CN113445154A - Flame-retardant low-melting-point polyester fiber and preparation method thereof - Google Patents
Flame-retardant low-melting-point polyester fiber and preparation method thereof Download PDFInfo
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- CN113445154A CN113445154A CN202110813935.1A CN202110813935A CN113445154A CN 113445154 A CN113445154 A CN 113445154A CN 202110813935 A CN202110813935 A CN 202110813935A CN 113445154 A CN113445154 A CN 113445154A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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Abstract
The application provides a flame-retardant low-melting-point polyester fiber and a preparation method thereof, wherein the flame-retardant low-melting-point polyester fiber comprises a first polyester matrix, a second polyester matrix and a third polyester matrix, wherein the first polyester matrix comprises first polyester; a second polyester matrix located on the surface of the first polyester matrix and comprising a second polyester, the second polyester having a melting point lower than the melting point of the first polyester; the first polyester matrix and the second polyester matrix are also dispersed with halogen-free phosphorus flame retardant and carbon material. The flame-retardant low-melting-point polyester fiber has excellent flame retardant property, mechanical property and oxidation resistance.
Description
Technical Field
The application relates to the field of chemical polyester fibers, in particular to a flame-retardant low-melting-point polyester fiber and a preparation method thereof.
Background
With the development of the times and the progress of science and technology, the rapid development of the polyester industry is also driven, the conventional polyester material cannot meet the requirements of people, and the differentiation and the functionalization of the polyester material are the development trend of the industry at present. The low-melting polyester is a modified polyester, has a lower melting point than that of a conventional polyester, is excellent in processing fluidity, and has good compatibility with the conventional polyester.
However, the low-melting-point polyester fiber has a low limiting oxygen index, belongs to a flammable material, brings potential safety hazards to people's life, life and property, and greatly limits the application range of the polyester fiber.
Disclosure of Invention
The technical problem to be solved by the technical scheme is that the flame retardance of the low-melting-point polyester fiber is poor.
One aspect of the present application provides a flame retardant low melting polyester fiber comprising a first polyester matrix comprising a first polyester; a second polyester matrix located on the surface of the first polyester matrix and comprising a second polyester, the second polyester having a melting point lower than the melting point of the first polyester; the first polyester matrix and the second polyester matrix are also dispersed with halogen-free phosphorus flame retardant and carbon material.
In the examples of the present application, the structural formula of the halogen-free phosphorus-based flame retardant is as follows:
in the examples of the present application, the melting point of the halogen-free phosphorus-based flame retardant is 110 ℃ to 130 ℃.
In the embodiment of the application, the weight ratio of the total weight of the halogen-free phosphorus-based flame retardant to the flame-retardant low-melting-point polyester fiber is 1 to (15-30), and the weight ratio of the carbon material in the second polyester matrix to the carbon material in the first polyester matrix is 1 to (2-4).
In an embodiment of the present application, the carbon material is dispersed in the first polyester matrix and the second polyester matrix in the form of nanoparticles, and the carbon material includes at least one of fullerene, graphene, nano carbon black, and carbon nanotube.
In an embodiment of the present application, the weight ratio of the total weight of the carbon material to the flame-retardant low-melting polyester fiber is 1: (50-200), and the weight ratio of the carbon material in the second polyester matrix and the first polyester matrix is 1: (3-5).
In embodiments herein, the first polyester comprises a terephthalic acid segment and an ethylene glycol segment, and the second polyester comprises a terephthalic acid segment, an isophthalic acid segment, an ethylene glycol segment, and a diethylene glycol segment.
In embodiments herein, the melting point of the first polyester is 230 ℃ to 280 ℃ and the melting point of the second polyester is 100 ℃ to 180 ℃.
In embodiments herein, the weight ratio of the first polyester matrix to the second polyester matrix is 1: (3-8).
Another aspect of the present application also provides a method for preparing a flame retardant low melting point polyester fiber, comprising: adding a halogen-free phosphorus flame retardant and a carbon material into first polyester and second polyester respectively, and modifying the first polyester and the second polyester by adopting a melt blending process to form a first polyester matrix and a second polyester matrix, wherein the melting point of the second polyester is lower than that of the first polyester; carrying out composite spinning by taking the first polyester matrix as an inner core and the second polyester matrix as a surface layer; and carrying out post-treatment to obtain the flame-retardant low-melting-point polyester fiber.
