CN102558492A - Combined material for solar water heater by using n-pentane as foaming agent and preparation method thereof - Google Patents
Combined material for solar water heater by using n-pentane as foaming agent and preparation method thereof Download PDFInfo
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- CN102558492A CN102558492A CN2011104312992A CN201110431299A CN102558492A CN 102558492 A CN102558492 A CN 102558492A CN 2011104312992 A CN2011104312992 A CN 2011104312992A CN 201110431299 A CN201110431299 A CN 201110431299A CN 102558492 A CN102558492 A CN 102558492A
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Abstract
The invention belongs to the technical field of polyurethane foam plastics, and in particular relates to a combined material for a solar water heater by using n-pentane as a foaming agent and a preparation method thereof. The combined material consists of a component A and a component B, wherein the component A consists of polyol, a foam stabilizing agent, water, a foaming agent and a catalyst; and the component B is polymeric diphenylmethane diisocyanate. When in use, the component material A and the component material B are sufficiently mixed so as to prepare polyurethane rigid foam for filling the solar water heater. According to the invention, the component A and the component B are sufficiently mixed and then filled in the cavity of the water tank of the solar water heater, thus flowability is good, pressure is low in a foaming process, the appearance of the water tank of the solar water heater can be well maintained, and simultaneously, an inner container is not flattened; the water tank has no decladding and foam cracking phenomena in the placing process at the low temperature environment of minus 35 DEG C; the surface of foam is smooth and has no cavity at the vacuum pipe position; and heat conducting coefficient is low, and heat preservation property is excellent, thereby completely meeting the use requirement and environment-friendly requirement of a customer.
Description
Technical field
The invention belongs to the urethane foam technical field, being specifically related to a kind of Skellysolve A that adopts is the solar water heater usefulness combination material and the method for making thereof of whipping agent.
Background technology
World's sun power always moved recoverable amount 168M m in 2006
2, suitable inventory 118GWth, energy supply 70,000,000,000 kWh, China is 90M m then
2, solar thermal utilization accounts for 53.6%.1990 back China become production gradually and use big country; The year output of China's solar water heater is 2 times of Europe; 4 times of North America have become maximum in the world solar water heater producing country and maximum Solar Heater Market at present, and still at the speed increase with annual 20%-30%.
Sun power industry PU (urethane) purposes mainly is the filling and the insulation of interlayer cavity of the water tank of solar water heater, because urethane can well be combined into one in foaming process, heat-insulating property is high, and urethane is used widely.
The sun power industry was brought into use polyurethane foam in 95,96 years; This moment, the sector was to play insulation effect in the interlayer with filling in after the polyphenyl foam moulding mostly, and along with gradually understanding and the understanding of industry to urethane, 1997-2000 also experiences more than half foamed heat insulating processes mostly; Just be close to inner bag and partly use half polyphenyl foam; Fill with cast polyurethane, the polyurethane foam volume accounts for half the again, and heat insulation effect improves than the former greatly.2000-2003 sun power industry begins to transfer to gradually all uses the polyurethane foam foamed heat insulating.
The sun power industry is being formulated relevant criterion at present, owing to do not have standard to say early stage in development, the one, high-pressure foam equipment, circular line, few time (1-3 time) is cast for main production line mode.The 2nd, in, the low pressure foaming machine, repeatedly (more than 7 times) be cast for the main mode of production.What possess scale at present transfers first kind of foaming mode gradually to.
The annular mode of production of few moulding of high-pressure foam equipment is higher for the foam material technical requirements, because the sun power wall of inner container is thinner, it is little to bear blow(ing)pressure, and the popularization of disposal pouring mode is limited by the seam interlock technology of bearing pressure and crust of inner bag.Require polyurethane foam material good fluidity in foaming process, blow(ing)pressure is low, the characteristics that slaking is fast, and integral-filled density is at 40-43kg/m
3Between.
In, low pressure repeatedly the mode of casting owing to be semi-free foaming mode; One end is open type cast, and particularly in winter airtight foaming space, the polyurethane foam material requires the foaming smell little; The reaction times of foamed material wants fast than the former; Blow(ing)pressure is less, and mobile general, integral-filled density is at 38-42kg/m
3
The sun power industry was high speed development in these several years, occurred the situation of diversified development now.The bright sun power of emperor all used 141b type combined polyether at present, once tested full water foamed system in 02 year, did not produce in batches, and the 245fa system was once paid close attention to, and did not adopt.Power promise, Sun Rain company 06 year are adopted the 245fa foaming system with the Honeywell Inc. cooperation successively, at present since the cost plateau because of, only short run is used.The sun power in Beijing Sang Pu sun power 06-08 outlet Europe is measured less for using full aqueous systems combined polyether.Other sun power producers are the 141b foaming system at present.
