CN109734861B - Environment-friendly combined polyether and polyurethane foam for solar water heater and preparation method thereof - Google Patents
Environment-friendly combined polyether and polyurethane foam for solar water heater and preparation method thereof Download PDFInfo
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- CN109734861B CN109734861B CN201811530185.1A CN201811530185A CN109734861B CN 109734861 B CN109734861 B CN 109734861B CN 201811530185 A CN201811530185 A CN 201811530185A CN 109734861 B CN109734861 B CN 109734861B
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Abstract
The application relates to a combined polyether for an environment-friendly solar water heater, which is prepared from the following raw materials in parts by weight: 40-55 parts of first polyether polyol, 20-30 parts of second polyether polyol, 0-15 parts of third polyether polyol, 10-20 parts of fourth polyether polyol, 2.0-3.0 parts of surfactant, 1.5-3.0 parts of catalyst, 1.0-2.0 parts of chemical foaming agent and 20-30 parts of physical foaming agent. The application also relates to a polyurethane foam prepared by utilizing the combined polyether and isocyanate and a preparation method thereof. The application also relates to the application of the polyurethane foam in the preparation of the water tank of the solar water heater. Compared with the conventional polyurethane foam product, the polyurethane foam product has the advantages of low heat conductivity coefficient, high efficiency, energy conservation, non-combustibility, no volatile organic matter contained, zero ozone consumption potential, environmental friendliness and no pollution.
Description
Technical Field
The application relates to the technical field of polyurethane and heat insulation materials, in particular to composite polyether for an environment-friendly solar water heater, a polyurethane raw material composition containing the composite polyether, polyurethane foam prepared from the polyurethane raw material composition and a preparation method of the polyurethane foam.
Background
Solar energy is used as a clean, efficient and continuous new energy source, and has wide development and utilization prospects. The core of the solar water heater is a vacuum tube, and the heat-insulating engineering water tank used in cooperation with the vacuum tube is also a big heart of the solar water heater, and the market demand is continuously expanded.
At present, low-carbon economy is more and more emphasized worldwide, enterprises are required to develop in a low-carbon environment-friendly direction, national decisions on energy conservation and emission reduction are more and more determined, and a new generation of products is required to be kept on the environment-friendly and energy-saving angle; the foaming process of the polyurethane rigid foam adopts a physical foaming agent all the time. According to the HCFCs elimination schedule specified by the Montreal protocol, the second-generation foaming agent formally enters a countdown phase, and cyclopentane has poor heat insulation effect, so that the requirements of increasingly severe energy conservation and emission reduction are difficult to meet, and special attention needs to be paid to explosion prevention, ventilation, installation of pentane alarm devices, anti-static equipment and the like.
Hydrofluorocarbon foaming agents represented by HFC-245fa are limited due to high GWP values and poor environmental protection characteristics, and are gradually eliminated in developed countries such as the United states and European Union, so that the development of a novel foaming agent with environmental protection and low thermal conductivity as combined polyether for heat preservation of solar water heaters is important at present.
Currently, the industry has developed a fourth generation of blowing agents, representative of which include HONEYWELL LBA, and FEA-1100 developed by DuPont. FEA-1100 has environmental sustainability and excellent thermal insulation properties and can replace other liquid foaming agents at low conversion cost. However, there are few reports on the use of the fourth generation foaming agent FEA-1100 in the preparation of insulation for electric water heaters.
For this reason, there is a continuous need in the art to develop a conjugate polyether and polyurethane foam for an environmentally friendly solar water heater and a method for preparing the same.
Disclosure of Invention
The present application aims to provide an environmentally friendly combined polyether for a solar water heater, so as to solve the technical problems in the prior art. By selecting the specific polyether polyol and adopting the fourth generation foaming agent, the combined polyether is environment-friendly when reacting with isocyanate, and the obtained polyurethane foam has lower thermal conductivity.
The application mainly solves the technical problems of environmental protection, energy conservation and the like in the production of the water tank of the solar water heater, and provides the preparation method of the environment-friendly combined polyether and polyurethane foam. The foaming agent adopted by the invention is cis-1, 1,1, 4, 4, 4-hexafluoro-2-butene (Z-HFO-1336mzz) developed by DuPont company in America, and is a fourth generation foaming agent with the trade name of FEA-1100, the ODP value of the foaming agent is zero, the GWP value is 8.9, the boiling point is 33 ℃, compared with HCFC-141b, the foaming agent has the advantages of lower heat conductivity coefficient, environmental protection, heat insulation, good heat preservation performance, nonflammability and the like, can replace other physical foaming agents with low conversion cost, effectively solves the problem of environmental pollution, and has wide application prospect. The polyurethane foam prepared from the combined polyether obviously improves the environmental protection performance of the polyurethane foam, and effectively improves the heat preservation effect, the strength and the size change rate of a solar water heater.
