CN101125910A - Hard polyurethane foam plastic and producing method thereof - Google Patents
Hard polyurethane foam plastic and producing method thereof Download PDFInfo
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- CN101125910A CN101125910A CNA2006100621657A CN200610062165A CN101125910A CN 101125910 A CN101125910 A CN 101125910A CN A2006100621657 A CNA2006100621657 A CN A2006100621657A CN 200610062165 A CN200610062165 A CN 200610062165A CN 101125910 A CN101125910 A CN 101125910A
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Abstract
The invention relates to a pyrex polyurethane foam plastic and the production method thereof. The raw materials are polyisocyanate, conjugate polyether and blowing catalyst, wherein the blowing catalyst consists of HFC-245fa, pentamethylene and nucleating agent; portions of raw materials by weight are: 100 portions of conjugate polyether, 1 to 10 portions of HFC-245fa, 6 to 12 portions of pentamethylene, 0.1 to 2.2 portions of nucleating agent, 100 to 130 portions of polyisocyanate. The steps of the production method are: a) the HFC-245fa, the pentamethylene and the nucleating agent are put into circularly transferring pump to mix with circularly; b) polyether glycol monomer, water, catalyst and stabilizer are mixed to prepare conjugate polyether; c) the mixture of the blowing catalyst and the nucleating agent and the conjugate polyether are fed into a static mixer; d) the mixture obtained from the step reacts with polyisocyanate that yields effervescence. The foam plastic of the invention has the advantages of environmental protection and low cost, and comprehensive properties thereof equivalent to the foaming ability of CEC-11. The invention opens up a novel shortcut for the application of HFC-245fa, erases the cost burden while is used alone, thus HEC-245fa can be largely popularized and used.
Description
Technical field
The present invention relates to the porous plastics technical field, more particularly, relate to a kind of rigid urethane foam and production method thereof.
Background technology
Rigid urethane foam has good heat-insulating property and certain intensity, is commonly used for the thermal insulation layer of refrigerator, refrigerator.The preparation method of traditional PU (urethane) porous plastics is to be whipping agent with CFC-11 (3 chloro-fluoromethane), with the mixture POL (comprising polyvalent alcohol, water, catalyzer, stablizer, whipping agent) and organic multiple isocyanate (MDI) high pressure mixing of combined polyether, generate the porous plastics of reticulated foams structure.
CFC-11 is the good PU whipping agent of a kind of heat-insulating property, and thermal conductivity (K value) is 0.0074W/mK (10 ℃ is as follows), and foam core density is 28-32kg/m3,23.8 ℃ of boiling points, and the thermal conductivity of hard bubbling is in the 0.016-0.018W/mK scope.CFC-11 is as whipping agent, and its foam insulation performance, security, foam process operability are best, and the raw material consumption is seldom, but because of the destruction to atmospheric ozone layer disabled.In present known alternative whipping agent, as c-pentane (pentamethylene), HFC-245fa (1,1,1,3,3---pentafluoropropane), though its environmental-protecting performance is good, but at aspects such as heat-insulating property, raw material consumptions, c-pentane and HFC-245fa can't reach the level of CFC-11 foaming technique.C-pentane (containing c/i-pentane) comprises that on Eurasia and other places China is at first extensively adopted, and then uses HFC-245fa in the U.S..Though c-pentane obtains easily, cheap but inflammable and explosive, heat retaining property is relatively poor, and the K value that it hard bubbles is about 0.020W/mK, and core density is usually at 35kg/m
3About; And HFC-245fa safety, do not fire, hard bubble the K value about 0.019W/mK, core density is at 31kg/m
3About, but complex manufacturing, price is higher and influenced its popularization, nucleator (as the perfluoro-hydrocarbon FA-188 of 3M company etc.) can effectively reduce PU foam K value, improve heat-insulating property, but it costs an arm and a leg.It is a kind of suitable with CFC-11 on over-all properties to press for searching in the PU industry, has the whipping agent of the feature of environmental protection again concurrently and uses this whipping agent to prepare the method for PU.
Summary of the invention
The technical problem to be solved in the present invention is at the deficiencies in the prior art, to provide the rigid urethane foam of being on close level of a kind of environment-friendly type, low cost, over-all properties and employing CFC-11 foaming technique.
Another technical problem that the present invention will solve is that the production method of the above-mentioned rigid urethane foam of preparation is provided.
