CN111303591A - PET (polyethylene terephthalate), phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as well as preparation method and application thereof - Google Patents

PET (polyethylene terephthalate), phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as well as preparation method and application thereof Download PDF

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CN111303591A
CN111303591A CN202010135145.8A CN202010135145A CN111303591A CN 111303591 A CN111303591 A CN 111303591A CN 202010135145 A CN202010135145 A CN 202010135145A CN 111303591 A CN111303591 A CN 111303591A
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pet
phosphaphenanthrene
flame retardant
flame
polyphosphazene
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张道海
宝冬梅
谭芳
罗迎春
田琴
何敏
秦舒浩
左晓玲
于杰
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Guizhou Minzu University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention relates to a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, and a preparation method and application thereof, belonging to the field of flame-retardant composite materials. The PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material consists of, by weight, 80-95 parts of PET, 2-5 parts of a gas-phase flame retardant, 2-5 parts of a condensed-phase flame retardant, 5-10 parts of a compatibilizer and 0.5 part of an antioxidant. The invention also discloses a preparation method and application of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material. The PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material can form double-base synergistic effect and three-element synergistic effect, and has excellent flame-retardant property, excellent interface compatibility and excellent mechanical property.

Description

PET (polyethylene terephthalate), phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as well as preparation method and application thereof
Technical Field
The invention belongs to the field of flame-retardant composite materials, and particularly relates to a PET (polyethylene terephthalate), phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as well as a preparation method and application thereof.
Background
Polyethylene terephthalate (PET) is a milky white or light yellow polymer with high crystallinity, has smooth and glossy surface, creep resistance, fatigue resistance, good friction resistance, small abrasion, high hardness, good electrical insulation performance, small temperature influence, no toxicity, weather resistance, good chemical stability and weak acid and organic solvent resistance, is widely applied to the electronic and electric industries and the automobile industry, and is used for various coil frameworks, transformers, televisions, recorder parts and shells, automobile lamp holders, lamp covers, white hot lamp holders, relays, selenium rectifiers and the like. However, since PET is easily burnt and there is a dripping phenomenon during burning, it is necessary to increase the flame retardancy of PET materials.
At present, a halogen-containing flame retardant (mainly a polybrominated biphenyl compound) is mainly applied to PET resin, and the halogen-containing flame retardant has a good flame retardant effect in PET materials, but can emit toxic and corrosive gases and smoke during combustion or high-temperature processing, so that environmental pollution can be caused, and human health is harmed. Since WEEE and RoHS were published in European Union 2003, and the requirements of people on the quality of life of the environment have been higher and higher, and various environmental protection documents of the state have been continuously provided, the trend of the high molecular flame retardant material is mainly halogen-free.
Among many halogen-free flame retardants, phosphorus-based flame retardants have been the focus of research in the field of flame retardancy. The phosphaphenanthrene-containing compound and the derivative thereof are novel flame retardants, have excellent flame retardant performance and are widely used for polymer-based halogen-free flame-retardant composite materials. Compared with common acyclic organic phosphate, the phosphaphenanthrene has better thermal stability and chemical stability, and also has the advantages of low phosphorus content, no halogen, low smoke, no toxicity, no migration, durable flame retardance and the like.
However, the phosphorus flame retardant has the defects that the carbon layer structure strength and compactness of the flame retardant which forms carbon after combustion are poor, and the oxygen-insulating and heat-insulating capabilities are weak; moreover, the compatibility between the flame retardant and a polymer matrix or a reinforcing material is poor, so that the mechanical property of the flame retardant is reduced when the flame retardant is used; the flame retardant effect of the phosphaphenanthrene flame retardant and the derivative thereof is mainly gas-phase flame retardant, and the condensed-phase flame retardant effect is weaker.
Therefore, it is necessary to provide a new flame retardant composite material of PET to solve the deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material. The PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material disclosed by the invention has a double-base synergistic effect and a three-element synergistic effect, and has excellent flame retardant property, excellent interface compatibility and excellent mechanical property.
The technical scheme for solving the technical problems is as follows: the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material consists of, by weight, 80-95 parts of PET, 2-5 parts of a gas-phase flame retardant, 2-5 parts of a condensed-phase flame retardant, 5-10 parts of a compatibilizer and 0.5 part of an antioxidant.
