CN112300543A - Halogen-free flame-retardant PET material and preparation method thereof - Google Patents
Halogen-free flame-retardant PET material and preparation method thereof Download PDFInfo
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- CN112300543A CN112300543A CN202010961738.XA CN202010961738A CN112300543A CN 112300543 A CN112300543 A CN 112300543A CN 202010961738 A CN202010961738 A CN 202010961738A CN 112300543 A CN112300543 A CN 112300543A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- 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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention relates to the technical field of PET (polyethylene terephthalate) materials, and provides a halogen-free flame-retardant PET material which at least comprises the following raw materials in percentage by weight: 7-15% of zinc hypophosphite, 4-12% of nitrogen flame retardant and the balance of polyolefin plastic. The method can enable the flame retardant property of the PET composite material to reach UL-94V-0 level, maintain good thermal stability and avoid the negative influence of high addition Zn-MEP on the mechanical property of the material.
Description
Technical Field
The invention relates to the technical field of PET (polyethylene terephthalate) materials, in particular to a halogen-free flame-retardant PET material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is one of the most important thermoplastic engineering materials at present, and has excellent wear resistance, heat resistance, corrosion resistance, electrical insulation and the like. PET is widely used in the production of fibers, films, bottled containers, and the like; in recent years, the demand ratio of PET in the fields of automobiles, household appliances, machinery, and the like has been increasing. Pure PET is extremely flammable in air, and the limiting oxygen index value is only 21%, so it becomes very important to improve the flame retardancy of PET.
At present, the flame retardant modes of PET materials are mainly three types: the first is reaction type flame-retardant PET, the second is additive type flame-retardant PET, and the third is the post-treatment of the finished product. The flame retardant in the reactive flame-retardant PET is used as a component of resin to participate in the synthesis reaction of the PET to become a chain link on a PET molecular chain, the chain link has high flame retardance and no precipitation phenomenon, but the process is relatively complex, and the production cost is high. The post-treatment of the finished product refers to the treatment of the surface of the PET material by using a flame retardant, and the method has the advantages of convenient and quick operation and the defects that the flame retardant attached to the surface falls off and the flame retardant property is seriously reduced after the finished product is used for a long time. The additive type flame-retardant PET is prepared by adding a flame retardant in the PET processing process, the used flame retardant and the PET basically do not undergo chemical change, the flame retardant and the PET are mainly dispersed in the PET in a physical mode to endow the material with flame retardance, and the method is convenient to process and wide in application range.
Disclosure of Invention
On the basis of the common general knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily without departing from the concept and the protection scope of the invention.
In order to solve the above technical problems, a first aspect of the present invention provides a halogen-free flame retardant PET material, which comprises the following raw materials by weight: 7-15% of zinc alkyl phosphinate, 4-12% of nitrogen flame retardant and the balance of polyester plastic.
As a preferred technical scheme, the halogen-free flame retardant PET material at least comprises the following raw materials in percentage by weight: 9-12% of zinc alkyl phosphinate, 5-10% of nitrogen flame retardant and the balance of polyester plastic.
As a preferred technical scheme, the halogen-free flame retardant PET material at least comprises the following raw materials in percentage by weight: 10 percent of zinc alkyl phosphinate, 8 percent of nitrogen flame retardant and the balance of polyester plastic.
In a preferred embodiment, the zinc alkyl phosphinate is at least one selected from the group consisting of zinc methyl ethyl phosphinate, zinc diphenyl phosphinate, zinc ethyl butyl phosphinate, zinc dibutyl phosphinate, zinc diethyl phosphinate, and zinc dimethyl phosphinate.
In a preferred embodiment, the nitrogen-based flame retardant is at least one selected from melamine cyanurate, melamine, and melamine polyphosphate.
As a preferred technical solution, the polyester plastic is polyethylene terephthalate.
As a preferable technical proposal, the intrinsic viscosity of the polyethylene terephthalate is 0.5 to 1.0 dl/g.