In the examples herein, the temperature of the melt blending process is from 280 ℃ to 350 ℃ when modifying the first polyester; and when the second polyester is modified, the temperature of the melt blending process is 180-260 ℃.
In the embodiment of the application, the spinning temperature is 320-420 ℃ and the spinning speed is 2800-3600 m/min during composite spinning.
Compared with the prior art, the flame-retardant low-melting-point polyester fiber and the preparation method thereof have the following beneficial effects:
the first polyester is modified by the halogen-free phosphorus flame retardant and the carbon material to form a first polyester matrix, and the second polyester is modified by the halogen-free phosphorus flame retardant and the carbon material to form a second polyester matrix, wherein the melting point of the second polyester is lower than that of the first polyester, and the second polyester matrix is positioned on the surface of the first polyester matrix, so that the adhesion of the flame-retardant low-melting-point polyester fiber and other materials can be realized by simple heating, the use of glue is omitted, and the environmental pollution can be reduced.
The addition of the halogen-free phosphorus flame retardant can improve the flame retardant property of the flame-retardant low-melting-point polyester fiber, and meanwhile, the halogen-free phosphorus flame retardant with a lower melting point is adopted, so that the halogen-free phosphorus flame retardant exists in a liquid form with better fluidity during processing, and further the halogen-free phosphorus flame retardant is better dispersed in the first polyester matrix and the second polyester matrix, and the flame retardant effect of the flame-retardant low-melting-point polyester fiber is further improved.
On one hand, the carbon material is promoted to be uniformly dispersed in a first polyester matrix and a second polyester matrix through the pi-pi conjugated effect between a C-C six-membered ring and a benzene ring due to the unique molecular structure characteristics of the carbon material, and the carbon material can be used as a heterogeneous nucleation point to promote the crystallization of polyester, so that the mechanical strength of the flame-retardant low-melting-point polyester fiber is improved, and excellent physical and mechanical properties are obtained; on the other hand, the carbon material also has free radical trapping capacity, and can trap oxidation free radicals in the processing process of the flame-retardant low-melting-point polyester fiber, so that the oxidation resistance of the second polyester with a low melting point is improved, and the problem of oxidative degradation caused by the low melting point is solved when the second polyester and the first polyester with a higher melting point are subjected to composite spinning under the same temperature shearing condition; the carbon material can also adjust the viscosity of the first polyester and the second polyester, so that the flowability of the first polyester matrix and the flowability of the second polyester matrix tend to be consistent, and the processing is facilitated.
The relative proportions of the first polyester, the second polyester, the halogen-free phosphorus flame retardant and the carbon material are controlled, so that the flame-retardant low-melting-point polyester fiber has good flame retardant property, mechanical property and oxidation resistance; by controlling the technological parameters during melt blending, the flame-retardant low-melting-point polyester fiber is successfully prepared and the production efficiency is considered at the same time.
Detailed Description
The following description is presented to enable any person skilled in the art to make and use the present disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present application. Thus, the present application is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
According to the technical scheme, the first polyester and the second polyester with the lower melting point are modified respectively by adopting the halogen-free phosphorus flame retardant and the carbon material to form the first polyester matrix and the second polyester matrix, the composite spinning process is carried out on the first polyester matrix and the second polyester matrix to form the flame-retardant low-melting-point polyester fiber with the first polyester matrix as an inner core and the second polyester matrix as a surface layer, and the flame-retardant low-melting-point polyester fiber has excellent physical and mechanical properties and oxidation resistance while having an excellent flame-retardant effect.
The flame-retardant low-melting polyester fiber and the preparation method thereof according to the technical scheme of the present application are described in detail by specific examples below.
The flame-retardant low-melting-point polyester fiber of the embodiment of the application comprises a first polyester matrix and a second polyester matrix, wherein the second polyester matrix is positioned on the surface of the first polyester matrix. In some embodiments, the flame retardant low melting polyester fiber is a sheath-core composite fiber with the first polyester matrix as an inner core and the second polyester matrix as a skin layer or sheath.
The first polyester matrix comprises a first polyester, which may have a melting point of 230 ℃ to 280 ℃, for example comprising terephthalic acid segments and ethylene glycol segments. In some embodiments, the first polyester has a number average molecular weight of 18000-25000 and a degree of polymerization of 100-140.
