CN103012739B - Flame retardant modified mdi and preparation method thereof - Google Patents
Flame retardant modified mdi and preparation method thereof Download PDFInfo
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- CN103012739B CN103012739B CN201210563372.6A CN201210563372A CN103012739B CN 103012739 B CN103012739 B CN 103012739B CN 201210563372 A CN201210563372 A CN 201210563372A CN 103012739 B CN103012739 B CN 103012739B
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Abstract
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to flame retardant modified MDI (diphenylmethane diisocyanate) and a preparation method thereof. The flame retardant modified MDI is prepared through reaction of isocyanate, reaction type flame retardant modifier, high molecular weight reaction type opening agent and storage stabilizer; by taking the total mass of isocyanate, the reaction type flame retardant modifier and the high molecular weight reaction type opening agent as 100%, the mass percent of isocyanate is 76-88%, the mass percent of the reaction type flame retardant modifier is 8-14%, and the mass percent of the high molecular weight reaction type opening agent is 4-10%; the storage stabilizer accounts for 15-20 ppm of the total weight of isocyanate, the reaction type flame retardant modifier and the high molecular weight reaction type opening agent; and isocyanate is the mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate in mass ratio of 0.8-1.8 to 1. Foam prepared by the modified MDI has greatly improved fire resistance, is hardly ignited at first, and is extinguished immediately when out of flame after long-time ignition.
Description
Technical field
The invention belongs to urethane synthesis technical field, be specifically related to a kind of flame-retardant modified MDI and preparation method thereof.
Background technology
Urethane cold curing high resilience foam plastic is a kind of novel high molecular synthetic material, because of advantages such as its snappiness, high-comfort, high efficiencies, is widely used in the civil areas such as automobile, sofa, mattress.At present, in cold curing high resilience foam plastic synthetic, B component material generally adopts TDI system, TDI/MDI mixed system and modification MDI system.TDI system and TDI/MDI mixed system are due to high expensive, and toxicity is too large, and the negative impact bringing in operating process is too many, and usage quantity is reducing gradually, and modification MDI system can solve these problems.But along with social development with the fire failure constantly occurring in recent years, people have higher requirement to polyurethane foam, require polyurethane foamed material under the prerequisite that meets existing performance, also will possess fire-retardant feature, thus in minimizing accident because of the foam quadratic loss bringing that burns.As everyone knows, urethane is as a kind of organic polymer material, very easily burning, and polyurethane foamed material is loose owing to having, the foam structure that is interconnected, has increased specific surface area, is more prone to burning.In order to meet market to fire-retardant demand, polyurethane foam production producer generally can add fire retardant to improve the flame retardant resistance of foam in polyurethane foam combination material A component material.A large amount of fire retardants add the performance that can affect foaming process on the one hand and reduce foam, on the other hand, foam in use fire retardant can move, and reduces the flame retardant resistance of foam, flame retardant resistance does not possess persistence.
In recent years, about the research of modification MDI and flame-retardant foam many, patent CN101353413 has reported a kind of modified isocyanate for cold curing high resilience foam plastic and preparation method thereof, the high rebound foam of preparing with it has good feel and rebound resilience, foam density is low, opening is good, can substitute the production of TDI for high rebound foam completely, but the foam of preparation does not possess flame retardant resistance; Patent CN101824131 has reported a kind of environmental-protection flame-retardant high-resilience foam material and preparation method thereof, and it adopts conventional high rebound foam formula system and conventional modification MDI to prepare high rebound foam.As everyone knows, the polyurethane foam that in the market prepared by conventional raw material does not have flame retardant resistance.Prior art is by being used fire resistant polymer polylol preparation A component material, thereby give polyurethane foam flame retardant properties, but this technical requirements B component material must adopt TDI system, and also there is certain problem in A component material in stability in storage, to storing working conditions and operation technological requirement harshness.
Summary of the invention
The object of this invention is to provide a kind of flame-retardant modified MDI and preparation method thereof, this flame-retardant modified MDI, as the B component material of producing high rebound foam, introduces ignition-proof element in molecular structure, thereby makes the foam of preparing reach lasting fire-retardant object.
