CN101298513A - Halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film material - Google Patents
Halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film material Download PDFInfo
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- CN101298513A CN101298513A CNA2008100389635A CN200810038963A CN101298513A CN 101298513 A CN101298513 A CN 101298513A CN A2008100389635 A CNA2008100389635 A CN A2008100389635A CN 200810038963 A CN200810038963 A CN 200810038963A CN 101298513 A CN101298513 A CN 101298513A
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Abstract
The invention relates to an environmental protective halogen-free inorganic nano-modified polyurethane electronic flame retarding film material. In order to overcome the problems of secondary harmful gas pollution etc. resulted from the burning of the existing halogen electronic flame retarding film, the invention synthesizes a new generation halogen-free environmental protective electronic flame retarding film by taking novel nano-inorganic silicate and phosphorous-nitrogenous compound as a flame retardant and taking polyurethane material as a structure. The halogen-free inorganic nano-modified polyurethane electronic flame retarding film material includes 20-60 part by weight of pre-polymerized material of the inorganic nano-modified polyurethane, 4-10 part by weight of micromolecule polyhydric alcohol, 0-10 part by weight of vegetable oil, 0.01-1 part by weight of antioxidant, 0-5 part by weight of plasticizer, 30-50 part by weight of phosphorus-nitrogen flame retardant, and 0-5 part by weigh of color paste. The halogen-free inorganic nano-modified polyurethane electronic flame retarding film has the characteristics of non-toxicity, low smoke and high efficiency during burning at high temperature, thus meeting the requirements of environmental protection.
Description
Technical field
The present invention relates to a kind of halogen-free inorganic nanometer modified high performance polyurethane electronic flame-retardant film material.Having solved existing is the electronic flame-retardant film of system with the halogen flame, and when high-temp combustion, the obnoxious flavour that is produced is to problems such as environment secondary pollutions.
The present invention as the fire-retardant barrier of solid phase, as the fire-retardant barrier of gas phase, is a structure synthetic a new generation halogen-free environment-friendly electronic flame-retardant film with the polyurethane material with phosphor nitrogen combustion inhibitor with novel inorganic nano silicate fire retardant.When high-temp combustion, have nontoxic, low cigarette, characteristics such as efficient meet the international environmental protection requirement, are applicable to national defence, medicine, the protecting materials of electronic applications such as automobile.
Background technology
At present the used electronic flame-retardant film of electron trade is basically based on halogen flame.Because halogen flame produces a large amount of obnoxious flavoures environment is caused secondary pollution in burning, it is the electronic flame-retardant film of system that international developed country has banned use of with the halogen flame.
In order to meet the requirement of world market, be badly in need of developing the high performance novel electron flame-retardant film material of halogen of new generation.
Summary of the invention
In order to solve existing is the problem that the electronic flame-retardant membrane technique of system exists with the halogen flame, the invention provides a kind of halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material, when high-temp combustion, have nontoxic, low cigarette, characteristics such as efficient.
The present invention solves the problems of the technologies described above the scheme of taking:
The present invention is by the surface effects of inorganic nano material, small-size effect, features such as the geometry specificity of thermotolerance and stratified nano materials make itself and the small organic molecule that contains reactive hydrogen adsorb combination mutually, generate the silicate modified urethane pre-polymerization of inorganic nano material with isocyanate-crosslinked reaction, and combine with phosphor nitrogen combustion inhibitor, form compact structure, Heat stability is good, the fire-retardant film of high-performance electronic of features such as barrier excellence.Under the high-temp combustion condition, novel inorganic nano silicate fire retardant is as the fire-retardant barrier of solid phase, phosphor nitrogen combustion inhibitor is as the fire-retardant barrier of gas phase, surface at body material has formed heat transfer, the barrier of mass transfer, completely cut off entering of extraneous oxygen, reduced the formation and the diffusion of the combustion heat, suppressed the thermal destruction of body material effectively.Avoid the transmission of volatile fuel, reach low cigarette, efficient, nontoxic flame retardant effect.
A kind of halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material comprises in weight part:
Urethane pre-polymerization material 20～60
Small molecules polyvalent alcohol 4～10
Vegetables oil 0～10
Antioxidant 0.001～1
Softening agent 0～5
Phosphor nitrogen combustion inhibitor 30～50
Mill base 0～5.
Concrete, the consumption of urethane pre-polymerization material can be 20,25,30,35,40,45,55 or 60 weight parts;
The consumption of small molecules polyvalent alcohol can be 4,5,6,7,8,9 or 10 weight parts;
The consumption of vegetables oil can be 0,2,4,6,8 or 10 weight parts;
The consumption of antioxidant can be 0.001,0.005,0.01,0.02,0.03,0.05,0.06,0.08,0.1,0.2,0.3,0.5,0.6,0.8 or 1 weight part;
Plasticizer dosage can be 0,1,2,3,4 or 5 weight parts;
The consumption of phosphor nitrogen combustion inhibitor can be 30,35,40,45 or 50 weight parts;
The consumption of mill base can be 0,1,2,3,4 or 5 weight parts.
