (III) and a method for preparing the same, wherein x, y and R6As defined herein. By using the compatibility modifier disclosed by the invention, the compatibility of polyolefin and a flame retardant can be obviously improved, and the flame retardant property of the existing flame-retardant polyolefin material can be improved.
Description
Technical Field
The invention relates to the field of polyolefin compounds and preparation thereof, in particular to flame-retardant polyolefin and a preparation method thereof, and a method for improving the compatibility of polyolefin and a flame retardant and simultaneously enhancing the flame retardance of the polyolefin by using a compatibility modifier and a preparation method thereof.
Background
Olefins have an important strategic position in the field of petrochemical industry. Polyolefins are important downstream sectors of the olefin industry, are economically important, and play a significant role in our daily lives. Polyolefins have very high annual yields and a wide range of applications, as well as excellent properties, including chemical stability, corrosion resistance, non-toxicity and low cost. However, common polyolefin polymers exhibit lower Limiting Oxygen Index (LOI) values (typically about 17.4, well below the passing value of 26.0, see, for example, Cullis, C.F.; Hirschler, M.M. char formation from polyolefms. relationships with low-temperature oxygen uptake and with flame activity in the presence of metal-halogen systems, Eur. Polymer.J. 1984, 20, 53-60.), high flammability and low flame resistance, i.e., no flame retardancy or poor flame retardancy, which severely limits their use in many important fields. Such as high voltage, heating and discharging environments, are highly combustible and emit a large amount of smoke, which can cause fire accidents, and have limited applications in the fields of electronic devices and wires.
In addition, the traditional halogen-containing flame retardant can release a large amount of toxic gases during combustion to cause great influence on the environment, so that the use of the halogen-containing flame retardant is limited, and the halogen-free flame retardant has good effect and does not release toxic gases during combustion to form a new research field of flame retardance.
Furthermore, in the art, in order to improve the flame retardant property of polyolefin itself having no flame retardancy or poor flame retardancy, it is a common method to blend polyolefin with a flame retardant (additive) agent to prepare a polyolefin material having flame retardant property. The use of various additives to improve the flame retardant properties of polyolefins has been extensively studied (see, for example, Liuying, Liang-Dynasty; synthesis of novel phosphorus and nitrogen containing flame retardants and performance studies of their flame retardant polyethylenes [ J ]; plastics industry, 2017, 45 (02): 33-36). In these studies, halogenated compounds have a long history as compatibilization modifiers for polyolefins; in addition, intumescent flame retardants are of interest because the porous carbon layer formed upon combustion of an intumescent flame retardant, such as a phosphorus-containing compound (e.g., ammonium polyphosphate), acts as a physical barrier to the transfer of heat and gas generation, and such flame retardants can also effectively prevent further degradation of the resulting polyolefin material. However, halogenated compounds are severely limited in their use because they produce highly toxic gaseous products upon combustion; meanwhile, since polyolefins are generally saturated carbon chain compounds, they are generally not well compatible with most flame retardants, which also causes the problem of phase separation of the prepared composite material, and thus the desired purpose of improving the flame retardant property of the polyolefin material is not achieved; in addition, at present, it is usually necessary to add a higher proportion of flame retardant to achieve the effect of improving the flame retardant property, which greatly reduces other properties such as mechanical properties and the like of the obtained material.
Therefore, there is a need in the art to develop a novel flame retardant polyolefin material having good flame retardant properties of the polymer itself, and also to develop a method of improving the compatibility of polyolefin with flame retardant while enhancing the flame retardancy of polyolefin.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a novel flame retardant polyolefin and a preparation method thereof; it is another object of the present invention to provide a method capable of improving the compatibility of polyolefin with a flame retardant while enhancing the flame retardancy of polyolefin.
To this end, in one aspect, the present invention provides a flame retardant polyolefin having a structure represented by formula (I) or (II):
wherein the content of the first and second substances,
m is a polymerization degree, and m is an integer of 200 to 2000;
n represents a spacer-CH2-and each n is independently an integer from 0 to 12;
q represents the number of ethylene units spaced among each of the phosphorus-containing ethylene unit, the silicon-containing ethylene unit and the boron-containing ethylene unit in the structure represented by the formula (I) or (II), and each q is independently an integer of 0 to 10;
r represents the number of silicon-containing ethylene units or boron-containing ethylene units in the structure represented by formula (I) or (II), and each r is independently 0 or 1;
R1、R2、R3、R4、R5independently selected from C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C1-C8Alkoxy radical, C6-C10Aryl or heteroaryl selected from the group consisting of thienyl, pyrrolyl and benzothienyl, and said aryl and said heteroaryl are optionally substituted with one or more groups selected from halogen, nitro, hydroxy and C1-C6Substituents in the alkyl group.
In a preferred embodiment, R1、R2、R3、R4、R5Independently selected from C1-C8Alkyl radical, C1-C8Alkoxy radical, C6-C10Aryl or heteroaryl selected from the group consisting of thienyl, pyrrolyl and benzothienyl, and said aryl and said heteroaryl are optionally substituted with one or more groups selected from halogen, nitro, hydroxy and C1-C6Substituent in alkyl; preferably, the aryl group is phenyl.
In a preferred embodiment, each n is independently an integer from 0 to 5.
In a preferred embodiment, each q is independently an integer from 0 to 2.
In a preferred embodiment, the polyolefin has a structure represented by the following formulas (1) to (10):
in another aspect, the present invention provides a process for preparing the flame retardant polyolefin described above, comprising: polymerizing ethylene monomers with corresponding phosphorus-containing ethylene monomers and optionally silicon-containing ethylene monomers and/or boron-containing ethylene monomers in the presence of a palladium phosphine sulfonate catalyst of formula (X),
wherein Me represents methyl, Ph represents phenyl, and DMSO represents dimethyl sulfoxide.
