CN100509903C - Hard polyurethane foam plastic - Google Patents
Hard polyurethane foam plastic Download PDFInfo
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- CN100509903C CN100509903C CNB200610022686XA CN200610022686A CN100509903C CN 100509903 C CN100509903 C CN 100509903C CN B200610022686X A CNB200610022686X A CN B200610022686XA CN 200610022686 A CN200610022686 A CN 200610022686A CN 100509903 C CN100509903 C CN 100509903C
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Abstract
The invention discloses a hard polyurethane foam plastic, which is characterized by the following: adopting complex polyether, catalyst, foamer, distill water and foamer as raw material A; using polymethylene polyphenyl polyisocyanates as raw material B; blending micromolecular hydroxy compound, tertiary amine catalyst and potassium oleate as catalyst; blending each component of raw material A evenly with component B; pouring the mass into mould; foaming; solidifying; obtaining the product with little toxicity and good environment-protective property.
Description
Technical field
The present invention relates to a kind of rigid urethane foam, especially a kind of rigid urethane foam that is specially adapted to the use of piping insulation aspect.
Background technology
Rigid urethane foam is most important lagging material, is widely used in the automobile boats and ships, petroleum pipe line, and the refrigerator freezer, covil construction, urban heat supplying, use as thermal insulation material and structured material in fields such as aerospace military project.CFC-11 (molecular formula CCl
3F) be typical case's representative of first-generation whipping agent, it is widely used in the urethane foam industry.But CFC (Chlorofluorocarbons (CFCs)) class whipping agent is very big to the destruction of ozonosphere, and according to " Montreal Protocol ", developed country forbade before 1996 comprehensively, and the deadline that China eliminates CFC is in July, 2007.HCFC-141b (molecular formula CH
3CFCl
2) be the most sophisticated whipping agent at commercial alternative CFC-11, but still having certain ozone, HCFC (Hydrochlorofluorocarbons) class whipping agent removes function and Greenhouse effect.Therefore they are a kind of transition whipping agent, will are zero environment-friendly type whipping agent by new 0DP (ozone depletion potential), and promptly third generation whipping agent replaces.The environment-friendly type whipping agent that substitutes HCFC-141b at present has water, liquid CO
2, pentane class and HFC (hydrogen fluorohydrocarbon) series.The Chinese invention patent application once disclosed a kind of prescription that uses third generation whipping agent to produce hard polyurethane foam for No. 200510094781.6, it has adopted HFC-245fa as whipping agent, though compliance with environmental protection requirements, boiling point that this whipping agent is on the low side and higher vapour pressure make its alternative HCFC-141b be restricted at existing piping insulation rigid foam production unit and technologic application.
From another perspective,, when making rigid urethane foam, also need to improve thereupon, therefore, be badly in need of providing a kind of catalyzer that can adapt to new whipping agent with the corresponding catalyzer of this whipping agent because first-generation whipping agent is about to be eliminated.Simultaneously, especially at the production of piping insulation rigid urethane foam, because the caliber of pipeline differs in size, when making the piping insulation rigid urethane foam, just require the employed catalyzer can be at the scope inner control foamed time of broad.Therefore, in order to obtain good environmental protection, the piping insulation rigid urethane foam that integrated materials performance is good just need be when changing new whipping agent, corresponding preferably can be at the catalyzer of the scope inner control foamed time of broad.
Summary of the invention
Purpose of the present invention promptly is preferred by to catalyzer, enable to adapt to novel whipping agent and piping insulation particular requirement, and then a kind of existing piping insulation production unit and good environmental protection, rigid urethane foam that integrated materials performance is good of being applicable to is provided with rigid urethane foam.
Rigid urethane foam of the present invention constitutes the A component of raw material with composite polyethers, catalyzer, foam stabilizer, distilled water and whipping agent, with the poly methylene poly phenyl poly isocyanate is the B component of raw material, the weight ratio of described A component and B component poly methylene poly phenyl poly isocyanate is 1:1.1～1.4, it is characterized in that the catalyzer in the A component is made by following component:
Totally 0.4～0.8 part of a, the micromolecular hydroxyl compound that constitutes by the mixture of glycerine, ethylene glycol and diethanolamine, wherein, the weight ratio of glycerine, ethylene glycol and diethanolamine is 2:1:1;
0.7～4.0 part of b, tertiary amine catalyst;
0.2～2.8 part of c, potassium oleate;
The composition of other raw material in the A component and weight part are:
1., composite polyethers: 100 parts
Described composite polyethers is by low functionality polyether glycol and the high functionality polyether glycol is composite makes;
Wherein, 40～50 parts of low functionality polyether glycols, functionality 3～4, hydroxyl value scope: 420～550mgKOH/g;
50～60 parts of high functionality polyether glycols, functionality 5～8, hydroxyl value scope: 420～530mgKOH/g;
2., described foam stabilizer is Si-C of bonding foam stabilizer, consumption is 1.4～2.0 parts;
3., distilled water is 1.0～1.8 parts
4., whipping agent is 5.0～9.0 parts;
Production method is: earlier composite polyethers, catalyzer, foam stabilizer, distilled water and whipping agent are mixed by above-mentioned weight part and obtain the raw material A component, then raw material A component and raw material B component are mixed by above-mentioned weight ratio and stir with stirrer immediately and obtain compound, at last compound is poured in the mould, obtained rigid urethane foam through foaming, solidifying.