Flame-retardant modified MDI of the present invention, is made up of isocyanic ester, reaction-type flame-retarding properties-correcting agent, high molecular response type pore-creating agent and storage stabilizing agent reaction; Wherein, taking isocyanic ester, reaction-type flame-retarding properties-correcting agent, high molecular response type pore-creating agent total mass as 100%, isocyanic ester accounts for 76 ~ 88%, and reaction-type flame-retarding properties-correcting agent accounts for 8 ~ 14%, and high molecular response type pore-creating agent accounts for 4 ~ 10%; Storage stabilizing agent is 15 ~ 20ppm of isocyanic ester, reaction-type flame-retarding properties-correcting agent and high molecular response type pore-creating agent three gross weight, isocyanic ester is the mixture of diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates, and the two mass ratio is 0.8 ~ 1.8:1.
Described diphenylmethanediisocyanate is one or more in 4,4-diphenylmethanediisocyanate or 2,4-diphenylmethanediisocyanate.Preferably MDI-100(Yantai ten thousand magnificent products), the magnificent product in MDI-50(Yantai ten thousand), 44C(Bayer product) or 0129M(Hensel step product) in one or more.
Described polyphenyl polymethylene polyisocyanates is the magnificent product in PM-200(Yantai ten thousand), M20S(BASF product), 44V20(Bayer product) in one or more.
Described reaction-type flame-retarding properties-correcting agent is selected from one or more in RB-79, RB-7980, RB-7970, is Albemarle Corporation's product.
Described high molecular response type pore-creating agent is that glycerine does initiator, and functionality is 3, oxyethane and propylene oxide ring-opening polymerization the silicone-modified polyether glycol taking organic siloxane modified number-average molecular weight as 5000 ~ 6000.The preferably large Nowe DK-12 in east.
Described storage stabilizing agent is one or more in hydrochloric acid, sulfuric acid, phosphoric acid or Benzoyl chloride.
The preparation method of described flame-retardant modified MDI, that the reaction-type flame-retarding properties-correcting agent based on formula ratio, high molecular response type pore-creating agent are added in reactor, stirring is warming up to 100 ~ 120 DEG C and vacuum hydro-extraction 2 ~ 3 hours, and vacuum tightness≤-0.09MPa, is cooled to 30 ~ 40 DEG C, add storage stabilizing agent, finally join together in isocyanic ester again, be warming up to 60 ~ 80 DEG C, insulation reaction 1 ~ 2 hour, be cooled to 40 DEG C ~ 50 DEG C, discharging sealing are preserved.
Beneficial effect of the present invention is as follows:
The flame retardant resistance of the foaming properties that modification MDI of the present invention makes obviously significantly improves, and foam starts to be difficult for lighting, and lights for a long time turning off stove and extinguishes immediately.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
8.1Kg reaction-type flame-retarding modifier R B-79,4.9Kg high molecular response type pore-creating agent DK-12 are added in reactor, stir and be warming up to 110 DEG C, regulate vacuum tightness-0.095MPa, dewater while stirring 2 hours, then be cooled to 40 DEG C, add the phosphoric acid of 2g to stir, sealing is preserved.The MDI-50 of pure MDI, 26Kg of 28.5Kg and the PM-200 of 32.5Kg are added in reactor, add while stirring the mixed modifier through processed, be slowly warming up to 65 DEG C, insulation reaction 2 hours, it is 26.8 that sampling detects NCO%, is cooled to 45 DEG C, and discharging sealing are preserved.
Embodiment 2
10.4Kg reaction-type flame-retarding modifier R B-7980,4Kg high molecular response type pore-creating agent DK-12 are added in reactor, stir and be warming up to 100 DEG C, regulate vacuum tightness-0.095MPa, dewater while stirring 2 hours, then be cooled to 40 DEG C, add the phosphoric acid of 1.8g to stir, sealing is preserved.The MDI-50 of pure MDI, 25.6Kg of 28Kg and the PM-200 of 32Kg are added in reactor, add while stirring the mixed modifier through processed, be slowly warming up to 70 DEG C, insulation reaction 1.5 hours, it is 26.5 that sampling detects NCO%, is cooled to 45 DEG C, and discharging sealing are preserved.
