CN107973879B - Copolymer, preparation method and application thereof, and nylon composition - Google Patents

Copolymer, preparation method and application thereof, and nylon composition Download PDF

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CN107973879B
CN107973879B CN201610939329.3A CN201610939329A CN107973879B CN 107973879 B CN107973879 B CN 107973879B CN 201610939329 A CN201610939329 A CN 201610939329A CN 107973879 B CN107973879 B CN 107973879B
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phosphate
caprolactam
monomer
copolymer
caprolactam copolymer
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CN107973879A (en
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计文希
殷建军
祝桂香
许宁
张龙贵
李娟�
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention relates to the field of polymer chemistry, and discloses a copolymer, a preparation method and application thereof, and a nylon composition. The copolymer comprises a phosphate structural unit shown as a formula (1) and a caprolactam structural unit shown as a formula (2), R1Is hydrogen or C1‑C5Straight or branched alkyl of R2And R3Each independently is C6‑C10Aryl or C1‑C5Straight or branched alkyl of R4Is hydrogen or C1‑C5Linear or branched alkyl. After the copolymer is fully mixed with nylon, the mixed nylon composition has better flame retardant property and mechanical property.

Description

Copolymer, preparation method and application thereof, and nylon composition
Technical Field
The invention relates to the field of polymer chemistry, in particular to a copolymer, a preparation method and application thereof and a nylon composition.
Background
Over the past 20 years, the development of consumer electronics has driven the development of the entire flame retardant engineering plastic industry. A large amount of engineering plastics, particularly flame retardant engineering plastics, are used in consumer electronics, and the main application fields of the engineering plastics are concentrated in the electronic and electrical industry, such as various connectors, switches, coil boxes, electric power communication equipment, electric tool shells and the like.
The flame retardant is widely applied to daily life of people, and plays an important role in the process of striving for valuable life saving time in disastrous events such as fire and the like. Currently, the consumption of flame retardants worldwide has only second place of plasticizers.
The flame retardants are classified into phosphorus-based, chlorine-based, bromine-based, antimony-based, aluminum-based, and boron-based flame retardants, and the like, according to the effective elements. Chlorine flame retardants and bromine flame retardants generate a large amount of toxic gases due to combustion, which causes serious environmental damage and is prone to secondary disasters. Inorganic flame retardants such as antimony-based, aluminum-based and boron-based flame retardants have low flame retardant efficiency, and usually a large amount of inorganic flame retardants need to be added to achieve a good flame retardant effect, but the existence of a large amount of inorganic flame retardants will seriously affect the mechanical properties of the material. With the continuous improvement of living standard of people, the flame retardant is determined to be developed towards the direction of environmental protection and high efficiency.
Therefore, two commands, namely WEEE and RoHs, issued by the European Union strictly limit the components of the flame retardant, China also starts to report the national standard of the combustion performance grade of building materials and products, wherein the halogen-free flame retardant material becomes the main development direction of the flame retardant.
Disclosure of Invention
The invention aims to provide a novel phosphate-caprolactam copolymer, a preparation method and application thereof and a nylon composition.
In order to achieve the above object, in a first aspect, the present invention provides a phosphate ester-caprolactam copolymer, wherein the phosphate ester-caprolactam copolymer comprises a phosphate ester structural unit represented by formula (1) and a caprolactam structural unit represented by formula (2);
Figure BDA0001138912880000021
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
In a second aspect, the present invention provides a method for preparing a phosphate-caprolactam copolymer, wherein the method comprises: in the presence of a solvent and an initiator, carrying out contact reaction on a first monomer shown as a formula (3) and a second monomer shown as a formula (4);
Figure BDA0001138912880000031
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
In a third aspect, the present invention provides a phosphate-caprolactam copolymer prepared by the above-described process.
In a fourth aspect, the present invention provides the use of the phosphate-caprolactam copolymer of the present invention as a flame retardant.
In a fifth aspect, the invention provides a nylon composition, which contains nylon and a flame retardant, wherein the flame retardant is the phosphate ester-caprolactam copolymer.
