CN103087504B - Flame-retardant thermoplastic polyurethane and preparation method thereof - Google Patents
Flame-retardant thermoplastic polyurethane and preparation method thereof Download PDFInfo
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- CN103087504B CN103087504B CN201310022859.8A CN201310022859A CN103087504B CN 103087504 B CN103087504 B CN 103087504B CN 201310022859 A CN201310022859 A CN 201310022859A CN 103087504 B CN103087504 B CN 103087504B
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Abstract
The invention discloses a flame-retardant application of phenyl aluminum hypophosphite in thermoplastic polyurethane (TPU), and flame-retardant TPU comprises the following components in parts by weight: 10-20 parts of the phenyl aluminum hypophosphite, 100 parts of TPU, 1-15 parts of flame-retardant synergist, 1-10 parts of smoke suppressant, 0.5-2 parts of antioxidant, 1 part of coupling agent and 0.5 part of lubricating agent. According to the flame-retardant TPU disclosed by the invention, coating modification treatment is firstly performed on the surface of the phenyl aluminum hypophosphite by using the flame-retardant synergist, then the phenyl aluminum hypophosphite is mixed with TPU masterbatch and other materials uniformly at a high speed, a twin-screw extruding machine is further used for mixing, extrusion and granulation, then molding treatment is performed, and the flame-retardant TPU prepared by the method has excellent fire resistance on the basis of ensuring mechanical properties; and simultaneously, the materials of the flame-retardant TPU disclosed by the invention are halogen-free, so that smoke generated during combustion is less, the environmental pollution is low, and the flame-retardant TPU can be widely applied to public places, home decoration and other occasions.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of flame-proof thermoplastic polyurethane and preparation method thereof.
Background technology
Thermoplastic polyurethane (TPU) has that wear resistance is good, durometer level is wide, high-tenacity and elongation high, the features such as good damping effect, oil resistance are good, are the synthetic materials of a class between plastics and rubber, are described as " third generation synthetic rubber ".Be widely used in industries such as automotive industry, aerospace, telecommunications, textile industries.
The weak point of TPU is very easily to burn, and discharges the toxic gases such as HCN, CO after burning, very easily causes people's death by suffocation.A large amount of heat is released in burning simultaneously, and flame transmission speed is fast, and with drip phenomenon, pole fire hazardous.Because TPU is widely used, therefore also more and more stricter, particularly more urgent to the raising of its flame retardant properties to the requirement of its over-all properties.
General TPU fire retardant contains halogen, not only to environment, but also can discharge harmful corrosive gases, the life and health of serious threat people, and then the application limiting TPU.
summary of the invention
The object of the invention is to the defect for above-mentioned thermoplastic polyurethane (TPU), a kind of flame-proof thermoplastic polyurethane and preparation method thereof is provided, this flame-proof thermoplastic polyurethane is on the basis ensureing its mechanical property, there is excellent flame retardant properties, the occasion such as public place, home decoration can be applied to widely.
The present invention is achieved through the following technical solutions:
A kind of flame-proof thermoplastic polyurethane, is made up of following parts by weight of component, phenyl hypo-aluminum orthophosphate 10-20 part, thermoplastic polyurethane 100 parts, retardant synergist 1-15 part, smoke suppressant 1-10 part, oxidation inhibitor 0.5-2 part, coupling agent 1 part, lubricant 0.5 part.
The further improvement project of the present invention is, described retardant synergist be zinc borate, Precondensed UreaFormaldehyde Resin, resol one or several.
The present invention further improvement project is, described smoke suppressant be magnesium hydroxide, aluminium hydroxide one or several.
The present invention further improvement project is, described oxidation inhibitor is irgasfos 168 or antioxidant 1010.
The present invention further improvement project is, described coupling agent is silane coupling agent.
The present invention further improvement project is, described lubricant is Zinic stearas or calcium stearate.
A preparation method for flame-proof thermoplastic polyurethane, comprises the following steps, by parts by weight of component according to claim 1,
(1) first with retardant synergist, surface coating modification process is carried out to phenyl hypo-aluminum orthophosphate, and then even with thermoplastic polyurethane, smoke suppressant, oxidation inhibitor, coupling agent, lubricant high-speed mixing;
(2) mixture that step (1) obtained loads that twin screw extruder mixes further, melting, extrude, and then carries out forming processes, finally obtains flame-proof thermoplastic polyurethane.