It is also an object of the present application to provide a polyurethane raw material composition comprising the conjugate polyether as described above.
It is also an object of the present invention to provide a method for preparing a polyurethane foam using the polyurethane raw material composition as described above.
It is also an object of the present application to provide a polyurethane foam prepared by the process as described above.
The application also aims to provide the application of the polyurethane foam in the preparation of the water tank of the solar water heater.
In order to achieve the above object, the present application provides the following technical solutions.
In a first aspect, the application provides a composite polyether for an environment-friendly solar water heater, which is characterized in that the composite polyether is prepared from the following raw material components in parts by weight:
wherein the first polyether polyol comprises polyether polyol with a hydroxyl value of 470-510mg KOH/g and a viscosity of 8000-11000 mPa.s;
wherein the second polyether polyol comprises polyether polyol with a hydroxyl value of 385-405mgKOH/g and a viscosity of 6000-10000 mPa.s;
wherein the third polyether polyol comprises a polyether polyol having a hydroxyl value of 415-435mgKOH/g and a viscosity of 4800-6200 mPa.s;
wherein the fourth polyether polyol comprises polyether polyol with the hydroxyl value of 435-465mgKOH/g and the viscosity of 2000-3000 mPa.s.
In one embodiment of the first aspect, the surfactant comprises a foam stabilizer.
In one embodiment of the first aspect, the chemical blowing agent is water;
and/or the physical foaming agent is a fourth generation foaming agent cis-1, 1,1, 4, 4, 4-hexafluoro-2-butene.
In one embodiment of the first aspect, the catalyst is a mixture of N, N-pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, N-dimethylbenzylamine, and BX 405.
In a second aspect, the present application provides a polyurethane raw material composition for an environmentally-friendly solar water heater, which is characterized by comprising a first component and a second component, wherein the first component is the environmentally-friendly combined polyether for the solar water heater according to the first aspect; wherein the second component is an isocyanate.
In one embodiment of the second aspect, the isocyanate is polymeric diphenylmethane diisocyanate.
In a third aspect, the present application provides a method for preparing a polyurethane foam for an environmentally-friendly solar water heater using the polyurethane raw material composition according to the second aspect, characterized in that the method comprises the steps of:
(1) mixing the raw material components of the first component to obtain a first mixture;
(2) mixing the first mixture and the second component, performing high-pressure foaming at a temperature of 20-25 ℃, and injecting the polyurethane foam into a mold to obtain the polyurethane foam for the environment-friendly solar water heater.
In one embodiment of the third aspect, in step (1), the mixing comprises sequentially adding the weighed first polyether polyol, second polyether polyol, third polyether polyol, fourth polyether polyol, foam stabilizer, chemical blowing agent, catalyst and physical blowing agent into a reaction device, and stirring at room temperature for 0.5 to 1.0 hour.
In an embodiment of the third aspect, the weight ratio of the first component to the second component is 1:1.15 to 1.25, preferably 1: 1.2.
In a fourth aspect, the present application provides an environmentally-friendly polyurethane foam for solar water heaters prepared by the method according to the third aspect.
In a fifth aspect, the present application provides the use of the polyurethane foam for an environmentally friendly solar water heater as described in the fourth aspect for the preparation of a water tank for a solar water heater.
Compared with the prior art, the polyurethane foam product has the advantages that (1) compared with the conventional polyurethane foam product, the polyurethane foam product has lower heat conductivity coefficient; (2) compared with the conventional solar water tank heat-insulation foam product, the polyurethane foam product prepared by the FEA-1100 foaming agent has the advantages of high efficiency, energy conservation, non-combustion, no volatile organic compound, zero ozone consumption potential, environmental friendliness and no pollution.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In one specific embodiment, the application provides an environment-friendly polyurethane raw material for a solar heat-preservation water tank, which consists of a component A and a component B, wherein the weight ratio of the component A to the component B is 1:1.15-1.25, particularly 1:1.2, the component A is a combined polyether, and the combined polyether comprises the following components in parts by weight
Wherein the component B is polymeric diphenylmethane diisocyanate.
