CN101343375B - Foaming agent and preparation method for rigid cellular plastic employing the foaming agent - Google Patents
Foaming agent and preparation method for rigid cellular plastic employing the foaming agent Download PDFInfo
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- CN101343375B CN101343375B CN2008100219032A CN200810021903A CN101343375B CN 101343375 B CN101343375 B CN 101343375B CN 2008100219032 A CN2008100219032 A CN 2008100219032A CN 200810021903 A CN200810021903 A CN 200810021903A CN 101343375 B CN101343375 B CN 101343375B
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Abstract
The invention aims to provide a foaming agent with low cost and low ODP value and a preparation method of the rigid foam plastic that adopts the foaming agent. The foaming agent is composed of fluorodichloromethane the weight percentage of which occupies 5 percent to 95 percent and dimethyl enther the weight percentage of which occupies 5 percent to 95 percent. Because the ODP value of the dimethyl enther is zero, the addition of the dimethyl enther can reduce the dosage of HCFC-141b, and the ODP value of the foaming agent is obviously reduced, which is favorable for protecting the environment. In addition, after being mixed according to a certain proportion, the two chemical compounds can be used as the foaming agent, the comprehensive performance can be obviously improved, the combustibleness can be reduced and even can not generate, the coefficient of thermal conductivity of the mixed gas is feasible, and the stability of the size of the made foam can be improved. The preparation method of the rigid foam plastic has the advantages that the raw material comprises polyisocyanic ester and polyatomic alcohol, and the adopted foaming agent is composed of HCFC-141b the weight percentage of which occupies 5 percent to 95 percent and the dimethyl enther the weight percentage of which occupies 5 percent to 95 percent.
Description
Invention field
The present invention relates to the preparation method of the rigid foam of a kind of whipping agent and this whipping agent of employing.
Background technology
In the presence of whipping agent, suitable polyisocyanates and polyol component reacted and to obtain rigid foam.Polyisocyanates and polyol component ratio can obtain polyurethane rigid foam plastic or urethane-modified polysiocyanurate rigid foams plastics not simultaneously.This material can be used as thermal insulation material, as the structured material of building board, piping insulation, refrigerator refrigerator.Freonll-11 (being called for short CFC) is widely used as whipping agent, but it has destruction to atmospheric ozone layer.At present; people more and more pay attention to environmental protection; recognize the importance of the environment of preserving our planet, protection ozonosphere; usually adopt three class whipping agents to substitute and eliminate ozone layer destroying substance C FC, i.e. the transitional surrogate of hydrogenation fluorochlorohydrocarbon (being called for short HCFC), hydro carbons and hydrogenation fluothane hydrocarbon (being called for short HFC) class surrogate.Hydro carbons and HFC class surrogate ozone depletion (being called for short ODP) value is zero, but has following problems: when adopting hydrocarbon blowing agents, need transform production unit, front-end investment is bigger, and it can not be used for spray coating foaming in addition, and application is restricted; When adopting the HFC compounds to make whipping agent, raw materials cost is too high also to be well-known, uses also to be restricted.Contain hydrogen in the transitional surrogate molecule of HCFC class, the chemical property instability is decomposed than being easier to, and its ODP value will be far smaller than CFC, so HCFC is taken as CFC whipping agent first-generation substitute products, and interior in a period of transition temporary transient the use.Wherein a fluorine ethylene dichloride (being called for short HCFC-141b) is the most sophisticated product of CFC alternative, the consistency of it and polyvalent alcohol and isocyanic ester is good, can directly use the HCFC-141b substitute CFC under the condition that does not increase equipment, consumption will be less than CFC when reaching same density and close physical property foams.The defective of HCFC-141b is that cost of material is higher, and it still has to a certain degree harm for environment.
Summary of the invention
The object of the present invention is to provide a kind of whipping agent, be used for the rigid foam preparation, cost is lower, and the ODP value is lower.
The present invention also aims to provide the preparation method of the rigid foam that adopts above-mentioned whipping agent.
Whipping agent of the present invention by 5～95wt%-dme of fluorine ethylene dichloride and 5～95wt% forms.
Because the dme price is lower, and ODP value is zero, and its adding has reduced the HCFC-141b consumption, has obviously reduced the cost and the ODP value of whipping agent, to protecting environment favourable.In addition, since dme have flammable, boiling point is lower, chemical property is stable, the more high characteristic of gas conduction coefficient; By contrast, HCFC-141b is strong polar compound, and foam is had plasticity, and the gas conduction coefficient is lower.Two kinds of compounds are mixed according to a certain percentage as whipping agent, and over-all properties improves significantly, and flammable the reduction even fired, and the mixed gas thermal conductivity is suitable.In addition, make foam size stability and be improved, can obtain more low-density stable foam body.This is that the gas in the abscess has higher vapour pressure under lower temperature because on the one hand, the dme boiling point is lower, make the pressure in the abscess bigger, offset the part atmosphere to the foamy external pressure, reduced the required anchorage force of bubble post, thereby improved foam size stability; On the other hand, because the plasticity of HCFC-141b all has certain solvency action to bubble wall and bubble post, make foam easily by atmospheric compressed distortion, make the dimensional stability variation, reduce its consumption, be equivalent to reduce plasticity, thereby improved the foamy dimensional stability.The foam size good stability has reduced bubble post required anchorage force, because this anchorage force is corresponding to certain density foam, density is high more, and the compressive strength of acquisition is high more, and bubble post anchorage force is also just high more, and vice versa.Thereby can obtain more low-density stable foam body.
