CN110951043A - High-efficiency halogen-free flame-retardant TPU material and preparation method thereof - Google Patents
High-efficiency halogen-free flame-retardant TPU material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to a high-efficiency halogen-free flame-retardant TPU material and a preparation method thereof. The high-efficiency halogen-free flame-retardant TPU material is prepared from polyester polyol, diisocyanate, a chain extender, a lubricant, a flame retardant and a catalyst, wherein the flame retardant is a hexaphenoxycyclotriphosphazene and phytate compound flame retardant. The efficient halogen-free flame retardant TPU material disclosed by the invention has the characteristics that the compatibility of the flame retardant in the TPU matrix is good, the dispersity is uniform, the flame retardant performance of the material can reach V-0 level by adding 18 wt% of the composite flame retardant through a preparation method of additive addition and in-situ synthesis, and the migration resistance and the mechanical property are good. The preparation method provided by the invention adopts one-step synthesis, is simple and easy to operate, and is scientific and reasonable.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to a high-efficiency halogen-free flame-retardant TPU material and a preparation method thereof.
Background
Polyurethane refers to a kind of high molecular material containing repeated urethane groups in the main chain of the molecule, and is a typical (AB) n-type block linear polymer, and soft segments and hard segments are alternately arranged to form a repeated structural unit. Due to the special molecular structure, the material has excellent physical and mechanical properties such as high modulus, high strength, high elongation, high elasticity, high wear resistance and the like, and is widely applied to a plurality of fields such as sheets, shoe materials, automobiles, cables, medical treatment, films and the like. At present, in some special fields, the TPU material is required to have certain special functional characteristics according to different use environments, and for example, the TPU with flame retardant grade is required in the fields of electric wires and cables, electronic appliances and the like. However, the Limited Oxygen Index (LOI) of the TPU material is about 18 percent, the TPU material belongs to a flammable material, and the TPU material has serious molten drops after combustion and releases a large amount of harmful gases during combustion, so that the TPU material needs to be subjected to flame retardant modification to meet the requirement.
At present, the most widely used method is to add flame retardant into TPU by a mechanical mixing method to make the composite material have flame retardance. For example, patent CN109385071A, "a TPU material with flame retardant property reaching V-0 level of vertical burning" and a preparation method thereof ", obtains a TPU material with excellent flame retardant property and V-0 level of vertical burning by applying a phosphorus-nitrogen flame retardant system, a carbon forming agent and a flame retardant auxiliary agent to thermoplastic polyurethane and simultaneously changing the proportion relationship among the components. However, although the method can prepare the TPU material with the flame retardant grade reaching V-0 grade, the total amount of the added flame retardant accounts for 68% of the TPU, and the high-dosage flame retardant has the problems of compatibility, dispersibility, interfacial property and the like in a TPU matrix, and is likely to volatilize and migrate to influence the stability of the material. Meanwhile, the TPU particles and the flame retardant are mixed to prepare the TPU, and the TPU is subjected to secondary processing to influence the overall performance of the material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the high-efficiency halogen-free flame retardant TPU material is provided, and the flame retardant grade of the TPU material can reach V-0 grade and the flame retardant efficiency is high by adding a small amount of hexaphenoxy cyclotriphosphazene (HPCTP) and phytate compound flame retardant in the production process of the TPU material; meanwhile, the invention also provides a preparation method of the compound, which is synthesized in one step, simple, easy to operate, scientific and reasonable.
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
wherein the dosage of the catalyst is 0.02-0.06% of the total mass of the raw materials.
The polyester polyol is polyester diol and comprises one or more of polyethylene adipate-1, 2-propylene glycol diol, polyethylene adipate-1, 4-butylene glycol diol or polyethylene adipate-1, 6-hexanediol diol, and the average molecular weight of the polyester polyol is 1000-3000.
The diisocyanate comprises 4,4 '-diphenylmethane diisocyanate (MDI), 4' -dicyclohexylmethane diisocyanate (H)12MDI), phenylene-1, 4-diisocyanate (PPDI), Toluene Diisocyanate (TDI) or 1, 5-Naphthalene Diisocyanate (NDI), preferably 4,4' -diphenylmethane diisocyanate (MDI).
