CN102516494B - Foaming composition for water tank of solar water heater - Google Patents
Foaming composition for water tank of solar water heater Download PDFInfo
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- CN102516494B CN102516494B CN 201110418919 CN201110418919A CN102516494B CN 102516494 B CN102516494 B CN 102516494B CN 201110418919 CN201110418919 CN 201110418919 CN 201110418919 A CN201110418919 A CN 201110418919A CN 102516494 B CN102516494 B CN 102516494B
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Abstract
The invention discloses a foaming composition for a water tank of a solar water heater, which is characterized by comprising the following main raw materials: a polyether foaming agent, sodium bicarbonate, chitosan and hollow glass beads. The improved polyether rigid foam composition can be used for reducing the phenomena that after being sprayed from a glossy jar and formed, a polyurethane material has high contractibility, the heat preservation effect of the water tank of the solar water heater is influenced and the water tank is deformed, bulged and barred, or even cracked.
Description
Technical field
The present invention relates to a kind of solar water heater water tank lagging material, particularly polyethers whipping agent is the composition of main component.
Background technology
Because environmental protection and energy saving are advocated in the whole world energetically, solar water heater has become domestic hot water's main source, and China's solar water heater has become first use state and the producing country of solar water heater in the world.As everyone knows, concerning solar water heater, especially solar vacuum-tube water heater, the lagging material of water tank mainly adopts polyurethane hard foam at present, because the polyurethane hard foam thermal conductivity is lower, convenient formation, but one of major defect of polyurethane hard foam is the moulding post shrinkage big (finishing moulding reaction back lather volume less than maximum volume in the moulding process), the existence of molding shrinkage, often make the foams final volume less than the cavity volume of filling, foam and housing take place peel off phenomenon; And capillary reason when foaming owing to polyurethane hard foam, connect bad between the hole wall of bubble, make aperture and connectedness reduce, lather collapse and collapsing after the reaction moulding, cause the water tank distortion, rise and heave stupefied even cracking, that is to say phenomenons such as often said " decortication ", " shelling " of solar water heater manufacturer, " extracting a backbone out ".Outward appearance, heat insulation effect even the work-ing life of goods have been had a strong impact on.Therefore, in most application scenarios, the employing thickening polyurethane hard foam layer that has, the employing that has improves filled and process density, take mode such as molded to solve, but thickening the polyurethane hard foam layer has increased the water tank outer volume, and cost improves, and take moldedly, also increased manufacture difficulty.
Summary of the invention
The composition that the purpose of this invention is to provide a kind of improved polyethers rigid foam for the manufacture of solar water heater water tank, can reduce the urethane material from the aerosol jar, spray the moulding post shrinkage big, influence the water-heater water tank heat insulation effect, avoid the water tank distortion and heaves phenomenon stupefied even that ftracture.
Main raw material and the parts by weight of heat-preserving water tank for solar water heater polyethers foaming composition of the present invention are:
Polyethers whipping agent 70-90 part;
Sodium bicarbonate 3-8 part;
Chitosan 3-6 part;
Hollow glass micropearl 5-8 part;
Above-described polyethers whipping agent full name single component polyether foam spackling is commonly called as whipping agent, foamed glue, spackling, is the product of aerosol technology and polyether foam technology cross coupled.It is a kind of components such as Ju ether Yu Ju Wu ﹑ Fa Pao Ji ﹑ catalyzer to be filled in special polyether product in the withstand voltage aerosol jar.When material sprayed from the aerosol jar, the polyethers material of foam shape can expand rapidly and form foam with moisture generation curing reaction in air or the matrix that touches.Foam after the curing has multiple effects such as Tian Feng ﹑ Nian Jie ﹑ Mi Feng ﹑ is heat insulation, the present invention uses the polyethers whipping agent of present domestic production, can arrive on the market and buy, also can directly order goods to producer, there are a lot of families in domestic manufacturer, for example: Shanghai Dongda Polyurethane Co., Ltd, Luoyang, Changzhou Wujin heat insulating material factory etc., can use so long as be used for the aerial fog type polyethers whipping agent of present solar water heater water tank.Open source literature also introduced Shanghai Dongda Polyurethane Co., Ltd the complete water type combined polyether (Chinese patent: CN l02079803 A), so the inventor adopts water miscible polyethers whipping agent.
