CN101392047A - Method for preparing polyurethane foam material by using polyatomic alcohol made by reclaimed grease - Google Patents
Method for preparing polyurethane foam material by using polyatomic alcohol made by reclaimed grease Download PDFInfo
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- CN101392047A CN101392047A CNA200710046114XA CN200710046114A CN101392047A CN 101392047 A CN101392047 A CN 101392047A CN A200710046114X A CNA200710046114X A CN A200710046114XA CN 200710046114 A CN200710046114 A CN 200710046114A CN 101392047 A CN101392047 A CN 101392047A
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Abstract
The invention relates to a preparation method of a polyurethane foam material, in particular to a method for preparing the polyurethane foam material by using recovered grease polyatomic alcohol. The polyurethane foam material consists of two components, namely, A and B; A is isocyanate and B is a material combining the polymer of the polyatomic alcohol and an addition agent, wherein, B contains 50 portions to 80 portions of the recovered grease polyatomic alcohol, 10 portions to 60 portions of petroleum polyether polyatomic alcohol, 0 portion to 30 portions of phthalic anhydride polyester polyol, 0 portion to 10 portions of cross-linking agents, 2 portions to 5 portions of foam stabilizers, 0.5 portion to 20 portions of catalyst, 10 portions to 50 portions of foaming agents, 6 portions to 20 portions of fire retarding agents and 0 portion to 2 portions of water. The detection result of relevant departments shows that all the performance indexes of the recovered oil type polyurethane foam material synthesized by the preparation method reach or are better than national standards.
Description
Technical field
The present invention relates to the preparation method of polyurethane foamed material, particularly with reclaiming the method that the grease polyvalent alcohol prepares polyurethane foamed material.
Background technology
Rigid urethane foam has obtained using widely in building energy saving field with plurality of advantages such as thermal conductivity are little.The polyurethane hard foam material that adopts spraying coating process to make influences, in the energy-saving heat preserving of external wall, roofing application is arranged with advantages such as base adhesive are strong more with continuous molding, seamless, no cold and hot bridge.
Usually polyurethane rigid foam plastic is that combination material by isocyanic ester and polyvalent alcohol forms through chemical reaction.Raw material is all from petroleum products, because the finiteness of petroleum resources, process of producing product is dangerous complicated, cost height and contaminate environment, and its price also fluctuates with the fluctuation of oil price.For this component of polyvalent alcohol, people begin to seek reproducible alternate resources.To reclaim grease (vegetables oil and animal grease) is that the polyvalent alcohol of raw material production can be used for producing urethane.The synthetic method of relevant vegetable oil polyol all has report both at home and abroad.As Chinese patent " a kind of preparation method of vegetable oil polyol " publication number: CN 1869184, having introduced with soybean wet goods vegetables oil is raw material, make the polyvalent alcohol product that has active gene through chemical reactions such as esterifications, the domestic suitability for industrialized production that has producer to realize vegetable oil polyol.Urban restaurant trade discharges a large amount of animal-plant oil, and some producers has released recovery grease type polyvalent alcohol through reclaiming to purify, but can not be with them as the body material synthesis of polyurethane, generally all is that a small amount of (＜20%) is added in the oil polyether glycol and uses.If adding proportion is excessive, easily cause defectives such as the contraction of PU foams, perforate, ultimate compression strength reduction, concerning spraying coating process, influence the cementability of foam and basic unit as it.Because addition is little, the economic benefit of being brought is limited thus.
Summary of the invention
In order to address the above problem, the hard polyurethane foam among the present invention is to be main raw material (〉=50%) to reclaim the grease polyvalent alcohol, by adding other raw material and auxiliary agent, improves its performance, makes the goods over-all properties meet or exceed pure petroleum product.Realized utilization of waste material, the purpose of environmental protection.