The present invention further improvement project is, melting, the extrusion temperature scope of described twin screw extruder are 100-150 DEG C.
The present invention further improvement project is, described forming processes condition is: temperature about 195 DEG C, pressure about 1.5Mpa, hot pressing about 20min, cold pressing about 15min.
Beneficial effect of the present invention:
First the present invention carries out coating modification process with retardant synergist to phenyl hypo-aluminum orthophosphate surface, then high-speed mixing is carried out with TPU master batch and unclassified stores even, extruding pelletization is mixed further again with twin screw extruder, then forming processes is carried out, fire-retardant TPU obtained is by this method on the basis ensureing its mechanical property, be provided with excellent flame retardant properties, simultaneously, material Halogen of the present invention, burning fuming amount is few, environmental pollution is little, can be applied to the occasion such as public place, home decoration widely.
Embodiment
Describe the present invention in detail below in conjunction with each embodiment, the component in following table mixed in twin screw extruder, the chemical property according to TPU is set in twin screw extruder temperature between 100-150 DEG C.Then obtained master batch is injection molded into sample, according to the flammability test of UL94 standard, its concrete regulation:
1. with 23 DEG C and 50% relative humidity adjustment sample;
2. position vertical for the sample of adjustment is placed on the about 20cm place of cotton pad apart from below;
3. each sample flame burns 2 times.
Table one
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| TPU | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Phenyl hypo-aluminum orthophosphate | 20 | 18 | 16 | 14 | 10 | 12 | 10 | 16 | 20 | 14 | 14 |
| Magnesium hydroxide | 7 | 10 | 3 | 7 | 2 | 7 | 7 | ||||
| Aluminium hydroxide | 3 | 5 | 4 | 1 | 8 | 7 | 3 | 3 | |||
| Zinc borate | 15 | 5 | 3 | 1 | 10 | 5 | |||||
| Precondensed UreaFormaldehyde Resin | 15 | 5 | 4 | 3 | 5 | 5 | |||||
| Resol | 15 | 5 | 5 | 5 | 4 | 3 | 5 | ||||
| Irgasfos 168 | 0.5 | 1 | 1.5 | 1.5 | 2 | 1.5 | |||||
| Antioxidant 1010 | 2 | 1.5 | 1 | 0.5 | 1.5 | ||||||
| Silane coupling agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Zinic stearas | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||||||
| Calcium stearate | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Preparation method is as follows:
Embodiment 1
Component each in upper table is weighed by weight, first with zinc borate, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature about 195 DEG C, about 1.5MPa, hot pressing about 20min, cold pressing about 15min.
Embodiment 2
Component each in upper table is weighed by weight, first with Precondensed UreaFormaldehyde Resin, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 3
Component each in upper table is weighed by weight, first with resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 4
Component each in upper table is weighed by weight, first with zinc borate, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100 DEG C of-150 DEG C of temperature ranges, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 5
Component each in upper table is weighed by weight, first with Precondensed UreaFormaldehyde Resin, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 6
Component each in upper table is weighed by weight, first with zinc borate, Precondensed UreaFormaldehyde Resin, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 7
Component each in upper table is weighed by weight, first with zinc borate, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195OC, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 8
Component each in upper table is weighed by weight, first with zinc borate, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 9
Component each in upper table is weighed by weight, first with Precondensed UreaFormaldehyde Resin, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100-150 DEG C of temperature range, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 10
Component each in upper table is weighed by weight, first with zinc borate, Precondensed UreaFormaldehyde Resin, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100 DEG C of-150 DEG C of temperature ranges, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Embodiment 11
Component each in upper table is weighed by weight, first with Precondensed UreaFormaldehyde Resin, resol, coating modification process is carried out to phenyl hypo-aluminum orthophosphate surface, by each component at high-speed mixer mixing 15min, then utilize twin screw extruder to mix further, melting in 100 DEG C of-150 DEG C of temperature ranges, to extrude, and on vulcanizer compressing tablet, temperature 195 DEG C, 1.5MPa, hot pressing 20min, cold pressing 15min.
Gained sample in embodiment 1-11 is carried out flame retardant test, and bar-shaped sample is of a size of: 125mm, wide 13.0mm, and thickness is 3.2mm, and combustionproperty performs according to UL94 standard, the results are shown in Table two.