Described water soluble polyether whipping agent can adopt the water soluble polyether whipping agent of buying on the market, perhaps adopts the raw material of following parts by weight:
5-7 parts of glycerin polyether resins, 3-5 parts of glycol ether resins, 0.2-0.3 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.1-0.3 part of N-dimethylcyclohexylamine, 0.1-0.3 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 3-5 parts in water.
Above-described sodium bicarbonate is a kind of inorganic foaming agent, white powder, and proportion 2.16, decomposition temperature is about 100-140 ℃, and emits portion C O
2, lose whole CO during to 270 ℃
2, join in the whipping agent and can when the rapid expansion temperature of material improves, emit portion C O
2Foam increases the gap, strengthens heat insulation effect.
Above-described chitosan is the low-molecular-weight chitosan of molecular weight (polymerization degree) 10,000 to 30,000, acetic acid with 1-3% before using dissolves, add low-molecular-weight chitosan, can make the polyethers material after the foaming have the hole that is interconnected, also have aperture between big hole wall, chitosan is adsorbed on internal surface of hole, the abscess that produces is not easy to vanish, the aperture is increased, thereby the rate of expansion of polyethers material is improved, heat insulation effect obviously improves.
Above-described hollow glass micropearl can be used nanometer SiO
2Replace hollow glass micropearl and nanometer SiO
2Particle diameter between the 10-100 nanometer, add hollow glass micropearl and nanometer SiO
2, make the percentage of open area of composite foam material increase, density reduces, and illustrates that obtained foam is more satisfactory.This can give the credit to hollow glass micropearl and nanometer SiO
2, in the foam forming process, brought into play the effect of pore-creating agent, prevent that also foam from shrinking simultaneously.Equally, hollow glass micropearl and nanometer SiO
2, also have the perforate effect for amidogen ether class composite foam, but the shrinkability of rigid foam in foaming process wants littler to the degree of dependence of perforate effect.The present invention records in experiment, adds hollow glass micropearl and nanometer SiO
2Can obviously prolong the set time of flexibility foam and amidogen ether class rigid foam, the aperture is increased.
Mechanism and advantage that heat-preserving water tank for solar water heater polyethers foaming composition of the present invention can replace existing polyurathamc are:
The formation of polyether foam need be experienced foaming process and two stages of maturing process.Expanding from the mixing of materials to the lather volume stops, and this process can be described as foaming process.In the foaming process, system is emitted a large amount of reaction heat, and reaction heat makes the whipping agent vaporization enter each abscess of foams, orders about cell volume and constantly expands.At this moment each abscess is subjected to the effect of two power: the pressure that barometric point and whipping agent expand and produce.When interior pressure during greater than external pressure, the volume of foaming system just constantly expands; When the abscess external and internal pressure equates, foams no longer expand, and after namely reaching so-called " rise expand time " foam and stopping to expand, the chemical reaction of system inside finishes fully, but carrying out slow interlinkage reaction, reach final strength until foams.This process is called the maturing process of foams.Lather volume expands and stops to indicate the end of foaming process, the beginning of maturing process.In maturing process, foams are no longer emitted a large amount of reaction heat, and temperature slowly reduces (finally can be down to envrionment temperature).At this moment the abscess internal pressure also reduces, and produces inside and outside differential pressure.Pressure reduction produces certain influence to the formation of foams: if the intensity of cell wall is enough to support pressure reduction, then tangible distortion can not take place in foams; If cell wall intensity a little less than, then foams shrink under differential pressure action.Usually be referred to as " molding shrinkage ", generally below 1%, can reach 5% when serious, in addition bigger.
