CN103146178B - Chemical polyurethane foaming agent and preparation method thereof - Google Patents
Chemical polyurethane foaming agent and preparation method thereof Download PDFInfo
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- CN103146178B CN103146178B CN201310095799.2A CN201310095799A CN103146178B CN 103146178 B CN103146178 B CN 103146178B CN 201310095799 A CN201310095799 A CN 201310095799A CN 103146178 B CN103146178 B CN 103146178B
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- foaming agent
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- whipping agent
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Abstract
The invention relates to a chemical polyurethane foaming agent and a preparation method thereof, and belongs to the technical field of synthesis of fine chemical products. The chemical polyurethane foaming agent is prepared by reacting semi carbazide, ethoxy azodiisobutyronitrile and a hydrazine hydrate. The foaming agent and the isocyanic acid radical are reacted to generate carbon dioxide, the foam structure of the polyurethane can be improved, and the excellent effect of the polyurethane chemical foaming agent is exerted. According to the foaming agent, the formed polyurethane foam structure is uniform, and the physical performances of the polyurethane foams are improved. The preparation process of the provided chemical foaming agent is simple and easy to operate, the comprehensive performance of the polyurethane foams is improved, and chemical foaming agent contributes to popularization.
Description
Technical field
The present invention relates to a kind of polyurethane chemistry whipping agent and preparation method thereof, belong to fine chemical product synthesis technical field.
Background technology
For a long time, because the Chlorofluorocarbons (CFCs) (CFCs) that is used as hard polyurethane foam whipping agent is to Atmospheric Ozone Layer Depletion effect, therefore its production and use are had to strict regulation.According to Montreal Protocol, developed country forbade before 1996 comprehensively.It was 2007 that China eliminates CFCs, and domestic large PU foam production producer has completed substituting of CFCs in 2005.Therefore, CFCs is a kind of transition whipping agent, will be replaced by new green-blowing agent.
A current effort target of polyurethane industrial is exactly to select the substitute products of CFCs, reduces and stop the application of CFCs.HCFCs hydrogenated chloride fluorine hydrocarbon is the now generally acknowledged transitional surrogate of CFCs, removes function and Greenhouse effect but Hydrochlorofluorocarbons class still has certain ozone.So HCFCs is also a kind of transition whipping agent.
At present, the whole world especially some developed countries all at accelerate development zero odp whipping agent.Environmental protection (third generation) whipping agent mainly refers to that ozone depletion potential (ODP) is zero, and (GWP) is less for Greenhouse effect potential, environment amenable green whipping agent.Urethane foam whipping agent used is divided into two types: one is to utilize chemical foaming agent and isocyanic ester generation chemical reaction, and emitting gas is pore forming material; Another kind of whipping agent is to select lower boiling unreactive hydrocarbons compounds, utilizes the reaction heat of foam system make it vaporization and foam.
Current, various countries more and more pay attention to environmental protection problem, based on whipping agents such as current C FCs and HCFCS to the destruction of ozonosphere by extensive concern.Therefore the polyurethane chemistry whipping agent of development of new, environmental protection is imperative.
Summary of the invention
The object of the present invention is to provide a kind of polyurethane chemistry whipping agent and preparation method thereof, this whipping agent has the feature of high-performance, environmental protection, zero odp, and the polyurethane foam structure that uses this whipping agent to form is even, has improved the physicals of polyurethane foam.
The preparation method of polyurethane chemistry whipping agent of the present invention, by Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts with hydrazine hydrate, the mol ratio of Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1-1.5:2-2.5:2-2.5, temperature of reaction 20-100 degree.When reaction, adopt the mode dripping to join in reaction mass catalyzer.After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 80-100 degree, and the insulation reaction time is 30-60 minute.Material after insulation reaction completes carries out vacuum hydro-extraction processing at 90-110 degree.
The catalyzer adopting when reaction is phosphorus molybdenum complex.
Whipping agent of the present invention in use, produces atmospheric carbon dioxide uniformly with isocyano after reacting, thereby reaches the effect of whipping agent.