On the basis of such scheme, described inorganic nanometer modified polyurethane pre-polymerization material is by inorganic nano silicate 5～40 weight parts, vegetables oil 10～30 weight parts, reactive hydrogen organism 5～50 weight parts, catalyzer 0.001～0.05 weight part, make with the reaction of isocyanic ester 20～50 weight parts, wherein:
The consumption of inorganic nano silicate can be 5,10,15,20,25,30,35 or 40 weight parts;
The consumption of vegetables oil can be 10,15,20,25 or 30 weight parts;
The organic consumption of reactive hydrogen can be 5,10,15,20,25,30,35,40,45 or 50 weight parts;
Catalyst consumption can be 0.001,0.005,0.01,0.015,0.02,0.03,0.04 or 0.05 weight part;
The consumption of isocyanic ester can be 20,25,30,35,40,45 or 50 weight parts.
On the such scheme basis, described small molecules polyvalent alcohol is ethylene glycol or propylene glycol; Described vegetables oil is the vegetables oil of crude vegetal or modification, is a kind of or its combination in Viscotrol C, soybean oil, plam oil, the transesterify modified castor oil.
Described reactive hydrogen organism is dibasic alcohol, diprotic acid, polyester polyol or polyether polyol, and wherein, dibasic alcohol comprises ethylene glycol, propylene glycol, butyleneglycol etc.
Described inorganic nano silicate is a kind of or its composition in nano level talcum, kaolin, the polynite, and wherein, the particle diameter of inorganic nano material is 1～10nm.
Described catalyzer is a kind of or its combination in amines catalyst, stannous octoate, mercaptan two fourth tin, the acetic acid dibutyl tins such as triethylenediamine, tetramethyl-Alkylenediamine, dimethylcyclohexylamine.
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2, a kind of or its combination in 2 '-diphenylmethanediisocyanate, the adjacent tolylene diisocyanate.
Described antioxidant is a tetramethylene (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters, triglycol two-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2, a kind of or its combination in 6-di-tert-butyl-4-methy phenol, the 2,6 ditertiary butyl p cresol.
Described softening agent is a kind of or its combination in dimixo-octyl phthalate, diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid heneicosane ester, aliphatic diacid ester, Uniflex DBS, the cyclic carbonate.
Described phosphor nitrogen combustion inhibitor is phosphoric acid ester fire retardant, melamine salt based flame retardant or melamine polyphosphate based flame retardant.
Described mill base is polyester type or polyester type polyurethane material general color paste.
At above-mentioned halogen-free inorganic nanometer modified polyurethane electronic flame-retardant preparation method of film material, comprising:
The preparation of A, urethane pre-polymerization material:
With nano silicate, vegetables oil contains the reactive hydrogen organism, catalyzer, and the heat temperature raising dehydration, temperature is controlled at 70～120 ℃, makes with isocyanate reaction, 1～2 hour reaction times, react completely, be chilled to room temperature;
The preparation of B, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material:
With urethane pre-polymerization material, the small molecules polyvalent alcohol, vegetables oil, antioxidant, softening agent, phosphor nitrogen combustion inhibitor, mill base is put into agitator.Be heated to 100～120 ℃, mix and make the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant material, this material extrudes through toothed gear pump or screw rod that pumping causes blade coating or the roller coating film former is made the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film.
The invention has the beneficial effects as follows:
1. the present invention utilizes novel nano inorganic silicic acid salt material to combine with polyurethane material and forms a kind of compact structure, and the intensity height is flexible good, the shielding material of anti-flaming thermal-insulation.
2. halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film of the present invention is a kind of halogen-free flame-retardant material, has avoided the secondary gas contamination that is produced in the burning.
3. halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film of the present invention utilizes the novel environment friendly fire retardant, is a kind of nontoxic, low cigarette, efficient, green ep-type material.
4. halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film of the present invention does not have toluene, non-xylol, no methylethylketone, harmful organic solvent such as formaldehydeless.
5. halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film of the present invention is a kind of Heat stability is good, the fire retardant material of hydrolysis.
Embodiment
Embodiment 1
The preparation of A, urethane pre-polymerization material:
With inorganic nano silicate 35 weight parts, vegetables oil 15 weight parts, reactive hydrogen organism 40 weight parts, catalyzer 0.005 weight part, the heat temperature raising dehydration, temperature is controlled at 70～120 ℃, react with isocyanic ester 30 weight parts, 1-2 hour insulated and stirred reaction times reacted completely, and it is standby to be chilled to room temperature;
The preparation of B, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material:
With urethane pre-polymerization material 40 weight parts, small molecules polyvalent alcohol 4 weight parts, plant 6 weight parts, antioxidant 0.01 weight part, softening agent 4 weight parts, phosphor nitrogen combustion inhibitor 45 weight parts, mill base 1 weight part is put into agitator, is heated to 100～120 ℃, mix and make the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant material, this material extrudes through toothed gear pump or screw rod that pumping causes blade coating or the roller coating film former is made the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film.