Theoretically, allowing foams growths stop the back foam structure, to reach stable immediately be the optimum method that solves foam contraction.And in fact, this is impossible realize for present urethane industry, i.e. moulding shrinking percentage can not be zero, then fully can be with molding shrinkage control in 1% but be aided with the foam process of science again by the production formula of adjusting foamed material.
At present, there is the people in foamed material, to add pore-creating agent, forms the very poor open celled foam of heat insulation effect.Though this method has been eliminated the pressure reduction in the foam maturing process, thereby reduce foam-formed shrinking percentage, pore-creating agent is selected when bad, and the heat-insulating property of foam reduces greatly, has the freezing possibility of water tank winter.Bad foam is the one of the main reasons that causes foam contraction, and its dimensional contraction rate is 2%~10%.
So the present invention adopts the polyethers whipping agent, and in material, add the inorganic foaming agent sodium bicarbonate again, low-molecular-weight chitosan, hollow glass micropearl or nanometer SiO
2, can increase foam and foam aperture is increased, foam is difficult for atrophy before curing, also is not easy to make thermal insulation layer to separate with water tank, more can not cause phenomenons such as " decortication ", " shelling ", " extracting a backbone out ".
At present, the solar water heater is that one or many cast free foaming forms with polyurethane foam, repeatedly to be cast for the master, in the foaming process, except being subjected to the normal atmosphere effect, is not subjected to the effect of other any ambient pressures.The polyurethane foam packing space must fill up before gelation process arrives fully, after the gel, if lather volume is still continuing expansion, formed foam, abscess will obviously elongate, and it is fibrous that severe patient can be, its physical and mechanical properties is very poor, and this area is referred to as " bad foam ".After its cooling, shrinking because condensation of gas in the abscess is serious, expands with gas expansion in the abscess in the back that is heated.Repeatedly Jiao Zhu foaming mode makes this " bad foam " proportion increase.Moreover the intersection foam of adjacent twice cast formation, because of the difference of shrinking percentage, when catching a cold, easily cause the foam cracking.The present invention adds sodium bicarbonate, low-molecular-weight chitosan, hollow glass micropearl or nanometer SiO
2Can make foam fill up segment space before gel, because of limited space, lather volume can't continue to expand after the gel, and the blow(ing) pressure of Chan Shenging voluntarily is conducive to form the abscess of ball-shaped structure, the foam bubble hole intensity height of this form, good stability, not yielding.
And because the solvent great majority of polyurethane foam also use freonll-11; the havoc that earth atmosphere is caused; at present domestic polyurethane foams replaces freonll-11 class whipping agent with other organic solvents; the present invention is owing to adopt water miscible polyethers; do not re-use freonll-11, protected the ecotope of the earth.
Embodiment
Embodiment 1
Earlier with 5 parts of glycerin polyether resins, 3 parts of glycol ether resins, 0.2 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.1 part of N-dimethylcyclohexylamine, 0.1 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 3 parts in water obtains polyurethane foams after the reaction, add 5 kilograms of sodium bicarbonates according to 80 kilograms of polyurethane foams then, 5.5 kilograms of chitosans, 8 kilograms of hollow glass micropearls are poured in the solar water heater water tank then, solidify 5-10 hour, can obtain the good solar water heater water tank of heat insulation effect, valve tube is installed just can be used.
Embodiment 2
Earlier with 6 parts of glycerin polyether resins, 4 parts of glycol ether resins, 0.25 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.2 part of N-dimethylcyclohexylamine, 0.25 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 4 parts in water obtains polyurethane foams after the reaction, add 6 kilograms of sodium bicarbonates according to 70 kilograms of polyurethane foams then, 6 kilograms of chitosans, 6 kilograms of hollow glass micropearls are poured in the solar water heater water tank then, solidify 5-10 hour, can obtain the good solar water heater water tank of heat insulation effect, valve tube is installed just can be used.