Above-mentioned whipping agent is selected different ratios according to different requirements, has relatively high expectations as heat-insulating property, and mixture is formed preferable by the HCFC-141b of 50～95wt% and the dme of 5～50wt%.Less demanding as heat-insulating property, mixture is formed preferable by the HCFC-141b of 5～50wt% and the dme of 50～95wt%.
The preparation method of rigid foam of the present invention, raw material comprises polyisocyanates and polyvalent alcohol, the whipping agent of employing is made up of the HCFC-141b of 5～95wt% and the dme of 5～95wt%.
The consumption of described whipping agent is easy to make decision by those skilled in the art, generally accounts for 3～25% of reaction raw materials polyisocyanates and polyol component gross weight.
The polyol component that is adopted in above-mentioned preparation method is known, and its average hydroxyl number is 280～1000, preferred 300～700mgKOH/g, and its hydroxy functionality is 2～8, preferential 3～8.It comprises three class polyvalent alcohols: the first kind is the reaction product of initiator and epoxy alkane, epoxy alkane can be oxyethane and/or propylene oxide, initiator comprises: alcohols such as ethylene glycol, glycol ether, propylene glycol, butyleneglycol, glycerine, TriMethylolPropane(TMP), trolamine, tri-isopropanolamine, tetramethylolmethane, sorbyl alcohol and sucrose, polyamines class such as quadrol, tolylene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines and alkamine such as thanomin, Yi Bingchunan, diethanolamine, diisopropanolamine (DIPA) and alkyl alcoholamine, and the polyol blends of this type of initiator preparation; Second class is a polyester polyol, it comprise by the ethylene glycol of suitable proportion and or other polyvalent alcohol and dicarboxylic acid or poly carboxylic acid condensation and the polyester polyol that makes; The 3rd class is a polymerized polyalcohol, and it comprises hydroxy-end capped polythioether, polymeric amide, polyesteramide, polycarbonate, polyacetal, polyolefine and polysiloxane.
The organic multiple isocyanate that adopts in above-mentioned preparation method is selected from the material that adopts usually in this area, and its average functionality is greater than 2.As the mixture of aromatic polyisocyanate and '-diphenylmethane diisocyanate (MDI) and its oligopolymer, this oligopolymer is referred to as " thick MDI " or polymeric MDI in the art.
Organic multiple isocyanate and polyvalent alcohol consumption depend on the character of the rigid foam that will make, and this point is maked decision for a person skilled in the art easily.
Water can be used together as chemical blowing promotor and above-mentioned whipping agent, its weight is generally 0.2%～5.5% of polyol component weight, is preferably 0.5～3.2%.
Except polyisocyanates and polyol component and whipping agent, generally also comprise one or more auxiliary agent or additives commonly used in making the rigid foam prescription in the reaction mixture of manufacturing rigid foam.Auxiliary agent comprises: tertiary amine, the isocyanate catalyst of organic tin, dimethylcyclohexylam,ne or triethylenediamine of silicon-carbon class A foam A stablizer, catalyzer such as dibutyl tin laurate and so on and so on.Optional additive comprises the filler of the haloalkylphosphate of low molecular weight polyols, fire retardant such as tricresyl phosphate chloropropyl ester of linking agent such as trolamine, tri-isopropanolamine and glycerine and so on and so on and carbon black and so on.
Above-mentioned whipping agent can be in advance and polyol component carry out premix, carry out hybrid reaction with polyisocyanates again; Or whipping agent, polyol component and polyisocyanates three components mix in foam gun head previous step.Described whipping agent can directly replace HCFC-141b, and processing parameter is basic identical when using HCFC-141b as whipping agent, can determine by known technology.
According to environmental requirement and economy requirement, adopt the composition of dme and HCFC-141b to make whipping agent, Zhi Bei urethane or urethane-modified polysiocyanurate rigid foams plastics still do not have the domestic and foreign literature report at present thus.
The present invention has the following advantages:
1) raw materials cost reduces;
2) because groundwater increment reduces, and compact density is lower, the cost of preparation foams reduces;
3) reduce the consumption of HCFC-141b, reduced the ODP value, environmentally friendly;
4) the dme source is quite abundant, and promotional value is arranged.
Embodiment
The present invention is illustrated with following embodiment, but is not subjected to the restriction of the following example.
Polyvalent alcohol A: mix according to 55: 30: 15 weight ratios by three kinds of polyether glycol H5822 (Hongbaoli Co. Ltd., Nanjing's product), H4027 (Hongbaoli Co. Ltd., Nanjing's product), H3210 (Hongbaoli Co. Ltd., Nanjing's product).