In a preferred embodiment, the polymerization reaction is carried out at a temperature of 20 to 100 ℃ for 1 to 24 hours; preferably, the polymerization reaction is carried out under an inert atmosphere of 6 to 10 atmospheres.
In another aspect, the present invention provides a method for improving the compatibility of a polyolefin with a flame retardant while enhancing the flame retardancy of the polyolefin, the method comprising: adding a compatibility modifier having a structure represented by formula (III) to a blend of a polyolefin, preferably polyethylene or polypropylene, and a flame retardant, preferably selected from one or more of ammonium polyphosphate and pentaerythritol,
wherein the content of the first and second substances,
x is polymerization degree, and x is an integer of 200 to 2000;
y represents a spacer-CH2-and y is an integer from 0 to 12;
R6is selected from C1-C8Alkoxy or hydroxy.
In another aspect, the present invention provides a method for preparing a compatibilizing modifier having the structure represented by formula (III),
the method comprises reacting ethylene monomer with a palladium phosphine sulfonate catalyst having a structure represented by formula (X)2＝CH(CH2)nC(O)R6The monomer (a) is subjected to a polymerization reaction,
wherein Me represents methyl, Ph represents phenyl, DMSO represents dimethyl sulfoxide; and x, y and R6As defined above.
In a preferred embodiment, the polymerization reaction is carried out at a temperature of 20 to 100 ℃ for 1 to 24 hours; preferably, the polymerization reaction is carried out under an inert atmosphere of 6 to 10 atmospheres.
The beneficial effects of the present invention include, but are not limited to, the following aspects:
1. the present invention provides novel flame retardant polyolefin compounds. The Limit Oxygen Index (LOI) value of the flame-retardant polyolefin is higher than the qualified value of 26.0 without adding any compatible modifier, namely the flame-retardant polyolefin has excellent flame-retardant performance and thermal stability.
2. The novel flame-retardant polyolefin can be obtained by carrying out polymerization reaction on an ethylene monomer, a specific phosphorus-containing ethylene monomer and an optional specific silicon-containing ethylene monomer and/or a boron-containing ethylene monomer in the presence of a palladium phosphine sulfonate catalyst, and has the advantages of simple preparation process, relatively warm reaction conditions and high reaction activity; in addition, a large number of flame-retardant polyolefin products with different polar monomer insertion ratios can be obtained by the method of the invention, the number of flame-retardant olefins is greatly enriched and different application requirements are met.
3. The invention provides a novel method for improving the compatibility of polyolefin and a flame retardant and simultaneously enhancing the flame retardance of the polyolefin. Furthermore, by using the compatibility modifier of the present invention, it is possible to achieve the desired flame retardant properties of the polyolefin by adding a significantly smaller amount of flame retardant than conventional, which not only enables cost savings, but also enables the flame retardant properties of the target polyolefin to be improved without compromising other properties of the target polyolefin, such as mechanical properties.
4. The compatibility modifier of the invention can be simply prepared by polymerizing ethylene monomers and specific polar monomers in the presence of a palladium phosphine sulfonate catalyst, and the preparation process is simple.
Drawings
FIG. 1 is a drawing of a flame retardant polyolefin product obtained according to example 1 of the present invention1H NMR spectrum.
FIG. 2 is a drawing of a flame retardant polyolefin product obtained according to example 2 of the present invention1H NMR spectrum.
FIG. 3 is a drawing of a flame retardant polyolefin product obtained according to example 31H NMR spectrum.
FIG. 4 is a flame retardant polyolefin product obtained according to example 4 of the present invention1H NMR spectrum.
FIG. 5 is a flame retardant polyolefin product obtained according to example 5 of the present invention1H NMR spectrum.
FIG. 6 is a flame retardant polyolefin product obtained according to example 6 of the present invention1H NMR spectrum.
Fig. 7(a) is a scanning electron microscope image of a blend of polyethylene and ammonium polyphosphate as a conventional flame retardant, and fig. 7(b) is a scanning electron microscope image of a blended material obtained after the blend of polyethylene and ammonium polyphosphate is added with polyolefin of formula (III) as a flame retardant.
Detailed Description
As a result of extensive and intensive studies by the present inventors, it has unexpectedly been found that a copolymer product polyolefin obtained by (co) polymerizing a vinyl monomer with a polar phosphorus-containing vinyl monomer and optionally a silicon-containing vinyl monomer and/or a boron-containing vinyl monomer itself (i.e., without adding any additional flame retardant) has good flame retardant properties, and thus the present invention provides a novel flame retardant polyolefin.
More specifically, the present invention provides a flame retardant polyolefin having a structure represented by formula (I) or (II) by polymerizing a vinyl monomer with a corresponding phosphorus-containing vinyl monomer and optionally a silicon-containing vinyl monomer and/or a boron-containing vinyl monomer in the presence of a palladium phosphine sulfonate catalyst of formula (X).
In this formula (X), Me represents a methyl group (correspondingly, MeO therein represents a methoxy group), Ph represents a phenyl group, and DMSO represents dimethyl sulfoxide, which forms a complex in the form of a solvate with metal Pd through a coordinate bond.
In the formulae (I) and (II):
the subscript m is the degree of polymerization of the resulting flame retardant polyolefin, and m may be an integer of 200 to 2000, preferably an integer of 200 to 1500.
The subscript n represents the spacer-CH in the parentheses "()"2-and each n independently at each occurrence can be an integer from 0 to 12, preferably from 0 to 5. It is noted herein that when n is 0, it means that the corresponding phosphorus-containing vinyl monomer, silicon-containing vinyl monomer and/or boron-containing vinyl monomer is directly linked to the main chain of the flame retardant polyolefin by a single bond without the above-mentioned spacer.