Because diversified development appears in the floride-free alternative orientation of above-mentioned said sun power industry; Carried out experiment level verification and the short run of systems such as full water, 141b, 245fa successively and used, changeable and accelerated warmer along with global climate, environmental issue has become important matters; Although also regulation the year two thousand thirty stops the production and consumption of HCFC comprehensively; Be frozen into M.L. (baseline values) in 2009 and 2010 to China's HCFC consumption by 2013, and cut down 10% in 2015, but along with development of global economy; Substituting of HCFC-141b whipping agent seemed very urgent; Manufacturing enterprise should take all factors into consideration at aspects such as product efficiency, cost and safety according to own enterprises'features, and the plan of eliminating is formulated in the call of active response national policy and environmental requirement in the lead as early as possible.
As the whipping agent of the third generation, Skellysolve A has following characteristics:
(1) the ODP value is zero, and GWP value is lower, and compliance with environmental protection requirements adopts pentane-blown technological, can one-time-reach-place, avoid replacing once more.
(2) combustiblematerials, blast easily.
(3) foamy density is low, and foamy core density is minimum can to drop to 34kg/m
3Thereby, reduce the foamy usage quantity, reduced the cost of foamed material.
(4) the mobile and release property raising of foamy, the foamy density distribution is more even, and demould time reduces, and has improved working efficiency.
Because Skellysolve A has certain danger, thus to accomplish following some: (1) Skellysolve A should leave the intensive zone away from personnel in, and storage tank will be embedded in underground; (2) use of Skellysolve A should be limited in certain zone; (3) forbid getting in the zone of using Skellysolve A with the irrelevant personnel of production operation; (4) all use equipment will have explosion-proof equipment; (5) in the production area antistatic aids to be arranged; (6) will there be Skellysolve A detection alarm device the production area; (7) will there be good ventilation, gas barrier in the production area.
Pentane class whipping agent has used decades at other field, even has also used about 10 years in the refrigerator industry, and security incident does not together take place, and therefore, as long as in strict accordance with safety regulation for operations production, accident is avoidable fully.
All kinds of whipping agent physical parameters see the following form:
At present; The combination material that is applied to the solar water heater water tank filling on the market is owing to polyether glycol, selection of catalysts are improper; Existence is with the foam and the mass defects such as the base material cohesive force is poor, internal cleavage, surface hole is many, thermal conductivity is high, the bubble sky is thick of its generation; And the whipping agent that the A component adopts is generally a fluorine ethylene dichloride (HCFC-141b), and this whipping agent still has destruction to atmospheric ozone layer, in 3-5, will be eliminated.
Summary of the invention
The purpose of this invention is to provide a kind of Skellysolve A that adopts is the solar water heater usefulness combination material and the method for making thereof of whipping agent; Selection through polyvalent alcohol and auxiliary agent; Successfully solved the mass defect of solar water heater water tank filling process; Selected third generation zero odp whipping agent Skellysolve A simultaneously for use, compliance with environmental protection requirements, solar water heater water tank foam and the base material cohesive force of using this combination material to make are strong; High and low temperature resistance excellence, smooth surface, heat-insulating property excellence satisfy the use and the environmental requirement of solar water heater fully.
A kind of Skellysolve A that adopts of the present invention is the solar water heater usefulness combination material of whipping agent, forms by A component and B component, wherein:
The A component does, by weight percentage:
Polyether glycol A:42～46%;
Polyether glycol B:26～30%;
Polyester polyol C:3～5%;
Biopolyol D:3～5%;
Suds-stabilizing agent: 1.2～2.0%;
Water: 1.2～1.6%
Whipping agent: 14～18%;
Catalyzer: 0.5～2.0%;
Wherein:
Polyether glycol A is 6.0 functionality, and molecular weight is 800～1000 polypropyleneoxide ethoxylated polyhydric alcohol,
Polyether glycol B is 4.0 functionality, and molecular weight is 500～700 polypropyleneoxide ethoxylated polyhydric alcohol,
Polyester polyol C is 2 functionality, and molecular weight is 300～400 benzoic anhydride polyester polyol,
Biopolyol D is 3 functionality, and molecular weight is 800～1000 castor oil polyhydric alcohol,
Suds-stabilizing agent is a SI-C class surfactant B-8525,
Whipping agent is a Skellysolve A,
Water is deionized water,
Catalyzer is a tertiary amine catalyst;
The B component is a polyphenyl polymethylene polyisocyanates.