The phosphate ester-caprolactam copolymer provided by the invention has the following advantages:
(1) the halogen is not contained, and the environment modeling is not damaged after the combustion;
(2) the phosphate ester-caprolactam copolymer has a caprolactam structure, and the structure can ensure that the flame retardant is fully mixed with the nylon, so that the mechanical property of the mixed nylon composition is not reduced or even increased;
(3) the flame retardance can reach V-0 grade by adding a small amount of the phosphate ester-caprolactam copolymer into the nylon composition, and the flame retardance efficiency is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a phosphate ester-caprolactam copolymer, wherein the phosphate ester-caprolactam copolymer comprises a phosphate ester structural unit represented by formula (1) and a caprolactam structural unit represented by formula (2);
Figure BDA0001138912880000041
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
According to the invention, in the phosphate-caprolactam copolymer, the phosphate structural unitThe caprolactam structural unit can fully mix the phosphate-caprolactam copolymer and the nylon, so that the mechanical property of the mixed nylon composition is not reduced or even increased. Preferably, R1Is hydrogen or C1-C3Linear alkyl radical of (2), R2And R3Each independently is C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C3Linear alkyl group of (1). More preferably, R1Hydrogen or methyl, preferably hydrogen; r2And R3Each independently is methyl or ethyl, preferably methyl; r4Is hydrogen or methyl.
The content of the phosphate ester structural unit and the caprolactam structural unit in the phosphate ester-caprolactam copolymer is not particularly limited, and the molar ratio of the phosphate ester structural unit to the caprolactam structural unit is preferably 0.01 to 100: 1, more preferably 0.1 to 10: 1, most preferably 0.2 to 5: 1.
the phosphate-caprolactam copolymer may further include a structural unit derived from a third monomer selected from at least one of an acrylate-based compound, a monovinyl aromatic compound, and an acrylamide-based compound, the acrylate-based compound may be one or more of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methyl methacrylate, 2-ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl methacrylate, dimethylaminoethyl methacrylate, and dodecyl methacrylate, the monovinyl aromatic compound may be one or more of styrene, vinyl toluene, 4-tert-butyl styrene, 4-methyl styrene, α -methyl styrene, and divinylbenzene, and the acrylamide-based compound may be one or more of methyl acrylamide, N-isopropyl acrylamide, N-methyl acrylamide, N-dimethyl acrylamide, and 2-acrylamide-2-methyl propanesulfonic acid, in order to reduce costs and increase processability and compatibility of the phosphate-caprolactam copolymer.
The content of the structural unit derived from the third monomer is not particularly limited in the present invention, and it is preferable that the molar ratio of the structural unit derived from the third monomer to the caprolactam structural unit is from 0.01 to 5: 1, more preferably 0.2 to 3: 1, most preferably 0.5-2: 1.
the molecular weight of the phosphate-caprolactam copolymer is not particularly limited in the present invention, but in order to improve the compatibility of the phosphate-caprolactam copolymer with nylon in subsequent applications, the number average molecular weight of the phosphate-caprolactam copolymer is preferably 300-.
In the present invention, the phosphate-caprolactam copolymer may be a random copolymer, a block copolymer, a graft copolymer or an alternating copolymer, and is preferably a random copolymer.
In a second aspect, the present invention provides a method for preparing a phosphate-caprolactam copolymer, wherein the method comprises: in the presence of a solvent and an initiator, carrying out contact reaction on a first monomer shown as a formula (3) and a second monomer shown as a formula (4);
Figure BDA0001138912880000061
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
In the invention, the first monomer can fully achieve the flame retardant effect in the obtained phosphate ester-caprolactam copolymer, and the second monomer can fully mix the obtained phosphate ester-caprolactam copolymer with nylon, so that the mechanical property of the mixed nylon composition is not reduced or even increased. Preferably, R1Is hydrogen or C1-C3Linear alkyl radical of (2), R2And R3Each independently is C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C3Linear alkyl group of (1). More preferably, R1Hydrogen or methyl, preferably hydrogen; r2And R3Each independently is methyl or ethyl, preferably methyl; r4Is hydrogen or methyl.