The subscript q represents the number of ethylene monomer units which may be separated from each other in the polymerization reaction of the phosphorus-containing ethylene unit, the silicon-containing ethylene unit and/or the boron-containing ethylene unit in the structure represented by the formula (I) or (II), and each q is independently an integer of 0 to 10, preferably an integer of 0 to 2, at each occurrence. It is to be noted here that when q is 0, it means that no ethylene monomer spacer unit is present between each of the phosphorus-containing ethylene unit, the silicon-containing ethylene unit and/or the boron-containing ethylene unit, that is, they are adjacent to each other. It is also to be noted herein that, although in the structure represented by the formula (I) or (II), the phosphorus-containing ethylene unit, the silicon-containing ethylene unit, and the boron-containing ethylene unit are shown in order from left to right, respectively, in the case where these three monomer units are present, the order of these monomers in the structure of the resulting flame-retardant polyolefin is not limited thereto, and specifically, the order from left to right in the polyolefin main chain therebetween may be the order of the phosphorus-containing ethylene unit, the silicon-containing ethylene unit, and the boron-containing ethylene unit, or may be the order of the silicon-containing ethylene unit, the phosphorus-containing ethylene unit, and the boron-containing ethylene unit, or the like.
The subscript r represents the number of silicon-containing ethylene units or boron-containing ethylene units in the structure of formula (I) or (II), and each r, at each occurrence, is independently 0 or 1. In other words, in the structure represented by formula (I) or (II), the silicon-containing vinyl monomer unit may or may not be present; likewise, the boron-containing ethylene monomer units may or may not be present.
Radicals R bound to phosphorus or silicon atoms1、R2、R3、R4、R5Each of which may be independently selected from C1-C8Alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or isomeric forms thereof such as isopropyl, tert-butyl, and the like; c2-C8Alkenyl groups such as ethenyl, propenyl, 1-n-butenyl, 1-n-pentenyl, 1-n-hexenyl, 1-n-heptenyl, 1-n-octenyl, or isomeric forms thereof such as 2-n-butenyl, 2-isopentenyl, and the like; c2-C8Alkynyl groups such as ethynyl, propynyl, n-butynyl, n-pentynyl, n-hexynyl and the like or isomeric forms thereof such as isopentynyl and the like; c1-C8Alkoxy such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy or isomeric forms thereof such as isopropoxy, tert-butoxy and the like; c6-C10Aryl radicals, e.g. phenyl, naphthyl or anthracenyl, and they may be unsubstituted, e.g. phenyl, or substituted with one or more groups selected from halogen, Nitro (NO)2) Hydroxyl (OH) and C1-C6Alkyl (e.g., methyl, ethyl, etc.) substituted with substituents that may be ortho, para, and/or meta, such as halophenyl, halonaphthyl, nitrophenyl, hydroxyphenyl (i.e., phenolic), benzyl, naphthylmethyl, etc.; or a heteroaryl group selected from the group consisting of thienyl, pyrrolyl and benzothienyl, which heteroaryl group may be unsubstituted or substituted with one or moreSelected from halogen, nitro, hydroxy and C1-C6The above substituents in the alkyl group. As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
In the present invention, preferably, R1、R2、R3、R4、R5Each independently selected from C1-C8Alkyl radical, C1-C8Alkoxy radical, C6-C10Aryl or heteroaryl selected from the group consisting of thienyl, pyrrolyl and benzothienyl, and said aryl and said heteroaryl are optionally substituted with one or more groups selected from halogen, nitro, hydroxy and C1-C6Substituent in alkyl; more preferably, the aryl group is phenyl.
As used in the present invention, the palladium phosphine sulfonate catalyst of formula (X) may be prepared by reacting the palladium phosphine sulfonate catalyst of formula (X) with a base such as palladium phosphine sulfonate in Na, y.n.; zhang, d.; prepared according to the reaction scheme described in Chen, C.L. modulating the polyolefins Properties through the Incorporation of Nitrogen-Containing Polar monomers.Poly. chem.2017, 8, 2405:
note: wherein "-O-" represents a methoxy group (i.e., MeO) attached to the rest of the molecule through an oxygen atom (O).
In the present invention, preferably, the temperature of the polymerization reaction may be 20 to 100 ℃, for example, about 80 ℃, and the polymerization time may be 1 to 24 hours, for example, 3 to 6 hours; more preferably, the pressure of the reactant ethylene gas is 6 to 10 (e.g., 8) atmospheres in the polymerization reaction. Particularly preferably, the polymerization reaction is carried out in an inert gas atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.
In the present invention, preferably, although not particularly limited, the polymerization reaction may be carried out in an organic solvent such as toluene, benzene, tetrahydrofuran, dichloromethane, or a combination thereof. More preferably, the solvent used is toluene.
Further, as a result of extensive and intensive studies by the present inventors, the present inventors have also unexpectedly found that the flame retardancy of a polyolefin can be enhanced while improving the compatibility of the polyolefin with a flame retardant by adding the polyolefin of a specific structure as a compatibility modifier.
More specifically, the inventors of the present invention have found that the addition or blending of a compatibility modifier having a structure represented by formula (III) improves the compatibility of a polyolefin with a flame retardant while enhancing the flame retardancy to an acceptable level (i.e., a Limit Oxygen Index (LOI) value of 26.0 or higher).
In formula (III):
the subscript x is the degree of polymerization of the polyolefin compound of formula (III) as the compatibility modifier, and x is an integer of 200 to 2000, preferably 200 to 1500.
The subscript y represents the spacer-CH in the parentheses "()"2-and y may be an integer from 0 to 12, preferably an integer from 0 to 5. Here, when y is 0, it represents the lower unit R6C (O) -is directly linked to the main chain of the polyolefin by a single bond, without the presence of the above-mentioned spacer.
