CN113234315A - Flame-retardant yellowing-resistant TPU cable material and preparation method and application thereof - Google Patents
Flame-retardant yellowing-resistant TPU cable material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant yellowing-resistant TPU cable material, and a preparation method and application thereof, and relates to the technical field of cable materials. The flame-retardant yellowing-resistant TPU cable material comprises the following raw materials in parts by weight: 60-90 parts of thermoplastic polyurethane, 10-20 parts of organic silicon modified phosphate, 10-15 parts of a metal oxide anti-yellowing agent, 5-15 parts of melamine cyanurate, 1-5 parts of a silane coupling agent and 0.5-2 parts of an antioxidant. After the raw materials are mixed in an internal mixer, the organic flame retardant and the inorganic flame retardant have good compatibility, dispersibility and synergy in a system, and the prepared TPU cable material has good flame retardance and yellowing resistance and is applied to various power industries.
Description
Technical Field
The invention relates to the technical field of cable materials, and particularly relates to a flame-retardant yellowing-resistant TPU cable material, and a preparation method and application thereof.
Background
The thermoplastic polyurethane elastomer (TPU) has excellent wear resistance, ozone resistance and radiation resistance, is widely applied to industries such as automobiles, buildings, engineering, shoe materials, home decoration, cables and the like, and is particularly widely applied to the cable industry. However, the TPU is an organic material, so that the TPU is easy to yellow and extremely easy to burn, and serious melting and dropping and release of a large amount of toxic gas are accompanied during burning, so that the use of the TPU and products thereof in the field of cables is seriously restricted. Therefore, the flame retardant modification research of TPU is the focus of research in the industry.
At present, halogen flame retardants are mainly used for flame retardance of TPU cable materials, such as halogen, phosphorus, expanded graphite, metal hydroxide and the like, most of flame retardance of TPU cable materials on the market is halogen flame retardants, but chlorine and bromine containing flame retardant materials easily emit irritant and corrosive toxic gases during combustion, and environmental regulations limit the use of halogen flame retardants. With the continuous development of society and the continuous improvement of green industry requirements, the development and production of halogen-free flame retardant TPU cables are more and more.
The patent CN105949746A discloses a preparation method of an elastomer halogen-free flame-retardant cable material, which comprises the steps of (1) adding organic rectorite and tetraisopropyl titanate into a high-speed mixer for mixing, then putting into a screw double extruder, adding TPU, melting and blending for 10-20min at the rotating speed of 400-600r/min, and then extruding and granulating to obtain a TPU/organic rectorite nano composite material; (2) drying SEBS and mixing with the prepared TPU/organic rectorite nano composite material rubber compound; (3) putting the prepared rubber compound, talcum powder, mica and carbon black into an internal mixer; (4) and conveying the mixture obtained after banburying into a screw extruder for extrusion processing through double-cone shearing. The elastomer halogen-free flame-retardant cable material disclosed by the invention has the comprehensive properties of oil resistance, heat resistance, softness, good resilience, solvent resistance, cold resistance, low smoke and the like, but the polymerization inhibition system mainly comprises inorganic substances and a carbon forming agent, the compatibility and the dispersibility in a TPU system are poor, particle aggregation is easily caused, and the mechanical properties of the TPU cable material are greatly influenced, such as the elastic modulus and the elongation are reduced.
Patent CN111961331A discloses a flame-retardant waterproof thermoplastic polyurethane elastomer cable material, which comprises the following components in parts by weight: 60-90 parts of TPU resin, 10-40 parts of flame retardant, 2-10 parts of char forming agent, 1-2 parts of dispersant, 0.5-1.5 parts of molecular chain repairing agent and 0.3-1 part of antioxidant; the flame retardant is surface modified hypophosphite, and the surface modified hypophosphite is obtained by modifying hypophosphite by using layered double hydroxide or layered silicate. The invention solves the problem of water absorption of the flame retardant, and can further improve the water resistance, flame retardance and mechanical properties of the cable material. The flame retardant mechanism of the surface modified hypophosphite in the patent is coacervate phase flame retardant, phosphoric acid substances are generated through degradation to promote the base material to form carbon, the flame retardant mechanism is relatively single, and the flame retardant efficiency needs to be improved.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention aims to provide a flame-retardant yellowing-resistant TPU cable material with good compatibility and good synergy, and the invention also aims to provide a preparation method and application of the flame-retardant yellowing-resistant TPU cable material.