The technical solution adopted for the present invention to solve the technical problems is: porous plastics uses polyisocyanates, combined polyether and whipping agent to be raw material, combined polyether by multiple polyether glycol monomer and catalyzer, suds-stabilizing agent, water, form, described whipping agent is made up of HFC-245fa, pentamethylene and nucleator; Each raw materials in part by weight is: 100 parts of combined polyethers, HFC-245fa are 1～10 part, 6～12 parts of pentamethylene, 0.1～2.2 part of nucleator, 100～130 parts of polyisocyanates.
In the above-mentioned porous plastics, each raw materials in part by weight is: 100 parts of combined polyethers, HFC-245fa are 6～8 parts, 7～9 parts of pentamethylene, 1.0～1.8 parts of nucleators, 115～125 parts of polyisocyanates.
The production method of above-mentioned porous plastics with polyisocyanates, combined polyether and whipping agent prepared in reaction, may further comprise the steps:
A) HFC-245fa, pentamethylene and nucleator are mixed with the circulation of circulation transferpump;
B) be mixed with combined polyether with polyether glycol monomer and water, catalyzer, stablizer;
C) whipping agent is delivered in the static mixer with combined polyether with the nucleator mixture mixes;
D) mixture and polyisocyanates reaction foaming.
The production method of above-mentioned porous plastics is mixed with pentamethylene after HFC-245fa is cooled to 10～15 ℃ again.
The production method of above-mentioned porous plastics with polyisocyanates, combined polyether and whipping agent prepared in reaction, may further comprise the steps:
A) after being mixed, pentamethylene and nucleator be delivered to static mixer;
B) be mixed with combined polyether with polyether glycol monomer and water, catalyzer, stablizer;
C) HFC-245fa is mixed with pentamethylene and nucleator with being delivered in the static mixer after combined polyether mixes;
D) mixture and polyisocyanates reaction foaming.
The production method of above-mentioned porous plastics is cooled to 5～10 ℃ with HFC-245fa, mixes mutually with 18～25 ℃ combined polyether again.
Above-mentioned foam production method, comprising the mixture of combined polyether, mixed foaming agent, nucleator and the pressure range of polyisocyanates mixed foaming is 110-160bar, and mixture warm is 18-25 ℃, and the foaming mould temperature is 30-50 ℃
The invention has the beneficial effects as follows:
1) the present invention makes full use of C-pentane advantage and the existing sophisticated a large amount of special-purpose assorted equipment of refrigerator industry cheaply; Sneak into certain amount of H FC-245fa, have good lather ultimate compression strength and the dimensional stability advantage of utilizing its lower boiling, high-vapor-pressure to bring, thus reducing foaming raw material consumption, reduction core density, its safety, non-combustible characteristic also can improve processing safety in addition.
2) use HFC-245fa and add the nucleator of minute quantity, effectively reduce mixed foaming agent (C-pentane+HFC-245fa) system foamy K value.Since an amount of HFC-245fa that uses, and reduce the foaming raw material consumption, simple C-pentane or the HFC-245fa foaming system that density polyurethane porous plastics cost compares in the hard of the present invention descended to some extent, can increase economic benefit of enterprises.
3) the reasonably combined use of C-pentane, HFC-245fa and three kinds of materials of nucleator makes the PU foam of producing have good environmental protection, energy-saving effect concurrently, and its over-all properties is equivalent to the PU foam of CFC-11 system.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the PU foaming schema of pentamethylene foaming in the prior art;
Fig. 2 is that the present invention is with the foaming schema of mixed foaming agent in the low temperature environment foaming;
Fig. 3 be the present invention with mixed foaming agent high (in) the foaming schema of warm environment foaming.
Embodiment
In the employed whipping agent of PU plastics, the c-pentane heat retaining property is relatively poor at present, and HFC-245fa can improve heat-insulating property with nucleator, but it costs an arm and a leg.Above material respectively has its significant relative merits, purpose of the present invention is exactly the advantage that makes full use of separately, overcome its deficiency, learn from other's strong points to offset one's weaknesses, thereby obtain aspect environmental protection, to meet on market demands, the over-all properties near density rigid foam among the PU (urethane) of CFC-11 system.The production method of rigid urethane foam of the present invention, raw materials used is polyisocyanates, combined polyether, whipping agent and a spot of nucleator.Nucleator is an organofluorine compound, principal item comprises the perfluoro-hydrocarbon of the trades mark such as FA-188 of 3M, ODP=0, the GWP value tens of to hundreds of scopes, the feature of environmental protection is good, fine and closely woven, even, the airtight abscess of faster formation when it can impel MDI (polyisocyanates) and polyether glycol to carry out chemical reaction, thus the foamy insulation capacity effectively improved, reduce its thermal conductivity.