In the present invention, described whipping agent can be HCFC (Hydrochlorofluorocarbons) class whipping agent, as HCFC-141b (molecular formula CH
3CFCl
2) whipping agent, also can be liquid HFC (hydrogen fluorohydrocarbon) series in the third generation environment-friendly type whipping agent, be the mixture of aglucon as HFC-365mf or with HFC-365mf.But,, be good to adopt the HFC-365/227 whipping agent especially from experiment effect.Therefore, except that catalyzer having been carried out preferably, the present invention also special recommendation adopts the HFC-365/227 whipping agent, and herein, said HFC-365/227 whipping agent is HFC-365mfc (molecular formula CH
3CF
2CH
2CF
3, chemical name 1,1,1,3,3-3-pentafluorobutane) and HFC-227ea (molecular formula CF
3CHFCF
3, chemical name 1,1,1,2,3,3,3 ,-heptafluoro-propane) binary blend, wherein, the weight ratio of HFC-365mfc and HFC-227ea is 93:7, this whipping agent boiling point is 30 ℃.This whipping agent can adopt commercially available product, and the trade names of selling as Su Hua chemical industry company limited (the German Su Wei fluorine chemistry Chinese soleagent of company limited) are Solkane
365/227 whipping agent etc.
As previously mentioned, the weight ratio of A component and B component (poly methylene poly phenyl poly isocyanate) is 1:1.1～1.4.Experimental result shows that when the weight ratio of A component and B component (poly methylene poly phenyl poly isocyanate) was 1:1.25, the integrated materials performance of products obtained therefrom was best, so the ratio of special recommendation A of the present invention, B two components is 1:1.25.
Porous plastics of the present invention can make (as 10～30 ℃) with foaming at normal temp, be not subject to seasonal restrictions, but the best reaction conditions of porous plastics manufacturing is that material mild condition temperature is advisable between 20～30 ℃ before A, the mixing of B component.
Need to prove, after raw material A component and raw material B component are mixed by above-mentioned weight ratio, high-speed stirring is even immediately, this process can adopt conventional whipping device to carry out, the stirrer rotating speed preferably is not less than 2500r/min, churning time fixes on about 6～10s according to the foam raw material cream time and is advisable, and guarantees before the raw material milky white it to be poured in the mould.For example, can with rotating speed the stirrer stirring 10s of 3000r/min.After obtaining compound, this compound is poured in the mould fast, after foaming, curing, can obtain rigid urethane foam.
As previously mentioned, recommending the third generation blowing agent H FC-365/227 that adopts among the present invention is binary blend (the weight ratio 93:7 of HFC-365mfc and HFC-227ea, 30 ℃ of boiling points), this mixed type whipping agent does not have flash-point (Iso 1516/1523), belongs to not flammable liquid whipping agent.Its ozone depletion potential 0DP value is zero, does not damage the ozone layer, and (GWP) is less for Greenhouse effect potential, is environment amenable green whipping agent, and prepared rigid urethane foam is corresponding to be beneficial to environmental protection.HFC-365/227 has thermodynamics and the chemical stability better than HCFC-141b, its vapour pressure is lower than HCFC-141b, security is higher in producing the rigid urethane foam process, and foaming machine is required lower, can be comparatively easily existing be to substitute utilization on the production unit of whipping agent and the technology with CFC-11 or HCFC-141b.The thermal conductivity of HFC-365/227 and HCFC-141b are very approaching, and the foam thermal insulation performance that makes is suitable.
When adopting HCFC-141b or HFC-365/227 as whipping agent, rigid urethane foam meets following wood property examination criteria among the present invention:
Buried steel pipeline rigid urethane foam anticorrosion insulating layer technological standard (SY/T0415-96) polyurethane foam layer performance index
The thermal test condition: 120 ℃, 96h
Product of the present invention can be applicable to the insulation aspect, and particularly piping insulation aspect is applicable on present all HCFC-141b foaming system piping insulation field devices and the technology.Because the composition to catalyzer has carried out preferably, thereby makes foamed time variable range broad (foamed time is in 10～180s, and variable range is big).Foamed time comprises milky white and two the main processes that rise, wherein cream time (foam raw material finishes to rise during this period of time to beginning foaming from stirring) variable range is about 10～60s, rise time (foam raw material finishes to rising to highest point from stirring, and stops foaming during this period of time) variable range is about 30～180s.
