CN101058669A - Flame-proof thermoplastic polyurethane mixture containing halogen-free expanded fire retardant - Google Patents
Flame-proof thermoplastic polyurethane mixture containing halogen-free expanded fire retardant Download PDFInfo
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- CN101058669A CN101058669A CN 200710068068 CN200710068068A CN101058669A CN 101058669 A CN101058669 A CN 101058669A CN 200710068068 CN200710068068 CN 200710068068 CN 200710068068 A CN200710068068 A CN 200710068068A CN 101058669 A CN101058669 A CN 101058669A
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Abstract
The invention discloses a flame-proof thermoplastic polyurethane compound with non-halogen bulking fire retardant, which comprises the following parts: 8-40% non-halogen bulking fire retardant and thermoplastic polyurethane polymer with limit stretching strength not less than 18Mpa, wherein the thermoplastic polyurethane polymer is one or more composition of thermoplastic polyester typed polyurethane elastic, thermoplastic polyether typed polyurethane elastic and thermoplastic polycarbonate typed polyurethane elastic.
Description
Technical field
The present invention relates to the preparation of a kind of halogen-free fire retardation thermoplastic polyurethane (TPU), adopt a kind of phosphorus nitrogen be the halogen-free expansion fire retardant of main ignition-proof element (JLS-PNP1) as unique flame-retardant additive, kept high tensile and the snappiness of TPU.Oxygen index reaches more than 30, the shore hardness scope between 72A～90A, not halogen-containing and heavy metal, especially not leaded, mercury, cadmium, sexavalent chrome heavy metal, and poly-dibromodiphenyl ether (PBDE) and poly-bromo biphenyl (PBB), be specially adapted to the wires and cables industry sheath material.
Background technology
At present, halogen-free fire retardation thermoplastic polyurethane (TPU) product mainly is by adding inorganic combustion inhibitor Mg (OH)
2And Al (OH)
3, composite flame-retardant agents such as melamine aminuria cyanic acid (melamine cyanurate) and phosphoric acid ester etc. prepare, these methods are existing open description of US5837760, CN1639245, JP54-85242, US5684071 and EP0389768.
Disclose at TPU use melamine aminuria cyanic acid about 25% at US5837760, phosphoric acid ester/phosphonic acid ester 3～15% can reach UL94-V0.
Use Mg (OH) is disclosed at EP0389768
2And Al (OH)
3, composite flame-retardant agent such as melamine aminuria cyanic acid (melamine cyanurate) and phosphoric acid ester is as the method for TPU fire retardant.
Disclose the method for use melamine aminuria cyanic acid as the TPU fire retardant at CN1639245 and JP54-85242, but flame retardant properties is low, LOI is 24, has drip phenomenon when burning.
There is following deficiency to some extent in the technology of above-mentioned patent disclosure, has influenced its use in every field:
1. the fire retardant consumption is big, and thermoplasticity TPU mechanical property is declined to a great extent, and especially causes the original snappiness characteristics of its body that follows the string, and the product that obtains can only be used for moulding, and difficulty is used for extrusion moulding;
2. after adding phosphoric acid ester, poor heat stability has the VOC organic volatile;
3. Flame Retardancy can be poor, and the molten drop phenomenon is arranged, and (LOI) is low for oxygen index, can only be used for the low fire-retardant occasion that requires;
4. melamine aminuria cyanic acid has Degradation to TPU, TPU is required high.
Summary of the invention
The technical issues that need to address of the present invention are, a kind of raising flexibility and physical strength are provided, excellent good flame retardant resistance is arranged simultaneously, and Halogen, the halogen-free expansible flame-retardant thermoplastic polyurethane material that meets the Rohs command request is with the high requirement that satisfies electric wire and the development characteristic of halogen-free flameproof.
The flame-proof thermoplastic polyurethane mixture that contains halogen-free expansion fire retardant of the present invention comprises the component of following weight:
Halogen-free expansion fire retardant 8～40%,
Its surplus of the thermoplastic polyurethane polymer of ultimate tensile strength 〉=18Mpa;
Described halogen-free expansion fire retardant (JLS-PNP1) is the product innovation that the applicant develops, and is open in Chinese patent literature CN1834138 " preparation method of expanding halide-free fire-retardant and products thereof "; The thermoplastic polyurethane polymer of described ultimate tensile strength 〉=25Mpa is a thermoplastic polyester type polyurethane elastomerics, thermoplastic polyether urethane elastomerics, the mixture of one or more in the thermoplastic poly carbonic ether type polyurethane elastomerics.