The technical scheme of the invention is as follows:
in order to solve the problems in the prior art, the invention provides a flame-retardant yellowing-resistant TPU cable material which comprises the following raw materials in parts by weight: 60-90 parts of thermoplastic polyurethane, 10-20 parts of organic silicon modified phosphate, 10-15 parts of a metal oxide anti-yellowing agent, 5-15 parts of Melamine Cyanurate (MCA), 1-5 parts of a silane coupling agent and 0.5-2 parts of an antioxidant.
In a further embodiment of the present invention, the metal oxide anti-yellowing agent in the present invention is one or two of titanium dioxide and aluminum oxide. The titanium dioxide and the aluminum oxide are commonly used as the synergistic flame retardant, so that the dosage of the flame retardant can be reduced, the mechanical property, the thermal property and the flame retardant property of the material can be improved, the compactness of a carbon layer can be promoted, the heat transfer can be reduced, and the emission of harmful gases can be reduced.
In a further embodiment of the present invention, the silane coupling agent is selected from one or more of KH550, KH560 and KH 570. The silane coupling agent can effectively modify the surface morphology of the metal oxide anti-yellowing agent, and increases the compatibility of the metal oxide in the TPU in a covalent bond mode, so that the stress concentration phenomenon is reduced, and the mechanical property of the TPU cable material is improved. The silane coupling agent is a common commercially available chemical, such as from corning, Nanjing eosin chemical group, and the like.
In a further embodiment of the present invention, the antioxidant in the present invention is selected from one or more of antioxidant 1010, antioxidant 626, and antioxidant 168. The antioxidant is hindered phenol or amine antioxidant, has good compatibility with TPU cable material, and effectively slows down the oxidation of TPU material, thereby improving the yellowing resistance. It is well known to those skilled in the art that the higher the amount of antioxidant added, the better the yellowing resistance, but the excessive amount of antioxidant does not further improve the yellowing resistance, but rather increases the raw material cost and affects the mechanical and electrical properties of the TPU cable material. The antioxidant is also a common commercial product.
As a further scheme of the invention, the Melamine Cyanurate (MCA) is widely applied to the flame retardance of polyamide, epoxy resin and thermoplastic polyester as a nitrogen flame retardant. The flame retardant mechanism is gas-phase flame retardant, and mainly inhibits combustion by degrading, absorbing heat, reducing the temperature of a combustion area, releasing non-combustible gas and diluting the concentration of the combustible gas.
In a further embodiment of the invention, the organic silicon modified phosphate is obtained by reacting hydroxyalkyl polysiloxane represented by the following formula A and polyphosphoric acid represented by the following formula B according to a molar ratio of 1: 2-2.2:
wherein m and n are integers greater than 0, and 8 < m + n < 100;
R1represents methyl or phenyl, and R1The same or different from each other;
R2represents methyl, phenyl or hydroxyA functional group, and R2The same or different from each other;
wherein a represents an integer of 5 to 15, b represents an integer of 0 to 10;
with the proviso that formula A contains at least 2 hydroxyl functional groups.