Radical R6Can be C1-C8Alkoxy such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy or isomeric forms thereof such as isopropoxy, tert-butoxy and the like; or may be a hydroxyl group (OH). It is to be noted here that when R is6In the case of an alkoxy group, the compatibility modifier is a polyolefin having an ester functionality; when R is6In the case of OH, the compatibility modifier is a polyolefin having carboxylic acid functionality (COOH).
Preferably, the compatibility modifier having the structure represented by formula (III) described above used in the present invention can be prepared by reacting ethylene monomer with a compound of formula CH in the presence of a palladium phosphine sulfonate catalyst having the structure represented by formula (X) described above2＝CH(CH2)nC(O)R6Is carried out byAnd polymerizing to obtain the product.
In the present invention, preferably, similarly to the above-mentioned polymerization reaction, the temperature of the polymerization reaction herein may be 20 to 100 ℃, for example, about 80 ℃, and the polymerization time may be 1 to 24 hours, for example, 3 to 6 hours; more preferably, the pressure of the reactant ethylene gas is 6 to 10 (e.g., 8) atmospheres in the polymerization reaction. Particularly preferably, the polymerization reaction is carried out in an inert gas atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.
In the present invention, preferably, the compatibility modifier of formula (III) is added thereto in an amount of 1 to 5% by weight based on the total mass of the blend of the polyolefin such as polyethylene and the flame retardant such as ammonium polyphosphate to be improved, for example, in an internal mixer, and then the mixture is kneaded uniformly at 190 ℃ at 160 ℃ and then extruded for pelletization, whereby the obtained polyolefin material has not only good compatibility with the flame retardant but also its flame retardant property is significantly improved.
Examples
In order to further illustrate the present invention, the following examples are given to describe the polyethylene having flame retardant properties and the preparation method thereof in detail.
Unless otherwise stated, all the processes of synthesizing the monomer compounds or polymerizing the polyolefin compounds in the present invention are carried out in a closed reaction vessel such as an autoclave under water and oxygen-free conditions; all substances sensitive to water or oxygen are stored in an inert atmosphere glove box; all solvents are rigorously dried to remove water, e.g., dried over anhydrous sodium sulfate or magnesium sulfate; ethylene gas, one of the reaction monomers, was purified by a water-removing oxygen-removing column; in addition, unless otherwise specifically stated, other raw materials or reagents used may be used as they are after purchase or after treatment such as deoxygenation and dehydration as required.
Unless otherwise indicated, the reaction products or intermediate products may be isolated via a silica gel column using 200-300 mesh silica gel; the nuclear magnetism detection is performed by using a Bruker 400MHz nuclear magnetism instrument; the molecular weight and the molecular weight distribution span of the resulting product or intermediate compound (from which the degree of polymerization of the polyolefin can be calculated) were determined by high temperature GPC (using polystyrene as standard, trichlorobenzene as solvent, 150 ℃).
According to the document Cullis, c.f.; flame retardancy of polyolefins obtained as described by Hirschler, M.M. char formation from polyolefms with low-temperature oxygen uptake and with flame reactivity in the presence of metal-halogen systems Eur.Polym.J.1984, 20, 53-60, is evaluated by the Limiting Oxygen Index (LOI) value, which is a measure of the flame retardancy of the polymer in a flame test, and which is the minimum oxygen concentration required for flame combustion of the material in a stream of oxygen and nitrogen mixed gas. Expressed as a volume percentage of oxygen. Among them, the LOI value is qualified above 26.0, the higher the value is, the better the flame retardant performance is, the test method is an expression method for evaluating the relative combustibility of plastics and other high molecular materials, because it is very effective to judge the difficulty of the combustion of the materials when the materials are contacted with flame in the air, and therefore the test method is regarded by all countries in the world, wherein the national standard of the corresponding oxygen index law issued by China can be referred to GB2406-80 (plastics) and GB5454-85 (textiles).
Preparation of the catalyst of formula (X):
the preparation was carried out according to the preparation methods mentioned in the aforementioned documents: two equivalents of n-butyllithium (n-BuLi) were added to a tetrahydrofuran solution in which benzenesulfonic acid was dissolved at 0 ℃ under nitrogen protection and reacted for 1 hour, and then one equivalent of chloro (2 ', 6 ' -dimethoxy- [1, 1 ' -biphenyl ] -2-yl) (phenyl) phosphine was added to the reaction system and reacted for 24 hours. Thereafter, the solvent was dried under reduced pressure and dissolved by adding a small amount of methylene chloride, and then the reaction mixture was immediately poured into a large amount of anhydrous ether and purified and isolated by, for example, chromatography (silica gel column separation) to give an intermediate ligand product. Next, the intermediate ligand product is dissolved in tetrahydrofuran solvent and left at 0 ℃ for standing, tetramethylethylenediamine dimethylpalladium chloride (TMEDAPdMeCl) precursor is added to the obtained solution and stirred overnight, then the precipitate is filtered out of the solution and washed with anhydrous ether for a plurality of times, after drying, it is dissolved in dimethyl sulfoxide (DMSO) solvent and stirred for 5min, and finally the dimethyl sulfoxide solvent is drained, thereby obtaining the desired target product, namely the palladium phosphine sulfonate catalyst of formula (X).
Preparation of flame retardant polyolefin:
example 1: copolymerization of vinyl monomer with allyl diethyl phosphite monomer (phosphorus-containing monomer P1, where n is 1) to prepare flame retardant polyolefin (i.e., a compound of formula (1) where q is 0 and r is 0)
Preparation of allyl diethyl phosphite monomer (P1): diethyl phosphite (60mmol, 8.28g) allyl chloride (70mmol, 7.35g) and sodium carbonate (100mmol, 10.5g) were poured into a round bottom flask containing 100ml tetrahydrofuran and heated in a water bath to 50 ℃ for reaction for 24 hours. After the reaction was complete, the solvent tetrahydrofuran was dried by rotary evaporator and distilled under reduced pressure twice (70 ℃ C., 50mm Hg) to give the desired product P1(52mmol, 9.25 g).