Embodiment 3
By the RB-7970 of 3.9Kg reaction-type flame-retarding modifier R B-79,5.5Kg, 6.3Kg high molecular response type pore-creating agent DK-12 adds in reactor, stirring is warming up to 100 DEG C, regulate vacuum tightness-0.095MPa, dewater while stirring 2 hours, then be cooled to 40 DEG C, add the phosphoric acid of 1.5g to stir, sealing is preserved.The MDI-50 of pure MDI, 25.2Kg of 27.6Kg and the PM-200 of 31.5Kg are added in reactor, add while stirring the mixed modifier that processed is good, be slowly warming up to 80 DEG C, insulation reaction 1 hour, it is 26.1 that sampling detects NCO%, is cooled to 45 DEG C, and discharging sealing are preserved.
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Foam density (Kg/cm 3） | 45.5 | 45.4 | 45.5 |
| Tensile strength (KPa) | 152 | 150 | 148 |
| Tear strength (N/m) | 245 | 243 | 244 |
| Elongation rate of tensile failure (%) | 110 | 108 | 112 |
| 25% indentation force deflection (N) | 192 | 188 | 185 |
| Rebound degree (%) | 64 | 65 | 65 |
| Rate of closed hole (%) | 6 | 8 | 5 |
| Demould time (s) | 240 | 250 | 250 |
| Flame retardant resistance | Certainly put out from fire | Certainly put out from fire | Certainly put out from fire |
High resilience A material formula used following (by weight percentage) above:
When the present invention makes cold curing high resilience foam, compared with existing modification MDI product (patent CN101353413 product), have similar hardness, elasticity, opening and mechanical property, demould time also shortens to some extent, but the flame retardant resistance of foam increases substantially.
Be compared as follows table 1 with the performance of contrast patent:
Table 1 performance comparison sheet
| ? | Contrast patent modification MDI | The embodiment of the present invention 2 modification MDI |
| Foam density (Kg/cm 3） | 45.5 | 45.4 |
| Tensile strength (KPa) | 148 | 150 |
| Tear strength (N/m) | 245 | 243 |
| Elongation rate of tensile failure (%) | 110 | 108 |
| 25% indentation force deflection (N) | 185 | 188 |
| Rebound degree (%) | 66 | 65 |
| Rate of closed hole (%) | 7 | 8 |
| Demould time (s) | 260 | 250 |
| Flame retardant resistance | Burning | Certainly put out from fire |
As can be seen from the above table, modification MDI of the present invention is very little with the foaming properties difference that contrast patent modification MDI makes, but flame retardant resistance obviously significantly improves, and foam starts to be difficult for lighting, and lights for a long time turning off stove and extinguishes immediately.
Claims (5)
1. a flame-retardant modified MDI, is characterized in that being made up of isocyanic ester, reaction-type flame-retarding properties-correcting agent, high molecular response type pore-creating agent and storage stabilizing agent reaction; Wherein, taking isocyanic ester, reaction-type flame-retarding properties-correcting agent, high molecular response type pore-creating agent total mass as 100%, isocyanic ester accounts for 76 ~ 88%, and reaction-type flame-retarding properties-correcting agent accounts for 8 ~ 14%, and high molecular response type pore-creating agent accounts for 4 ~ 10%; Storage stabilizing agent is 15 ~ 20ppm of isocyanic ester, reaction-type flame-retarding properties-correcting agent and high molecular response type pore-creating agent three gross weight, and isocyanic ester is the mixture of diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates;
Reaction-type flame-retarding properties-correcting agent is one or more in RB-79, RB-7980 or RB-7970;
High molecular response type pore-creating agent is that glycerine does initiator, and functionality is 3, oxyethane and propylene oxide ring-opening polymerization the silicone-modified polyether glycol taking organic siloxane modified number-average molecular weight as 5000 ~ 6000;
Storage stabilizing agent is one or more in hydrochloric acid, sulfuric acid, phosphoric acid or Benzoyl chloride;
Reaction-type flame-retarding properties-correcting agent based on formula ratio, high molecular response type pore-creating agent are added in reactor, stirring is warming up to 100 ~ 120 DEG C and vacuum hydro-extraction 2 ~ 3 hours, vacuum tightness≤-0.09MPa, be cooled to 30 ~ 40 DEG C, add storage stabilizing agent, finally join together again in isocyanic ester, be warming up to 60 ~ 80 DEG C, insulation reaction 1 ~ 2 hour, is cooled to 40 DEG C ~ 50 DEG C, and discharging sealing are preserved.