The organic silicon phosphate is used as a novel flame retardant, combines the advantages of organic silicon flame retardants and phosphate flame retardants, and mainly plays a role in condensed phase flame retardance. The organic silicon flame retardant has the advantages of high efficiency, low toxicity, environmental friendliness and the like, can also be used as a carbon-forming smoke suppressant, and can improve the heat resistance and the processability of the material. After the organosilicon is added, the decomposition temperature of the composite flame-retardant system is increased, the thermal stability of the composite flame-retardant system is improved, and the thermal dispersion temperature is increased along with the increase of the silicon content, which is mainly because an oxygen-insulating and heat-insulating protective layer is formed by-Si-O-bonds and-Si-C-bonds contained in the organosilicon modified phosphate ester flame retardant under the high-temperature condition, so that the thermal decomposition of a matrix material is inhibited while the escape of combustion decomposition products is prevented. Meanwhile, the phosphate group can be decomposed into oxyacid of phosphorus at high temperature, so that dehydration reaction during material decomposition is promoted, a catalytic carbonization effect is achieved, a large amount of heat is absorbed in the process, and a compact carbon layer which is difficult to combust and isolates oxygen and combustible gas is formed.
The m + n is the number of silicon chain links in the polysiloxane, and the low number of the silicon chain links can cause the molecular weight of the organic silicon to be too small, so that the organic silicon cannot play a role in coacervation phase polymerization inhibition in the silicon flame retardant; the flame retardant efficiency can be greatly improved due to the excessively high number of silicon chain links, but the difference between the polarity of the organic silicon phosphate and the polarity of the TPU material is too large, so that the compatibility of the organic silicon phosphate and the TPU material is poor, and the appearance and the mechanical property of the cable material are influenced.
As a further scheme of the invention, the preparation method of the organic silicon phosphate comprises the following steps: under the nitrogen environment, the raw materials A and B are stirred for esterification reaction for 6 to 6.5 hours at the temperature of between 90 and 92 ℃ until the acid value is not changed any more. As is known to the person skilled in the art, the reaction is polyphosphoric acid andthe esterification reaction of the alkyl hydroxyl can be carried out without a catalyst. Polyphosphoric acid is a common commercial product, and the effective content (according to P)2O5Calculated) is generally 85% or more.
The raw material A is hydroxyalkyl polysiloxane, which is known in the industry and is synthesized by the following steps: under the nitrogen environment, the platinum catalyst catalyzes the addition of hydrogen-containing silicone oil and allyl polyether, and the addition reaction is hydrosilylation.
As a further scheme of the invention, the preparation method of the flame-retardant yellowing-resistant TPU cable material comprises the following steps: (A) weighing the metal oxide according to the proportion, drying the metal oxide for 4-4.5h at the temperature of 110-112 ℃ to constant weight, then placing the metal oxide in a high-speed stirrer with the rotating speed of 2000-2200r/min, heating the metal oxide to 80-85 ℃, then adding a silane coupling agent solution diluted by absolute ethyl alcohol, stirring the mixture for 15-20min, then taking the mixture out, and drying the mixture for 4-4.5h at the temperature of 80-82 ℃ to obtain a modified metal oxide for later use; (B) adding the thermoplastic polyurethane into an internal mixer, and internally mixing for 5-10min at the rotating speed of 100-. And (2) weighing organic silicon modified phosphate, Melamine Cyanurate (MCA), an antioxidant and the modified metal oxide obtained in the step (A) according to a proportion, adding the organic silicon modified phosphate, the Melamine Cyanurate (MCA) and the antioxidant into the melted thermoplastic polyurethane, banburying for 20-25min at the temperature of 170-180 ℃, and then extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
1. the flame retardant mechanisms of the inorganic flame retardant and the organic silicon phosphate flame retardant are combined to form a new flame retardant synergistic system, so that the flame retardant efficiency and the flame retardant synergy are improved;
2. after surface treatment, the flame retardant has good compatibility and dispersibility in a system, and the influence on the mechanical property of the TPU cable is reduced;
3. the preparation method is relatively simple and has high construction efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer.