As a preferable technical proposal, the intrinsic viscosity of the polyethylene terephthalate is 0.68 to 0.82 dl/g.
The second aspect of the invention provides a preparation method of the halogen-free flame retardant PET material, which at least comprises the following steps:
(1) and (3) drying: drying the polyester plastic and the zinc alkyl phosphinate;
(2) mixing raw materials: mixing the dried polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: and adding the mixture into a double-screw extruder, extruding, air-drying, granulating and drying to obtain the halogen-free flame-retardant PET material.
The third aspect of the invention provides a sheet-shaped flame-retardant PET material prepared from the halogen-free flame-retardant PET material, and the preparation method at least comprises the following steps: and carrying out plate vulcanization on the halogen-free flame-retardant PET material to obtain the halogen-free flame-retardant PET material.
Compared with the prior art, the invention has the following remarkable advantages and effects:
the invention provides a halogen-free flame-retardant PET material, wherein zinc methylethylphosphinate (Zn-MEP) and Melamine Cyanurate (MCA) are compounded for use, so that excellent synergistic effect can be generated in the PET material, the using amount of the zinc methylethylphosphinate can be reduced, the production cost is reduced, the material keeps good flame retardance on the basis of maintaining the thermal stability and the mechanical property of the material, and the flame retardance of the PET composite material can reach UL-94V-0 level by the method.
The technical solutions, gist, and advantages of the present invention will be more readily understood by reference to the following detailed description.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to examples, but the present invention is not limited to the scope of the examples.
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The invention provides a halogen-free flame-retardant PET material, which at least comprises the following raw materials in percentage by weight: 7-15% of zinc alkyl phosphinate, 4-12% of nitrogen flame retardant and the balance of polyester plastic.
In some embodiments, the halogen-free flame retardant PET material comprises, by weight: 9-12% of zinc alkyl phosphinate, 5-10% of nitrogen flame retardant and the balance of polyester plastic.
In some embodiments, the halogen-free flame retardant PET material comprises, by weight: 10 percent of zinc alkyl phosphinate, 8 percent of nitrogen flame retardant and the balance of polyester plastic.
In some embodiments, the zinc alkyl phosphinate is selected from at least one of zinc methyl ethyl phosphinate, zinc diphenyl phosphinate, zinc ethyl butyl phosphinate, zinc dibutyl phosphinate, zinc diethyl phosphinate, zinc dimethyl phosphinate; preferably, the zinc alkyl phosphinate is zinc methyl ethyl phosphinate.
In the invention, the inventor finds that the flame retardant effect of zinc alkyl phosphinate on PET is more obvious than that of other materials aiming at PET materials, the inventor thinks that the melting point of zinc salt is close to that of PET, the zinc salt and the PET can reach better compatibility in the processing process, and the zinc salt can be more uniformly dispersed in PET base materials to improve the flame retardant efficiency and avoid precipitation; the ester group contained in the PET is unstable and easily degraded under acidic conditions, and the degradation of the PET can be promoted by decomposing the zinc alkyl hypophosphite to generate an acidic phosphorus-containing compound, and a non-combustible substance is formed on the surface of the PET to cover the surface of the material.
In some embodiments, the nitrogen-based flame retardant is selected from at least one of melamine cyanurate, melamine polyphosphate; preferably, the nitrogen-based flame retardant is melamine cyanurate.
The inventor finds that alkyl zinc phosphinate in the PET material is dominant in the system, so that the flame retardant effect of the PET material can be obviously reduced by reducing the using amount of the alkyl zinc phosphinate, and the nitrogen flame retardant and the alkyl zinc phosphinate are compounded for use, so that the flame retardant effect is met, the cost of the flame retardant system is greatly reduced, and the mechanical property of the material is prevented from being greatly influenced by the flame retardant. The inventor finds that especially the effect is more excellent when the zinc methylethylphosphinate (Zn-MEP) is compounded with the Melamine Cyanurate (MCA).
In some embodiments, the polyester plastic is polyethylene terephthalate.