The amount of the first monomer and the second monomer used in the present invention is not particularly limited as long as a phosphate ester-caprolactam copolymer can be obtained. However, in order to reduce the cost and obtain a phosphate-caprolactam copolymer with higher flame retardancy, it is preferable that the molar ratio of the amount of the first monomer to the amount of the second monomer is 0.01 to 100: 1, preferably 0.1 to 10: 1, most preferably 0.2 to 5: 1.
in the present invention, in order to reduce the cost and increase the processability and compatibility of the obtained phosphate-caprolactam copolymer, it is preferable that the method further comprises adding a third monomer selected from at least one of acrylate compounds, monovinyl aromatic compounds and acrylamide compounds to the reaction system during the contact reaction, so that the obtained phosphate-caprolactam copolymer further comprises structural units derived from the third monomer, wherein the acrylate compounds can be one or more of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methyl methacrylate, 2-ethyl methacrylate, butyl acrylate, butyl methacrylate, octyl methacrylate, dimethylaminoethyl methacrylate and dodecyl methacrylate, the monovinyl aromatic compounds can be one or more of styrene, vinyl toluene, 4-tert-butyl styrene, 4-methyl styrene, α -methyl styrene and divinylbenzene, and the acrylamide compounds can be one or more of methacrylamide, acrylamide, N-isopropylacrylamide, N-dimethyl acrylamide, N-dimethyl acrylamide and 2-methyl acrylamide.
In the present invention, the amount of the third monomer is not particularly limited, and preferably, the molar ratio of the amount of the third monomer to the amount of the second monomer is 0.01 to 5: 1, more preferably 0.2 to 3: 1, most preferably 0.5-2: 1.
in the present invention, the amount of the solvent to be used is not particularly limited as long as the reaction raw material can be sufficiently dissolved. Preferably, the weight ratio of the amount of the solvent to the total amount of the monomers is 0.1 to 10: 1, preferably 2 to 10: 1.
the kind of the solvent is not particularly limited in the present invention, and may be conventionally selected in the art, for example, the solvent may be at least one of dioxane, tetrahydrofuran, acetone, and toluene.
In the present invention, the amount of the initiator is not particularly limited as long as the contact reaction can be smoothly performed. Preferably, the weight ratio of the amount of the initiator to the total amount of the monomers is 0.0005 to 0.05: 1, preferably 0.001 to 0.03: 1.
the kind of the initiator is not particularly limited in the present invention, and may be conventionally selected in the art, and preferably, the initiator is a radical polymerization initiator, and specifically may be at least one of Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN), potassium persulfate, and ammonium persulfate.
The conditions for the contact reaction are not particularly limited in the present invention, and may be conventionally selected in the art. Preferably, the conditions of the contact reaction include: the temperature is 60-120 ℃, preferably 80-100 ℃; the time is 2 to 12 hours, preferably 6 to 10 hours.
In the present invention, in order to improve the reaction efficiency of the contact reaction and reduce the generation of by-products, the method may preferably further include: prior to the contact reaction, the system is deoxygenated. The method of removing oxygen in the present invention is not particularly limited, and may be a method of removing oxygen that is conventional in the art, for example, the method of removing oxygen is: charging nitrogen gas into the system for 20-50 min.
In the present invention, in order to reduce the production cost of the phosphate-caprolactam copolymer, it is preferable that the method further comprises recovering the unreacted monomer in the reaction solution after the completion of the contact reaction. The specific recovery process can be performed by methods conventional in the art, and those skilled in the art are aware of this and will not be described herein.
In a third aspect, the present invention also provides a phosphate-caprolactam copolymer prepared by the above method. The phosphate ester-caprolactam copolymer does not contain halogen, and does not harm the environment after combustion.