As described above, the rigid foam performance produced of the present invention meets buried steel pipeline rigid urethane foam anticorrosion insulating layer technological standard (SY/T0415-96).
Compared with prior art, though the organic tin catalyst is active high in the prior art, be the custom catalysts in the urethane foam industry, toxicity is big, and environmental pollution is serious.Used catalyst system does not contain organic tin in the product of the present invention, catalyst toxicity is littler, and environmental-protecting performance is better, and foamed time is in 10～180s, variable range is big, fully enough adapts to novel whipping agent and the piping insulation particular requirement with rigid urethane foam.When adopting third generation blowing agent H FC-365/227 further, whipping agent ozone depletion potential (0DP) is zero, does not damage the ozone layer, and is friendly more to environment.In addition, the present invention has fine and closely woven abscess with the rigid foam that HFC-365/227 does whipping agent production, good heat insulating ability, and especially thermotolerance (test condition is 120 ℃) and ultimate compression strength are better.
Content of the present invention further illustrates with the following Examples, but content of the present invention is not limited only to content related among the embodiment.
Embodiment
In following each embodiment, related composite polyethers is by low functionality polyether glycol and the high functionality polyether glycol is composite makes, wherein, and the functionality 3～4 of low functionality polyether glycol, hydroxyl value scope: 420～550mgKOH/g; The functionality 5～8 of high functionality polyether glycol, hydroxyl value scope: 420～530mgKOH/g.Simultaneously, related micromolecular hydroxyl compound constitutes by the mixture of glycerine, ethylene glycol and diethanolamine, and wherein, the weight ratio of glycerine, ethylene glycol and diethanolamine is 2:1:1.In addition, related HFC-365/227 whipping agent all is binary blend of HFC-365mfc and HFC-227ea, and wherein, the weight ratio of HFC-365mfc and HFC-227ea is 93:7.Only lift A in following examples, the material temperature all was 28 ℃ before the B component was mixed, and envrionment temperature is the example that is about 25 ℃.The purpose of above-mentioned definition is just to repeat no more in following examples in addition herein.
Embodiment 1: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 40 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 60 grams; Micromolecular hydroxyl compound 0.6 gram; Tertiary amine catalyst 1.5 grams; Potassium oleate 0.5 gram; Si-C of bonding foam stabilizer 1.8 grams; Distilled water 1.0 grams; HCFC-141b (molecular formula CH
3CFCl
2) whipping agent 8.0 grams; The gross weight of A component is 113.4 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.25 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 141.8 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 2: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 40 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 60 grams; Micromolecular hydroxyl compound 0.4 gram; Tertiary amine catalyst 4.0 grams; Potassium oleate 2.6 grams; Si-C of bonding foam stabilizer 1.8 grams; Distilled water 1.0 grams; HFC-365/227 whipping agent 9.0 grams; The gross weight of A component is 118.8 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.1 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 130.7 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 3: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 45 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 55 grams; Micromolecular hydroxyl compound 0.8 gram; Tertiary amine catalyst 1.8 grams; Potassium oleate 0.2 gram; Si-C of bonding foam stabilizer 1.6 grams; Distilled water 1.2 grams; HFC-365/227 whipping agent 7.0 grams; The gross weight of A component is 112.6 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.4 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 157.6 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 4: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 50 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 50 grams; Micromolecular hydroxyl compound 0.6 gram; Tertiary amine catalyst 3.8 grams; Potassium oleate 2.8 grams; Si-C of bonding foam stabilizer 2.0 grams; Distilled water 1.8 grams; HFC-365/227 whipping agent 8.0 grams; The gross weight of A component is 119.0 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.25 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 148.8 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 5: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 40 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 60 grams; Micromolecular hydroxyl compound 0.7 gram; Tertiary amine catalyst 2.0 grams; Potassium oleate 0.4 gram; Si-C of bonding foam stabilizer 1.5 grams; Distilled water 1.1 grams; HFC-365/227 whipping agent 5.0 grams; The gross weight of A component is 110.7 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.25 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 138.4 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 6: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 40 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 60 grams; Micromolecular hydroxyl compound 0.5 gram; Tertiary amine catalyst 1.0 grams; Potassium oleate 0.2 gram; Si-C of bonding foam stabilizer 1.4 grams; Distilled water 1.4 grams; HFC-365/227 whipping agent 7.5 grams; The gross weight of A component is 112.0 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.25 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 140.0 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Embodiment 7: make rigid urethane foam according to following prescription:
The composition of each raw material and weight in the A component:
By low functionality polyether glycol 40 grams and the composite composite polyethers that makes 100 grams of high functionality polyether glycol 60 grams; Micromolecular hydroxyl compound 0.6 gram; Tertiary amine catalyst 0.7 gram; Potassium oleate 0.4 gram; Si-C of bonding foam stabilizer 1.4 grams; Distilled water 1.5 grams; HFC-365/227 whipping agent 7.5 grams; The gross weight of A component is 112.1 grams.