The present invention contains the flame-proof thermoplastic polyurethane mixture of halogen-free expansion fire retardant, and preferred components by weight percent is:
Halogen-free expansion fire retardant 10～30%,
Titanium dioxide 0.5～5%,
Auxiliary agent: oxidation inhibitor, the mixture 0.5～5% of metal deactivator and UV light absorber,
Its surplus of the thermoplastic polyurethane polymer of ultimate tensile strength 〉=25Mpa.
Above-mentioned halogen-free expansion fire retardant, the organo-silicon coupling agent with halogen-free expansion fire retardant weight 0.1～3% (being preferably 0.2～2.5%) carries out surface activation process earlier; Described organo-silicon coupling agent is a γ-An Bingjisanyiyangjiguiwan, chain alkyl Trimethoxy silane vinyltrimethoxy silane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-glycidyl ether oxygen propyl, Trimethoxy silane, the mixture of one or more of vinyl three ('beta '-methoxy oxyethyl group) silane.
As preferably, halogen-free expansion fire retardant weight is 10～30%, and organo-silicon coupling agent is 0.3～2.5% of a weight.
Titanium dioxide (TiO of the present invention
2) be rutile-type, consumption is a flame-proof thermoplastic polyurethane mixture 0.5～5%, preferable amount is 1～4% weight.
As preferably, titanium dioxide is rutile-type, is 1～4% of flame-proof thermoplastic polyurethane mixture weight; Oxidation inhibitor is one or more of hindered phenol and phosphorous acid class, accounts for 0.01～0.3% of mixture weight; UV light absorber is a benzotriazole category, and one or more of benzophenone and hindered amines account for 0.01～0.2% of mixture weight.
A kind of preparation method who contains the thermoplastic polyurethane mixture of halogen-free expansion type flame-proof of the present invention mixes at the high speed kneader for elder generation, and on the twin screw extruder that the multistage heating is arranged, processing temperature is 150～190 ℃ with above-mentioned compound, melt extrude, pelletizing, cooling is sieved.
The method for preparing electric wire and cable jacket that contains the thermoplastic polyurethane mixture of halogen-free expansion fire retardant of the present invention, the processing temperature scope of compound particles is 120～180 ℃, in L/D=20～30 that the multistage heating is arranged, compression ratio 2.2～3.5, the single screw extrusion machine that band extruding type or crowded tubular type are got to know prepares the halogen-free flame-retardant wire cable sheath.This electric wire is characterized in that comprising at least more than one metallic conductor, and described conductor is covered by non-conductive polymkeric substance.
Compared with prior art, the present invention has obviously improved the mechanical flame retardant properties of halogen-free fire retardation thermoplastic polyurethane, material itself can pass through UL94-V0, oxygen index (LOI) is greater than 30, hardness influence to TPU is little, can obtain Shore A hardness 72～95 according to different TPU compositions, tensile strength is greater than 12Mpa, and elongation at break is greater than 500% flame-retardant mixture.Satisfy the requirement of electric wire and cable jacket.
Embodiment
Below further specify of the present invention with embodiment, but the present invention is not limited to these embodiment.The flame retardant resistance of the Performance evaluation criterion material that is adopted UL-94 and oxygen index.The cable that obtains adopts single vertical combustion experiment to estimate.
Embodiment 1:
1, the preparation of halogen-free expansion fire retardant JLS-PNP1: in reactor, add Vanadium Pentoxide in FLAKES (P
2O
5Content 〉=98%) 43.47kg adds Secondary ammonium phosphate (primary ammonium phosphate content 〉=95%) 36.32kg simultaneously, stirring heating, and logical 20 minutes ammonias of 1 liter/minute, and keep ammonia to be pressed in 0.2Mpa.When being raised to 250 ℃, become the thickness syrupy liq, 250 ℃ kept 1 hour, became the pressed powder of white.Under agitation, logical 2 liters/minute nitrogen is cooled to 50 ℃, and crushing screening obtains compound (III).Under-5 ℃, 1000kg (III) is joined 3m
3In 85% ethanol, stirred 30 minutes, add with pyridine activatory benzyl triphenyl hydroxide phosphine 0.2kg, under agitation evenly add the nitrogenous aerotex of 230kg, reacted 3 hours, filter, drying is pulverized and is obtained JLS-PNP1 1217kg.The about 10 μ m of particle diameter.