Example 1
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester:
adding 98.0 parts of average structural formula CH into a reaction kettle provided with a mechanical stirring device, a condenser pipe and a thermometer2＝CH-CH2O(CH2CH2O)10(CH2CH(CH3)O)2Allyl polyether of H, 0.18 part by mass of a 2% isopropanol solution of platinum-vinylsiloxane chelate and 0.45 part by mass of 2, 6-di-tert-butyl-p-cresol were heated to 80 ℃ under a nitrogen atmosphere, and when this temperature had been reached, 49.4 parts by weight of an average of the formula H (CH)3)2SiO(Si(CH3)2O)8Si(CH3)2H hydrogen-containing polysiloxane. The reaction was stirred at 80 ℃ for 5h to give a hydroxyalkyl polysiloxane of the average formula:
wherein the content of the first and second substances,
and then maintaining the nitrogen environment, adding 11.2 parts of polyphosphoric acid, and stirring at 90 ℃ for esterification reaction for 6 hours until the acid value is not changed any more, thereby obtaining the organic silicon modified phosphate.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 10 parts of titanium dioxide, drying at 110 ℃ for 4h to constant weight, placing in a high-speed stirrer at the rotating speed of 2000r/min, heating to 80 ℃, adding a KH550 silane coupling agent (2 parts) solution diluted by absolute ethyl alcohol, stirring for 15min, taking out, and drying at 80 ℃ for about 4h to obtain the surface-modified titanium dioxide for later use.
(B) 80 parts of thermoplastic polyurethane are added to an internal mixer and are mixed for 5min at 180 ℃ at a speed of 100r/min until the thermoplastic polyurethane is molten. Weighing 15 parts of organic silicon modified phosphate, 10 parts of Melamine Cyanurate (MCA), 1 part of antioxidant 1010 and the modified metal oxide obtained in the step (A), adding the mixture into the melted thermoplastic polyurethane, banburying at the temperature of 170 ℃ for 25min, and extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
Example 2
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester:
adding 110.0 parts of average structural formula CH into a reaction kettle provided with a mechanical stirring device, a condensing tube and a thermometer2＝CH-CH2O(CH2CH2O)10H allyl polyether, 0.1 part by mass of a 2% solution of platinum-vinylsiloxane chelate in isopropanol and 0.3 part by mass of 2, 6-di-tert-butyl-p-cresol, heated to 80 ℃ under a nitrogen atmosphere, and when this temperature is reached, 50 parts by weight of a solution of the average formula (CH)3)3SiO(Si(CH3)2O)25(HSi(CH3)O)10Si(CH3)3The hydrogen-containing polysiloxane of (1). The reaction was stirred at 80 ℃ for 5h to give a hydroxyalkyl polysiloxane of the average formula:
wherein the content of the first and second substances,
and then maintaining the nitrogen environment, adding 15.3 parts of polyphosphoric acid, and stirring at 90 ℃ for esterification reaction for 6 hours until the acid value is not changed any more, thereby obtaining the organic silicon modified phosphate.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 10 parts of alumina, drying at 110 ℃ for 4h to constant weight, placing in a high-speed stirrer at the rotating speed of 2000r/min, heating to 80 ℃, adding a KH560 silane coupling agent (1 part) solution diluted by absolute ethyl alcohol, stirring for 15min, taking out, and drying at 80 ℃ for about 4h to obtain surface-modified alumina for later use.