The present invention adopts the mixture of C-pentane (containing ring/iso-pentane) and HFC-245fa as whipping agent, and wherein the share that accounts for of C-pentane is 50-90wt% (calculating by weight), the share 10-50wt% that HFC-245fa accounts for.And accounting for 50-75wt% with C-pentane, HFC-245fa accounts for the proportioning best results of 25-50wt%.Combined polyether usually by 4-5 kind polyether glycol monomer and catalyzer, suds-stabilizing agent, water, form, the polyvalent alcohol type mainly comprises sucrose glyceryl polyvalent alcohol, glyceryl polyvalent alcohol, sorbyl alcohol polylol, aromatic series polylol etc.Nucleator is dissolved in earlier among the C-pentane before use, and principal item comprises the perfluoro hydro carbons, and 5-6 carbon atom arranged usually, and boiling point 40-50 ℃, and have ODP=0 and the characteristic of GWP very little (usually tens between hundreds of).
The concrete ratio of components of each raw material of PU foam of the present invention such as following table 1, calculate with the parts by weight of each composition:
Table 1
| The component title | Combined polyether | C-pentane | HFC-245fa | Nucleator | MDI |
| Proportioning (parts by weight) | 100 | 6～12 | 1～10 | 0.1～2.2 | 100～130 |
| Best proportioning (parts by weight) | 100 | 7～9 | 6～8 | 1.0～1.8 | 115～125 |
Below, specifically tell about foam preparation processes of the present invention.
Present general pentamethylene foam production operational path as shown in Figure 1, pentamethylene is sent into static mixer (MEF) by transferpump through pipeline in the earth jar, meanwhile, combined polyether also is transported to this static mixer, and both mix after deliver to foaming production line by pipeline; And another main ingredient MDI that carries out the PU foam production also simultaneously delivers to foaming production line by pump via pipeline.
The present invention adopts the production method that foams with HFC-245fa and C-pentane mixed type whipping agent referring to Fig. 2 and Fig. 3, flow process shown in Figure 2 is fit to the relatively low environment of temperature, as environment below 20 ℃, HFC-245fa and nucleator are delivered in the pentamethylene the earth jar via transferpump, and carry out self-circulation repeatedly by the circulation transferpump, make HFC-245fa, nucleator and pentamethylene fully dissolve, mix, deliver in the static mixer through pipeline by transferpump then; Meanwhile, the combined polyether for preparing also is transported to this static mixer, and the three mixes after deliver to foaming production line by pipeline, carries out foam production with the MDI that is also delivered to via pipeline by pump (organic multiple isocyanate) at foaming line.During foaming, mixture and MDI wherein freely steep density: 23-27kg/m by injection head high pressure mixing foaming under 110-160bar pressure of high pressure foaming machine
3, core density: 30～38kg/m
3, the foaming mould temperature is controlled at 30～50 ℃, expects warm 18-25 ℃.Bubble material by high-pressure injection to the refrigerator body intermediate course, after overcuring drying tunnel operation, moulding, the demoulding, the product after obtaining foaming.
Above-mentioned pentamethylene the earth jar generally is embedded in underground, and the mixed dissolution of foaming additive and pentamethylene carries out underground, and the possibility of leakage is little.Premix operation by this flow process whipping agent and combined polyether is comparatively convenient, but because the volatility of HFC-245fa is big, in the operating process that joins pentamethylene the earth jar, prevent the volatilization loss of HFC-245fa, can earlier HFC-245fa suitably be cooled to 10-15 ℃ of scope, join again in the earth jar.
Referring to Fig. 3, under the higher relatively environment of envrionment temperature,, nucleator ratio in technical requirements in pentamethylene the earth jar can be pumped into as environment more than 30 ℃, and use by being pumped into static mixer again after in the earth jar, stirring, mixing, all the other are the same.In actually operating, because the boiling characteristics of HFC-245fa, the married operation of HFC-245fa and combined polyether POL has certain difficulty, and concrete operations can be cooled to HFC-245fa 5-10 ℃ earlier, POL can be expected that temperature control is the 18-25 ℃ of premix operation of carrying out both again simultaneously.This programme is fit to the high southern area of temperature to be used.