Preparation of flame retardant polyolefin product: in a glove box, 18mL of toluene and 3.56g of allyl diethyl phosphite monomer were added to a 350mL autoclave (equipped with air and liquid inlet ports, magnetic stirring, oil bath heating, and thermometer) under a nitrogen atmosphere. After the closure, the autoclave was connected to a high-pressure line via a gas inlet and the pipe was evacuated, and then the reaction system was heated to 80 ℃ using an oil bath and kept warm for 15 minutes. Thereafter, a solution of palladium phosphine sulfonate catalyst of formula (X) (18mg) dissolved in 2ml of dichloromethane (dichloromethane was used to better dissolve the catalyst) was injected into the reaction mixture by syringe via the inlet port, which was closed after the injection was completed. Then, the gas source was switched, ethylene gas was introduced through the gas inlet until the pressure of ethylene gas was 8 atm, and the reaction was maintained for 3 hours. The reaction was stopped, the reaction vessel was opened after cooling, 50ml of ethanol was added thereto, a precipitate was obtained by filtration under reduced pressure, and it was dried in a vacuum oven (60 ℃ C.) to obtain a white solid (7.8 g).
FIG. 1 is a drawing of a flame retardant polyolefin product obtained according to example 11H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
For the obtained flame-retardant polyolefin, the molecular weight was 12000 and the molecular weight distribution span was 3.6 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 428 as calculated; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 2: copolymerization of ethylene monomer with diethyl hexyl-5-ene-1-phosphonate monomer (phosphorus containing monomer P2, where n is 4) to prepare a flame retardant polyolefin (i.e., a compound of formula (2) where q is 0 and r is 0)
Preparation of diethyl hexyl-5-en-1-phosphonate monomer (P2): the procedure was the same as that for the preparation of the P1 monomer of example 1, except that allyl chloride was changed to 6-chloro-1-hexene.
Preparation of flame retardant polyolefin product: the same procedures used in example 1 were repeated except for using 4.4g of diethyl hexyl-5-en-1-phosphonate monomer in place of diethyl allylphosphite monomer to give a white solid product (9.6 g).
FIG. 2 is a drawing of a flame retardant polyolefin product obtained according to example 21H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
For the obtained flame-retardant polyolefin, the molecular weight measured by high-temperature GPC was 36900 and the molecular weight distribution span was 2.5, and based on the result, the polymerization degree m of the obtained polyolefin was 1317 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 3: copolymerization of ethylene monomer with (diethoxyphosphine) methyl methacrylate monomer (phosphorus-containing monomer P3) to prepare flame-retardant polyolefin (i.e., compound of formula (3) wherein q is 0 and r is 0)
Preparation of methyl (diethoxyphosphorus) methacrylate monomer (P3): diethyl phosphite (60mmol, 8.28g) and paraformaldehyde (60mmol, 5.4g) were poured into a round-bottomed flask containing 60mL of ethanol and reacted under reflux for 12h, then the solvent ethanol was dried by a rotary evaporator and the product was dissolved with addition of velvet tetrahydrofuran, then triethylamine (100mmol, 10.1g) and acryloyl chloride (100mmol, 9.1g) were added and reacted at normal temperature for 12h, and then the by-product triethylamine hydrochloride formed therefrom was filtered and distilled under reduced pressure (120 ℃, 50mm Hg) to obtain the desired product P3.
Preparation of flame retardant polyolefin product: the preparation process was the same as in example 1 except that 4.44g of methyl (diethoxyphosphorus) methacrylate monomer was used instead of allyldiethyl phosphite monomer, to give a white solid product (6.1 g).
FIG. 3 is a drawing of a flame retardant polyolefin product obtained according to example 31H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
With respect to the obtained flame-retardant polyolefin, the molecular weight was 10300 and the molecular weight distribution span was 2.7 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 367 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 4: copolymerization of ethylene monomer with allyl diethyl phosphite monomer (phosphorus-containing monomer P1, where n is 1) and vinyltrimethoxysilane monomer (silicon-containing monomer Si1, where n is 0) to prepare a flame retardant polyolefin (i.e., a compound of formula (4), where q is 2 and r is 1)
Monomer P1 was prepared as described in example 1, while vinyltrimethoxysilane monomer (Si1) was purchased from Annaiji chemical company.
Preparation of flame retardant polyolefin product: the preparation process was the same as in example 1 except that two monomers, 3.56g of allyl diethyl phosphite and 3g of vinyltrimethoxysilane, were used instead of the allyl diethyl phosphite monomer, to obtain a white solid product (4.2 g).
FIG. 4 is a drawing of a flame retardant polyolefin product obtained according to example 41H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
For the obtained flame-retardant polyolefin, the molecular weight was 10100 and the molecular weight distribution span was 3.2 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 360 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 5: copolymerization of ethylene monomer with diethyl hexyl-5-ene-1-phosphonate monomer (phosphorus containing monomer P2 where n is 4) and vinyltrimethoxysilane monomer (silicon containing monomer Si1 where n is 0) to prepare a flame retardant polyolefin (i.e., a compound of formula (5) where q is 2 and r is 1)
Monomer P2 was prepared as described in example 2, while monomer Si1 was purchased from Annaige chemical Co.
Preparation of flame retardant polyolefin product: the same procedures used in example 1 were repeated except for using two monomers, 4.4g of diethyl hexyl-5-en-1-phosphonate and 3g of vinyltrimethoxysilane, in place of the allylic diethyl phosphite monomer to give a white solid product (6.2 g).