Find after deliberation, whipping agent of the present invention reacts with isocyano and generates carbonic acid gas, can also improve the foam structure of urethane simultaneously, has brought into play the effect of excellent polyurethane chemistry whipping agent.Use whipping agent of the present invention, the polyurethane foam structure of formation is even, has improved the physicals of polyurethane foam.
The present invention does not change existing polyurethane production equipment and production technique.The present invention reacts the carbonic acid gas generating with isocyano be a kind of zero odp whipping agent that can substitute current C FCs and HCFCs class whipping agent completely.
Compared with whipping agent of the prior art, the present invention has following beneficial effect:
(1) the white material of chemical foaming agent provided by the invention and urethane has good consistency, and not volatile, has greatly improved the stability in storage of the white material of urethane;
(2) chemical foaming agent provided by the invention has better foam performance in polyurethane foam process, thereby this whipping agent can be cross-linked and improve foamy body with multiple isocyanos in the process of reaction;
(3) chemical foaming agent provided by the invention has good dispersiveness in polyethers, in foaming process, make gas be dispersed in more uniformly in material, thereby greatly improved abscess-size, the polyurethane foam structure that uses this whipping agent to form is even, has improved the physicals of polyurethane foam;
(4) simple, the easy handling of the preparation technology of chemical foaming agent provided by the invention, has improved polyurethane foam over-all properties and has been beneficial to popularization.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
By Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts with hydrazine hydrate, Urea,amino-, the mol ratio of hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1:2:2, temperature of reaction 20 is spent.When reaction, adopt the mode dripping to join in reaction mass catalyzer phosphorus molybdenum complex.After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 90 degree, and the insulation reaction time is 40 minutes.Material after insulation reaction completes carries out vacuum hydro-extraction processing at 100 degree.
Embodiment 2
By Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts with hydrazine hydrate, Urea,amino-, the mol ratio of hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1.2:2.2:2, temperature of reaction 50 is spent.When reaction, adopt the mode dripping to join in reaction mass catalyzer phosphorus molybdenum complex.After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 80 degree, and the insulation reaction time is 60 minutes.Material after insulation reaction completes carries out vacuum hydro-extraction processing at 110 degree.
Embodiment 3
By Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts with hydrazine hydrate, Urea,amino-, the mol ratio of hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1.5:2:2, temperature of reaction 80 is spent.When reaction, adopt the mode dripping to join in reaction mass catalyzer phosphorus molybdenum complex.After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 100 degree, and the insulation reaction time is 30 minutes.Material after insulation reaction completes carries out vacuum hydro-extraction processing at 90 degree.
Embodiment 4
By Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts with hydrazine hydrate, Urea,amino-, the mol ratio of hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1:2.5:2.5, temperature of reaction 100 is spent.When reaction, adopt the mode dripping to join in reaction mass catalyzer phosphorus molybdenum complex.After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 90 degree, and the insulation reaction time is 50 minutes.Material after insulation reaction completes carries out vacuum hydro-extraction processing at 100 degree.
Embodiment 5
It is specific as follows with the performance of the polyurethane foam making that the polyurethane chemistry whipping agent that embodiment 1 makes is prepared polyurethane foam using method:
Get 100 parts of refrigerator polyethers, 8 parts of chemical foaming agents, 2 parts of suds-stabilizing agents for refrigerator, catalyzer is appropriate, stir evenly, by this material and black material MDI by weight proportion 1:1 at 22 degree rapid stirrings, cream time is 15 seconds, the wire drawing time is 65 seconds, and gel time is within 75 seconds, to make polyurethane foam, and the polyurethane foam density obtaining is 25kg/m
3, the hot Xi Shuo≤20W/mK of Dao, compressive strength > 110KPa.