Table 2 is listed the proportioning raw materials and the K value after the foaming (test of carrying out with flow process shown in Figure 3) of two specific embodiments of the present invention:
Table 2
| Catalyzer | 2.0 | 2.0 | |
| Suds-stabilizing agent | 2.5 | 2.5 | |
| Water | 1.7 | 1.8 | |
| Nucleator | 2.0 | 1.8 | |
| Whipping agent | Ring thing alkane | 9 | 8 |
| HFC-245fa | 7 | 8 | |
| Foaming raw material ratio of mixture (MDI: POL) | 120∶100 | 120∶100 | |
| K value (W/mK) | 0.0170 | 0.0173 | |
The rigid urethane foam that adopts the inventive method to produce, thermal conductivity K value reduces significantly.Common ring pentane system, generally in the 0.020-0.022W/mK scope, pentamethylene adds the mixed system of HFC-245fa to foamy thermal conductivity K value, if when not using nucleator, the K value is usually in the 0.0190-0.0205W/mK scope, and as using nucleator, the K value can be in the 0.0170-0.0190W/mK scope; Foam core density is usually at 29-33kg/m
3Scope, best at 30-31kg/m
3, its over-all properties is all suitable with the CFC-11 foaming system.Another meaning of the present invention is to have opened up a new shortcut for the application of HFC-245fa, the cost pressure when having eliminated its independent use, thus make HFC-245fa be able to large scale application.More concrete testing data reference table 3 and table 4, as follows:
Table 3
| Nucleator | 1.8 | |||
| Pentamethylene/HFC-245fa | 8/8 | 10/6 | 12/4 | 15 |
| MDI/POL | 120/100 | |||
| Foam core density (kg/m 3) | 30.8 | 32.3 | 33.5 | 34.5 |
| Average K value (W/mK) | 0.0178 | 0.0181 | 0.0186 | 0.0198 |
Annotate: test institute's column data amount of attaching most importance to umber in the table with flow process shown in Figure 2.
Table 4
| Pentamethylene/HFC-245fa | 8/8 | |||
| Nucleator | 2 | 1.5 | 1 | 0 |
| MDI/POL | 120/100 | |||
| Foam core density (kg/m 3) | 30.3 | 31.0 | 31.4 | 31. 9 |
| Average K value (W/mK) | 0.0171 | 0.0183 | 0.0189 | 0.0193 |
Annotate: test institute's column data amount of attaching most importance to umber in the table with flow process shown in Figure 3.
Claims (7)
1. rigid urethane foam, raw materials used is polyisocyanates, combined polyether and whipping agent, combined polyether by multiple polyether glycol monomer and catalyzer, suds-stabilizing agent, water, form, it is characterized in that: described whipping agent is made up of HFC-245fa, pentamethylene and nucleator; Each raw materials in part by weight is: 100 parts of combined polyethers, HFC-245fa are 1～10 part, 6～12 parts of pentamethylene, 0.1～2.2 part of nucleator, 100～130 parts of polyisocyanates.
2. porous plastics according to claim 1 is characterized in that: each raw materials in part by weight is: 100 parts of combined polyethers, HFC-245fa are 6～8 parts, 7～9 parts of pentamethylene, 1.0～1.8 parts of nucleators, 115～125 parts of polyisocyanates.
3. according to the production method of the described porous plastics of claim 1,, it is characterized in that may further comprise the steps with polyisocyanates, combined polyether and whipping agent prepared in reaction:
A) HFC-245fa, pentamethylene and nucleator are mixed with the circulation of circulation transferpump;
B) be mixed with combined polyether with polyether glycol monomer and water, catalyzer, stablizer;
C) whipping agent is delivered in the static mixer with combined polyether with the nucleator mixture mixes;
D) mixture and polyisocyanates reaction foaming.
4. the production method of porous plastics according to claim 3 is characterized in that: mix with pentamethylene after HFC-245fa is cooled to 10～15 ℃ again.
5. according to the production method of the described porous plastics of claim 1,, it is characterized in that may further comprise the steps with polyisocyanates, combined polyether and whipping agent prepared in reaction:
A) after being mixed, pentamethylene and nucleator be delivered to static mixer;
B) be mixed with combined polyether with polyether glycol monomer and water, catalyzer, stablizer;
C) HFC-245fa is mixed with pentamethylene and nucleator with being delivered in the static mixer after combined polyether mixes;
D) mixture and polyisocyanates reaction foaming.
6. the production method of porous plastics according to claim 5 is characterized in that: HFC-245fa is cooled to 5～15 ℃, mixes mutually with 18～25 ℃ combined polyether.