Wherein, tertiary amine catalyst adopts N, N, N ', N ", N "-propylene glycol solution and 1,3 of pentamethyl-diethylenetriamine, triethylene diamine 33wt%, 5-three (dimethylaminopropyl) Hexahydrotriazine, wherein three's mass ratio is 1: 3～5: 6～10.N, N, N '; N "; N "-pentamethyl-diethylenetriamine selects for use US Air gasification worker's PC-5, the propylene glycol solution of triethylene diamine 33% to select US Air gasification worker's A-33,1,3 for use, and 5-three (dimethylaminopropyl) Hexahydrotriazine is selected US Air gasification worker's PC-41 for use.
Suds-stabilizing agent B-8525 manufacturer is German high Schmidt.
The solar water heater that employing Skellysolve A according to the invention is a whipping agent is with the method for making of combination material, and concrete method for making is following:
Preparation A component material: load weighted polyether glycol, polyester polyol, biopolyol are packed into stir in the reaction kettle earlier; Add load weighted catalyzer, whipping agent, water, suds-stabilizing agent then; Reaction was stirred 2～3 hours at normal temperatures, got final product barrelling;
B component material is a polyphenyl polymethylene polyisocyanates, selects for use the commercially available prod to get final product;
A, B component material are pressed A: B=100: 100～105 weight ratio is mixed, and promptly can be made into the solar water heater filling and uses hard polyurethane foam.
The invention has the advantages that A, B component inject the solar water heater water tank cavity behind thorough mixing, good fluidity, pressure is low in the foaming process, can keep the outward appearance of solar water heater water tank preferably, does not have the flat inner bag phenomenon of squeezing simultaneously; Be low to moderate that water tank does not have shelling, foam cracking phenomena in-35 ℃ the low temperature environment put procedure; The smooth nothing of valve tube place foam surface cavity; The foam abscess is fine and smooth, and thermal conductivity is low, and heat-insulating property is excellent, meets client's use and environmental requirement fully.A, B material all is under 20-25 ℃ normal temperature, to carry out, not only save energy but also reduce energy supply equipment and loaded down with trivial details operation.Producing solar water heater by A, B component material also is under normal temperature, normal pressure, to carry out with polyurethane foamed material, and technology is simple, and is easy to operate, and it is low to volatilize, the no three wastes, and constant product quality, production cost is low.Use the polyurethane foam products quality index through detecting the solar water heater filling, can reach:
Moulding core density: 32-40Kg/m
3
Compressive strength: >=140kPa
Thermal conductivity :≤0.020mW/mK
Dimensional stability
-20℃，24h： ≤0.5％
100℃，24h： ≤1.0％
Rate of closed hole: >=92%
Performance has reached solar water heater fully and has filled the requirement with rigid urethane foam.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1:
100 kilograms in preparation A component material, weighing: 44 kilograms of polyether glycol A (6 functionality, molecular weight are 850 polypropyleneoxide ethoxylated polyhydric alcohol) respectively; 28 kilograms of polyether glycol B (4.0 functionality, molecular weight are 610 polypropyleneoxide ethoxylated polyhydric alcohol), polyester polyol C (2 functionality; Molecular weight is 340 benzoic anhydride polyester polyol) 4 kilograms, 4 kilograms of biopolyol D (3 functionality, molecular weight are 260 castor oil polyhydric alcohol); 0.1 kilogram of catalyst P C-5, catalyst A-330.5 kilogram, 0.6 kilogram of catalyst P C-41; 1.3 kilograms of deionized waters, 1.5 kilograms of B-8525,16 kilograms of Skellysolve As.Load weighted polyether glycol packed into stirs in the reaction kettle, add respectively then the catalyzer that weighs up, water, stablizer, whipping agent,, stir composite reaction at normal temperatures; Stirred 2 hours; Taking-up is tested, and satisfies processing parameter, sends satisfied foam; Promptly get A component specification product, from reaction kettle, take out the barrelling warehouse-in.
B component material is a polyphenyl polymethylene polyisocyanates.
With A, B component material by A: B=100: 100 weight proportions are mixed and made into solar water heater and fill and use polyurethane foam, testing product quality index.