Polyvalent alcohol B: mix according to 45: 25: 30 weight ratios by three kinds of polyether glycol H5822 (Hongbaoli Co. Ltd., Nanjing's product), H4027 (Hongbaoli Co. Ltd., Nanjing's product), HP3201 (Hongbaoli Co. Ltd., Nanjing's product).
Catalyzer: PC-8 (U.S.'s gas companies is produced), K-15:(U.S. gas companies are produced);
Silicon-carbon class A foam A stablizer: B8462 (Degussa company product);
Polyisocyanates: polymeric MDI, NCO content are 31.0%, and average functionality is 2.7.
Above-mentioned mixed polyvalent alcohol is added in the mixing tank, the according to the form below ratio adds catalyzer, suds-stabilizing agent and water again, and thorough mixing is even, with pump it is conveyed in the high-pressure unit test tank, add whipping agent dme and HCFC-141b more in proportion, continue to mix.Said components is mixed by high pressure machine gun head with polyisocyanates and is reacted, and prepares urethane and urethane-modified polysiocyanurate rigid foams plastics.
Adopt whipping agent of the present invention to prepare the processing parameter of urethane and urethane-modified polysiocyanurate rigid foams plastics and product performance respectively as shown in Table 1 and Table 2.The result shows: adopt different HCFC-141b and dme foaming agent consumption, the rigid foam performance of preparation is close, but when the consumption of dme increases, become core density to reduce, stable foams have lower density, mean and to reduce the foamy filling weight, the foam cost is reduced.
Table 1 adopts the present invention to prepare the processing parameter and the product performance of polyurethane rigid foam plastic
Table 2 adopts the present invention to prepare the processing parameter and the product performance of urethane-modified polysiocyanurate rigid foams plastics
Claims (7)
1. whipping agent is characterized in that it is made up of the fluorine ethylene dichloride of 5～95wt% and the dme of 5～95wt%.
2. whipping agent as claimed in claim 1 is characterized in that it is made up of the fluorine ethylene dichloride of 50～95wt% and the dme of 5～50wt%.
3. whipping agent as claimed in claim 1 is characterized in that it is made up of the fluorine ethylene dichloride of 5～50wt% and the dme of 50～95wt%.
4. the preparation method of a rigid foam, raw material comprises polyisocyanates and polyvalent alcohol, it is characterized in that the whipping agent that adopts is made up of the fluorine ethylene dichloride of 5～95wt% and the dme of 5～95wt%.
5. the preparation method of rigid foam as claimed in claim 4, the consumption that it is characterized in that described whipping agent is 3～25% of polyisocyanates and a polyvalent alcohol gross weight.
6. as the preparation method of claim 4 or 5 described rigid foams, it is characterized in that also making water as chemical blowing promotor, its consumption is 0.2%～5.5% of a polyol component weight
7. the preparation method of rigid foam as claimed in claim 6, the consumption that it is characterized in that water is 0.5～3.2% of a polyol component weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100219032A CN101343375B (en) | 2008-08-18 | 2008-08-18 | Foaming agent and preparation method for rigid cellular plastic employing the foaming agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100219032A CN101343375B (en) | 2008-08-18 | 2008-08-18 | Foaming agent and preparation method for rigid cellular plastic employing the foaming agent |
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| Publication Number | Publication Date |
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| CN101343375A CN101343375A (en) | 2009-01-14 |
| CN101343375B true CN101343375B (en) | 2011-02-09 |
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| CN2008100219032A Expired - Fee Related CN101343375B (en) | 2008-08-18 | 2008-08-18 | Foaming agent and preparation method for rigid cellular plastic employing the foaming agent |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102716810B (en) * | 2012-06-21 | 2014-02-19 | 冯益生 | Foaming agent for flotation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036970A (en) * | 1988-02-22 | 1989-11-08 | 纳幕尔杜邦公司 | Closed-cell polyurethane foam compositions |
| WO1992017558A1 (en) * | 1991-03-28 | 1992-10-15 | E.I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane |
| CN1069499A (en) * | 1991-08-19 | 1993-03-03 | 纳幕尔杜邦公司 | Be used to prepare the whipping agent and the processing method of polyurethane foamed material |
-
2008
- 2008-08-18 CN CN2008100219032A patent/CN101343375B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036970A (en) * | 1988-02-22 | 1989-11-08 | 纳幕尔杜邦公司 | Closed-cell polyurethane foam compositions |
| WO1992017558A1 (en) * | 1991-03-28 | 1992-10-15 | E.I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane |
| CN1069499A (en) * | 1991-08-19 | 1993-03-03 | 纳幕尔杜邦公司 | Be used to prepare the whipping agent and the processing method of polyurethane foamed material |
Non-Patent Citations (2)
| Title |
|---|
| 安孟学.发泡剂的发展.《塑料橡胶加工助剂》.化工工业出版社,2002,670-671. * |
| 王宏伟.氢氯氟烃(HCFCs)发泡剂在聚氨酯硬泡沫中的应用.《聚氨酯工业》.1995,(第3期),3-7. * |
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