2, halogen-free expansion fire retardant JLS-PNP1 is carried out surface activation process with the γ-An Bingjisanyiyangjiguiwan of JLS-PNP1 weight 1%, the flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A80, ultimate tensile strength is about 35Mpa) 76.5%,
Halogen-free expansion fire retardant after the processing (JLS-PNP1) 20%,
Titanium dioxide (TiO
2) 3.0%,
Oxidation inhibitor/metal deactivator (1024) 0.2%,
Oxidation inhibitor (168) 0.2%,
UV light absorber (UV-327) 0.1%.
Mix the twin screw of back, under 155～185 ℃ of scopes, extrude the thermoplastic polyurethane mixture that pelletizing obtains halogen-free expansion type flame-proof at Φ 65.
Embodiment 2: halogen-free expansion fire retardant JLS-PNP1 preparation and surface treatment are with specific embodiment 1.The flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
Polyether(poly)urethane (Shore A85, ultimate tensile strength is about 25Mpa) 76.5%,
Halogen-free expansion fire retardant after the processing (JLS-PNP1) 20%,
Titanium dioxide (TiO
2) 3%,
Oxidation inhibitor/metal deactivator (1024) 0.2%,
Oxidation inhibitor (168) 0.2%,
UV light absorber (UV-327) 0.1%.
Mix the twin screw of back, under 150～180 ℃ of scopes, extrude the thermoplastic polyurethane mixture that pelletizing obtains halogen-free expansion type flame-proof at Φ 65.
Embodiment 3: halogen-free expansion fire retardant JLS-PNP1 prepares with specific embodiment 1.γ-An Bingjisanyiyangjiguiwan treat surface with 0.5% is handled.Prescription and working method are with specific embodiment 1.
Embodiment 4: halogen-free expansion fire retardant JLS-PNP1 preparation and surface treatment are with specific embodiment 1.The flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A80, ultimate tensile strength is about 35Mpa) 61.2%,
Polyether(poly)urethane (Shore A85, ultimate tensile strength is about 25Mpa) 15.3%,
Halogen-free expansion fire retardant (JLS-PNP1) 20%,
Titanium dioxide (TiO
2) 3%,
Oxidation inhibitor/metal deactivator (1024) 0.2%,
Oxidation inhibitor (168) 0.2%,
UV light absorber (UV-327) 0.1%.
Mix the twin screw of back, under 155～185 ℃ of scopes, extrude the thermoplastic polyurethane mixture that pelletizing obtains halogen-free expansion type flame-proof at Φ 65.
Embodiment 5: halogen-free expansion fire retardant JLS-PNP1 preparation and surface treatment are with specific embodiment 1.Working method is with specific embodiment 1.The flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A92, ultimate tensile strength is about 40Mpa) 76.5%,
Halogen-free expansion fire retardant (JLS-PNP1) 20%,
Titanium dioxide (TiO
2) 3%,
Oxidation inhibitor/metal deactivator (1024) 0.2%,
Oxidation inhibitor (168) 0.2%,
UV light absorber (UV-327) 0.1%.
Embodiment 6-13: halogen-free expansion fire retardant JLS-PNP1 preparation and surface treatment are with specific embodiment 1.Other compositions and working method are with embodiment 1.
| Sequence number | PAUR | Polyether(poly)urethane | JLS-PNP1 |
| Embodiment 6 | 81.5% (Shore A80, ultimate tensile strength is about 35Mpa) | 0 | 15％ |
| Embodiment 7 | 71.5% (Shore A80, ultimate tensile strength is about 35Mpa) | 0 | 25％ |
| Embodiment 8 | 61.2% (Shore A92, ultimate tensile strength is about 40Mpa) | 15.3% (Shore A85, ultimate tensile strength is about 25Mpa) | 20％ |
| Embodiment 9 | 45.9% (Shore A80, ultimate tensile strength is about 35Mpa) | 30.6% (Shore A85 draws the limit to stretch intensity and is about 25Mpa) | 20％ |
| Embodiment 10 | 0 | 71.5% (Shore A85, ultimate tensile strength is about 25Mpa) | 25％ |
| Embodiment 11 * | 79.5% (Shore A80, ultimate tensile strength is about 35Mpa) | 0 | 20％ |
| Embodiment 12 | 86.5% (Shore A80, ultimate tensile strength is about 35Mpa) | 0 | 10％ |
| Embodiment 13 | 56.5% (Shore A80, ultimate tensile strength is about 35Mpa) | 0 | 40％ |
Wherein embodiment 11
*: do not add titanium dioxide (TiO
2).