In a fourth aspect, the present invention provides the use of the phosphate-caprolactam copolymer as a flame retardant. The phosphate structure in the phosphate-caprolactam copolymer can ensure that the phosphate-caprolactam copolymer achieves the effect of full flame retardance.
In a fifth aspect, the invention further provides a nylon composition, which contains nylon and a flame retardant, wherein the flame retardant is the phosphate ester-caprolactam copolymer.
The phosphate ester-caprolactam copolymer has a caprolactam structure, so that the flame retardant and the nylon can be fully mixed by the structure, and the effect of chain extension and viscosity increase is achieved, so that the mechanical property of the nylon is not reduced but increased to a certain extent.
The content of the flame retardant in the nylon composition is not particularly limited in the present invention, and may be conventionally selected in the art. Since the phosphate-caprolactam copolymer and the nylon can be sufficiently mixed, the nylon composition can have high flame retardancy by adding a small amount of the phosphate-caprolactam copolymer to the nylon composition. Therefore, the flame retardant is preferably contained in an amount of 0.1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and most preferably 10 to 15 parts by weight, based on 100 parts by weight of the total weight of the nylon composition.
Preferably, the nylon composition of the present invention may further comprise an antioxidant, and the content of the antioxidant may be conventionally selected in the art, for example, the antioxidant may be contained in an amount of 0.05 to 0.5 parts by weight, preferably 0.1 to 0.2 parts by weight, based on 100 parts by weight of the total weight of the nylon composition.
The selection of the antioxidant in the present invention is particularly limited and may be a selection conventionally used in the art, and for example, the antioxidant may be at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) and 4, 4' -bis (α -dimethylphenyl) diphenylamine (antioxidant ZM-405).
In the present invention, the nylon composition may be prepared by a method conventional in the art, for example, by the following method: drying the nylon, the flame retardant and the optional antioxidant, uniformly mixing at the temperature of 210-260 ℃, and then granulating by a double-screw extruder at the rotating speed of 200-400 rpm.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
flame retardancy of the nylon composition was measured by ASTM5025 standard method;
the tensile strength of the nylon composition was measured by the method of ASTM D638, and the tensile speed during the test was 50 mm/min.
The microstructure in the polymer is measured by AVANCE DRX 400MHz nuclear magnetic resonance instrument of Bruker company of Switzerland, the measurement adopts normal temperature, the method is nuclear magnetic resonance hydrogen spectrometry, the solvent is deuterated chloroform, and the concentration of the sample is 10mg/m L.
The phosphate ester monomer a, the phosphate ester monomer b and the phosphate ester monomer c are prepared by amidation reaction of corresponding acyl chloride and a phosphate ester compound;
acrylic acid-caprolactam monomer a and methacrylic acid-caprolactam monomer b are prepared by amidation reaction of corresponding acyl chloride and a-aminocaprolactam, wherein the a-aminocaprolactam is prepared by the method of example 1 in the patent US 7399855;
methyl acrylate, styrene, acrylamide were all purchased from carbofuran corporation.
Preparation example 1
0.05mol of a phosphate ester monomer a (having a structure represented by the formula (3) wherein,R1is H-, R2And R3Is CH3-) and 0.05mol of an acrylic acid-caprolactam monomer a (having a structure represented by the formula (4) wherein R is4H-) is dissolved in 100ml of dioxane, 0.3g of initiator BPO is added, nitrogen is introduced to remove oxygen, the temperature is raised to 90 ℃ after 30 minutes to start polymerization, the reaction is finished after 8 hours, the reaction product is precipitated in ether to remove unreacted monomers, and the reaction product is dried in vacuum to obtain a phosphate-caprolactam copolymer A1, the number average molecular weight of which is 400, the phosphate-caprolactam copolymer A1 is a random copolymer consisting of a phosphate structural unit shown in a formula (1) and a caprolactam structural unit shown in a formula (2), and the molar ratio of the phosphate structural unit to the caprolactam structural unit is 1: 1.