Embodiment 2
A, urethane pre-polymerization preparation methods are with example 1;
The preparation of B, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material:
With urethane pre-polymerization material 36 weight parts, small molecules polyvalent alcohol 5 weight parts, plant 4 weight parts, antioxidant 0.01 weight part, softening agent 5 weight parts, phosphor nitrogen combustion inhibitor 50 weight parts, mill base 1 weight part is put into agitator, is heated to 100～120 ℃, mix and make the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant material, this material extrudes through toothed gear pump or screw rod that pumping causes blade coating or the roller coating film former is made the halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film.
Claims (10)
1, a kind of halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material, comprise inorganic nanometer modified polyurethane pre-polymerization material 20～60 weight parts, small molecules polyvalent alcohol 4～10 weight parts, vegetables oil 0～10 weight part, antioxidant 0.01～1 weight part, softening agent 0～5 weight part, phosphor nitrogen combustion inhibitor 30～50 weight parts, mill base 0～5 weight part.
2, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 1, it is characterized in that: described inorganic nanometer modified polyurethane pre-polymerization material is by inorganic nano silicate 5～40 weight parts, vegetables oil 10～30 weight parts, reactive hydrogen organism 5～50 weight parts, catalyzer 0.0001～0.05 weight part makes with the reaction of isocyanic ester 20～50 weight parts.
3, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 1 is characterized in that: described small molecules polyvalent alcohol is ethylene glycol or propylene glycol; Described vegetables oil is the vegetables oil of crude vegetal or modification, is a kind of or its combination in Viscotrol C, soybean oil, plam oil, the transesterify modified castor oil.
4, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 1, it is characterized in that: described antioxidant is a tetramethylene (3,5-di-t-butyl-4-hydroxy phenylpropionic acid) methyl esters, triglycol two-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2, a kind of or its combination in 6-di-tert-butyl-4-methy phenol, the 2,6 ditertiary butyl p cresol; Described softening agent is a kind of or its combination in dimixo-octyl phthalate, diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid heneicosane ester, aliphatic diacid ester, Uniflex DBS, the cyclic carbonate.
5, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 1 is characterized in that: described phosphor nitrogen combustion inhibitor is phosphoric acid ester fire retardant, melamine salt based flame retardant or melamine polyphosphate based flame retardant.
6, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 1 is characterized in that: described mill base is polyester type or polyether(poly)urethane material general color paste.
7, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 2 is characterized in that: described reactive hydrogen organism is dibasic alcohol, diprotic acid, polyester polyol or polyether polyol.
8, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 2, it is characterized in that: described inorganic nano silicate is a kind of or its composition in nano level talcum, kaolin, the polynite, wherein, the particle diameter of inorganic nano silicate is 1～10nm.
9, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 2 is characterized in that: described catalyzer is a kind of or and the composition in triethylenediamine, tetramethyl-Alkylenediamine, dimethylcyclohexylamine, stannous octoate, mercaptan two fourth tin, the acetic acid dibutyl tin.
10, halogen-free inorganic nanometer modified polyurethane electronic flame-retardant mould material according to claim 2, it is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2, a kind of or its combination in 2 '-diphenylmethanediisocyanate, the adjacent tolylene diisocyanate.
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| CN2008100389635A CN101298513B (en) | 2008-06-13 | 2008-06-13 | Halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film material |
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| CN2008100389635A CN101298513B (en) | 2008-06-13 | 2008-06-13 | Halogen-free inorganic nanometer modified polyurethane electronic flame-retardant film material |
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| CN101298513B CN101298513B (en) | 2010-10-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504373A (en) * | 2011-11-28 | 2012-06-20 | 山东省自主创新促进中心 | Environment-friendly and flame retardant type stereo garage |
| CN102127293B (en) * | 2010-01-12 | 2012-10-03 | 深圳市富洋密封件有限公司 | Formula and production process of thermoplastic polyurethane hydraulic sealing ring material |
| CN104086878A (en) * | 2014-06-30 | 2014-10-08 | 邹玲姣 | Fire retardant composition |
| CN108962490A (en) * | 2018-07-02 | 2018-12-07 | 安徽坤和电气有限公司 | The preparation method of high-strength cable |
| CN108948728A (en) * | 2018-07-02 | 2018-12-07 | 安徽坤和电气有限公司 | The preparation method of flame retardant cable |
-
2008
- 2008-06-13 CN CN2008100389635A patent/CN101298513B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127293B (en) * | 2010-01-12 | 2012-10-03 | 深圳市富洋密封件有限公司 | Formula and production process of thermoplastic polyurethane hydraulic sealing ring material |
| CN102504373A (en) * | 2011-11-28 | 2012-06-20 | 山东省自主创新促进中心 | Environment-friendly and flame retardant type stereo garage |
| CN102504373B (en) * | 2011-11-28 | 2013-08-07 | 山东省自主创新促进中心 | Environment-friendly and flame retardant type stereo garage |
| CN104086878A (en) * | 2014-06-30 | 2014-10-08 | 邹玲姣 | Fire retardant composition |
| CN108962490A (en) * | 2018-07-02 | 2018-12-07 | 安徽坤和电气有限公司 | The preparation method of high-strength cable |
| CN108948728A (en) * | 2018-07-02 | 2018-12-07 | 安徽坤和电气有限公司 | The preparation method of flame retardant cable |
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