FIG. 5 is a drawing of a flame retardant polyolefin product according to example 51H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
For the obtained flame-retardant polyolefin, the molecular weight measured by high-temperature GPC was 15500 and the molecular weight distribution span was 5.3, and based on the result, the polymerization degree m of the obtained polyolefin was 553 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 6: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and vinyltrimethoxysilane monomer (silicon-containing monomer Si1, where n is 0) to prepare a flame retardant polyolefin (i.e., a compound of formula (6) where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3, while monomer Si1 was purchased from anigium chemicals.
Preparation of flame retardant polyolefin product: the preparation process was the same as in example 1 except that two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 3g of vinyltrimethoxysilane, were used instead of the allyldiethyl phosphite monomer, to give a white solid product (1.7 g).
FIG. 6 is a drawing of a flame retardant polyolefin product obtained according to example 61H NMR spectrum, wherein the solvent used is 1, 1, 2, 2-tetrachloroethane, and the detection temperature is 120 ℃.
For the obtained flame-retardant polyolefin, the molecular weight was 8900 and the molecular weight distribution span was 3.7 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 317 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 7: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and B- (5-hexenyl) -9-boronic acid cyclo [3.3.1] nonane monomer (boron-containing monomer B1, where n is 4) to prepare flame retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3.
Preparation of B- (5-hexenyl) -9-boronic acid cyclo [3.3.1] nonane monomer (B1): 9-bbn (100mmol, 12.2g) was dissolved in 100Ml tetrahydrofuran, followed by dropwise addition of methanol (100mmol, 3.2g) for 12 hours. Then 6-chloro-1-hexene is prepared into a Grignard reagent and added into the system to react for 12 hours, and then the solvent is pumped to obtain the product.
Preparation of flame retardant polyolefin product: the procedure was carried out in the same manner as in example 1 except for using two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 4.1g B- (5-hexenyl) -9-boronic acid cyclo [3.3.1] nonane, in place of the allyldiethyl phosphite monomer, to obtain a white solid product (1.4 g).
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 15800 and the molecular weight distribution span was 4.4 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 289 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 8: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3), B- (5-hexenyl) -9-boronic acid cyclo [3.3.1] nonane monomer (boron-containing monomer BI, where n is 4) and vinyltrimethoxysilane monomer (silicon-containing monomer Si1, where n is 0) to prepare flame retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3; monomer B1 was prepared as described in example 7; and monomer Si1 was purchased from annaigi chemical company.
Preparation of flame retardant polyolefin product: the procedure was carried out in the same manner as in example 1 except for using three monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate, 4.1g B- (5-hexenyl) -9-boronic acid cyclo [3.3.1] nonane and 3g of vinyltrimethoxysilane, in place of the allyldiethyl phosphite monomer to obtain a product (0.4g) as a white solid.
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 9100 and the molecular weight distribution span was 6.2 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 325 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 9: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and trimethyl (vinyl) silane monomer (silicon-containing monomer Si2, where n is 0) to prepare flame retardant polyolefin (where q is 1 and r is 1)
Monomer P3 was prepared as described in example 3, while trimethyl (vinyl) silane monomer (Si2) was purchased from bailingwei chemicals.
Preparation of flame retardant polyolefin product: the preparation process was the same as in example 1 except for using two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 2g of trimethyl (vinyl) silane, in place of the allyldiethyl phosphite monomer, to obtain a white solid product (0.8 g).
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 8300 and the molecular weight distribution span was 3.2 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 298 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 10: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and Dimethyldiethylvinylsilane monomer (silicon-containing monomer Si3, where n is 0) to prepare flame retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3, while dimethyldivinylsilane monomer (Si3) was purchased from Shanghai Aladdin Biotech Ltd.
Preparation of flame retardant polyolefin product: the same procedures used in example 1 were repeated except for using 4.44g of methyl (diethoxyphosphorus) methacrylate and 2.2g of dimethyldivinylsilane as monomers in place of the allyldiethyl phosphite monomer to obtain a white solid product (0.07 g).
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 8000 and the molecular weight distribution span was 3.1 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 288 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 11: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and triphenylvinylsilane monomer (silicon-containing monomer Si4, where n is 0) to prepare flame-retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3, while triphenylvinylsilane monomer (Si4) was purchased from Annaige chemical Co.
Preparation of flame retardant polyolefin product: the preparation process was the same as in example 1 except for using two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 5.8g of triphenylvinylsilane, instead of the allyldiethyl phosphite monomer, to obtain a product (0.06g) as a white solid.
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight measured by high-temperature GPC was 7100 and the molecular weight distribution span was 6.2, and based on the result, the polymerization degree m of the obtained polyolefin was 254 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 12: copolymerization of vinyl monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and 1, 1' - (vinylsilyl) tripyrrole monomer (silicon-containing monomer Si5, where n is 0) to prepare flame retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3.
Preparation of 1, 1', 1 ″ - (vinylsilyl) trispyrrole monomer (Si 5): triazolylchlorosilane (10mmol, 3g) was dissolved in 100Ml tetrahydrofuran and then allylmagnesium chloride (10mmol) was added for 12h and distilled under reduced pressure (100 ℃ C., 50mm Hg) to give the desired product, monomer Si 5.
Preparation of flame retardant polyolefin product: the same procedures used in example 1 were repeated except for using two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 5.0g of 1, 1' - (vinylsilyl) tripyrrole, in place of the allylic diethyl phosphite monomer to obtain a product (0.02g) as a white solid.