The second polyester matrix comprises a second polyester, the melting point of the second polyester is lower than the melting point of the first polyester, and the melting point of the second polyester is 100-180 ℃. The second polyester with a lower melting point is positioned on the surface layer of the flame-retardant low-melting-point polyester fiber, and the second polyester can be melted at a lower temperature, so that the polyester fiber can be bonded with other materials by simple heating, and the use of glue is omitted, thereby reducing the environmental pollution. The second polyester may include a terephthalic acid segment, an isophthalic acid segment, an ethylene glycol segment, and a diethylene glycol segment. In some embodiments, the second polyester has a number average molecular weight of 15000-21000 and a degree of polymerization of 80-120.
Controlling the weight ratio of the first polyester matrix to the second polyester matrix to be 1: (3-8) ensuring that the second polyester matrix can completely cover the first polyester matrix without wasting raw materials.
In the embodiment of the present application, a halogen-free phosphorus-based flame retardant and a carbon material are further dispersed in the first polyester matrix and the second polyester matrix. The halogen-free phosphorus flame retardant is a phosphorus-containing heterocyclic oxide containing active hydrogen, and the structural formula of the halogen-free phosphorus flame retardant is as follows:
When the first polyester and the second polyester are modified to form the first polyester matrix and the second polyester matrix, the halogen-free phosphorus flame retardant with the lower melting point can be used for enabling the halogen-free phosphorus flame retardant to exist in a liquid form, so that the halogen-free phosphorus flame retardant has excellent fluidity, can be well dispersed in the first polyester matrix and the second polyester matrix, and further improves the flame retardant effect of the polyester fiber. In the embodiment of the application, the melting point of the halogen-free phosphorus flame retardant is 110-130 ℃.
Although the halogen-free phosphorus flame retardant can reduce the flame retardant effect of the polyester fiber, the content of the halogen-free phosphorus flame retardant is not more and better, and on one hand, the high addition amount of the halogen-free phosphorus flame retardant can greatly increase the cost; on the other hand, the addition of the halogen-free phosphorus flame retardant can destroy the interfacial continuity of the polymer matrix, and excessive halogen-free phosphorus flame retardant can also agglomerate to cause the reduction of the mechanical property of the polyester fiber. The weight ratio of the total weight of the halogen-free phosphorus flame retardant to the flame-retardant low-melting-point polyester fiber is 1: 15-30. The weight ratio of the halogen-free phosphorus flame retardant in the second polyester matrix to the halogen-free phosphorus flame retardant in the first polyester matrix is 1: 2-4.
The molecular structure of the carbon material can be a six-membered ring formed by connecting carbon-carbon single bonds. For example, the carbon material may include at least one of fullerene, graphene, nano-carbon black, carbon nanotube, or other carbon material. The carbon material is dispersed in the first polyester matrix and the second polyester matrix in the form of nanoparticles. As the carbon-carbon single bonds in the carbon material are connected into a six-membered ring structure similar to the benzene ring structure in the polyester, the carbon material can be promoted to be uniformly dispersed in the first polyester matrix and the second polyester matrix through the pi-pi conjugate effect between the C-C six-membered ring and the benzene ring, and the carbon material can be used as a heterogeneous nucleation point to promote the crystallization of the polyester, so that the mechanical strength of the flame-retardant low-melting-point polyester fiber is improved, and excellent physical and mechanical properties are obtained.
The carbon material also has free radical trapping capacity, and can trap oxidized free radicals in the processing process of the flame-retardant low-melting-point polyester fiber, so that the oxidation resistance of the second polyester with a low melting point is improved, and the problem of oxidative degradation caused by the low melting point is solved when the second polyester with the low melting point and the first polyester with the higher melting point are subjected to composite spinning under the same temperature shearing condition.
Meanwhile, since the melting point of the first polyester is relatively high and the melting point of the second polyester is low, when the first polyester and the second polyester are processed at the same temperature, the flowability of the first polyester is low and the flowability of the second polyester is high, so that the processing flowability of the first polyester and the processing flowability of the second polyester are not matched, and the material processing is not facilitated. When the proper carbon materials are respectively added into the first polyester matrix and the second polyester matrix, the viscosity of the first polyester and the viscosity of the second polyester are adjusted, so that the flowability of the first polyester matrix and the flowability of the second polyester matrix tend to be consistent.