Moulding core density: 36.4kg/m
3
Compressive strength: 158kPa
Thermal conductivity: 0.0199mW/mK
Dimensional stability
-20℃，24h： 0.17％
100℃，24h： 0.43％
Rate of closed hole: 95.2%
Embodiment 2:
100 kilograms in preparation A component material, weighing: 46 kilograms of polyether glycol A (6 functionality, molecular weight are 900 polypropyleneoxide ethoxylated polyhydric alcohol) respectively; 26 kilograms of polyether glycol B (4.0 functionality, molecular weight are 650 polypropyleneoxide ethoxylated polyhydric alcohol), polyester polyol C (2 functionality; Molecular weight is 320 benzoic anhydride polyester polyol) 5 kilograms, 5 kilograms of biopolyol D (3 functionality, molecular weight are 250 castor oil polyhydric alcohol); 0.1 kilogram of catalyst P C-5, catalyst A-330.4 kilogram, 0.8 kilogram of catalyst P C-41; 1.2 kilograms of deionized waters, 1.5 kilograms of B-8525,14 kilograms of Skellysolve As.Load weighted polyether glycol packed into stirs in the reaction kettle, add respectively then the catalyzer that weighs up, water, stablizer, whipping agent,, stir composite reaction at normal temperatures; Stirred 2 hours; Taking-up is tested, and satisfies processing parameter, sends satisfied foam; Promptly get A component specification product, from reaction kettle, take out the barrelling warehouse-in.
B component material is a polyphenyl polymethylene polyisocyanates.
With A, B component material by A: B=100: 105 weight proportions are mixed and made into solar water heater and fill and use polyurethane foam, testing product quality index.
Moulding core density: 35.4kg/m
3
Compressive strength: 162kPa
Thermal conductivity: 0.0197mW/mK
Dimensional stability
-20℃，24h： 0.13％
100℃，24h： 0.35％
Rate of closed hole: 94.2%
Embodiment 3:
100 kilograms in preparation A component material, weighing: 45 kilograms of polyether glycol A (6 functionality, molecular weight are 880 polypropyleneoxide ethoxylated polyhydric alcohol) respectively; 27 kilograms of polyether glycol B (4.0 functionality, molecular weight are 600 polypropyleneoxide ethoxylated polyhydric alcohol), polyester polyol C (2 functionality; Molecular weight is 340 benzoic anhydride polyester polyol) 4 kilograms, 5 kilograms of biopolyol D (3 functionality, molecular weight are 270 castor oil polyhydric alcohol); 0.1 kilogram of catalyst P C-5, catalyst A-330.5 kilogram, 0.7 kilogram of catalyst P C-41; 1.4 kilograms of deionized waters, 1.3 kilograms of B-8525,15 kilograms of Skellysolve As.Load weighted polyether glycol packed into stirs in the reaction kettle, add respectively then the catalyzer that weighs up, water, stablizer, whipping agent,, stir composite reaction at normal temperatures; Stirred 2 hours; Taking-up is tested, and satisfies processing parameter, sends satisfied foam; Promptly get A component specification product, from reaction kettle, take out the barrelling warehouse-in.
B component material is a polyphenyl polymethylene polyisocyanates.
With A, B component material by A: B=100: 105 weight proportions are mixed and made into solar water heater and fill and use polyurethane foam, testing product quality index.
Moulding core density: 35.8kg/m
3
Compressive strength: 168kPa
Thermal conductivity: 0.0198mW/mK
Dimensional stability
-20℃，24h： 0.08％
100℃，24h： 0.24％
Rate of closed hole: 94.8%.
Claims (3)
- One kind adopt Skellysolve A be the solar water heater of whipping agent with combination material, it is characterized in that forming by A component and B component, wherein:The A component does, by weight percentage:Polyether glycol A:42～46%;Polyether glycol B:26～30%;Polyester polyol C:3～5%;Biopolyol D:3～5%;Suds-stabilizing agent: 1.2～2.0%;Water: 1.2～1.6%Whipping agent: 14～18%;Catalyzer: 0.5～2.0%;Wherein:Polyether glycol A is 6.0 functionality, and molecular weight is 800～1000 polypropyleneoxide ethoxylated polyhydric alcohol,Polyether glycol B is 4.0 functionality, and molecular weight is 500～700 polypropyleneoxide ethoxylated polyhydric alcohol,Polyester polyol C is 2 functionality, and molecular weight is 300～400 benzoic anhydride polyester polyol,Biopolyol D is 3 functionality, and molecular weight is 800～1000 castor oil polyhydric alcohol,Suds-stabilizing agent is a SI-C class surfactant B-8525,Whipping agent is a Skellysolve A,Water is deionized water,Catalyzer is a tertiary amine catalyst;The B component is a polyphenyl polymethylene polyisocyanates.