preparation example 2
0.01mol of a phosphate ester monomer b (having a structure represented by the formula (3) wherein R1Is CH3-，R2And R3Is CH3CH2-) and 0.1mol of an acrylic acid-caprolactam monomer b (having a structure represented by the formula (4) wherein R is4Is CH3-) was dissolved in 20ml of dioxane, 0.01g of AIBN initiator was added, oxygen was removed by nitrogen gas, polymerization was started by raising the temperature to 80 ℃ after 20 minutes, the reaction was terminated after 10 hours, the reaction product was precipitated in diethyl ether, unreacted monomers were removed, and the reaction product was dried under vacuum to give a phosphate-caprolactam copolymer A2 which had a number average molecular weight of 15000 and was a random copolymer composed of a phosphate structural unit represented by the formula (1) and a caprolactam structural unit represented by the formula (2) and had a molar ratio of the phosphate structural unit to the caprolactam structural unit of 0.1: 1.
preparation example 3
0.1mol of a phosphate ester monomer c (having a structure represented by the formula (3) wherein R1Is H-, R2And R3Is CH3-) and 0.01mol of acrylic acid-caprolactam monomer b are dissolved in 50m L dioxane, 0.1g of initiator BPO is added, nitrogen is introduced to remove oxygen, the temperature is raised to 100 ℃ after 50 minutes to start polymerization, the reaction is ended after 6 hours of reaction, the reaction product is precipitated in ether, the unreacted monomer is removed, and the reaction product is dried in vacuum to obtain the phosphate ester-caprolactam copolymer A3, which has a number average molecular weight of 20000, is a random copolymer composed of a phosphate structural unit represented by formula (1) and a caprolactam structural unit represented by formula (2), and the molar ratio of the phosphate structural unit to the caprolactam structural unit is 10: 1.
preparation example 4
A phosphate-caprolactam copolymer was prepared by following the procedure of preparation example 1 except that the amount of the phosphate monomer a was 0.02mol and the amount of the acrylic acid-caprolactam monomer a was 0.08 mol. To obtain a phosphate ester-caprolactam copolymer A4 having a number average molecular weight of 2000, which is a random copolymer composed of a phosphate ester structural unit represented by formula (1) and a caprolactam structural unit represented by formula (2), and the molar ratio of the phosphate ester structural unit to the caprolactam structural unit is 0.25: 1.
preparation example 5
A phosphate-caprolactam copolymer was prepared by following the procedure of preparation example 1, except that the polymerization temperature was 60 ℃ and the time was 6 hours. Obtaining a phosphate ester-caprolactam copolymer A5 having a number average molecular weight of 6000, which is a random copolymer composed of a phosphate ester structural unit represented by formula (1) and a caprolactam structural unit represented by formula (2), and the molar ratio of the phosphate ester structural unit to the caprolactam structural unit is 1: 1.
preparation example 6
A phosphate-caprolactam copolymer was prepared in the same manner as in preparation example 1, except that 0.02mol of a third monomer, methyl acrylate, was additionally added to the reaction system while dissolving the phosphate monomer a and the acrylic acid-caprolactam monomer a in dioxane. Obtaining a phosphate ester-caprolactam copolymer A6 having a number average molecular weight of 10000, which is a random copolymer composed of a phosphate ester structural unit represented by formula (1), a caprolactam structural unit represented by formula (2), and a structural unit derived from methyl acrylate, and the molar ratio of the phosphate ester structural unit, the caprolactam structural unit, the structural unit derived from methyl acrylate is 1: 1: 0.5.
preparation example 7
A phosphate-caprolactam copolymer was prepared in the same manner as in preparation example 1, except that 0.05mol of a third monomer of styrene was additionally added to the reaction system while dissolving the phosphate ester monomer a and the acrylic acid-caprolactam monomer a in dioxane. To obtain a phosphate ester-caprolactam copolymer A7 having a number average molecular weight of 2000, which is a random copolymer composed of a phosphate ester structural unit represented by formula (1), a caprolactam structural unit represented by formula (2), and a structural unit derived from styrene, and the molar ratio of the phosphate ester structural unit, the caprolactam structural unit, the structural unit derived from styrene is 1: 1: 1.