In the examples of the present application, the weight ratio of the total weight of the carbon material to the flame-retardant low-melting polyester fiber is 1: (50-200). The weight ratio of the carbon materials in the second polyester matrix to the first polyester matrix is 1: 3-5.
The embodiment of the application also provides a preparation method of the flame-retardant low-melting-point polyester fiber, which comprises the following steps:
step S1: adding a halogen-free phosphorus flame retardant and a carbon material into first polyester and second polyester respectively, and modifying the first polyester and the second polyester by adopting a melt blending process to form a first polyester matrix and a second polyester matrix, wherein the melting point of the second polyester is lower than that of the first polyester;
step S2: carrying out composite spinning by taking the first polyester matrix as an inner core and the second polyester matrix as a surface layer;
step S3: and carrying out post-treatment to obtain the flame-retardant low-melting-point polyester fiber.
In step S1, a melt blending process is employed, in which a halogen-free phosphorus-based flame retardant and a carbon material are added to the first polyester to modify the first polyester, and a halogen-free phosphorus-based flame retardant and a carbon material are added to the second polyester to modify the first polyester, so that the halogen-free phosphorus-based flame retardant and the carbon material are uniformly dispersed in the first polyester and the second polyester to form a first polyester matrix and a second polyester matrix.
The temperature is selected in consideration of the melting point or viscous flow temperature and thermal degradation temperature of the material to be processed when performing the melt blending process. In the embodiment, when the first polyester is modified, the temperature of the melt blending process is 280-350 ℃; and when the second polyester is modified, the temperature of the melt blending process is 180-260 ℃. The melt blending process can adopt an extrusion processing process, wherein the rotating speed of a screw is 60r/min-150 r/min. The selection of the temperature and the screw rotation speed of the melt blending process also needs to consider the production efficiency.
Because the melting point of the halogen-free phosphorus flame retardant is lower than the temperature of the melt blending process, the halogen-free phosphorus flame retardant is in a liquid state with better fluidity during melt blending, and is further better dispersed in the first polyester matrix and the second polyester matrix, so that the flame retardant effect is improved. On one hand, the carbon material has the capacity of capturing oxidizing free radicals, can improve the oxidation resistance of the second polyester with low melting point, and is beneficial to subsequent composite spinning; on the other hand, the six-membered ring of the carbon material and the benzene ring of the polyester generate pi-pi conjugated effect, so that the carbon material is uniformly dispersed in the polyester to be used as a heterogeneous nucleation point, the crystallization of the polyester is further promoted, and the mechanical strength of the flame-retardant low-melting-point polyester fiber is improved; the carbon material may also adjust the viscosity such that the first polyester matrix and the second polyester matrix have matching flowability during processing.
In the step S2, composite spinning is performed with the first polyester matrix as an inner core and the second polyester matrix as a surface layer, and the temperature during composite spinning needs to be higher than the melting points of the first polyester and the second polyester and lower than the thermal degradation temperatures of the first polyester and the second polyester. In the embodiment of the application, the spinning temperature is 320-420 ℃, and the spinning speed is 2800-3600 m/min.
In the step S3, the post-processing includes drawing, curling, cutting, and drying. The parameters of the traction, the curling, the cutting and the drying are determined according to the actual situation.
Example 1
(1) Adding 1g of flame retardant (DOPO, melting point 110 deg.C) and 0.5g of fullerene into 25g of second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol, diethylene glycol, molecular weight 15000, degree of polymerization 80, melting point 100 deg.C), and melt-blending at 180 deg.C to obtain second polyester matrix;
(2) adding 3g of flame retardant (DOPO, melting point 110 ℃) and 1.5g of fullerene into 75g of first polyester (polyethylene terephthalate, molecular weight is 18000, polymerization degree is 100, and melting point is 230 ℃), and carrying out melt blending at 280 ℃ to obtain a first polyester matrix;
(3) and (3) carrying out composite spinning at 320 ℃ by taking the second polyester matrix as a skin layer and the first polyester matrix as a core layer, and carrying out post-treatment to obtain the flame-retardant low-melting-point polyester fiber with the skin-core structure.