In some embodiments, the polyethylene terephthalate has an intrinsic viscosity of 0.5 to 1.0 dl/g.
In some embodiments, the polyethylene terephthalate has an intrinsic viscosity of 0.68 to 0.82 dl/g; more preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.68 dl/g.
The polyethylene terephthalate in the present invention is preferably purchased from at least one of the certified chemical fibers SD500, FG720 and BG802, although the purchase source is not particularly limited.
The zinc methylethylphosphinate (Zn-MEP) serving as a characteristic flame retardant of the PET can be used in additive flame-retardant PET, the material has good flame retardant effect when the addition amount of the single use of the flame retardant reaches 19 percent or more, wherein the using amount of the zinc methylethylphosphinate is higher, which not only causes larger influence on the mechanical property of the PET material, the use cost is higher, but the inventor finds that the zinc methylethylphosphinate (Zn-MEP) and the Melamine Cyanurate (MCA) are selected to be compounded, can generate the technical effect of synergistic flame retardance, on one hand, not only can greatly reduce the dosage of the methyl ethyl zinc phosphinate, maintain the flame retardance of the PET material and keep good flame retardance, and the mechanical property of the PET material is less influenced, and in addition, the compound system can also ensure that the thermal stability and the flame retardant effect of the PET in the PET system are kept in a relatively balanced state.
Compared with the rest two flame retardants MPP and ME, the MPP contains phosphorus element, still has condensed phase flame retardant effect on the flame retardant mechanism, and the two condensed phase flame retardants are compounded, so that the problem that heat accumulation cannot transfer heat in time exists, and the flame retardant efficiency can be weakened; as a small molecular flame retardant, the ME has poorer compatibility with a matrix than that of the large molecular MCA, the content and the type of inert gases which can be decomposed by the ME are obviously inferior to those of the large molecular flame retardant MCA, and the gas-phase flame retardant effect is inferior to that of the MCA.
In the invention, the inventor finds that especially for injection-grade PET, the synergistic effect of the special dosage of zinc methylethylphosphinate (Zn-MEP) Melamine Cyanurate (MCA) is more excellent, and the zinc salt and the MCA are compounded, so that the synergistic effect can be generated between the two flame retardants, the gas phase-condensed phase flame retardant of an N-P system has the maximum effect, the MCA releases a large amount of inert gas at the high temperature of about 300-350 ℃, the combustible in the air is diluted, the flame retardant effect on the gas phase is achieved, and simultaneously, cyanuric acid generated by the decomposition of the MCA can accelerate the degradation of the PET to generate dropping and leave a combustion area, and the heat on the material is taken away to avoid the accumulation of local heat; then at about 400 ℃, the zinc salt is heated and decomposed to generate a large amount of phosphorus-containing oxides, which play a role in dehydrating and carbonizing PET molecular chains, and the carbides cover the PET surface to block external heat sources and oxygen sources, so that the material is prevented from further degradation, and a flame retardant effect is achieved on a condensed phase. By compounding the zinc salt and the MCA, the flame retardant mechanisms of the zinc salt and the MCA are combined, so that the flame retardant efficiency is improved to the maximum extent.
The second aspect of the invention provides a preparation method of the halogen-free flame retardant PET material, which at least comprises the following steps:
(1) and (3) drying: drying the polyester plastic and the zinc alkyl phosphinate;
(2) mixing raw materials: mixing the dried polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: and adding the mixture into a double-screw extruder, extruding, air-drying, granulating and drying to obtain the halogen-free flame-retardant PET material.
In some preferred embodiments, the preparation method of the halogen-free flame retardant PET material at least comprises the following steps:
(1) and (3) drying: drying the polyester plastic at 90-150 ℃ for 15-36 hours, and drying the zinc alkyl hypophosphite at 90-150 ℃ for 2-10 hours;
(2) mixing raw materials: mixing polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: and adding the mixture into a double-screw extruder, controlling the processing temperature to be 210-265 ℃, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material.