(B) 65 parts of thermoplastic polyurethane are added to an internal mixer and are mixed for 5min at 180 ℃ at a speed of 100r/min until the thermoplastic polyurethane is molten. And (2) weighing 20 parts of organic silicon modified phosphate, 15 parts of Melamine Cyanurate (MCA), 1 part of antioxidant 626 and the modified metal oxide obtained in the step (A), adding into the melted thermoplastic polyurethane, banburying at the temperature of 180 ℃ for 20min, and extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
Example 3
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester:
115.5 parts of average structural formula CH are added into a reaction kettle provided with a mechanical stirring device, a condenser pipe and a thermometer2＝CH-CH2O(CH2CH2O)5(CH2CH(CH3)O)5H allyl polyether, 0.12 part by mass of a 2% solution of platinum-vinylsiloxane chelate in isopropanol and 0.45 part by mass of 2, 6-di-tert-butyl-p-cresol, heated to 80 ℃ under a nitrogen atmosphere, and when this temperature is reached, 50 parts by weight of a solution of the average formula (CH)3)3SiO(Si(CH3)2O)23((C6H5)Si(CH3)O)15(HSi(CH3)O)14Si(CH3)3The hydrogen-containing polysiloxane of (1). The reaction was stirred at 80 ℃ for 5h to give a hydroxyalkyl polysiloxane of the average formula:
wherein the content of the first and second substances,
and then maintaining the nitrogen environment, adding 14.6 parts of polyphosphoric acid, and stirring at 90 ℃ for esterification reaction for 6 hours until the acid value is not changed any more, thereby obtaining the organic silicon modified phosphate.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 15 parts of titanium dioxide, drying at 110 ℃ for 4h to constant weight, placing in a high-speed stirrer at the rotating speed of 2000r/min, heating to 80 ℃, adding a KH550 silane coupling agent (5 parts) solution diluted by absolute ethyl alcohol, stirring for 15min, taking out, and drying at 80 ℃ for about 4h to obtain the surface-modified titanium dioxide for later use.
(B) Adding 60 parts of thermoplastic polyurethane into an internal mixer, internally mixing for 5min at 180 ℃ at the rotating speed of 100r/min until the thermoplastic polyurethane is molten, weighing 10 parts of organic silicon modified phosphate, 10 parts of Melamine Cyanurate (MCA), 1.5 parts of antioxidant 168 and the modified metal oxide obtained in the step (A), adding into the molten thermoplastic polyurethane, internally mixing for 25min at the temperature of 175 ℃, and then extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
Example 4
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester:
adding 167 parts of average structural formula CH into a reaction kettle provided with a mechanical stirrer, a condenser pipe and a thermometer2＝CH-CH2O(CH2CH2O)10(CH2CH(CH3)O)10H allyl polyether, 0.24 part of 2 mass percent isopropanol solution of platinum-vinyl siloxane chelate and 0.6 part of 2, 6-di-tert-butyl-p-cresol, heating to 80 ℃ under nitrogen atmosphere, and when the temperature is reached, dropwise adding 50 parts of (CH) as an average formula3)3SiO(Si(CH3)2O)80(HSi(CH3)O)20Si(CH3)3The hydrogen-containing polysiloxane of (1). The reaction was stirred at 80 ℃ for 5h to give a hydroxyalkyl polysiloxane of the average formula:
wherein the content of the first and second substances,
and then maintaining the nitrogen environment, adding 11.1 parts of polyphosphoric acid, and stirring at 90 ℃ for esterification reaction for 6 hours until the acid value is not changed any more, thereby obtaining the organic silicon modified phosphate.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 8 parts of titanium dioxide and 4 parts of alumina, drying for 4 hours at 110 ℃ to constant weight, placing in a high-speed stirrer with the rotating speed of 2000r/min, heating to 80 ℃, adding a KH550 silane coupling agent (3 parts) solution diluted by absolute ethyl alcohol, stirring for 15 minutes, taking out, and drying at 80 ℃ for about 4 hours to obtain surface-modified titanium dioxide and alumina for later use.