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 6020 and the molecular weight distribution span was 5.4 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 215 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Example 13: copolymerization of ethylene monomer with methyl (diethoxyphosphorus) methacrylate monomer (phosphorus-containing monomer P3) and tris (benzo [ b ] thiophen-2-yl) (vinyl) silane monomer (silicon-containing monomer Si6, where n is 0) to prepare flame retardant polyolefin (where q is 2 and r is 1)
Monomer P3 was prepared as described in example 3.
Preparation of tris (benzo [ b ] thiophen-2-yl) (vinyl) silane monomer (Si 6): the procedure is as for the preparation of the monomer Si5 in example 12, except that the tripyrrolylchlorosilane is replaced by a triphenothienylchlorosilane.
Preparation of flame retardant polyolefin product: the same procedures used in example 1 were repeated except for using two monomers, 4.44g of methyl (diethoxyphosphorus) methacrylate and 9.0g of tris (benzo [ b ] thiophen-2-yl) (vinyl) silane, in place of the allyl diethyl phosphite monomer to give a white solid product (0.01 g).
Of the resulting flame-retardant polyolefin product1The H NMR spectrum is not shown; for the obtained flame-retardant polyolefin, the molecular weight was 6300 and the molecular weight distribution span was 3.2 as measured by high-temperature GPC, and based on the result, the polymerization degree m of the obtained polyolefin was 226 by calculation; the results of the flame retardant properties (LOI values) measured at the same time are shown in Table 1.
Table 1: flame retardant performance results of the resulting flame retardant polyolefins
| Example numbering | Limiting oxygen index value (%) |
| 1 | 27.0 |
| 2 | 26.5 |
| 3 | 28.0 |
| 4 | 28.5 |
| 5 | 28 |
| 6 | 29.5 |
| 7 | 28.5 |
| 8 | 29.0 |
| 9 | 28.5 |
| 10 | 28.5 |
| 11 | 30.5 |
| 12 | 32.5 |
| 13 | 29.0 |
As can be seen from the results in table 1, the polyolefin obtained by the present invention has good flame retardant properties by itself, so that in use, no additional flame retardant needs to be added, thereby ensuring that other properties of the polyolefin material, such as mechanical properties and the like, are not deteriorated.
In addition, the compounds of the formulae (7) to (10) according to the invention can also be synthesized correspondingly in a similar manner to that described above.
Example 14: preparation of the compatibility modifier of the formula (III)
Vinyl monomer and methyl undecylenate monomer (i.e., in the compound of formula (III), y is 9, R6Methoxy) copolymerization to prepare polyolefin compatibility modifiers of formula (III)
In a glove box, 18mL of toluene and 4.0g of methyl undecylenate monomer were added to a 350mL autoclave (equipped with gas and liquid inlet ports, magnetic stirring device, oil bath heating device and thermometer) under a nitrogen atmosphere. After the closure, the autoclave was connected to a high-pressure line via an air inlet and the pipe was evacuated, and then the reaction system was heated to 80 ℃ using an oil bath and kept warm for 15 minutes. Thereafter, a solution of the palladium phosphine sulfonate catalyst of formula (X) (18mg) dissolved in 2ml of dichloromethane was injected into the reaction mixture through a syringe via a liquid inlet hole, which was closed after completion of the injection. Then, the gas source was switched, ethylene gas was introduced through the gas inlet until the pressure of ethylene gas was 8 atm, and the reaction was maintained for 3 hours. The reaction was stopped, the reaction vessel was opened after cooling, 50ml of ethanol was added thereto, a precipitate was obtained by filtration under reduced pressure, and it was dried in a vacuum oven (60 ℃ C.) to obtain a white solid (11.2 g). For nuclear magnetic data of this compound, see literature: na, y.n.; dai, s.y.; chen, C.L. Direct Synthesis of Polar-Functionalized Linear Low-Density Polyethylene (LLDPE) and Low-Density Polyethylene (LDPE). Macromolecules2018, 51, 4040-.
With respect to the resultant polyolefin compatibility modifier, the molecular weight was 107000 and the molecular weight distribution span was 2.2 as measured by high temperature GPC, and based on the result, the polymerization degree x of the resultant polyolefin was 3821 as calculated.
Example 15: preparation of conventional polyolefins
In a glove box, 48mL of toluene was added under nitrogen to a 350mL autoclave (equipped with air and liquid inlet ports, magnetic stirring, oil bath heating, and thermometer). After the closure, the autoclave was connected to a high-pressure line via an air inlet and the pipe was evacuated, and then the reaction system was heated to 80 ℃ using an oil bath and kept warm for 15 minutes. Thereafter, a solution of the palladium phosphine sulfonate catalyst of formula (X) (12mg) dissolved in 2ml of dichloromethane was injected into the reaction mixture through a syringe via a liquid inlet hole, which was closed after completion of the injection. Then, the gas source was switched, ethylene gas was introduced through the gas inlet until the pressure of ethylene gas was 8 atm, and the reaction was maintained for 3 hours. The reaction was stopped, the reaction vessel was opened after cooling, 50ml of ethanol was added thereto, a precipitate was obtained by filtration under reduced pressure, and it was dried in a vacuum oven (60 ℃ C.) to obtain a white solid (24.0 g).
With respect to the obtained flame-retardant polyolefin, the molecular weight was 388000 as measured by high-temperature GPC and the molecular weight distribution span was 2.1, and based on the result, the polymerization degree of the obtained polyolefin was 1385 by calculation.
Use of a compatibility modifier of formula (III):
application example 1: improving the compatibility of polyolefin and flame retardant and its flame retardancy
1 part of the compatibility modifier prepared in example 14 was added to 99 parts by mass of a flame-retardant polyolefin blend (obtained by mixing 75 parts by mass of the polyethylene obtained in example 15 with 25 parts by mass of ammonium polyphosphate as a flame retardant, which is commercially available from Jinquan chemical company of Jinan and whose flame retardant property results are shown in Table 2 below) in an internal mixer, and the mixture was uniformly stirred at 180 ℃ and then extruded and pelletized to obtain a modified flame-retardant polyolefin blend.