Example 2
(1) Adding 1g of flame retardant (DOPO, melting point 120 ℃) and 0.2g of graphene into 20g of second polyester (a copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight is 17000, polymerization degree is 95, and melting point is 130 ℃), and carrying out melt blending at 190 ℃ to obtain a second polyester matrix;
(2) adding 4g of flame retardant (DOPO, melting point 120 ℃) and 0.8g of graphene into 80g of first polyester (polyethylene terephthalate, molecular weight is 19000, polymerization degree is 110, melting point is 250 ℃), and carrying out melt blending at 300 ℃ to obtain a first polyester matrix;
(3) the second polyester matrix is used as a skin layer, the first polyester matrix is used as a core layer, composite spinning is carried out at 350 ℃, the post-treatment is carried out in the same way as in the example 1, and the flame-retardant low-melting-point polyester fiber with the skin-core structure is obtained.
Example 3
(1) Adding 2g of flame retardant (DOPO, melting point 110 ℃) and 0.5g of carbon nano tube into 25g of second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight is 19000, polymerization degree is 105, and melting point is 160 ℃), and carrying out melt blending at 200 ℃ to obtain a second polyester matrix;
(2) adding 4g of flame retardant (DOPO, melting point 130 ℃) and 1.5g of carbon nano tube into 75g of polyester (polyethylene terephthalate, molecular weight is 22000, polymerization degree is 125, and melting point is 265 ℃) to carry out melt blending at 320 ℃ to obtain a first polyester matrix;
(3) the second polyester matrix as the skin layer and the first polyester matrix as the core layer were subjected to composite spinning at 380 ℃ and the same post-treatment as in example 1 to obtain a skin-core flame-retardant low-melting polyester fiber.
Example 4
(1) Adding 1g of flame retardant (DOPO, melting point 120 ℃) and 0.3g of nano carbon black into 10g of second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight is 21000, polymerization degree is 120, and melting point is 180 ℃), and carrying out melt blending at 260 ℃ to obtain a second polyester matrix;
(2) adding 3g of flame retardant (DOPO, melting point of 120 ℃) and 1.5g of nano carbon black into 90g of polyester (polyethylene terephthalate, molecular weight is 25000, polymerization degree is 140 and melting point is 280 ℃), and carrying out melt blending at 350 ℃ to obtain a first polyester matrix;
(3) the second polyester matrix as the skin layer and the first polyester matrix as the core layer were subjected to composite spinning at 420 ℃ and the same post-treatment as in example 1 to obtain a skin-core flame-retardant low-melting-point polyester fiber.
Comparative example 1
Composite spinning was performed at 350 ℃ using an unmodified second polyester (a copolymer of phthalic acid, isophthalic acid, ethylene glycol, and diethylene glycol, molecular weight of 17000, polymerization degree of 95, and melting point of 130 ℃) as a sheath layer and an unmodified first polyester (polyethylene terephthalate, molecular weight of 19000, polymerization degree of 110, and melting point of 250 ℃) as a core layer, and the same post-treatment as in example 1 was performed to obtain a sheath-core polyester fiber.
Comparative example 2
(1) Adding 5g of flame retardant (DOPO, melting point 120 ℃) and 1g of graphene into 100g of second polyester (a copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight is 17000, polymerization degree is 95, and melting point is 130 ℃), and carrying out melt blending at 190 ℃ to obtain a second polyester matrix;
(2) composite spinning was performed at 350 ℃ using the second polyester matrix as a sheath layer and the unmodified first polyester (polyethylene terephthalate, molecular weight 19000, polymerization degree 110, melting point 250 ℃) as a core layer, and the same post-treatment as in example 1 was performed to obtain a sheath-core polyester fiber.
Comparative example 3
(1) Adding 6g of flame retardant (DOPO, melting point 130 ℃) and 2g of carbon nano tube into 100g of first polyester (polyethylene terephthalate, molecular weight is 22000, polymerization degree is 125, melting point is 265 ℃) and carrying out melt blending at 320 ℃ to obtain a first polyester matrix;
(2) an unmodified second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol, and diethylene glycol, molecular weight 19000, degree of polymerization 105, and melting point 160 ℃) was used as a sheath layer, and the first polyester matrix was used as a core layer, and composite spinning was performed at 380 ℃ and the same post-treatment as in example 1 was performed to obtain a sheath-core polyester fiber.