In some more preferred embodiments, the method for preparing the halogen-free flame retardant PET material at least comprises the following steps:
(1) and (3) drying: drying polyester plastics at 120 ℃ for 24 hours, and drying zinc alkyl phosphinate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
The third aspect of the invention provides a sheet-shaped flame-retardant PET material prepared from the halogen-free flame-retardant PET material, and the preparation method at least comprises the following steps: and carrying out plate vulcanization on the halogen-free flame-retardant PET material to obtain the halogen-free flame-retardant PET material.
In some preferred embodiments, the sheet-like flame-retardant PET material is prepared by a method comprising at least the steps of: preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The reagents and starting materials used in the present invention are commercially available.
In the following examples, the sheet flame retardant PET material was prepared by the steps of:
(1) and (3) drying: drying polyester plastics at 120 ℃ for 24 hours, and drying zinc alkyl phosphinate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 1: comparison of synergistic effect of different nitrogen flame retardants on Zn-MEP/PET at the same ratio
The halogen-free flame-retardant PET material at least comprises the following raw materials in percentage by weight: 10 percent of zinc alkyl phosphinate, 8 percent of nitrogen flame retardant and the balance of polyester plastic.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The sheet-shaped flame-retardant PET material comprises the following steps:
preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
The zinc alkyl phosphinate is zinc methyl ethyl phosphinate.
In Table 1, the synergistic effect comparison results of different nitrogen flame retardants to Zn-MEP/PET in the same ratio are selected. Wherein MCA is melamine cyanurate for short, and ME is melamine for short; MPP is melamine polyphosphate for short.
TABLE 1Comparison of synergistic effect of different nitrogen flame retardants on Zn-MEP/PET at the same ratio
| Examples | Nitrogen-series flame retardantAgent for treating cancer | Flame retardant rating UL-94 |
| Examples 1 to 1 | MCA | V-0 |
| Examples 1 to 2 | ME | V-2 |
| Examples 1 to 3 | MPP | V-2 |
Through experiments, the inventor finds that the flame retardant effect of Zn-MEP compounded MCA on PET is obviously better than that of the other two groups, and on the basis, a Zn-MEP/MCA system is investigated.
Example 2
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 19% of zinc methylethylphosphinate, and the balance of polyester plastic.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyolefin plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic and zinc methylethylphosphinate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 3
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 20% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyolefin plastic at 120 ℃ for 24 hours, and drying melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 4
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 10% of zinc methylethylphosphinate, 8% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyester plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 5
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 10% of zinc methylethylphosphinate, 8% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterized chemical fiber FG 720. The intrinsic viscosity of the polyethylene terephthalate was 0.75 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyolefin plastic at 120 ℃ for 24 hours, and drying methyl ethyl zinc phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 6
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 10% of zinc methylethylphosphinate, 8% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical chemical fiber BG 802. The intrinsic viscosity of the polyethylene terephthalate was 0.82 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyester plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 7
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 10% of zinc methylethylphosphinate, 9% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyester plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 8
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 11% of zinc methylethylphosphinate, 8% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyolefin plastic at 120 ℃ for 24 hours, and drying methyl ethyl zinc phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 9
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 13 percent of zinc methyl ethyl phosphinate, 7 percent of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyester plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Example 10
A sheet-shaped flame-retardant PET material at least comprises the following raw materials in percentage by weight: 12% of zinc methyl ethyl phosphinate, 8% of melamine cyanurate and the balance of polyester plastics.
The polyester plastic is polyethylene terephthalate and is purchased from China petrochemical characterization chemical fiber SD 500. The intrinsic viscosity of the polyethylene terephthalate was 0.68 dl/g.