Table two
| Performance index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Combustionproperty | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-0 | V-0 | V-0 | V-0 |
To sum up, the phenyl hypo-aluminum orthophosphate system be applied in the present invention, it has good flame retardant effect to TPU.
Above-mentioned embodiment does not limit technical scheme of the present invention in any form, and the technology that the mode that every employing is equal to replacement or equivalence change obtains all drops on protection scope of the present invention.
Claims (8)
1. a flame-proof thermoplastic polyurethane, it is characterized in that: be made up of following parts by weight of component, phenyl hypo-aluminum orthophosphate 10-20 part, thermoplastic polyurethane 100 parts, retardant synergist 1-15 part, smoke suppressant 1-10 part, oxidation inhibitor 0.5-2 part, coupling agent 1 part, lubricant 0.5 part;
Comprise the following steps, by above-mentioned parts by weight of component,
(1) first with retardant synergist, surface coating modification process is carried out to phenyl hypo-aluminum orthophosphate, and then even with thermoplastic polyurethane, smoke suppressant, oxidation inhibitor, coupling agent, lubricant high-speed mixing;
(2) mixture that step (1) obtained loads that twin screw extruder mixes further, melting, extrude, and then carries out forming processes, finally obtains flame-proof thermoplastic polyurethane.
2. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described retardant synergist be zinc borate, Precondensed UreaFormaldehyde Resin, resol one or several.
3. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described smoke suppressant be magnesium hydroxide, aluminium hydroxide one or several.
4. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described oxidation inhibitor is irgasfos 168 or antioxidant 1010.
5. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described coupling agent is silane coupling agent.
6. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described lubricant is Zinic stearas or calcium stearate.
7. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: melting, the extrusion temperature scope of described twin screw extruder are 100-150 DEG C.
8. flame-proof thermoplastic polyurethane according to claim 1, is characterized in that: described forming processes condition is: temperature 195 DEG C, pressure 1.5Mpa, hot pressing 20min, cold pressing 15min.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103709432B (en) * | 2013-12-18 | 2015-10-21 | 南京师范大学 | A kind of high flame retardant rigid urethane foam and preparation method thereof |
| JP6151678B2 (en) * | 2014-10-15 | 2017-06-21 | 大和化学工業株式会社 | Flame retardant polyurethane resin and flame retardant synthetic leather |
| CN105860594A (en) * | 2016-05-10 | 2016-08-17 | 什邡市太丰新型阻燃剂有限责任公司 | Synthesis method of organosilicone modified superfine aluminum hypophosphite |
| CN105778151A (en) * | 2016-05-11 | 2016-07-20 | 闽江学院 | Halogen-free flame retardant for silica gel, application of halogen-free flame retardant and flame-retardant silica gel product |
| CN105924932A (en) * | 2016-05-18 | 2016-09-07 | 安徽华能电缆集团有限公司 | Explosion-proof cable sheath material and preparation method thereof |
| CN106832884A (en) * | 2017-01-22 | 2017-06-13 | 江苏欣润塑胶有限公司 | A kind of halogen-free flame-retardant TPU |
| CN111333913A (en) * | 2020-03-18 | 2020-06-26 | 博硕科技(江西)有限公司 | Preparation method and application of functional microencapsulated hypophosphite flame retardant |
| CN111961331B (en) * | 2020-10-23 | 2021-02-02 | 中广核高新核材科技（苏州）有限公司 | Flame-retardant waterproof thermoplastic polyurethane elastomer cable material and preparation method thereof |
| CN115260745A (en) * | 2022-08-31 | 2022-11-01 | 北京化工大学 | TPU flame-retardant composite material and preparation method and application thereof |
| CN116948386B (en) * | 2023-06-08 | 2023-12-22 | 江苏通上新材料科技有限公司 | Flame-retardant composite cable material and preparation method and application thereof |
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Effective date of registration: 20160524 Address after: 224555, Yancheng City Binhai County, Jiangsu Province Coastal Industrial Zone, Zhongshan Road Patentee after: JIANGSU FUBIYA CHEMICALS CO., LTD. Address before: 224500 North Zone of Coastal Industrial Park, Yancheng City Binhai Economic Development Zone, Jiangsu Patentee before: Binhai Jinxiang Chemical Auxiliary Co., Ltd. |