Comparative example 4
(1) Adding 1g of flame retardant (DOPO, melting point 110 ℃) into 25g of second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight of 15000, polymerization degree of 80 and melting point of 100 ℃), and carrying out melt blending at 180 ℃ to obtain a second polyester matrix;
(2) adding 3g of flame retardant (DOPO, melting point 110 ℃) into 75g of first polyester (polyethylene terephthalate, molecular weight is 18000, polymerization degree is 100, and melting point is 230 ℃), and carrying out melt blending at 280 ℃ to obtain a first polyester matrix;
(3) composite spinning was performed at 320 ℃ using the second polyester matrix as the sheath layer and the first polyester matrix as the core layer, and the same post-treatment as in example 1 was performed to obtain a sheath-core polyester fiber.
Comparative example 5
(1) Adding 0.3g of nano carbon black into 10g of second polyester (copolymer of phthalic acid, isophthalic acid, ethylene glycol and diethylene glycol, molecular weight is 21000, polymerization degree is 120, and melting point is 180 ℃), and carrying out melt blending at 260 ℃ to obtain a second polyester matrix;
(2) adding 1.5g of nano carbon black into 90g of first polyester (polyethylene terephthalate, the molecular weight is 25000, the polymerization degree is 140, and the melting point is 280 ℃), and carrying out melt blending at 350 ℃ to obtain a first polyester matrix;
(3) composite spinning was performed at 420 ℃ using the second polyester matrix as the sheath layer and the first polyester matrix as the core layer, and the same post-treatment as in example 1 was performed to obtain a sheath-core polyester fiber.
The following properties were tested for the polyester fibers prepared in the examples and comparative examples:
(1) flame retardant property: the samples were tested for limiting oxygen index using a limiting oxygen index apparatus (cf. ASTM D2863), with 5 samples per set being tested. The test results are shown in table 1.
(2) Mechanical properties: the samples were tested for fiber tensile strength using a fiber tensile tester (ISO 11566-. The test results are shown in table 1.
(3) Antioxidant capacity: the oxidation induction time of the sample is tested by differential scanning calorimeter (experimental condition: N)2Under the condition, the temperature is raised to 400 ℃ and is kept constant for 3 min; then the atmosphere is switched to O2Keeping the temperature for 120 min. The time at which the oxidation exothermic peak begins to appear is defined as the oxidation induction time), and each group of samples was tested 5 times, and the average value thereof was taken. The test results are shown in table 1.
TABLE 1 test results for flame retardant low melting polyester fibers
Comparing the test data of examples 1 to 4 and comparative example 1, the polyester fiber of comparative example 1 is itself a flammable material since the limiting oxygen index of the polyester fiber of comparative example 1 is only 21%. In the embodiments 1 to 4, after the flame retardant and the carbon material are added into the skin layer and the core layer, the flame retardant property of the prepared polyester fiber is greatly improved, the limited oxygen index of the polyester fiber exceeds 27 percent, and the polyester fiber becomes a flame-retardant material and can completely meet the flame retardant property requirement of the fields of buildings, building materials, automobile industry and the like on polyester fiber fabrics. This is because, after adding the flame retardant and the carbon material, on the one hand, the low melting point of the flame retardant makes it have a certain plasticizing effect on the polyester, and on the other hand, the heterogeneous nucleation effect of the carbon material makes it have a certain enhancing effect on the polyester, so the mechanical properties of the polyester fibers of examples 1-4 are not reduced after flame retardant modification, but rather are improved to a certain extent; on the other hand, after the carbon material is added, the carbon material has excellent capture capability on oxygen-containing free radicals, so that the thermal degradation of the polyester fiber is inhibited to a great extent, the time of the oxidation reaction is obviously prolonged, and the spinning processing of the polyester fiber is facilitated.
For comparative example 2, only the flame retardant and the carbon material were added to the skin layer, and although the flame retardant in the skin layer can improve the flame retardant performance of the skin layer material, the core layer polyester, which is not flame retardant treated after thermal degradation of the skin layer, still cannot resist the erosion of heat, resulting in the failure of good flame retardant and antioxidant effects of the polyester fiber as a whole. Moreover, the carbon material is dispersed in the skin layer, so that the polyester of the core layer lacks heterogeneous nucleation points and can be crystallized only by means of thermal fluctuation, and the crystallization speed is low, the crystallinity is low, and the mechanical property of the polyester is particularly deteriorated.