Embodiment 14-18: halogen-free expansion fire retardant JLS-PNP1 preparation and surface treatment are with specific embodiment 1.Other compositions and working method are with embodiment 1.
| Sequence number | Oxidation inhibitor/metal deactivator (1024) | Oxidation inhibitor (168) | UV light absorber (UV-327) |
| Embodiment 14 | 0 | 0 | 0 |
| Embodiment 15 | 0 | 0.2％ | 0.1％ |
| Embodiment 16 | 0.1％ | 0.1％ | 0.05％ |
| Embodiment 17 | 0.2％ | 0 | 0.1％ |
| Embodiment 18 | 0.2％ | 0.2％ | 0 |
Comparative Examples 1: the flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
Polyether(poly)urethane (Shore A92, the about 40Mpa of ultimate tensile strength) 66.7%,
Melamine aminuria cyanic acid 32.8%,
Oxidation inhibitor/metal deactivator (1024) 0.2%,
Oxidation inhibitor (168) 0.2%,
UV light absorber (UV-327) 0.1%.
Melamine aminuria cyanic acid adopts JLS-MC15, and median size is 3 μ m, maximum particle diameter≤3 μ m.Melamine aminuria cyanic acid purity is 〉=99.8%.Mix the twin screw of back, under 160～185 ℃ of scopes, extrude pelletizing and obtain flame-proof thermoplastic polyurethane mixture at Φ 65.
Comparative Examples 2: the flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A92, the about 40Mpa of ultimate tensile strength) 68%,
Melamine aminuria cyanic acid (JLS-MC15) 31.5%,
Other compositions and working method are with Comparative Examples 1.
Comparative Examples 3: the flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A92, the about 40Mpa of ultimate tensile strength) 68%,
Phosphoric acid ester 4%,
Melamine aminuria cyanic acid (JLS-MC15) 25%,
Other compositions are with Comparative Examples 1.
Phosphoric acid ester is a tetraphenyl bisphenol-A bisphosphate (BDP).Mix the twin screw of back, under 150～180 ℃ of scopes, extrude pelletizing and obtain flame-proof thermoplastic polyurethane mixture at Φ 65.
Comparative Examples 4: the flame-proof thermoplastic polyurethane mixture weight proportion is as follows:
PAUR (Shore A80, the about 35Mpa of ultimate tensile strength) 68%,
Melamine aminuria cyanic acid (JLS-MC15) 31.5%,
Other compositions and working method are with Comparative Examples 1.
Flame retardant resistance and other performances see attached list 1.
Heat aging performance sees attached list 2.
Subordinate list 1: material and cable performance contrast
| Sequence number | Density g/cm 3 | Hardness Shore A | The LOI oxygen index | UL94 (0.8mm) | Tensile strength Mpa | Rate % is stretched in fracture | Single vertical combustion experiment |
| Embodiment 1 | 1.26 | 77 | 35 | V-0 | 23.9 | 880 | VW-1 |
| Embodiment 2 | 1.23 | 80 | 30 | V-1 | 14.2 | 560 | Failure |
| Embodiment 3 | 1.26 | 78 | 34 | V-0 | 21.8 | 620 | VW-1 |
| Embodiment 4 | 1.25 | 84 | 33 | V-0 | 21.2 | 770 | VW-1 |
| Embodiment 5 | 1.27 | 88 | 36 | V-0 | 29.6 | 490 | VW-1 |
| Embodiment 6 | 1.22 | 76 | 28 | V-2 | 25.3 | 720 | Failure |
| Embodiment 7 | 1.29 | 81 | 38 | V-0 | 24.1 | 430 | VW-1 |
| Embodiment 8 | 1.26 | 89 | 34 | V-0 | 22.9 | 420 | VW-1 |
| Embodiment 9 | 1.25 | 86 | 31 | V-1 | 12.1 | 310 | VW-1 |
| Embodiment 10 | 1.28 | 88 | 32 | V-0 | 9.6 | 450 | VW-1 |
| Embodiment 11 | 1.20 | 78 | 31 | V-1 | 17.7 | 670 | VW-1 |
| Embodiment 12 | 1.21 | 76 | 28 | Failure | 25.0 | 780 | Failure |
| Embodiment 13 | 1.30 | 89 | 43 | V-0 | 13.6 | 279 | The VW-1 surface is crude |
| Comparative Examples 1 | 1.35 | 95 | 25 | Failure | 12.0 | 320 | VW-1 |
| Comparative Examples 2 | 1.35 | 94 | 23 | Failure | 12.6 | 310 | Failure |
| Comparative Examples 3 | 1.30 | 88 | 27 | V-1 | 19.7 | 450 | VW-1 |
| Comparative Examples 4 | 1.35 | 85 | ≤22 | Failure | 6.9 | 510 | Can not unwrapping wire, the surface is crude |
Subordinate list 2: heat aging performance
| Sequence number | Initial tensile strength Mpa | Initial collapse is stretched rate % | Retention rate after the thermal ageing, % | Outward appearance | |
| Tensile strength | Rate is stretched in fracture | ||||