Earlier that the A component is evenly mixed in a container, by predetermined proportion B component poly methylene poly phenyl poly isocyanate is added in the A component then, with stirrer with rotating speed 3000r/min high-speed stirring 10s, at last compound is poured in the mould, the compound reaction is very fast, obtain rigid urethane foam through foaming, curing, wherein the A component is 1:1.25 (weight ratio) with the ratio of B component poly methylene poly phenyl poly isocyanate, i.e. B component poly methylene poly phenyl poly isocyanate 140.1 grams.
In the present embodiment, the wood property of prepared finished product such as following table:
Claims (2)
1, a kind of rigid urethane foam, it constitutes the A component of raw material with composite polyethers, catalyzer, foam stabilizer, distilled water and whipping agent, with the poly methylene poly phenyl poly isocyanate is the B component of raw material, the weight ratio of described A component and B component poly methylene poly phenyl poly isocyanate is 1:1.1～1.4, it is characterized in that the catalyzer in the A component is made by following component:
Totally 0.4～0.8 part of a, the micromolecular hydroxyl compound that constitutes by the mixture of glycerine, ethylene glycol and diethanolamine, wherein, the weight ratio of glycerine, ethylene glycol and diethanolamine is 2:1:1;
0.7～4.0 part of b, tertiary amine catalyst;
0.2～2.8 part of c, potassium oleate;
The composition of other raw material in the A component and weight part are:
1., composite polyethers: 100 parts
Described composite polyethers is by low functionality polyether glycol and the high functionality polyether glycol is composite makes;
Wherein, 40～50 parts of low functionality polyether glycols, functionality 3～4, hydroxyl value scope: 420～550mgKOH/g;
50～60 parts of high functionality polyether glycols, functionality 5～8, hydroxyl value scope: 420～530mgKOH/g;
2., described foam stabilizer is Si-C of bonding foam stabilizer, consumption is 1.4～2.0 parts;
3., distilled water is 1.0～1.8 parts
4., whipping agent is 5.0～9.0 parts;
Production method is: earlier composite polyethers, catalyzer, foam stabilizer, distilled water and whipping agent are mixed by above-mentioned weight part and obtain the raw material A component, then raw material A component and raw material B component are mixed by above-mentioned weight ratio and stir with stirrer immediately and obtain compound, at last compound is poured in the mould, obtained rigid urethane foam through foaming, solidifying.
2, rigid urethane foam as claimed in claim 1 is characterized in that the weight ratio of described A component and B component poly methylene poly phenyl poly isocyanate is 1:1.25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610022686XA CN100509903C (en) | 2006-12-28 | 2006-12-28 | Hard polyurethane foam plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610022686XA CN100509903C (en) | 2006-12-28 | 2006-12-28 | Hard polyurethane foam plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016367A CN101016367A (en) | 2007-08-15 |
| CN100509903C true CN100509903C (en) | 2009-07-08 |
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ID=38725604
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|---|---|---|---|
| CNB200610022686XA Expired - Fee Related CN100509903C (en) | 2006-12-28 | 2006-12-28 | Hard polyurethane foam plastic |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798377B (en) * | 2010-03-24 | 2011-09-21 | 山东东大聚合物股份有限公司 | Environment-friendly composite applicable to pipeline heat insulation and preparation method thereof |
| CN101787203B (en) * | 2010-03-24 | 2011-12-07 | 山东东大聚合物股份有限公司 | Composite material adopting pentafluorobutane as foaming agent for solar water heater and preparation method thereof |
| CN102235736A (en) * | 2010-04-29 | 2011-11-09 | 江苏宝信空调设备制造有限公司 | Heat preservation device for defrosting tray of fan coil |
| US20140093721A1 (en) * | 2011-05-02 | 2014-04-03 | Bayer Intellectual Property Gmbh | High-temperature-resistant foams having low thermal conductivity |
| CN103332520A (en) * | 2013-07-09 | 2013-10-02 | 江苏久久防水保温隔热工程有限公司 | Production method for light high-strength and energy-saving cloth guide roller |
| PL3115389T3 (en) * | 2015-07-07 | 2020-09-07 | Evonik Operations Gmbh | Preparation of polyurethane foam |
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