The flame-retardant composite material has the beneficial effects that:
(1) through the reaction of the gas-phase flame retardant, the condensed-phase flame retardant and the compatibilizer, a cross-linked network structure is generated, so that the mechanical property of the PET flame-retardant composite material is effectively improved.
(2) Adding a gas-phase flame retardant, wherein the flame retardant mechanism is gas-phase flame retardant; adding a condensed phase flame retardant, wherein the flame retardant mechanism is condensed flame retardant. The two flame retardants form synergistic flame retardance based on two flame retardant mechanisms, so that the flame retardant performance of the PET flame retardant composite material is improved, and the flame retardant effect is obviously better than that of the PET composite material added with a single flame retardant.
(3) The flame-retardant composite material disclosed by the invention is wide in raw material source, easy to obtain, low in cost and good in using effect.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the gas-phase flame retardant is reactive phosphaphenanthrene.
The beneficial effect of adopting the further scheme is that: the reactive phosphaphenanthrene flame retardant has a hydroxyl reaction group, so that the reactive phosphaphenanthrene flame retardant can effectively perform crosslinking reaction with a compatibilizer, the improvement of mechanical properties is facilitated, and meanwhile, the flame retardant effect of the reactive phosphaphenanthrene flame retardant is good.
Further, the reactive phosphaphenanthrene is DOPO-HQ, DOPS-HQ, DOPO-PHBA, DOPS-PHBA, (DOPO)2P-PPD-PH sum (DOPS)2-P-PPD-PH, in a mixture of one or more of the following formulae:
Figure BDA0002396276630000031
the beneficial effect of adopting the further scheme is that: the reactive phosphaphenanthrene flame retardant has a hydroxyl reaction group, so that the reactive phosphaphenanthrene flame retardant can effectively perform crosslinking reaction with a compatibilizer, the improvement of mechanical properties is facilitated, and meanwhile, the flame retardant effect of the reactive phosphaphenanthrene flame retardant is good.
Further, the condensed phase flame retardant is a reactive polyphosphazene, and the structural formula is as follows:
Figure BDA0002396276630000032
wherein the content of the first and second substances,
Figure BDA0002396276630000033
Figure BDA0002396276630000041
the beneficial effect of adopting the further scheme is that: the reactive polyphosphazenes all have hydroxyl reactive groups, so that the reactive polyphosphazenes can effectively perform crosslinking reaction with a compatibilizer, the mechanical property can be promoted, and the flame retardant effect of the reactive polyphosphazenes is good.
Further, the compatibilizer is one or a mixture of glycidyl methacrylate grafted ethylene-octene copolymer, ethylene-butyl acrylate-glycidyl methacrylate terpolymer and styrene-acrylonitrile grafted glycidyl methacrylate.
The beneficial effect of adopting the further scheme is that: the epoxy resin has epoxy active groups, and can be favorably reacted with reactive phosphaphenanthrene flame retardants, reactive polyphosphazenes and PET matrix resin to generate a cross-linked network structure.
Further, the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The beneficial effect of adopting the further scheme is that: the oxygen content is reduced, and the flame retardant effect is further improved.
The second purpose of the invention is to provide the application of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material in the field of electronic components.
The technical scheme for solving the technical problems is as follows: an electronic component comprises the PET, the phosphaphenanthrene and the polyphosphazene double-base synergistic flame-retardant composite material.
The electronic component adopts the PET, the phosphaphenanthrene and the polyphosphazene double-base synergistic flame-retardant composite material, and has coil frameworks, transformers, television and recorder parts.
The invention also aims to provide application of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material in the field of automobiles.
The technical scheme for solving the technical problems is as follows: an automobile part comprises the PET, the phosphaphenanthrene and the polyphosphazene double-base synergistic flame-retardant composite material.
The automobile part adopts the PET, the phosphaphenanthrene and the polyphosphazene double-base synergistic flame-retardant composite material, and is provided with a shell, an automobile lamp holder, a lampshade, a white heat lamp holder, a relay and a selenium rectifier.
The fourth purpose of the invention is to provide a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material. The preparation method has simple process, all the components are uniformly dispersed, and in addition, after the components are dried, the components are favorably mixed, the mixing degree is high, the internal stress is not generated, and thus the mechanical property is not influenced.
The technical scheme for solving the technical problems is as follows: a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material comprises the following steps:
s1, weighing the following raw materials in parts by weight: evenly mixing 80-95 parts of PET, 2-5 parts of a gas-phase flame retardant, 2-5 parts of a condensed-phase flame retardant, 5-10 parts of a compatibilizer and 0.5 part of an antioxidant to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
and S3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and granulating to obtain the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material.
The preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material has the beneficial effects that:
(1) the preparation method has simple process, all the components are uniformly dispersed, and in addition, after the components are dried, the components are favorably mixed, the mixing degree is high, the internal stress is not generated, and thus the mechanical property is not influenced.
(2) The preparation method has good environmental protection property and does not generate waste;
(3) the particle-packed PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material prepared by the preparation method has uniform particles, and is beneficial to being processed into different products in the later period.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The embodiment provides a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material which comprises, by weight, 90 parts of PET, 2.5 parts of a gas-phase flame retardant, 2.5 parts of a condensed-phase flame retardant, 5 parts of a compatibilizer and 0.5 part of an antioxidant.
Wherein the gas phase flame retardant is reactive phosphaphenanthrene (DOPO)2-P-PPD-PH, the structural formula of which is specifically shown below:
Figure BDA0002396276630000061
wherein the coacervate phase flame retardant is a reactive polyphosphazene, and the structural formula is shown as follows:
Figure BDA0002396276630000062
wherein the compatibilizer is ethylene-butyl acrylate-glycidyl methacrylate terpolymer (PTW).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The embodiment also provides a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, which comprises the following steps:
s1, weighing the following raw materials in parts by weight: 90 parts of PET, 2.5 parts of a gas-phase flame retardant, 2.5 parts of a condensed-phase flame retardant, 5 parts of a compatibilizer and 0.5 part of an antioxidant, and uniformly mixing to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
and S3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and granulating to obtain the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material.
And drying the obtained PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, adding the dried PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
Example 2
The embodiment provides a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material which comprises, by weight, 90 parts of PET, 2 parts of a gas-phase flame retardant, 2 parts of a condensed-phase flame retardant, 5 parts of a compatibilizer and 0.5 part of an antioxidant.
Wherein the gas phase flame retardant is reactive phosphaphenanthrene (DOPO)2-P-PPD-PH, the structural formula of which is specifically shown below:
Figure BDA0002396276630000071
wherein the coacervate phase flame retardant is a reactive polyphosphazene, and the structural formula is shown as follows:
Figure BDA0002396276630000072
wherein the compatibilizer is ethylene-butyl acrylate-glycidyl methacrylate terpolymer (PTW).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The embodiment also provides a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, which comprises the following steps:
s1, weighing the following raw materials in parts by weight: 90 parts of PET, 2 parts of a gas-phase flame retardant, 2 parts of a condensed-phase flame retardant, 5 parts of a compatibilizer and 0.5 part of an antioxidant, and uniformly mixing to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
and S3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and granulating to obtain the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material.
And drying the obtained PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, adding the dried PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
Example 3
The embodiment provides a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material which comprises, by weight, 80 parts of PET, 4 parts of a gas-phase flame retardant, 3 parts of a condensed-phase flame retardant, 6 parts of a compatibilizer and 0.5 part of an antioxidant.
Wherein the gas phase flame retardant is reactive phosphaphenanthrene (DOPS)2-P-PPD-PH, the structural formula of which is specifically shown below:
Figure BDA0002396276630000081
wherein the coacervate phase flame retardant is a reactive polyphosphazene, and the structural formula is shown as follows:
Figure BDA0002396276630000091
wherein the compatibilizer is glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The embodiment also provides a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, which comprises the following steps:
s1, weighing the following raw materials in parts by weight: 80 parts of PET, 4 parts of a gas-phase flame retardant, 3 parts of a condensed-phase flame retardant, 6 parts of a compatibilizer and 0.5 part of an antioxidant to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
and S3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and granulating to obtain the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material.
And drying the obtained PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, adding the dried PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
Example 4
The embodiment provides a PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material which comprises, by weight, 95 parts of PET, 5 parts of a gas-phase flame retardant, 4 parts of a condensed-phase flame retardant, 7 parts of a compatibilizer and 0.5 part of an antioxidant.
Wherein the gas-phase flame retardant is reactive phosphaphenanthrene DOPO-PHBA, and the structural formula is shown as follows:
Figure BDA0002396276630000101
wherein the coacervate phase flame retardant is a reactive polyphosphazene, and the structural formula is shown as follows:
Figure BDA0002396276630000102
wherein the compatibilizer is styrene-acrylonitrile grafted glycidyl methacrylate (SAG).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The embodiment also provides a preparation method of the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, which comprises the following steps:
s1, weighing the following raw materials in parts by weight: 95 parts of PET, 5 parts of a gas-phase flame retardant, 4 parts of a condensed-phase flame retardant, 7 parts of a compatibilizer and 0.5 part of an antioxidant, and uniformly mixing to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
and S3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and granulating to obtain the PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material.