(B) Adding 90 parts of thermoplastic polyurethane into an internal mixer, internally mixing for 5min at the rotating speed of 100r/min at 180 ℃ until the thermoplastic polyurethane is molten, weighing 15 parts of organic silicon modified phosphate, 5 parts of Melamine Cyanurate (MCA), 2 parts of antioxidant 1010 and the modified metal oxide obtained in the step (A), adding the mixture into the molten thermoplastic polyurethane, internally mixing for 25min at the temperature of 175 ℃, and then extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
Example 5
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester:
adding 206 parts of average structural formula CH into a reaction kettle provided with a mechanical stirrer, a condenser pipe and a thermometer2＝CH-CH2O(CH2CH2O)15(CH2CH(CH3)O)10Allyl polyether of H, 0.32 part of isopropanol solution of platinum-vinylsiloxane chelate with a mass fraction of 2% and 0.8 part of 2, 6-di-tert-butyl-p-cresol, heated to 80 ℃ under nitrogen, and when this temperature is reached, 50 parts of an average of the formula H (CH) are added dropwise3)2SiO(Si(CH3)2O)70(HSi(CH3)O)15SiH(CH3)2The hydrogen-containing polysiloxane of (1). The reaction was stirred at 80 ℃ for 5h to give a hydroxyalkyl polysiloxane of the average formula:
wherein the content of the first and second substances,
and then maintaining the nitrogen environment, adding 11 parts of polyphosphoric acid, and stirring at 90 ℃ for esterification reaction for 6 hours until the acid value is not changed any more, thereby obtaining the organic silicon modified phosphate.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 12 parts of titanium dioxide, drying at 110 ℃ for 4h to constant weight, placing in a high-speed stirrer at the rotating speed of 2000r/min, heating to 80 ℃, adding a KH550 silane coupling agent (3 parts) solution diluted by absolute ethyl alcohol, stirring for 15min, taking out, and drying at 80 ℃ for about 4h to obtain surface-modified titanium dioxide for later use.
(B) 80 parts of thermoplastic polyurethane are added to an internal mixer and are mixed for 5min at 180 ℃ at a speed of 100r/min until the thermoplastic polyurethane is molten. Weighing 15 parts of organic silicon modified phosphate, 12 parts of Melamine Cyanurate (MCA), 0.5 part of antioxidant 1010 and the modified metal oxide obtained in the step (A), adding the mixture into the melted thermoplastic polyurethane, banburying at the temperature of 175 ℃ for 25min, and extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
Example 6
The embodiment of the invention prepares a flame-retardant yellowing-resistant TPU cable material, which comprises the following specific steps:
preparing organic silicon modified phosphate ester: the preparation method is the same as example 5.
Preparing a flame-retardant yellowing-resistant TPU cable material:
(A) weighing 20 parts of titanium dioxide, drying at 110 ℃ for 4h to constant weight, placing in a high-speed stirrer at the rotating speed of 2000r/min, heating to 80 ℃, adding a KH550 silane coupling agent (2 parts) solution diluted by absolute ethyl alcohol, stirring for 15min, taking out, and drying at 80 ℃ for about 4h to obtain the surface-modified titanium dioxide for later use.
(B) 85 parts of thermoplastic polyurethane are added to an internal mixer and mixed for 5min at 180 ℃ at a speed of 100r/min until the thermoplastic polyurethane is molten. And (2) weighing 20 parts of organic silicon modified phosphate, 10 parts of Melamine Cyanurate (MCA), 1 part of antioxidant 1010 and the modified metal oxide obtained in the step (A), adding into the melted thermoplastic polyurethane, banburying at 175 ℃ for 25min, and extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The block sample obtained in the embodiment is hot pressed for 10min under 10MPa on a pressure forming machine to prepare a TPU standard plate for testing, the vertical combustion is tested according to GB/T2408-1996, and the sample size is 125mm x 12.5mm x 1.6 mm; the oxygen index was tested according to GB/T2408 + 1993 with sample size 85mm 10mm 1.6 mm.
The detailed test data of the flame-retardant yellowing-resistant TPU cable materials prepared in the above examples 1-6 are shown in Table 1.