2. flame-retardant modified MDI according to claim 1, is characterized in that: the two mass ratio of diphenylmethanediisocyanate and polyphenyl polymethylene polyisocyanates is 0.8 ~ 1.8:1.
3. flame-retardant modified MDI according to claim 1, is characterized in that: diphenylmethanediisocyanate is 4,4--diphenylmethanediisocyanate and/or 2,4-diphenylmethanediisocyanate.
4. flame-retardant modified MDI according to claim 3, is characterized in that: diphenylmethanediisocyanate is one or more in MDI-100, MDI-50,44C or 0129M.
5. flame-retardant modified MDI according to claim 1, is characterized in that: polyphenyl polymethylene polyisocyanates is one or more in PM-200, M20S or 44V20.
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| CN201210563372.6A CN103012739B (en) | 2012-12-21 | 2012-12-21 | Flame retardant modified mdi and preparation method thereof |
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| CN103012739B true CN103012739B (en) | 2014-10-29 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665316B (en) * | 2013-12-09 | 2016-03-02 | 山东一诺威聚氨酯股份有限公司 | The preparation method of organic-silicon-modified MDI |
| CN107602794B (en) * | 2017-09-15 | 2020-03-20 | 山东一诺威聚氨酯股份有限公司 | Polyurethane seat composite material and preparation method thereof |
| CN108503789B (en) * | 2018-03-02 | 2020-11-10 | 黎明化工研究设计院有限责任公司 | Open-cell polyurethane high-resilience foam composition and foam preparation method |
| CN112480857A (en) * | 2020-11-06 | 2021-03-12 | 南通天洋新材料有限公司 | Flame-retardant moisture-curing polyurethane hot melt adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052018A2 (en) * | 2003-11-21 | 2005-06-09 | Albemarle Corporation | Flame retardant, additive compositions, and flame retardant polyurethanes |
| CN101343416A (en) * | 2008-08-20 | 2009-01-14 | 南京德美世创化工有限公司 | Foam homogenizing agent for high-MDI system polyurethane high-springback foam |
| CN101353413A (en) * | 2008-08-08 | 2009-01-28 | 山东东大一诺威聚氨酯有限公司 | Modified isocyanate for cold curing high resilience foam plastic and preparation thereof |
| CN102140163A (en) * | 2010-11-26 | 2011-08-03 | 山东东大一诺威聚氨酯有限公司 | Modified MDI (methane diisocyanate) for cold curing water-blown self-skinning polyurethane foam and preparation method thereof |
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Patent Citations (4)
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| WO2005052018A2 (en) * | 2003-11-21 | 2005-06-09 | Albemarle Corporation | Flame retardant, additive compositions, and flame retardant polyurethanes |
| CN101353413A (en) * | 2008-08-08 | 2009-01-28 | 山东东大一诺威聚氨酯有限公司 | Modified isocyanate for cold curing high resilience foam plastic and preparation thereof |
| CN101343416A (en) * | 2008-08-20 | 2009-01-14 | 南京德美世创化工有限公司 | Foam homogenizing agent for high-MDI system polyurethane high-springback foam |
| CN102140163A (en) * | 2010-11-26 | 2011-08-03 | 山东东大一诺威聚氨酯有限公司 | Modified MDI (methane diisocyanate) for cold curing water-blown self-skinning polyurethane foam and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| 刘益军."聚氨酯原料及助剂手册".《聚氨酯原料及助剂手册》.化学工业出版社,2005,(第1版),第11,453-455，511页. |
| 刘益军."聚氨酯原料及助剂手册".《聚氨酯原料及助剂手册》.化学工业出版社,2005,(第1版),第11,453-455,511页. * |
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