7. according to claim 3 or 4 or 5 or 6 described foam production methods, it is characterized in that, comprising the mixture of combined polyether, mixed foaming agent, nucleator and the pressure range of polyisocyanates mixed foaming is 110-160bar, mixture warm is 18-25 ℃, and the foaming mould temperature is 30-50 ℃.
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| WO2012051761A1 (en) * | 2010-10-22 | 2012-04-26 | 南京宝新聚氨酯有限公司 | Quickly reactive composition for preparing hard polyurethane foam with low density |
| CN101775206B (en) * | 2010-02-04 | 2012-07-18 | 东南大学 | Degradable polyurethane semihard foam material and preparation method thereof |
| WO2013091128A1 (en) * | 2011-12-19 | 2013-06-27 | Honeywell International Inc | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
| CN104448222A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Low-conductivity polyurethane thermal insulation material for ultrathin refrigerator freezers and preparation method thereof |
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| CN106750489A (en) * | 2016-12-26 | 2017-05-31 | 青岛海尔股份有限公司 | Foaming agent and hard polyurethane foam |
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| CN108276546A (en) * | 2017-12-28 | 2018-07-13 | 青岛海尔股份有限公司 | Polyurethane rigid foam plastic and preparation method thereof |
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| CN101775206B (en) * | 2010-02-04 | 2012-07-18 | 东南大学 | Degradable polyurethane semihard foam material and preparation method thereof |
| WO2012051761A1 (en) * | 2010-10-22 | 2012-04-26 | 南京宝新聚氨酯有限公司 | Quickly reactive composition for preparing hard polyurethane foam with low density |
| RU2557234C2 (en) * | 2010-10-22 | 2015-07-20 | Наньцзин Хунбаоли Полиуритэйн Ко., Лтд. | Fast-reacting composition for preparation of low-density solid polyurethane foam |
| CN107641214A (en) * | 2011-12-19 | 2018-01-30 | 霍尼韦尔国际公司 | Composition comprising 1,1,3,3,3 pentafluoropropanes and pentamethylene |
| WO2013091128A1 (en) * | 2011-12-19 | 2013-06-27 | Honeywell International Inc | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
| US20140378559A1 (en) * | 2011-12-19 | 2014-12-25 | Honeywell International Inc. | Compositions of 1,1,1,3,3-pentafluoropropane and cyclopentane |
| CN104448222A (en) * | 2014-11-27 | 2015-03-25 | 山东一诺威新材料有限公司 | Low-conductivity polyurethane thermal insulation material for ultrathin refrigerator freezers and preparation method thereof |
| CN104448222B (en) * | 2014-11-27 | 2017-01-04 | 山东一诺威新材料有限公司 | Ultra-thin refrigerator low conductivity type polyurethane heat insulation material and preparation method thereof |
| CN105985504A (en) * | 2015-01-27 | 2016-10-05 | 瀚寅(上海)新材料科技有限公司 | Medium-density rigid polyurethane foam material and preparation method thereof |
| CN104877106A (en) * | 2015-06-05 | 2015-09-02 | 苏州市湘园特种精细化工有限公司 | Flame-retardant rigid foam material and preparation method thereof |
| CN105440258A (en) * | 2015-12-17 | 2016-03-30 | 上海东大聚氨酯有限公司 | Hard polyurethane foam, raw material composition, preparation method, and applications thereof |
| CN106750489A (en) * | 2016-12-26 | 2017-05-31 | 青岛海尔股份有限公司 | Foaming agent and hard polyurethane foam |
| CN106750489B (en) * | 2016-12-26 | 2019-11-26 | 青岛海尔股份有限公司 | Foaming agent and hard polyurethane foam |
| CN107513265A (en) * | 2017-08-31 | 2017-12-26 | 苏州市苏真床垫有限公司 | A kind of preparation method of goose down foaming mattress |
| CN108276546A (en) * | 2017-12-28 | 2018-07-13 | 青岛海尔股份有限公司 | Polyurethane rigid foam plastic and preparation method thereof |
| WO2020078672A1 (en) * | 2018-10-16 | 2020-04-23 | Arcelik Anonim Sirketi | Rigid polyurethane foam, production method therefor and cooling device comprising the same |
| CN113372528A (en) * | 2021-01-11 | 2021-09-10 | 安徽科技学院 | High-strength flame-retardant polyurethane foam plastic and preparation method thereof |
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