preparation example 8
A phosphate-caprolactam copolymer was prepared in the same manner as in preparation example 1, except that 0.1mol of a third monomer, acrylamide, was additionally added to the reaction system while dissolving the phosphate monomer a and the acrylic acid-caprolactam monomer a in dioxane. To obtain a phosphate ester-caprolactam copolymer A8 having a number average molecular weight of 50000, which is a random matter composed of a phosphate ester structural unit represented by formula (1), a caprolactam structural unit represented by formula (2), and a structural unit derived from acrylamide, and the molar ratio of the phosphate ester structural unit, the caprolactam structural unit, the structural unit derived from acrylamide is 1: 1: 2.
comparative preparation example 1
A phosphate-caprolactam copolymer was prepared by following the procedure of preparation example 1, except that acrylic acid-caprolactam monomer a was replaced with the same molar amount of N-vinylcaprolactam. The phosphate ester-caprolactam copolymer DA1 was obtained.
Example 1
Uniformly mixing 90 parts by weight of nylon 6, 10 parts by weight of flame retardant (the flame retardant is phosphate ester-caprolactam copolymer A1) and 0.2 part by weight of antioxidant 1010 at 260 ℃, extruding by a double-screw extruder at the rotating speed of 300rpm, and carrying out quenching granulation. Thus, nylon composition B1 was obtained. The mechanical properties and flame retardancy of B1 were measured, and the results are shown in table 1.
Examples 2 to 8
Nylon compositions were prepared according to the method of example 1, except that the flame retardant a1 was replaced with the same parts by weight of the flame retardants a2, A3, a4, a5, a6, a7, A8, respectively, to give nylon compositions B2, B3, B4, B5, B6, B7, B8. The results of measurements of mechanical properties and flame retardancy of B2, B3, B4, B5, B6, B7 and B8 are shown in table 1.
Comparative example 1
A nylon composition was prepared by following the procedure of example 1 except that the flame retardant A1 was replaced with the same parts by weight of the flame retardant DA1 to give a nylon composition D1. The mechanical properties and flame retardancy of D1 were measured, and the results are shown in table 1.
Comparative example 2
A nylon composition was prepared by the method of example 1 except that the flame retardant A1 was replaced with the same parts by weight of the flame retardant decabromodiphenylethane to give a nylon composition D2. The mechanical properties and flame retardancy of D2 were measured, and the results are shown in table 1.
Comparative example 3
A nylon composition was prepared by following the procedure of example 1, except that no flame retardant was added, to obtain a nylon composition D3. The mechanical properties and flame retardancy of D3 were measured, and the results are shown in table 1.
TABLE 1
Item B1 B2 B3 B4 B5 B6 B7 B8 D1 D2 D3
Tensile strength 75.2 73.5 72.0 68.9 70.2 69.5 70.7 68.3 64.2 66.8 68.1
Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-0 V-2
As can be seen from the results in Table 1, the phosphate-caprolactam copolymer provided by the invention can have a flame retardant effect equivalent to that of decabromodiphenylethane when used as a flame retardant. Furthermore, as can be seen from a comparison of the results of example 1 and comparative example 1, the flame retardancy and mechanical properties of the flame retardant prepared from the monomer containing N-vinylcaprolactam are somewhat reduced.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (27)

1. A phosphate ester-caprolactam copolymer comprising a phosphate ester structural unit represented by the formula (1) and a caprolactam structural unit represented by the formula (2);
Figure 793469DEST_PATH_IMAGE002
the compound of the formula (1),
Figure 913871DEST_PATH_IMAGE004
the compound of the formula (2),
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
2. The phosphate-caprolactam copolymer of claim 1, wherein R1Is hydrogen or methyl; r2And R3Each independently is methyl or ethyl; r4Is hydrogen or methyl.