The preparation method comprises the following steps:
(1) and (3) drying: drying polyester plastic at 120 ℃ for 24 hours, and drying zinc methyl ethyl phosphinate and melamine cyanurate at 120 ℃ for 5 hours;
(2) mixing raw materials: mixing polyester plastic, zinc methylethylphosphinate and melamine cyanurate to obtain a mixture;
(3) preparation: adding the mixture into a double-screw extruder, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the halogen-free flame-retardant PET material; the temperatures of the twin-screw extruder from the first zone to the ninth zone were set to 210 ℃, 230 ℃, 245 ℃, 255 ℃, 252 ℃ respectively.
(4) Preheating the halogen-free flame-retardant PET material on a flat vulcanizing machine for 5 minutes, wherein the temperatures of an upper hot plate and a lower hot plate are 270 ℃ and 270 ℃, respectively, then exhausting for 10-15 times, carrying out hot pressing for 1 minute under 10MPa, and then carrying out cold pressing for 1 minute under 5MPa to obtain the flaky flame-retardant PET material.
Performance testing
(1) And (3) testing the flame retardant grade: the flame retardant rating test of the present invention was performed according to GB/T2408-1996.
(2) Tensile strength test standard: GB/T1040-2006.
(3) Flame retardant rating test standard: GB/T2408-1996.
The test results are shown in table 2.
TABLE 2 test results of mechanical properties and flame retardancy
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim the description of selected embodiments in the best possible combination contemplated. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims. The scope is broad and the examples presented herein are based on all possible implementations.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The halogen-free flame-retardant PET material is characterized by comprising the following raw materials in percentage by weight: 7-15% of zinc alkyl hypophosphite, 4-12% of nitrogen flame retardant and the balance of polyester plastic.
2. The halogen-free flame retardant PET material according to claim 1, characterized in that the raw materials comprise, in weight percent: 9-12% of zinc alkyl hypophosphite, 5-10% of nitrogen flame retardant and the balance of polyester plastic.
3. The halogen-free flame retardant PET material according to claim 1, characterized in that the raw materials comprise, in weight percent: 10% of zinc alkyl hypophosphite, 8% of nitrogen flame retardant and the balance of polyester plastic.
4. The halogen-free flame retardant PET material according to any one of claims 1 to 3, wherein the zinc alkyl phosphinate is at least one selected from the group consisting of zinc methyl ethyl phosphinate, zinc diphenyl phosphinate, zinc ethyl butyl phosphinate, zinc dibutyl phosphinate, zinc diethyl phosphinate and zinc dimethyl phosphinate.
5. Halogen free flame retardant PET material according to any of claims 1-3, characterized in that the nitrogen based flame retardant is selected from at least one of melamine cyanurate, melamine polyphosphate.
6. Halogen free flame retardant PET material according to any of claims 1-3, characterized in that the polyester plastic is polyethylene terephthalate.
7. The halogen-free flame retardant PET material of claim 6 wherein the intrinsic viscosity of the polyethylene terephthalate is 0.5 to 1.0 dl/g.
8. The halogen-free flame retardant PET material of claim 6 wherein the intrinsic viscosity of the polyethylene terephthalate is 0.68 to 0.82 dl/g.
9. A method for preparing halogen-free flame retardant PET material according to any of claims 1 to 8, characterized in that the steps at least comprise:
(1) and (3) drying: drying polyester plastics, zinc alkyl phosphinate and nitrogen flame retardant;
(2) mixing raw materials: mixing the dried polyester plastic, zinc alkyl phosphinate and a nitrogen flame retardant to obtain a mixture;
(3) preparation: and adding the mixture into a double-screw extruder, extruding, air-drying, granulating and drying to obtain the halogen-free flame-retardant PET material.
10. A sheet-like flame retardant PET material prepared from the halogen free flame retardant PET material according to any of claims 1 to 8, characterized in that the preparation method comprises at least the steps of: the halogen-free flame-retardant PET material according to any one of claims 1 to 8 is obtained by vulcanizing a flat plate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113621179A (en) * | 2021-08-30 | 2021-11-09 | 利尔化学股份有限公司 | Surface-modified zinc alkyl phosphinate flame retardants and modified polycarbonates based thereon |
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