CN100509899C - Hard polyurethane foam plastic prepared by third-generation foaming agent - Google Patents
Hard polyurethane foam plastic prepared by third-generation foaming agent Download PDFInfo
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- CN100509899C CN100509899C CNB2006100226840A CN200610022684A CN100509899C CN 100509899 C CN100509899 C CN 100509899C CN B2006100226840 A CNB2006100226840 A CN B2006100226840A CN 200610022684 A CN200610022684 A CN 200610022684A CN 100509899 C CN100509899 C CN 100509899C
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Abstract
The invention discloses a hard polyurethane foam plastic through the third foamer, which comprises the following steps: adopting built-up polyether, catalyst, even-foam agent, distill agent and foamerThe invention discloses a hard polyurethane foam plastic through the third foamer, which comprises the following steps: adopting built-up polyether, catalyst, even-foam agent, distill agent and foamer as raw material A; using polymethylene polyphenyl polyisocyanates as raw material B; selecting HFC-365/227 foamer as foamer; setting the weight rate of component A and B at 1:1.1-1.4 to blend togethe as raw material A; using polymethylene polyphenyl polyisocyanates as raw material B; selecting HFC-365/227 foamer as foamer; setting the weight rate of component A and B at 1:1.1-1.4 to blend together; pouring the mass into mould; foaming; solidifying; obtaining the product with little toxicity and good environment-protective property. r; 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 contain the rigid urethane foam of HFC-365/227 whipping agent, it is specially adapted to the piping insulation aspect.
Background technology
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, it is found that in recent years CFC (Chlorofluorocarbons (CFCs)) class whipping agent is very big to the destruction of ozonosphere.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, HC series (mainly containing pentamethylene, three kinds of Skellysolve A and iso-pentane) and HFC (hydrogen fluorohydrocarbon) series.
At present, the whipping agent that China uses aspect piping insulation mainly is HCFC-141b, and full water foamed foam thermal conductivity is big, because CO
2The thermal conductivity of self is bigger, and the heat retaining property that hard bubbles that utilizes it to make is poor, and foam is easily sent out shortcake and become fragile; Liquid CO
2Whipping agent need be contained in the high pressure vessel, the HC class is inflammable and explosive, the boiling point of HFC-245fa (15.3 ℃) is on the low side, vapour pressure higher (approximately being the twice of HCFC-141b), so they existing be that the production unit and the technologic application of whipping agent all is restricted with HCFC-141b.A kind of prescription that uses third generation whipping agent to produce hard polyurethane foam is disclosed for No. 200510094781.6 as the Chinese invention patent application, 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.Therefore, the zero 0DP whipping agent of being badly in need of providing a kind of energy to substitute HCFC-141b is applied on the existing piping insulation production unit, and good environmental protection, the rigid urethane foam that integrated materials performance is good.
Summary of the invention
The purpose of this invention is to provide a kind of being applicable on the existing piping insulation production unit, and good environmental protection, rigid urethane foam that integrated materials performance is good.
Environmental protection described in the present invention (third generation) whipping agent is meant that mainly ozone depletion potential (0DP) is zero, and (GWP) is less for Greenhouse effect potential, environment amenable green whipping agent.
The rigid urethane foam of third generation whipping agent of the present invention manufacturing is characterised in that it is 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, and wherein the composition of each raw material and weight part are in the A component:
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 catalyzer 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;
3., described foam stabilizer is Si-C of bonding foam stabilizer, consumption is 1.4～2.0 parts;
4., distilled water is 1.0～1.8 parts;
Described whipping agent is the HFC-365/227 whipping agent, and consumption is 5.0～9.0 parts; Described 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;
When the weight of A component was 1, the weight that constitutes the poly methylene poly phenyl poly isocyanate of above-mentioned B component was 1.1～1.4, and the weight ratio of promptly above-mentioned A component and B component poly methylene poly phenyl poly isocyanate is 1:1.1～1.4;
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, above-mentioned blowing agent H FC-365/227 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, 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
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.
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, obtain rigid urethane foam through foaming, solidifying.
As previously mentioned, 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.
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, particularly piping insulation aspect, be applicable on present all HCFC-141b foaming system piping insulation field devices and the technology that foamed time variable range broad, foamed time comprise 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 the aforementioned existing similar products, third generation blowing agent H FC-365/227 (HFC-365mfc and HFC-227ea binary mixture have been adopted in the product of the present invention, weight ratio 93:7,30 ℃ of boiling points), this whipping agent ozone depletion potential (ODP) is zero, not damaging the ozone layer, is the green whipping agent friendly more to environment.The organic tin catalyst is active high in the prior art, and the foamed time variable range is big, be the custom catalysts in the urethane foam industry, but toxicity is big, and environmental pollution is serious.The used catalyst system of prescription of the present invention does not contain organic tin, and catalyst toxicity is littler, and environmental-protecting performance is better, and foamed time is in 10～180s, and variable range is big.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: 420～550mgK0H/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 HFG-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 0.4 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 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 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 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 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 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 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 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 0.5 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 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 0.6 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 of third generation whipping agent manufacturing, it is characterized in that it is 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, and wherein the composition of each raw material and weight part are in the A component:
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 catalyzer 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;
3., described foam stabilizer is Si-C of bonding foam stabilizer, consumption is 1.4～2.0 parts;
4., distilled water is 1.0～1.8 parts;
Described whipping agent is the HFC-365/227 whipping agent, and consumption is 5.0～9.0 parts; Described HFC-365/227 whipping agent is the binary blend of HFC-365mfc and HFC-227ea, and wherein, the weight ratio of HFC-365mfc and HFC-227ea is 93:7;
When the weight of A component was 1, the weight that constitutes the poly methylene poly phenyl poly isocyanate of above-mentioned B component was 1.1～1.4, and the weight ratio of promptly above-mentioned A component and B component poly methylene poly phenyl poly isocyanate is 1:1.1～1.4;
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.
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|---|---|---|---|
| CNB2006100226840A CN100509899C (en) | 2006-12-28 | 2006-12-28 | Hard polyurethane foam plastic prepared by third-generation foaming agent |
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|---|---|---|---|
| CNB2006100226840A CN100509899C (en) | 2006-12-28 | 2006-12-28 | Hard polyurethane foam plastic prepared by third-generation foaming agent |
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| CN100509899C true CN100509899C (en) | 2009-07-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665578B (en) * | 2009-09-28 | 2011-08-17 | 关志强 | Foaming agent used for thermal-insulating polyurethane plastics |
| 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 |
| CN101831268B (en) * | 2010-03-24 | 2011-12-14 | 山东东大聚合物股份有限公司 | Double-component environmental-protection polyurethane adhesive for rock wool color steel sandwich panels by continuous process 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 |
| WO2012077728A1 (en) * | 2010-12-08 | 2012-06-14 | 東ソー株式会社 | Catalyst composition for manufacturing polyurethane resin, and method for producing polyurethane resin using same |
| CN102504163B (en) * | 2011-11-08 | 2013-11-06 | 上海东大聚氨酯有限公司 | Conjugate polyether for hard polyurethane foam and using method thereof |
| 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 |
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