The chain extender is micromolecular dihydric alcohol and comprises one or more of 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol or 1, 6-hexanediol.
The lubricant comprises one or more of glyceryl monostearate, stearic acid amide, ethylene bis-stearic acid amide, pentaerythritol stearate, E wax or oleic acid amide, and two or more of the components can be mixed in any proportion.
The flame retardant is a hexaphenoxycyclotriphosphazene and phytate compound flame retardant, wherein the using amount of the Hexaphenoxycyclotriphosphazene (HPCTP) is 8-15% of the total mass of the raw materials; the phytate comprises one or more of sodium phytate, magnesium phytate and calcium phytate, and the dosage of the phytate is 10-20% of the total mass of the raw materials. Wherein the molecular structure of the phytate is as follows:
the catalyst comprises one of organic bismuth, organic tin or titanate catalyst, preferably tin octoate (T-9).
The preparation method of the high-efficiency halogen-free flame-retardant TPU material comprises the following steps:
(1) adding polyester polyol, a lubricant and a catalyst into a reaction kettle A, uniformly mixing, adding diisocyanate into a reaction kettle B, adding a chain extender into a reaction kettle C, and adding Hexaphenoxycyclotriphosphazene (HPCTP) and phytate into an additive auxiliary equipment;
(2) adding the raw materials in the reaction kettles A, B and C into a rotary mixer, uniformly mixing, injecting into a double-screw extruder, injecting the mixture of Hexaphenoxycyclotriphosphazene (HPCTP) and phytate into the double-screw extruder through an additive device for reaction and plasticization, and granulating through an underwater granulator to obtain the high-efficiency halogen-free flame-retardant TPU material.
The temperature of the reaction kettle A in the step (1) is 95-110 ℃, the temperature of the reaction kettle B is 65-75 ℃, and the temperature of the reaction kettle C is 45-65 ℃.
The rotating speed of the rotary mixer in the step (2) is 2000-3000 r/min, the rotating speed of the additive equipment is 15-60r/min, the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed is 180-240 r/min.
Preferably, the preparation method of the high-efficiency halogen-free flame retardant TPU material comprises the following steps:
(1) adding polyester polyol, a lubricant and a catalyst into a reaction kettle A with a mechanical stirring and temperature control system, and setting the temperature to be 95-110 ℃; placing diisocyanate in a reaction kettle B, and setting the temperature to be 65-75 ℃; placing the chain extender into a C reaction kettle, and setting the temperature to be 45-65 ℃; adding Hexaphenoxycyclotriphosphazene (HPCTP) and phytate into the additive auxiliary equipment.
(2) When the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 2000 r/min-3000 r/min by a filling system with accurate measurement, the raw materials are uniformly mixed and then injected into a feeding port of a double-screw extruder, the accurately measured Hexaphenoxycyclotriphosphazene (HPCTP) and phytate are injected into the feeding port of the double-screw extruder by an additional auxiliary agent device, the mixture is uniformly reacted and plasticized in a cylinder of the double-screw extruder, and the mixture is cut into elliptical particles with uniform particle size by an underwater granulator. Wherein the temperature of the double-screw extruder is 150-200 ℃, the rotating speed of the double-screw extruder is 180-240 r/min, and the rotating speed of the added auxiliary agent equipment is 15-60 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phytate is an organic phosphate with a special molecular structure, and particularly shows an excellent flame retardant effect when being applied to a polyester TPU material after being compounded with hexaphenoxycyclotriphosphazene, and the flame retardant property of the material can reach V-0 grade only by 18 percent of the addition amount of a flame retardant.
(2) The efficient halogen-free flame retardant TPU material disclosed by the invention has the characteristics of good compatibility and uniform dispersibility of the flame retardant in the TPU matrix, migration resistance (no powder discharge after 96 hours of accelerated test) and high mechanical property retention rate by a preparation method of additive addition and in-situ synthesis.