Embodiment 6
It is specific as follows with the performance of the polyurethane foam making that the polyurethane chemistry whipping agent that embodiment 2 makes is prepared polyurethane foam using method:
Get 100 parts of spraying polyethers, 6 parts of chemical foaming agents, 2 parts of suds-stabilizing agents for spraying, catalyzer is appropriate, stirs evenly, and this material and black material MDI 1:1.05 use by weight proportion spraying machine are done to spraying experiment, cream time is 3 seconds, the wire drawing time is 8 seconds, and gel time is within 9 seconds, to make polyurethane foam, and the polyurethane foam density obtaining is 32kg/m
3, the hot Xi Shuo≤21W/mK of Dao, compressive strength > 150KPa.
Embodiment 7
It is specific as follows with the performance of the polyurethane foam making that the polyurethane chemistry whipping agent that embodiment 3 makes is prepared polyurethane foam using method:
Get 100 parts of sheet material polyethers, 5 parts of chemical foaming agents, 2 parts of suds-stabilizing agents for sheet material, catalyzer is appropriate, stir evenly, by this material and black material MDI by weight proportion 1:1.1 at 20 degree rapid stirrings, cream time is 15 seconds, and the wire drawing time is 55 seconds, and gel time is within 60 seconds, to make polyurethane foam.The polyurethane foam density obtaining is 41kg/m
3, the hot Xi Shuo≤22W/mK of Dao, compressive strength > 160 KPa.
Claims (1)
1. a polyurethane chemistry whipping agent, is characterized in that: by Urea,amino-, hydroxyethyl Diisopropyl azodicarboxylate reacts and makes with hydrazine hydrate;
Wherein, Urea,amino-, the mol ratio of hydroxyethyl Diisopropyl azodicarboxylate and hydrazine hydrate is 1-1.5:2-2.5:2-2.5; Temperature of reaction is 20-100 degree; The catalyzer adopting when reaction is phosphorus molybdenum complex; Catalyzer adopts the mode dripping to join in reaction mass; After catalyzer is added dropwise to complete, carry out insulation reaction, holding temperature is 80-100 degree, and the insulation reaction time is 30-60 minute; Material after insulation reaction completes carries out vacuum hydro-extraction processing at 90-110 degree.
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| CN201310095799.2A CN103146178B (en) | 2013-03-22 | 2013-03-22 | Chemical polyurethane foaming agent and preparation method thereof |
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| CN201310095799.2A CN103146178B (en) | 2013-03-22 | 2013-03-22 | Chemical polyurethane foaming agent and preparation method thereof |
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| CN103146178B true CN103146178B (en) | 2014-08-20 |
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| WO2016171038A1 (en) * | 2015-04-23 | 2016-10-27 | 三菱瓦斯化学株式会社 | Gas-generating agent, and process for producing foamed object using same |
| CN109422906B (en) * | 2017-08-24 | 2021-03-19 | 山东理工大学 | Ethanolamine alkaline blowing agents and use for producing polyurethane solar foam materials |
| CN107417886A (en) * | 2017-09-07 | 2017-12-01 | 烟台市顺达聚氨酯有限责任公司 | A kind of spraying polyurethane material of environment-friendly foaming agent and preparation method thereof |
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| BE755134A (en) * | 1969-08-21 | 1971-02-01 | Bayer Ag | POLYURETHANE ELASTOMERS LINEAR SEQUENCES |
| CN101219974B (en) * | 2008-01-22 | 2010-07-14 | 浙江海虹控股集团有限公司 | Method for recovery utilization of mother solution hydrochloric acid for ADC foaming agent production |
| CN101838224B (en) * | 2009-03-19 | 2013-01-09 | 华东理工大学 | Method for reducing grain size of AC foaming agent |
| RU2430930C2 (en) * | 2009-11-30 | 2011-10-10 | Общество с ограниченной ответственностью "Сектор-НН" | Polycomponent flocculating systems for removing paint materials from recycled water |
| CN102516131B (en) * | 2011-10-26 | 2013-09-04 | 广东省食品工业研究所 | Synthesis method of food grade modified foaming agent azodicarbonamide |
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