TABLE 1 flame retardancy test of different TPU Cable materials
| Phenomenon of combustion | Burning time-s | Oxygen index% | |
| Example 1 | No molten drop and little black smoke | 5 | 30.1 |
| Example 2 | Less molten drop and less black smoke | 8 | 28.1 |
| Example 3 | Less molten drop and less black smoke | 7 | 29.4 |
| Example 4 | No molten drop and little black smoke | 12 | 26.7 |
| Example 5 | No molten drop and little black smoke | 6 | 29.3 |
| Example 6 | No molten drop and little black smoke | 7 | 29.5 |
From the data, the organic flame retardant and the inorganic flame retardant of the flame-retardant yellowing-resistant TPU cable materials prepared in the examples 1-6 have good compatibility, dispersibility and synergy in a system, and the prepared TPU cable materials have good flame retardance and yellowing resistance and are applied to various power industries.
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 (8)
1. The flame-retardant yellowing-resistant TPU cable material is characterized by comprising the following raw materials in parts by weight: 60-90 parts of thermoplastic polyurethane, 10-20 parts of organic silicon modified phosphate, 10-15 parts of a metal oxide anti-yellowing agent, 5-15 parts of melamine cyanurate, 1-5 parts of a silane coupling agent and 0.5-2 parts of an antioxidant.
2. The flame retardant yellowing-resistant TPU cable material of claim 1, wherein the metal oxide yellowing-resistant agent is one or two selected from titanium dioxide and aluminum oxide.
3. The flame retardant yellowing-resistant TPU cable material of claim 1, wherein the silane coupling agent is selected from one or more of KH550, KH560 and KH 570.
4. The flame retardant yellowing-resistant TPU cable material of claim 1, wherein the antioxidant is selected from one or more of antioxidant 1010, antioxidant 626 and antioxidant 168.
5. The flame-retardant yellowing-resistant TPU cable material according to claim 1, wherein the organosilicon modified phosphate is obtained by reacting hydroxyalkyl polysiloxane represented by the following formula A with polyphosphoric acid represented by the following formula B in a molar ratio of 1: 2-2.2:
wherein m and n are integers greater than 0, and 8 < m + n < 100;
R1represents methyl or phenyl, andR1the same or different from each other;
R2represents a methyl, phenyl or hydroxy functional group, and R2The same or different from each other;
wherein a represents an integer of 5 to 15, b represents an integer of 0 to 10;
with the proviso that formula A contains at least 2 hydroxyl functional groups.
6. The flame-retardant yellowing-resistant TPU cable material of claim 5, wherein the preparation method of the organic silicon phosphate comprises the following steps: under the nitrogen environment, the raw materials A and B are stirred for esterification reaction for 6 to 6.5 hours at the temperature of between 90 and 92 ℃ until the acid value is not changed any more.
7. The preparation method of the flame-retardant yellowing-resistant TPU cable material of claims 1-6 is characterized by comprising the following steps:
(A) weighing the metal oxide according to the proportion, drying the metal oxide for 4-4.5h at the temperature of 110-112 ℃ to constant weight, then placing the metal oxide in a high-speed stirrer with the rotating speed of 2000-2200r/min, heating the metal oxide to 80-85 ℃, then adding a silane coupling agent solution diluted by absolute ethyl alcohol, stirring the mixture for 15-20min, then taking the mixture out, and drying the mixture for 4-4.5h at the temperature of 80-82 ℃ to obtain a modified metal oxide for later use;
(B) adding the thermoplastic polyurethane into an internal mixer, and internally mixing for 5-10min at the rotating speed of 100-. And (2) weighing the organic silicon modified phosphate, the melamine cyanurate, the antioxidant and the modified metal oxide obtained in the step (A) according to the proportion, adding the organic silicon modified phosphate, the melamine cyanurate, the antioxidant and the modified metal oxide into the melted thermoplastic polyurethane, banburying for 20-25min at the temperature of 170-180 ℃, and then extruding and granulating by a double-screw extruder to obtain the flame-retardant yellowing-resistant TPU cable material.
8. The application of the flame-retardant yellowing-resistant TPU cable material disclosed in claims 1-7 in various power industries.
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