And drying the obtained PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material, adding the dried PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
Comparative example 1
The comparative example provides a PET flame-retardant composite material which comprises, by weight, 90 parts of PET, 5 parts of a gas-phase flame retardant, 5 parts of a compatibilizer and 0.5 part of an antioxidant.
Wherein the gas phase flame retardant is reactive phosphaphenanthrene (DOPO)2-P-PPD-PH, the structural formula of which is specifically shown below:
Figure BDA0002396276630000111
wherein the compatibilizer is ethylene-butyl acrylate-glycidyl methacrylate terpolymer (PTW).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The comparative example was prepared by the same preparation method as example 1, and the comparative PET flame retardant composite was obtained.
And drying the obtained comparative PET flame-retardant composite material, adding the dried comparative PET flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
Comparative example 2
The comparative example provides a PET flame-retardant composite material, which comprises 90 parts of PET, 5 parts of condensed phase flame retardant, 5 parts of compatibilizer and 0.5 part of antioxidant in parts by weight.
Wherein the coacervate phase flame retardant is a reactive polyphosphazene, and the structural formula is shown as follows:
Figure BDA0002396276630000121
wherein the compatibilizer is ethylene-butyl acrylate-glycidyl methacrylate terpolymer (PTW).
Wherein the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The comparative example was prepared by the same preparation method as example 1, and the comparative PET flame retardant composite was obtained.
And drying the obtained comparative PET flame-retardant composite material, adding the dried comparative PET flame-retardant composite material into an injection molding machine, performing injection molding to obtain a standard sample strip, and performing performance test on the standard sample strip.
The standard bars of examples 1-4 and comparative examples 1-2 were subjected to the following performance tests:
(1) vertical burning performance: the test was performed according to the vertical method of GB/T2408-1996, with at least 5 splines per group.
(2) The flame retardant rating test is that the flame spread delaying performance of the material or the treated material is marked, and the flame retardant rating is gradually increased from V2, V1 to V0 according to the rating system divided by the flame retardant rating: v0 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 30 seconds, and no combustible can fall off; v1 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 60 seconds, and no combustible can fall off, and V2 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 60 seconds, and the combustible can fall off.
(3) Mechanical property tests including tensile strength, flexural strength and notched impact strength: one sample was tested for 10 splines and the results averaged over 10 test values. Tensile strength was tested according to GB/T1040-2006 and flexural strength was tested according to GB/T9341-2000.
The notch impact strength was notched by 4mm using a notch sampling machine and tested in accordance with GB/T1043-2008.
All test data were collected and compiled as in table 1 below.
TABLE 1 composite Performance test
Figure BDA0002396276630000131
From the data of table 1, the following conclusions can be drawn:
(1) in general, the mechanical properties of polymer-based flame retardant materials decrease with increasing flame retardant content. According to the test results in table 1, it can be seen that, compared with the conventional materials, the samples prepared by the technical scheme of the present invention have the same experimental conditions, wherein the amount of the reactive phosphaphenanthrene flame retardant in example 1 is 2.5 parts, the amount of the reactive polyphosphazene in example 2 is 2 parts, and the amount of the reactive polyphosphazene in example 2 is 2 parts. It can be seen from the data of examples 1 and 2 that, by using the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene, the content of the flame retardant is increased, not only the mechanical properties of the PET flame-retardant composite material are not reduced, but also the mechanical properties of the PET flame-retardant composite material are increased, because the reactive hydroxyl group in the reactive phosphaphenanthrene flame retardant, the reactive hydroxyl group in the reactive polyphosphazene, and the reactive hydroxyl group in the PET matrix resin can react with the epoxy group in the ethylene-butyl acrylate-glycidyl methacrylate terpolymer compatibilizer, the interfacial adhesion between the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene is enhanced, the interfacial adhesion between the reactive phosphaphenanthrene flame retardant and the PET matrix is increased, and the interfacial strength between the reactive polyphosphazene and the PET matrix is enhanced, the PET flame-retardant composite material forms a network cross-linking structure, and the mechanical property of the PET flame-retardant composite material is better along with the increase of the use amount of the reactive phosphaphenanthrene and the reactive polyphosphazene, so that the reactive phosphaphenanthrene and the reactive polyphosphazene have the flame retardant effect in the PET flame-retardant composite material and have the function of interface compatibilization; the two flame retardant PET composites of example 1 and example 2 were rated V0, except that the different amounts of reactive phosphaphenanthrene and reactive polyphosphazene resulted in differences in mechanical properties of the flame retardant PET composite.