| Embodiment 1 | 23.9 | 880 | 93 | 92 | Constant |
| Embodiment 2 | 14.2 | 560 | 89 | 97 | Constant |
| Embodiment 4 | 21.2 | 770 | 92 | 93 | Constant |
| Embodiment 5 | 29.6 | 490 | 87 | 90 | Constant |
| Embodiment 11 | 17.7 | 670 | 85 | 91 | Slightly yellow |
| Embodiment 14 | 23.8 | 860 | 56 | 60 | Tawny |
| Embodiment 15 | 24.0 | 880 | 67 | 72 | Deep yellow |
| Embodiment 16 | 24.1 | 870 | 81 | 85 | Yellow |
| Embodiment 17 | 23.9 | 880 | 72 | 81 | Light yellow |
| Embodiment 18 | 23.9 | 880 | 87 | 92 | Slightly yellow |
Claims (7)
1, a kind of flame-proof thermoplastic polyurethane mixture that contains halogen-free expansion fire retardant comprises the component of following weight:
Halogen-free expansion fire retardant 8～40%,
Its surplus of the thermoplastic polyurethane polymer of ultimate tensile strength 〉=18Mpa;
The thermoplastic polyurethane polymer of described ultimate tensile strength 〉=18Mpa is a thermoplastic polyester type polyurethane elastomerics, thermoplastic polyether urethane elastomerics, the mixture of one or more in the thermoplastic poly carbonic ether type polyurethane elastomerics.
2, the flame-proof thermoplastic polyurethane mixture that contains halogen-free expansion fire retardant according to claim 1 is characterized in that:
Halogen-free expansion fire retardant 10～30%,
Titanium dioxide 0.5～5%,
Oxidation inhibitor, the mixture 0.5～5% of metal deactivator and UV light absorber,
Its surplus of the thermoplastic polyurethane polymer of ultimate tensile strength 〉=25Mpa.
3, flame-proof thermoplastic polyurethane mixture according to claim 1 and 2, it is characterized in that described halogen-free expansion fire retardant, the organo-silicon coupling agent with halogen-free expansion fire retardant weight 0.1～3% carries out surface activation process to halogen-free expansion fire retardant earlier; Described organo-silicon coupling agent is a γ-An Bingjisanyiyangjiguiwan, chain alkyl Trimethoxy silane vinyltrimethoxy silane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-glycidyl ether oxygen propyl, Trimethoxy silane, the mixture of one or more of vinyl three ('beta '-methoxy oxyethyl group) silane.
4, flame-proof thermoplastic polyurethane mixture according to claim 3 is characterized in that described organo-silicon coupling agent is 0.3～2.5% of a halogen-free expansion fire retardant weight.
5, flame-proof thermoplastic polyurethane mixture according to claim 2 is characterized in that described titanium dioxide is rutile-type, is 1～4% of flame-proof thermoplastic polyurethane mixture weight; Oxidation inhibitor is one or more of hindered phenol and phosphorous acid class, accounts for 0.01～0.3% of mixture weight; Described UV light absorber is a benzotriazole category, and one or more of benzophenone and hindered amines account for 0.01～0.2% of mixture weight.
6, flame-proof thermoplastic polyurethane mixture according to claim 3 is characterized in that described titanium dioxide is rutile-type, is 1～4% of flame-proof thermoplastic polyurethane mixture weight; Oxidation inhibitor is one or more of hindered phenol and phosphorous acid class, accounts for 0.01～0.3% of mixture weight; Described UV light absorber is a benzotriazole category, and one or more of benzophenone and hindered amines account for 0.01～0.2% of mixture weight.
7, flame-proof thermoplastic polyurethane mixture according to claim 4 is characterized in that described titanium dioxide is rutile-type, is 1～4% of flame-proof thermoplastic polyurethane mixture weight; Oxidation inhibitor is one or more of hindered phenol and phosphorous acid class, accounts for 0.01～0.3% of mixture weight; Described UV light absorber is a benzotriazole category, and one or more of benzophenone and hindered amines account for 0.01～0.2% of mixture weight.
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