In one embodiment, the conjugate polyether of the present application comprises a polyether polyol. Polyether polyols suitable for the purposes of this application include, but are not limited to, products obtained by polymerizing an epoxide such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran in the presence of a polyfunctional initiator. Suitable initiators contain a plurality of active hydrogen atoms, specific examples of which include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, aniline, diphenylmethane diamine, ethylene diamine, cyclohexane dimethanol, resorcinol, bisphenol a, glycerol, trimethylolpropane, 1,2, 6-hexanetriol, pentaerythritol, or combinations thereof.
In one embodiment, the first polyether polyol is a polyether polyol having a hydroxyl value of 470-510mg KOH/g and a viscosity of 8000-11000m Pa.s, and the preferred polyether polyol of the present invention is NJ-6206 (manufactured by Tankun Ningwu New materials Co., Ltd.).
In one embodiment, the second polyether polyol is a polyether polyol having a hydroxyl value of 385-405mgKOH/g and a viscosity of 6000-10000mPa.s, and the preferred polyether polyol of the present invention is Donol R8238 (manufactured by Shanghai Dongda chemical Co., Ltd.).
In one embodiment, the third polyether polyol is a polyether polyol having a hydroxyl value of 415-.
In one embodiment, the fourth polyether polyol is polyether polyol with hydroxyl value of 435-465mgKOH/g and viscosity of 2000-3000mPa.s, and the preferred polyether polyol of the present invention is YD-450BC (manufactured by North Hei Asia east chemical Co., Ltd.).
The conjugate polyether of the present application may further include a surfactant, which generally supports homogenization of the blowing agent and the polyol, and adjusts the cell structure of the polyurethane foam. The surfactant may comprise any suitable surfactant or mixture of surfactants known in the art.
In one embodiment, the surfactant herein comprises a foam stabilizer. In one embodiment, the foam stabilizer may be a foam stabilizer conventional in the art, preferably under the designation L-6978 (manufactured by Mitigo advanced materials (China) Co., Ltd.).
The conjugate polyethers described herein may also include chemical and physical blowing agents. As used herein, the term "chemical blowing agent" refers to a blowing agent that chemically reacts with an isocyanate, polyol, or other component and releases a gas for foaming. In one embodiment, the chemical blowing agent is water, preferably deionized water.
As used herein, the term "physical blowing agent" refers to a blowing agent that does not chemically react with either the isocyanate or the polyol. The physical blowing agent may be a gas or a liquid. Liquid physical blowing agents typically evaporate to a gas when heated and typically revert to a liquid when cooled. In one embodiment, the physical blowing agent is a fourth generation blowing agent, FEA-1100, cis-1, 1,1, 4, 4, 4-hexafluoro-2-butene (Z-HFO-1336 mzz).
In one embodiment, the conjugate polyether described herein further comprises a catalyst. Catalysts are typically used to catalyze the reaction between the isocyanate and the polyol and are not consumed in the reaction. The catalyst is a mixture of N, N, N, N, N-pentamethyl diethylene triamine, N, N-dimethyl cyclohexylamine, N, N-dimethyl benzylamine and BX 405.
In one embodiment, the preparation method of the environment-friendly polyurethane for solar energy comprises the following steps:
(1) the component A is combined polyether, and is prepared by the following steps: sequentially adding the weighed first polyether polyol, second polyether polyol, third polyether polyol, fourth polyether polyol, foam stabilizer, chemical foaming agent, catalyst and physical foaming agent into a reaction kettle, stirring for 0.5-1.0 hour at normal temperature, and fully mixing.
(2) B, preparation of a component: weighing polymeric diphenylmethane diisocyanate for use
Mixing the component A and the component B according to the ratio of 1: mixing at a weight ratio of 1.15-1.25, foaming at 20-25 deg.C, and high-pressure foaming to obtain polyurethane foam, and injecting into a mold.
The invention is the FEA-1100 physical foaming agent, which improves the flowing property of the foam, has even density distribution, improves the compression strength of the foam, reduces the heat conductivity coefficient and the like.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The sources of the raw materials used in the following examples are as follows.
Polyether polyol NJ-6206 (manufactured by Tankun Ningwu New materials Co., Ltd.).
A fourth polyether polyol onol r8238 (manufactured by shanghai dongda chemical limited).
Polyether polyol YD-8206H (manufactured by Tandow Ningwu New Material Co., Ltd.).
Polyether polyol YD-450BC (manufactured by Hibei Asia east chemical group Co., Ltd.).
Silicone type foam stabilizer L-6978 was purchased from Michigan advanced materials (China) Co.
Isocyanate is polymeric MDI available from Tantario, model PM 200.
Physical blowing agent FEA-1100 was purchased from DuPont, China group, Inc.