(2) Example 1 of the present invention is different from comparative examples 1 and 2 in that: the addition amounts of the reactive phosphaphenanthrene and the reactive polyphosphazene in the raw material formula in the comparative example 1 are respectively 2.5 parts, the sum of the flame retardants obtained by adding the reactive phosphaphenanthrene and the reactive polyphosphazene is 5 parts, while the addition amount of the reactive phosphaphenanthrene in the raw material formula in the comparative example 1 is only 5 parts, the addition amount of the reactive polyphosphazene in the raw material formula in the comparative example 2 is only 5 parts, and the rest experimental raw materials and conditions are the same. As shown in table 1, the flame retardant rating of the PET flame retardant composite material in comparative example 1 and comparative example 2 is V2, while the flame retardant rating of the PET flame retardant composite material in example 1 is V0, which indicates that the flame retardant effect of the PET composite material with the reactive phosphaphenanthrene and the reactive polyphosphazene added separately is poor, because the reactive phosphaphenanthrene or the reactive polyphosphazene added separately has only gas phase or condensed phase flame retardant in the PET flame retardant composite material as main component, while the PET flame retardant composite material with the reactive phosphaphenanthrene and the reactive polyphosphazene added in example 1 has both gas phase and condensed phase double-base synergistic flame retardant, and also has excellent nitrogen phosphorus sulfur triple-element synergistic flame retardant, so the PET flame retardant composite material in example 1 has excellent flame retardant performance.
In addition, example 2 is different from the PET flame retardant composite of comparative examples 1 and 2 in that: the addition amount of the reactive phosphaphenanthrene flame retardant in example 2 is 2 parts, the addition amount of the reactive polyphosphazene is 2 parts, the sum of the flame retardants obtained by adding the two is 4 parts, only 5 parts of the reactive phosphaphenanthrene is added in the raw material formula in comparative example 1, only 5 parts of the reactive polyphosphazene is added in the raw material formula in comparative example 2, and the rest of the experimental raw materials and conditions are the same. As seen from Table 1, the flame retardant grade of the PET flame retardant composite material in example 2 is V0 grade, while the flame retardant grade of the PET flame retardant composite material in comparative example 1 and comparative example 2 is only V2 grade, which shows that the reactive phosphaphenanthrene and the reactive polyphosphazene have excellent double-base synergistic effect and nitrogen-phosphorus-sulfur synergistic flame retardant effect, so that the PET flame retardant composite material added with the reactive phosphaphenanthrene and the reactive polyphosphazene with lower contents can obtain excellent flame retardant property.
(3) Compared with the comparative examples 1-2, the samples prepared by the technical scheme of the invention have excellent double-base synergistic effect and nitrogen-phosphorus-sulfur synergistic flame-retardant effect by adding the reactive phosphaphenanthrene and the reactive polyphosphazene with lower contents, so that the obtained PET flame-retardant composite material can obtain excellent flame-retardant performance which is obviously better than the PET flame-retardant composite material added with a single flame retardant and the known PET composite material on the market at present.
According to the invention, both the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene are provided with hydroxyl reactive groups, the compatibilizer with epoxy active groups is added, the epoxy active groups can react with the reactive phosphaphenanthrene flame retardant, the reactive polyphosphazene and the PET matrix resin to generate a cross-linked network structure, and the interface structures between the reactive phosphaphenanthrene flame retardant and the PET matrix resin, between the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene and between the reactive polyphosphazene and the PET matrix resin are enhanced, so that the flame retardant property and the interface bonding force of the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene to the PET matrix resin are enhanced, the mechanical property is not reduced due to the addition of the flame retardant, and the mechanical property of the PET flame-retardant composite material is also enhanced.