For comparative example 3, only the flame retardant and the carbon material are added to the core layer, and although the core layer polyester has good flame retardant property and oxidation resistance after flame retardant modification, when the fiber is heated or ignited, the low-melting point polyester of the skin layer cannot resist heat erosion, and a thermal oxidation degradation reaction occurs quickly, so that the overall flame retardant property and oxidation resistance of the polyester fiber are not good. Moreover, the skin layer has no heterogeneous nucleation effect of the carbon material, and the core layer has the heterogeneous nucleation effect of the carbon material, so that the mechanical property of the skin layer is poorer than that of the core layer, and the overall mechanical property of the polyester fiber is further influenced.
For comparative example 4, only a flame retardant was added to the skin layer and the core layer, and no carbon material was added. Due to the addition of the flame retardant, the polyester fiber has good flame retardant performance, and the limit oxygen index of the polyester fiber reaches 27 percent of that of a flame-retardant material. However, the mechanical strength of the polyester fiber is low due to the lack of reinforcement of the carbon material.
For comparative example 5, only the carbon material was added to the skin layer and the core layer, and no flame retardant was added. The polyester fiber in comparative example 5 is still a flammable material although it has high mechanical strength due to lack of flame retardant modification effect of the flame retardant.
Finally, it should be understood that the embodiments of the application disclosed herein are illustrative of the principles of the embodiments of the present application. Other modified embodiments are also within the scope of the present application. Accordingly, the disclosed embodiments are presented by way of example only, and not limitation. Those skilled in the art may implement the present application in alternative configurations according to the embodiments of the present application. Thus, embodiments of the present application are not limited to those embodiments described with precision in the application.
Claims (12)
1. A flame retardant low melting polyester fiber comprising:
a first polyester matrix comprising a first polyester;
a second polyester matrix located on the surface of the first polyester matrix and comprising a second polyester, the second polyester having a melting point lower than the melting point of the first polyester;
the first polyester matrix and the second polyester matrix are also dispersed with halogen-free phosphorus flame retardant and carbon material.
2. The flame-retardant low-melting-point polyester fiber as claimed in claim 1, wherein the structural formula of the halogen-free phosphorus flame retardant is as follows:
3. the flame-retardant low-melting-point polyester fiber according to claim 1, wherein the melting point of the halogen-free phosphorus-based flame retardant is 110 ℃ to 130 ℃.
4. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein the weight ratio of the total weight of the halogen-free phosphorus-based flame retardant to the flame-retardant low-melting-point polyester fiber is 1: (15-30), and the weight ratio of the halogen-free phosphorus-based flame retardant in the second polyester matrix to the first polyester matrix is 1: (2-4).
5. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein the carbon material is dispersed in the form of nanoparticles in the first polyester matrix and the second polyester matrix, and the carbon material comprises at least one of fullerene, graphene, nano carbon black, and carbon nanotubes.
6. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein the weight ratio of the total weight of the carbon material to the flame-retardant low-melting-point polyester fiber is 1: 50-200, and the weight ratio of the carbon material in the second polyester matrix to the first polyester matrix is 1: 3-5.
7. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein said first polyester comprises a terephthalic acid segment and an ethylene glycol segment, and said second polyester comprises a terephthalic acid segment, an isophthalic acid segment, an ethylene glycol segment, and a diethylene glycol segment.
8. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein the melting point of the first polyester is 230 ℃ to 280 ℃ and the melting point of the second polyester is 100 ℃ to 180 ℃.
9. The flame-retardant low-melting-point polyester fiber according to claim 1, wherein the weight ratio of the first polyester matrix to the second polyester matrix is 1: 3-8.
10. A method for preparing a flame-retardant low-melting polyester fiber according to any one of claims 1 to 9, comprising:
adding a halogen-free phosphorus flame retardant and a carbon material into first polyester and second polyester respectively, and modifying the first polyester and the second polyester by adopting a melt blending process to form a first polyester matrix and a second polyester matrix, wherein the melting point of the second polyester is lower than that of the first polyester;
carrying out composite spinning by taking the first polyester matrix as an inner core and the second polyester matrix as a surface layer;
and carrying out post-treatment to obtain the flame-retardant low-melting-point polyester fiber.
11. The method for preparing the flame-retardant low-melting-point polyester fiber according to claim 10, wherein the temperature of the melt blending process is 280-350 ℃ when the first polyester is modified; and when the second polyester is modified, the temperature of the melt blending process is 180-260 ℃.
12. The method for preparing the flame-retardant low-melting-point polyester fiber according to claim 10, wherein the spinning temperature is 320-420 ℃ and the spinning speed is 2800-3600 m/min during composite spinning.
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