Examples 1 to 3 and comparative examples 1 to 2
The weight parts of the respective raw material components in examples 1 to 3 and comparative examples 1 to 2 are specifically shown in Table 1
Table 1 parts by weight of each raw material component in examples 1 to 3 and comparative examples 1 to 2.
The polyurethane foams of examples 1-3 and comparative examples 1-2 were prepared as follows:
(1) preparation of the composite polyether A component: uniformly mixing all the components of the raw material composition of the combined polyether except the foaming agent, pressurizing by a sealed container to 0.1Mpa, and adding the foaming agent mixture from the bottom of the reaction kettle through a pipeline to be uniformly mixed;
(2) preparation of polyurethane foam: and (2) reacting the component A and the component B of the combined polyether at 22 ℃ according to a corresponding ratio, and injecting the mixture into a mold to prepare the rigid polyurethane foam heat-insulating material for the solar water heater.
Table 2 shows the data of the foam product performance tests of examples 1 to 3 and comparative examples 1 to 2
Table 2 foam product performance test data for examples 1-3 and comparative examples 1-2.
The polyurethane foams produced in examples 1-3 and comparative examples 1-2 were compared with the polyurethane foam products produced in comparative examples, and the results are shown in Table 2. As can be seen from Table 2, the polyurethane foams obtained according to the present invention have higher compressive strength, better dimensional stability and lower thermal conductivity.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. The environment-friendly combined polyether for the solar water heater is characterized by being prepared from the following raw materials in parts by weight:
wherein the first polyether polyol is NJ-6206 produced by new materials of Symphingwu GmbH, the hydroxyl value of the polyether polyol is 470-510mg KOH/g, and the viscosity of the polyether polyol is 8000-11000 mPa.s;
wherein the second polyether polyol is Donol R8238 produced by Shanghai Dongdong chemical Co., Ltd, and has a hydroxyl value of 385-405mgKOH/g and a viscosity of 6000-10000 mPa.s;
wherein the third polyether polyol is NJ-8206H produced by Tanking Ningwu New materials GmbH, the hydroxyl value is 415-;
wherein the fourth polyether polyol is YD-450BC produced by the Asian east chemical group Co., Ltd, and has a hydroxyl value of 435-465mgKOH/g and a viscosity of 2000-3000 mPa.s;
wherein the chemical foaming agent is water;
wherein the physical foaming agent is a fourth generation foaming agent cis-1, 1,1, 4, 4, 4-hexafluoro-2-butene;
the catalyst is a mixture of N, N, N, N, N-pentamethyl diethylene triamine, N, N-dimethyl cyclohexylamine, N, N-dimethyl benzylamine and BX 405.
2. The environmentally friendly solar water heater conjugate polyether of claim 1, wherein the surfactant comprises a foam stabilizer.
3. An environment-friendly polyurethane raw material composition for a solar water heater, which is characterized by comprising a first component and a second component, wherein the first component is the environment-friendly combined polyether for the solar water heater as claimed in claim 1 or 2; wherein the second component is an isocyanate.
4. The environment-friendly polyurethane raw material composition for a solar water heater according to claim 3, wherein the isocyanate is polymeric diphenylmethane diisocyanate.
5. A method for preparing a polyurethane foam for an environmentally-friendly solar water heater using the polyurethane raw material composition as set forth in claim 3 or 4, characterized in that the method comprises the steps of:
(1) mixing the raw material components of the first component to obtain a first mixture;
(2) mixing the first mixture and the second component, performing high-pressure foaming at a temperature of 20-25 ℃, and injecting the polyurethane foam into a mold to obtain the polyurethane foam for the environment-friendly solar water heater.
6. The method of preparing polyurethane foam for an environmentally friendly solar water heater as set forth in claim 5, wherein the mixing in the step (1) comprises adding weighed first polyether polyol, second polyether polyol, third polyether polyol, fourth polyether polyol, foam stabilizer, chemical foaming agent, catalyst and physical foaming agent in sequence into the reaction apparatus, and stirring at normal temperature for 0.5-1.0 hour.
7. The method for preparing the polyurethane foam for the environment-friendly solar water heater as claimed in claim 5, wherein the weight ratio of the first component to the second component is 1: 1.15-1.25.
8. The method for preparing the polyurethane foam for the environment-friendly solar water heater as claimed in claim 5, wherein the weight ratio of the first component to the second component is 1: 1.2.
9. An environmentally friendly polyurethane foam for solar water heaters prepared by the method of any one of claims 5-7.
10. Use of the environmentally friendly polyurethane foam for solar water heater according to claim 9 for preparing water tank of solar water heater.
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