3. The phosphate-caprolactam copolymer of claim 2, wherein R1Is hydrogen.
4. The phosphate-caprolactam copolymer of claim 2, wherein R2And R3Is methyl.
5. The phosphate-caprolactam copolymer of claim 1, wherein the molar ratio of the phosphate structural units to the caprolactam structural units is from 0.01 to 100: 1.
6. the phosphate-caprolactam copolymer of claim 1, wherein the molar ratio of the phosphate structural units to the caprolactam structural units is from 0.1 to 10: 1.
7. the phosphate-caprolactam copolymer of claim 1, wherein the phosphate-caprolactam copolymer further comprises structural units derived from a third monomer selected from at least one of an acrylate compound, a monovinyl aromatic compound, and an acrylamide compound.
8. The phosphate-caprolactam copolymer of claim 7, wherein the molar ratio of the structural units derived from a third monomer to the caprolactam structural units is from 0.01 to 5: 1.
9. the phosphate-caprolactam copolymer of claim 7, wherein the molar ratio of the structural units derived from a third monomer to the caprolactam structural units is from 0.5 to 2: 1.
10. the phosphate-caprolactam copolymer as claimed in any one of claims 1 to 9, wherein the number average molecular weight of the phosphate-caprolactam copolymer is 300-.
11. The phosphate-caprolactam copolymer as claimed in any one of claims 1 to 9, wherein the number average molecular weight of the phosphate-caprolactam copolymer is 300-.
12. The phosphate-caprolactam copolymer of any of claims 1-9, wherein the phosphate-caprolactam copolymer is a random copolymer.
13. A method of preparing the phosphate-caprolactam copolymer of any one of claims 1 to 12, comprising: in the presence of a solvent and an initiator, carrying out contact reaction on a first monomer shown as a formula (3) and a second monomer shown as a formula (4);
Figure 162450DEST_PATH_IMAGE006
the compound of the formula (3),
Figure 760922DEST_PATH_IMAGE008
formula (4);
wherein R is1Is hydrogen or C1-C5Straight or branched alkyl of R2And R3Each independently is C6-C10Aryl or C1-C5Straight or branched alkyl of R4Is hydrogen or C1-C5Linear or branched alkyl.
14. The method of claim 13Wherein R is1Is hydrogen or methyl; r2And R3Each independently is methyl or ethyl; r4Is hydrogen or methyl.
15. The method of claim 14, wherein R1Is hydrogen.
16. The method of claim 14, wherein R2And R3Is methyl.
17. The method of claim 13, wherein the molar ratio of the amount of the first monomer to the amount of the second monomer is from 0.01 to 100: 1.
18. the method of claim 17, wherein the molar ratio of the amount of the first monomer to the amount of the second monomer is from 0.1 to 10: 1.
19. the method of any of claims 13-18, wherein the method further comprises: in the contact reaction process, adding a third monomer into the reaction system, wherein the third monomer is at least one selected from acrylate compounds, monovinyl aromatic compounds and acrylamide compounds.
20. The method of claim 19, wherein the molar ratio of the amount of the third monomer to the amount of the second monomer is from 0.01 to 5: 1.
21. the method of claim 19, wherein the molar ratio of the amount of the third monomer to the amount of the second monomer is from 0.5 to 2: 1.
22. the method of any one of claims 13-18, wherein the conditions of the contact reaction comprise: the temperature is 60-120 ℃; the time is 2-12 hours.
23. The method of claim 22, wherein the conditions of the contact reaction comprise: the temperature is 80-100 ℃; the time is 6-10 hours.
24. Use of the phosphate-caprolactam copolymer of any one of claims 1 to 12 as a flame retardant.
25. A nylon composition comprising nylon and a flame retardant, wherein the flame retardant is the phosphate-caprolactam copolymer of any one of claims 1-12.
26. The nylon composition of claim 25, wherein the flame retardant is present in an amount of 0.1-30 parts by weight, based on 100 parts by weight of the total nylon composition.
27. The nylon composition of claim 25, wherein the flame retardant is present in an amount of 3-20 parts by weight, based on 100 parts by weight of the total nylon composition.
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