More importantly, the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene generate double-base synergistic effect of gas-phase flame retardance and condensed-phase flame retardance in the PET matrix resin. Therefore, the flame retardant effect of the reactive phosphaphenanthrene flame retardant is mainly gas-phase flame retardant. The reactive polyphosphazene is mainly used for coacervate phase flame retardant action, the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene are subjected to synergistic flame retardant action, the gas phase flame retardant action of the phosphaphenanthrene is achieved, the polyphosphazene is used for enhancing the coacervate phase flame retardant action, in the combustion process, not only the oxygen content of gas generated during the combustion of the phosphaphenanthrene is reduced, the phosphoric acid generated during the combustion of the phosphaphenanthrene promotes the carbonization action, the carbon layer structure is more compact, and the heat insulation and oxygen isolation capabilities are stronger. And the char forming capability of the material is stronger in the combustion process of the polyphosphazene.
In addition, the reactive phosphaphenanthrene flame retardant and the reactive polyphosphazene also generate a nitrogen-phosphorus-sulfur three-element synergistic flame retardant effect, so that the reactive phosphaphenanthrene and the reactive polyphosphazene generate a double-base synergistic flame retardant effect and a nitrogen-phosphorus-sulfur three-element synergistic flame retardant effect, and have more excellent flame retardant property.
In addition, the raw materials adopted by the invention have wide sources, are easy to obtain, have low cost and good use effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. The PET, phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material is characterized by comprising, by weight, 80-95 parts of PET, 2-5 parts of a gas-phase flame retardant, 2-5 parts of a condensed-phase flame retardant, 5-10 parts of a compatibilizer and 0.5 part of an antioxidant.
2. The PET and phosphaphenanthrene and polyphosphazene biradicals synergistic flame retardant composite as claimed in claim 1, wherein the gas phase flame retardant is a reactive phosphaphenanthrene.
3. The PET and phosphaphenanthrene and polyphosphazene bi-based synergistic flame retardant composite as claimed in claim 2, wherein the reactive phosphaphenanthrene is DOPO-HQ, DOPS-HQ, DOPO-PHBA, DOPS-PHBA, (DOPO)2P-PPD-PH sum (DOPS)2-P-PPD-PH, in a mixture of one or more of the following formulae:
Figure FDA0002396276620000011
4. the PET and phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as claimed in claim 1, wherein the condensed phase flame retardant is a reactive polyphosphazene, and has the following structural formula:
Figure FDA0002396276620000012
wherein the content of the first and second substances,
Figure FDA0002396276620000021
5. the PET and phosphaphenanthrene and polyphosphazene biradical synergistic flame retardant composite as claimed in claim 1, wherein the compatibilizer is a mixture of one or more of glycidyl methacrylate grafted ethylene-octene copolymer, ethylene-butyl acrylate-glycidyl methacrylate terpolymer and styrene-acrylonitrile grafted glycidyl methacrylate.
6. The PET flame retardant composite with phosphaphenanthrene and polyphosphazene diradicals synergy according to any of the claims 1-5, characterized in that the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
7. An electronic component, which is characterized by comprising the PET, the phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as defined in any one of claims 1-6.
8. An automobile part comprising the PET flame-retardant composite material according to any one of claims 1 to 6, which is synergistic with both phosphaphenanthrene and polyphosphazene.
9. A method for preparing a PET and phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as defined in any one of claims 1 to 5, comprising the steps of:
s1, weighing the following raw materials in parts by weight: evenly mixing 80-95 parts of PET, 2-5 parts of a gas-phase flame retardant, 2-5 parts of a condensed-phase flame retardant, 5-10 parts of a compatibilizer and 0.5 part of an antioxidant to obtain a mixture;
s2, drying the mixture obtained in the step S1 at 80 ℃ to constant weight to obtain a dried material;
s3, adding the dried material obtained in the step S2 into a double-screw extruder, blending and extruding at the temperature of 220-250 ℃, and cooling, drawing and pelletizing to obtain the flame-retardant composite material.
CN202010135145.8A 2020-02-29 2020-02-29 PET (polyethylene terephthalate), phosphaphenanthrene and polyphosphazene double-base synergistic flame-retardant composite material as well as preparation method and application thereof Withdrawn CN111303591A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512227A (en) * 2021-04-13 2021-10-19 何顺伦 High-flame-retardant PET (polyethylene terephthalate) foam material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512227A (en) * 2021-04-13 2021-10-19 何顺伦 High-flame-retardant PET (polyethylene terephthalate) foam material and preparation method thereof
CN113512227B (en) * 2021-04-13 2023-03-24 何顺伦 High-flame-retardant PET (polyethylene terephthalate) foam material and preparation method thereof

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