- 2. the solar water heater that employing Skellysolve A according to claim 1 is a whipping agent is characterized in that with the combination material tertiary amine catalyst adopts N, N; N '; N ", N "-propylene glycol solution and 1,3 of pentamethyl-diethylenetriamine, triethylene diamine 33wt%; 5-three (dimethylaminopropyl) Hexahydrotriazine, wherein three's mass ratio is 1: 3～5: 6～10.
- 3. the solar water heater that to prepare the said employing Skellysolve A of claim 1 be whipping agent is characterized in that with the method for making of combination material:Preparation A component material: load weighted polyether glycol, polyester polyol, biopolyol are packed into stir in the reaction kettle earlier; Add load weighted catalyzer, whipping agent, water, suds-stabilizing agent then; Reaction was stirred 2～3 hours at normal temperatures, got final product barrelling;A, B component material are pressed A: B=100: 100～105 weight ratio is mixed, and promptly can be made into the solar water heater filling and uses hard polyurethane foam.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924678A (en) * | 2012-11-02 | 2013-02-13 | 山东东大一诺威新材料有限公司 | Solar water heater foaming combined polyether and preparation method thereof |
| CN103772637A (en) * | 2013-12-31 | 2014-05-07 | 广西宾阳县荣良新材料科技有限公司 | Thermal insulation material for water tank of solar water heater |
| CN104558476A (en) * | 2014-12-19 | 2015-04-29 | 上海东大聚氨酯有限公司 | Premixed polyether, raw material composition, polyurethane foam, and preparation method and application thereof |
| CN106084735A (en) * | 2016-06-20 | 2016-11-09 | 青岛天地鸿华新能源科技有限公司 | A kind of preparation technology of PUR packing material |
| CN106188486A (en) * | 2016-08-01 | 2016-12-07 | 山东诺威新材料有限公司 | Warming solar energy engineering water tank polyurethane and preparation method thereof |
| CN106832212A (en) * | 2017-02-06 | 2017-06-13 | 山东诺威新材料有限公司 | Storage-type electric water heater polyurethane composition polyethers and its preparation method and application |
| CN112358601A (en) * | 2020-12-09 | 2021-02-12 | 淄博汇德聚氨酯制品股份有限公司 | Pipeline heat-insulating material and preparation method and application thereof |
| CN114853974A (en) * | 2022-06-20 | 2022-08-05 | 河北亚东化工集团有限公司 | Polyurethane combined polyether for metal carving board and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102924678A (en) * | 2012-11-02 | 2013-02-13 | 山东东大一诺威新材料有限公司 | Solar water heater foaming combined polyether and preparation method thereof |
| CN102924678B (en) * | 2012-11-02 | 2014-06-25 | 山东一诺威新材料有限公司 | Solar water heater foaming combined polyether and preparation method thereof |
| CN103772637A (en) * | 2013-12-31 | 2014-05-07 | 广西宾阳县荣良新材料科技有限公司 | Thermal insulation material for water tank of solar water heater |
| CN103772637B (en) * | 2013-12-31 | 2016-08-17 | 广西宾阳县荣良新材料科技有限公司 | A kind of solar water heater water tank insulation material |
| CN104558476A (en) * | 2014-12-19 | 2015-04-29 | 上海东大聚氨酯有限公司 | Premixed polyether, raw material composition, polyurethane foam, and preparation method and application thereof |
| CN104558476B (en) * | 2014-12-19 | 2017-07-04 | 上海东大聚氨酯有限公司 | Combined polyether, feedstock composition, polyurethane foam and its production and use |
| CN106084735A (en) * | 2016-06-20 | 2016-11-09 | 青岛天地鸿华新能源科技有限公司 | A kind of preparation technology of PUR packing material |
| CN106188486A (en) * | 2016-08-01 | 2016-12-07 | 山东诺威新材料有限公司 | Warming solar energy engineering water tank polyurethane and preparation method thereof |
| CN106832212A (en) * | 2017-02-06 | 2017-06-13 | 山东诺威新材料有限公司 | Storage-type electric water heater polyurethane composition polyethers and its preparation method and application |
| CN106832212B (en) * | 2017-02-06 | 2019-10-25 | 山东一诺威新材料有限公司 | Storage-type electric water heater polyurethane rigid foam material and preparation method thereof |
| CN112358601A (en) * | 2020-12-09 | 2021-02-12 | 淄博汇德聚氨酯制品股份有限公司 | Pipeline heat-insulating material and preparation method and application thereof |
| CN114853974A (en) * | 2022-06-20 | 2022-08-05 | 河北亚东化工集团有限公司 | Polyurethane combined polyether for metal carving board and preparation method and application thereof |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120711 |