Detailed Description
The present invention will be further described with reference to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
poly-1, 4-butylene glycol adipate diol (M ═ 2000): 53.04 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 22.85 percent
1, 4-Butanediol (BDO): 5.71 percent
Stearic acid amide: 0.2 percent of
Oleic acid amide: 0.2 percent of
Hexaphenoxycyclotriphosphazene (HPCTP): 8 percent of
Sodium phytate: 10 percent;
wherein the dosage of the catalyst stannous octoate (T-9) is 0.03 percent of the total mass of the raw materials.
The preparation method comprises the following steps: 5304g of poly (1, 4-butylene adipate) glycol (M ═ 2000), 20g of stearic acid amide, 20g of oleic acid amide and 3g of stannous octoate are added into a reaction kettle A with a mechanical stirring and temperature control system, the temperature is set to be 110 ℃, and stirring is carried out; 2285g of MDI-100 is placed in a B reaction kettle, and the temperature is set to be 75 ℃; 571g of BDO were placed in a C reactor with a set temperature of 65 ℃. After the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 2500r/min according to the components through a filling system with accurate measurement, and the raw materials are uniformly mixed and injected into a feeding port of a double-screw extruder; fully mixing 800g of HPCTP and 1000g of sodium phytate, adding the mixture into an additional auxiliary agent device with the rotating speed of 25r/min, accurately metering and injecting the mixture into a feeding port of a double-screw extruder, uniformly reacting and plasticizing the mixture in a cylinder of the double-screw extruder, and cutting the mixture into elliptical particles with uniform particle size by an underwater granulator, wherein the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Example 2
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
polyethylene-1, 2-propanediol adipate glycol (M ═ 3000): 41.89 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 25.93 percent
1, 4-Butanediol (BDO): 6.98 percent
Pentaerythritol stearate: 0.1 percent of
E, wax: 0.1 percent of
Hexaphenoxycyclotriphosphazene (HPCTP): 10 percent of
Magnesium phytate: 15 percent;
wherein the dosage of the catalyst bismuth neodecanoate (C-83) is 0.05 percent of the total mass of the raw materials.
The preparation method comprises the following steps: 4189g of polyethylene glycol adipate-1, 2-propylene glycol diol (M ═ 3000), 10g of pentaerythritol stearate, 10g of E wax, and 5g of bismuth neodecanoate (C-83) were added to a reaction vessel a equipped with a mechanical stirring and temperature control system, and stirred at a set temperature of 100 ℃; placing 2593g of MDI-100 in a B reaction kettle, and setting the temperature to be 70 ℃; 698g of BDO was placed in a C reactor, setting the temperature at 60 ℃. After the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 3000r/min according to the components through a filling system with accurate measurement, and the raw materials are uniformly mixed and injected into a feeding port of a double-screw extruder; adding 1000g of HPCTP and 1500g of magnesium phytate into an additional auxiliary agent device with the rotating speed of 45r/min after fully mixing, accurately metering and injecting the mixture into a feeding port of a double-screw extruder, uniformly reacting and plasticizing the mixture in a cylinder of the double-screw extruder, and cutting the mixture into elliptical particles with uniform particle size by an underwater granulator, wherein the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed of the double-screw extruder is 220 r/min.
Example 3
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
polyethylene adipate 1, 4-butanediol glycol (M ═ 1000): 31.15 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 26.68 percent of
1, 4-Butanediol (BDO): 7.07 percent
Ethylene bis stearamide: 0.1 percent of
Hexaphenoxycyclotriphosphazene (HPCTP): 15 percent of
Calcium phytate: 20 percent;
wherein the dosage of the catalyst stannous octoate (T-9) is 0.06 percent of the total mass of the raw materials.
The preparation method comprises the following steps: adding 3115g of polyethylene glycol adipate-1, 4-butanediol glycol diol (M is 1000), 10g of ethylene bis stearamide and 6g of stannous octoate into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 110 ℃, and stirring; 2668g of MDI-100 is placed in a B reaction kettle, and the temperature is set to 65 ℃; 707g of BDO were placed in a C reactor with a set temperature of 50 ℃. After the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 2200r/min according to the components through a filling system with accurate measurement, and the raw materials are uniformly mixed and injected into a feeding port of a double-screw extruder; the method comprises the steps of fully mixing 1500g of HPCTP and 2000g of calcium phytate, adding the mixture into an additional auxiliary agent device with the rotating speed of 60r/min, accurately metering and injecting the mixture into a feeding port of a double-screw extruder, uniformly reacting and plasticizing the mixture in a cylinder of the double-screw extruder, and cutting the mixture into elliptical particles with uniform particle size by an underwater granulator, wherein the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed of the double-screw extruder is 240 r/min.