FIG. 4(a) is a scanning electron micrograph of a flame retardant polyolefin blend prior to the addition of no compatibilizing modifier of the invention, and FIG. 4(b) is a scanning electron micrograph of a flame retardant polyolefin blend after the addition of a compatibilizing modifier of the invention. As can be seen from fig. 4(a), before the addition, the compatibility of polyethylene and ammonium polyphosphate is poor, and a significant phase separation phenomenon exists; as can be seen from fig. 4(b), the compatibility between polyethylene and ammonium polyphosphate is greatly improved after the compatibility modifier of the present invention is added.
For the obtained modified flame retardant polyolefin blend, the measured flame retardant performance test results are shown in table 2 below.
Application example 2: improving the compatibility of polyolefin and flame retardant and its flame retardancy
To 99 parts by mass of a flame-retardant polyolefin blend (obtained by mixing 75 parts by mass of the polyethylene obtained in example 15 with 18 parts by mass of ammonium polyphosphate and 7 parts by mass of pentaerythritol as flame retardants, wherein ammonium polyphosphate is available from Jinquan chemical industry of Jinan and pentaerythritol is available from national chemical Co., Ltd.) was added 1 part of the polyolefin compatibility modifier prepared in example 14 in an internal mixer, and after stirring uniformly at 180 ℃, extrusion granulation was carried out to obtain a modified flame-retardant polyolefin blend.
The result observed by a scanning electron microscope (not shown) is the same as that of application example 1, namely, after the compatibility modifier of the invention is added, the compatibility of polyethylene with ammonium polyphosphate and pentaerythritol is greatly improved; in addition, the results of the measured flame retardant properties are shown in Table 2 below.
Application example 3: improving the compatibility of polyolefin and flame retardant and its flame retardancy
To 97 parts by mass of an existing flame-retardant polyolefin blend (obtained by mixing 75 parts by mass of the polyethylene obtained in example 15 with 18 parts by mass of ammonium polyphosphate obtained from Jinquan chemical engineering, pentaerythritol obtained from national chemical Co., Ltd.) and 7 parts by mass of pentaerythritol obtained from example 15, 3 parts by mass of the polyolefin compatibility modifier prepared in example 14 was added in an internal mixer, and after stirring uniformly at 180 ℃, extrusion granulation was carried out to obtain a modified flame-retardant polyolefin blend.
The result observed by a scanning electron microscope (not shown) is the same as that of application example 1, namely, after the compatibility modifier of the invention is added, the compatibility of polyethylene with ammonium polyphosphate and pentaerythritol is greatly improved; in addition, the results of the measured flame retardant properties are shown in Table 2 below.
TABLE 2
It can be seen from the results in table 2 that, after the compatibility modifier of the present invention is added, not only the compatibility of the polyolefin with the conventional flame retardant is greatly improved, but also the flame retardancy of the flame retardant polyolefin obtained by using the conventional flame retardant is greatly improved, and both the compatibility modifier and the flame retardant polyolefin can reach acceptable or even good levels.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A flame retardant polyolefin having a structure according to formula (I) or (II):
wherein the content of the first and second substances,
m is a polymerization degree, and m is an integer of 200 to 2000;
n represents a spacer-CH2-and each n is independently an integer from 0 to 12;
q represents the number of ethylene units spaced among each of the phosphorus-containing ethylene unit, the silicon-containing ethylene unit and the boron-containing ethylene unit in the structure represented by the formula (I) or (II), and each q is independently an integer of 0 to 10;
r represents the number of silicon-containing ethylene units or boron-containing ethylene units in the structure represented by formula (I) or (II), and each r is independently 0 or 1;
R1、R2、R3、R4、R5independently selected from C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C1-C8Alkoxy radical, C6-C10Aryl or heteroaryl selected from the group consisting of thienyl, pyrrolyl and benzothienyl, and said aryl and said heteroaryl are optionally substituted with one or more groups selected from halogen, nitro, hydroxy and C1-C6Substituents in the alkyl group.
2. Flame retardant polyolefin according to claim 1, wherein R is1、R2、R3、R4、R5Independently selected from C1-C8Alkyl radical, C1-C8Alkoxy radical, C6-C10Aryl or heteroaryl selected from the group consisting of thienyl, pyrrolyl and benzothienyl, and said aryl and said heteroaryl are optionally substituted with one or more groups selected from halogen, nitro, hydroxy and C1-C6Substituents in the alkyl group.
3. Flame retardant polyolefin according to claim 2, wherein the aryl group is a phenyl group.
4. The flame retardant polyolefin of claim 1, wherein each n is independently an integer from 0 to 5.
5. The flame retardant polyolefin of claim 1, wherein each q is independently an integer from 0 to 2.
6. The flame-retardant polyolefin according to claim 1, wherein the flame-retardant polyolefin has a structure represented by the following formulas (1) to (10):
7. a process for preparing the flame retardant polyolefin according to any one of claims 1-6, the process comprising: polymerizing ethylene monomers with corresponding phosphorus-containing ethylene monomers and optionally silicon-containing ethylene monomers and/or boron-containing ethylene monomers in the presence of a palladium phosphine sulfonate catalyst of formula (X),
wherein Me represents methyl, Ph represents phenyl, and DMSO represents dimethyl sulfoxide.
8. The method according to claim 7, wherein the polymerization reaction is carried out at a temperature of 20 to 100 ℃ for 1 to 24 hours.
9. The method according to claim 7, wherein the polymerization is carried out under an inert atmosphere of 6 to 10 atm.
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