Embodiment 3
Earlier with 7 parts of glycerin polyether resins, 5 parts of glycol ether resins, 0.3 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.3 part of N-dimethylcyclohexylamine, 0.3 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 5 parts in water obtains polyurethane foams after the reaction, add 7 kilograms of sodium bicarbonates according to 85 kilograms of polyurethane foams then, 5 kilograms of chitosans, nanometer SiO
210 kilograms, be poured into then in the solar water heater water tank, solidified 5-10 hour, can obtain the good solar water heater water tank of heat insulation effect, valve tube is installed just can be used.
Embodiment 4
Earlier with 7 parts of glycerin polyether resins, 5.5 parts of glycol ether resins, 0.28 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.15 part of N-dimethylcyclohexylamine, 0.26 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 4.5 parts in water obtains polyurethane foams after the reaction, add 4 kilograms of sodium bicarbonates according to 75 kilograms of polyurethane foams then, 4 kilograms of chitosans, nanometer SiO
25 kilograms, be poured into then in the solar water heater water tank, solidified 5-10 hour, can obtain the good solar water heater water tank of heat insulation effect, valve tube is installed just can be used.
Application Example 1
In October, 2011, the applicant has made 2 solar water heaters, hot well tank adopts the polyurethane foams of the Zhejiang Province company production of buying on the market as lagging material, because it is bad that whipping agent is filled, casing and foaming thermal-insulating have separation phenomenon, cloudy weather (temperature 18-25 ℃), 70 ℃ of the highest water temperatures; In November, 2011, adopt solar water heater water tank foaming composition of the present invention to fill cloudy weather (temperature 15-24 ℃), 80 ℃ of the highest water temperatures, the foaming composition raw materials cost is basic identical, illustrates that solar water heater water tank foaming composition heat insulation effect of the present invention is significantly improved.
Below be the performance of 500mm solar water heater hot water storage tank of the present invention:
500mm external diameter hot water storage tank performance subordinate list
Product type | φ58/2100 |
Sheating material | δ=0.4 import aluminium plating zinc plate |
Liner material | δ=0.41SUS304-2B food grade stainless steel plate |
Lagging material | The modified polyether foam material |
Insulation layer thickness | 70mm |
The valve tube hole count | 20/24/30/36 |
Sealing material | High quality silicon rubber volume |
Test pressure | 1.2MPa |
Average heat loss factor (W/ ㎡ ℃) | 0.77 |
Water examination | The surface of each parts of water-heater contact water does not have burn into and gets rusty, and the water quality free from extraneous odour does not have other insalubrious materials |
Water-in | φ 20mm SUS304-2B food grade stainless steel plate |
Water outlet | φ 20mm SUS304-2B food grade stainless steel plate |
Venting port | φ 20mm SUS304-2B food grade stainless steel plate |
Appearance requirement | Case surface is smooth, and coating is evenly level and smooth, does not have obvious wrinkle, cut, dirt and other defect |
Empty solarization requirement | Too under 17000KJ/ ㎡ condition, the water-heater of water filling shines through continuing two skies in whole day solar irradiation amount, and each parts does not have breakage, does not have distortion and other influences the generation of water-heater changes of properties |
From last table explanation, polyethers foaming composition of the present invention has advantages such as heat insulation effect improves, average heat waste is less, and water tank is indeformable.
Claims (3)
1. solar water heater water tank foaming composition, it is characterized in that: its main raw material and parts by weight are:
Polyethers whipping agent 70-90 part;
Sodium bicarbonate 3-8 part;
Chitosan 3-6 part;
Hollow glass micropearl 5-8 part;
Described polyethers whipping agent adopts the raw material of following parts by weight:
5-7 parts of glycerin polyether resins, 3-5 parts of glycol ether resins, 0.2-0.3 part of suds-stabilizing agent water-soluble silicon oil, catalyst n, 0.1-0.3 part of N-dimethylcyclohexylamine, 0.1-0.3 part of solidifying agent dibutyl tin laurate, 10 parts of polyphenyl polyisocyanates, 3-5 parts in water.