Comparative example 1
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
poly-1, 4-butylene glycol adipate diol (M ═ 2000): 64.74 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 27.89 percent
1, 4-Butanediol (BDO): 6.97 percent
Stearic acid amide: 0.2 percent of
Oleic acid amide: 0.2 percent;
wherein the dosage of the catalyst stannous octoate (T-9) is 0.03 percent of the total mass of the raw materials.
The preparation method comprises the following steps: 6474g of poly (1, 4-butylene adipate) glycol (M ═ 2000), 20g of stearic acid amide, 20g of oleic acid amide and 3g of stannous octoate are added into a reaction kettle A with a mechanical stirring and temperature control system, the temperature is set to be 110 ℃, and stirring is carried out; 2789g of MDI-100 is placed in a B reaction kettle, and the set temperature is 75 ℃; 697g of BDO were placed in a C reactor with a set temperature of 65 ℃. When the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 2500r/min through a filling system with accurate measurement, the raw materials are uniformly mixed and then injected into a feeding port of a double-screw extruder, the mixture is uniformly reacted and plasticized in a cylinder body of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Comparative example 2
The high-efficiency halogen-free flame-retardant TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
poly-1, 4-butylene glycol adipate diol (M ═ 2000): 58.24 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 25.09 percent
1, 4-Butanediol (BDO): 6.27 percent
Stearic acid amide: 0.2 percent of
Oleic acid amide: 0.2 percent of
Sodium phytate: 10 percent;
wherein the dosage of the catalyst stannous octoate (T-9) is 0.03 percent of the total mass of the raw materials.
The preparation method comprises the following steps: 5824g of poly 1, 4-butylene adipate diol (M ═ 2000), 20g of stearic acid amide, 20g of oleic acid amide and 3g of stannous octoate were added to a reaction kettle a with a mechanical stirring and temperature control system, the temperature was set at 110 ℃, and stirring was performed; 2509g of MDI-100 is placed in a B reaction kettle, and the temperature is set to be 75 ℃; 627g of BDO was placed in a C reactor setting at 65 ℃. After the materials in each reaction kettle are uniformly stirred and the temperature is stable, the raw materials in A, B and C reaction kettles are added into a rotary mixer with the rotating speed of 2500r/min according to the components through a filling system with accurate measurement, and the raw materials are uniformly mixed and injected into a feeding port of a double-screw extruder; adding 1000g of sodium phytate into an additional auxiliary agent device with the rotating speed of 25r/min, accurately metering and injecting the sodium phytate into a feeding port of a double-screw extruder, uniformly reacting and plasticizing a mixture in a cylinder of the double-screw extruder, and cutting the mixture into elliptical particles with uniform particle size by an underwater granulator, wherein the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Performance detection
The performance test is carried out on the halogen-free flame retardant TPU materials prepared in the embodiments 1-3 and the comparative examples 1-2, namely the Shore hardness test of the thermoplastic polyurethane elastomer is carried out according to GB/T531-2009 standard; the mechanical property test executes GB/T528-2009 standard; the flame retardant performance test implements UL-94 standard; migration resistance: in a constant temperature and humidity chamber, the precipitation condition of the material surface is observed at 85 ℃ and 85 percent humidity. The results are shown in Table 1.
TABLE 1 summary table of TPU material property testing
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Hardness (shoreA) | 85 | 90 | 95 | 85 | 85 |
| Tensile Strength (MPa) | 34 | 30 | 32 | 35 | 35 |
| Flame retardant rating | V-0 | V-0 | V-0 | / | V-1 |
According to the detection results, the high-efficiency halogen-free flame retardant TPU material disclosed by the invention has the advantages that the flame retardant efficiency of the halogen-free flame retardant is improved by adding the Hexaphenoxycyclotriphosphazene (HPCTP) and phytate compound flame retardant, and the flame retardant performance of the material can reach V-0 level only by 18% of the addition amount of the flame retardant. By the preparation method of additive addition and in-situ synthesis, the flame retardant has the characteristics of good compatibility and uniform dispersibility in the TPU matrix, migration resistance, high flame retardance and good mechanical property.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A high-efficiency halogen-free flame retardant TPU material is characterized in that: the catalyst is prepared from the following raw materials in percentage by mass and a catalyst:
wherein the dosage of the catalyst is 0.02-0.06% of the total mass of the raw materials.
2. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the polyester polyol is polyester diol and comprises one or more of polyethylene adipate-1, 2-propylene glycol diol, polyethylene adipate-1, 4-butylene glycol diol or polyethylene adipate-1, 6-hexanediol diol, and the average molecular weight of the polyester polyol is 1000-3000.
3. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the diisocyanate is one of 4,4 '-diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, phenylene-1, 4-diisocyanate, toluene diisocyanate or 1, 5-naphthalene diisocyanate.
4. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the chain extender is micromolecular dihydric alcohol and is one or more of 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol or 1, 6-hexanediol.
5. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the lubricant is one or more than one of glyceryl monostearate, stearic acid amide, ethylene bis-stearic acid amide, pentaerythritol stearate, E wax or oleamide in any proportion.
6. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the catalyst is organic bismuth, organic tin or titanate catalyst.
7. The high efficiency halogen free flame retardant TPU material of claim 1, wherein: the flame retardant is a hexaphenoxycyclotriphosphazene and phytate compound flame retardant, wherein the dosage of the hexaphenoxycyclotriphosphazene is 8-15% of the total mass of the raw materials, the phytate comprises one or more of sodium phytate, magnesium phytate or calcium phytate, the dosage of the phytate is 10-20% of the total mass of the raw materials, and the molecular structure of the phytate is as follows:
8. a preparation method of the high-efficiency halogen-free flame retardant TPU material as claimed in any one of claims 1 to 7 is characterized in that: the method comprises the following steps:
(1) adding polyester polyol, a lubricant and a catalyst into a reaction kettle A, uniformly mixing, adding diisocyanate into a reaction kettle B, adding a chain extender into a reaction kettle C, and adding a flame retardant into an auxiliary agent adding device;
(2) adding the raw materials in the reaction kettles A, B and C into a rotary mixer, uniformly mixing, injecting the mixture into a double-screw extruder, injecting the flame retardant into the double-screw extruder through an additional auxiliary agent device for reaction and plasticization, and granulating the mixture by an underwater granulator to obtain the high-efficiency halogen-free flame-retardant TPU material.
9. The preparation method of the high-efficiency halogen-free flame retardant TPU material of claim 8, wherein the method comprises the following steps: the temperature of the reaction kettle A in the step (1) is 95-110 ℃, the temperature of the reaction kettle B is 65-75 ℃, and the temperature of the reaction kettle C is 45-65 ℃.
10. The preparation method of the high-efficiency halogen-free flame retardant TPU material of claim 8, wherein the method comprises the following steps: the rotating speed of the rotary mixer in the step (2) is 2000-3000 r/min; the rotating speed of the additive equipment is 15-60 r/min; the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed is 180-240 r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112143215A (en) * | 2020-10-16 | 2020-12-29 | 界首市宏达塑业有限公司 | High-flame-retardant polyurethane plastic particle and preparation method thereof |
| CN112480353A (en) * | 2020-11-30 | 2021-03-12 | 山东一诺威聚氨酯股份有限公司 | Super-oil-resistant heat-resistant TPU material and preparation method thereof |
| CN116589655A (en) * | 2023-06-21 | 2023-08-15 | 眉山尤博瑞新材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143215A (en) * | 2020-10-16 | 2020-12-29 | 界首市宏达塑业有限公司 | High-flame-retardant polyurethane plastic particle and preparation method thereof |
| CN112480353A (en) * | 2020-11-30 | 2021-03-12 | 山东一诺威聚氨酯股份有限公司 | Super-oil-resistant heat-resistant TPU material and preparation method thereof |
| CN116589655A (en) * | 2023-06-21 | 2023-08-15 | 眉山尤博瑞新材料有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
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