2. solar water heater water tank foaming composition according to claim 1, it is characterized in that: described chitosan is molecular weight 10,000 to 30,000, before using with the acetic acid dissolving of 1-3%.
3. solar water heater water tank foaming composition according to claim 1 is characterized in that: described hollow glass micropearl nanometer SiO
2Replace hollow glass micropearl or nanometer SiO
2Particle diameter between the 10-100 nanometer.
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CN 201110418919 CN102516494B (en) | 2011-12-15 | 2011-12-15 | Foaming composition for water tank of solar water heater |
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CN 201110418919 CN102516494B (en) | 2011-12-15 | 2011-12-15 | Foaming composition for water tank of solar water heater |
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CN102516494A CN102516494A (en) | 2012-06-27 |
CN102516494B true CN102516494B (en) | 2013-09-11 |
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CN103319678B (en) * | 2013-07-15 | 2015-09-09 | 广西吉宽太阳能设备有限公司 | Solar water heater water tank polyurethane hard foam lagging material |
CN103342792B (en) * | 2013-07-15 | 2015-05-13 | 广西吉宽太阳能设备有限公司 | Polyurethane rigid foam organic fireproof heat preservation material for solar water tank |
CN103333310B (en) * | 2013-07-15 | 2015-11-18 | 广西超星太阳能科技有限公司 | Solar water heater water tank organic fire prevention foaming composition |
CN103435769B (en) * | 2013-07-15 | 2015-11-18 | 广西超星太阳能科技有限公司 | Solar water heater water tank inorganic fire foaming thermal-insulating |
CN103319677B (en) * | 2013-07-15 | 2016-02-03 | 广西吉顺能源科技有限公司 | Solar water heater water tank polyether glycol cellular insulant |
CN103396523B (en) * | 2013-07-15 | 2016-02-24 | 山东晨光节能产品研发有限公司 | Solar water heater water tank polyether glycol glycol foam organic fireproof thermal-insulation material |
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CN103333308B (en) * | 2013-07-15 | 2015-11-18 | 广西超星太阳能科技有限公司 | Solar water heater water tank perlite foaming thermal-insulating |
CN104744658A (en) * | 2013-12-31 | 2015-07-01 | 深圳市富安娜家居用品股份有限公司 | Gel polyurethane sponge and preparation method thereof |
CN103791653B (en) * | 2014-01-23 | 2016-02-24 | 天津市助友传感仪器技术有限公司 | A kind of building ecological energy conserving system |
CN103899884A (en) * | 2014-03-12 | 2014-07-02 | 广西吉宽太阳能设备有限公司 | Anti-slip positioning ring for heat preservation pipe and heat preservation pipe |
CN105778036A (en) * | 2016-05-18 | 2016-07-20 | 毛文辉 | Environment-friendly type solar thermal-insulation building material |
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CN1328082A (en) * | 2000-06-14 | 2001-12-26 | 北京市瑞德宝生物降解制品公司 | Fully biodegradable foamed composition and its shaping process |
FR2827515B1 (en) * | 2001-07-20 | 2005-06-03 | Oreal | FOAMING COMPOSITION BASED ON SILICA AND CATIONIC POLYMER |
US20070237811A1 (en) * | 2006-04-10 | 2007-10-11 | Scherr George H | Chitosan wound dressing |
CN102108172A (en) * | 2010-01-20 | 2011-06-29 | 威海世创新材料科技有限公司 | Chitosan/polyvinyl alcohol (PVA) porous composite material and preparation method thereof |
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Effective date of registration: 20180725 Address after: 253500 111 Ma Miao village, Yi Du Kou Township, Lingxian County, Dezhou, Shandong Patentee after: Du Lili Address before: 530001 Anji Avenue, 47 - 5, Nanning, the Guangxi Zhuang Autonomous Region, 2 floor, Yongkang hardware and Electrical City, room A252. Patentee before: Guangxi Jikuang Solar Energy Equipment Co., Ltd. |
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Granted publication date: 20130911 Termination date: 20181215 |