The hard polyurethane foam raw material is made up of A, B two components.The A component is an isocyanic ester; The B component is the combination material of polyvalent alcohol and auxiliary agent.A component structure properties is stable, and is little to the product properties influence.End product quality depends primarily on the influence of the interpolation of the molecular structure of each raw material among the component B and other auxiliary agent to agent structure and product performance.Wherein adding the oil polyether glycol, mainly is to utilize it to contain the multitudinous sugared structure of high functionality, has improved foamy intensity.Reduce reactive behavior simultaneously, prolonged gel time, improved the side's of going out rate.Wherein adding benzoic anhydride polyester polyol, mainly is to introduce the cyclic skeleton structure, increases foamy ultimate compression strength, prevents foam contraction.Foamy heatproof and flame retardant properties have been improved simultaneously.Add linking agent and can improve foamy toughness, prevent the foam cracking, improve bonding strength.Increasing the suds-stabilizing agent consumption is in order to reduce the surface tension of each component material, to make each component energy thorough mixing.
In the preferred '-diphenylmethane diisocyanate of A component isocyanic ester (being called for short MDI), the polymethine polyphenyl polyisocyanate (being called for short PAPI) one or both.
The B component is polyvalent alcohol and auxiliary agent.Wherein, reclaiming the weight percent that the grease polyvalent alcohol accounts for this polyhydric alcohol polymer is 30%～90%.
Wherein, reclaim the polyvalent alcohol that the grease polyvalent alcohol selects for use the catering industry refiltered oil to make through purification.
Wherein, oil polyether glycol preferably sucrose type polyether glycol; Sorbyl alcohol type polyether glycol; In the quadrol type polyether glycol one or more.
Wherein, polyester polyol adopts one or more in phthalic anhydride, glycol ether type polyester polyol, the glycerol type polyester polyol.
Wherein, one or more in the preferred glycol ether of linking agent, propylene glycol, the trolamine.
Wherein, preferred one or more in triethylene diamine (33% dipropylene glycol solution), dimethyl cyclohexyl amine, two lauric acid diisobutyl tin, potassium oleate, triethylamine of catalyzer.
Wherein, suds-stabilizing agent is an organic silicon surfactant.
Wherein, whipping agent is one or more in fluoro trichloromethane (CFC11), a fluorine ethylene dichloride (HCFC141b), the pentamethylene.
Wherein, fire retardant is selected dimethyl methyl phosphonate (being called for short TCPP), three (chloro isopropyl) phosphoric acid ester (being called for short DMMP), three (β-chloroethyl) phosphoric acid ester (being called for short TCEP) for use.
The B component is by weight composed as follows:
Reclaim 50～80 parts of grease polyvalent alcohols; 10～60 parts of oil polyether glycols; 0～30 part of benzoic anhydride polyester polyol; 0～10 part of linking agent; 2～5 parts of suds-stabilizing agents; 0.5～20 part of catalyzer; 10～50 parts of whipping agents; 6～20 parts of fire retardants; 0～2 part in water.
In the application usually the A component press 1:1 with the B component, or the A component is excessive a little evenly sprays or cast in the certain thickness insulation water-proof layer of formation in the basic units such as body of wall or roofing through the high pressure painting machine.Detected through relevant department by aforesaid method synthetic refiltered oil type polyurethane porous plastics, every performance index reach or are better than national standard, and are specifically described as follows:
Project standard (JC/T998-2006) oil type polyurethane refiltered oil type polyurethane
Density kg/m3 〉=30 〉=38 〉=39
Thermal conductivity w/ (m.k)≤0.024≤0.020≤0.022
Bonding strength kpa 〉=100 〉=260 〉=230
Tensile strength kpa 〉=250 〉=350 〉=320
Water-intake rate %≤3≤2≤2
Dimensional stabilizing %≤1≤1≤1
Oxygen index 〉=26 〉=27 〉=26.5
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
B component: reclaim 50 parts of grease polyvalent alcohols
40 parts of multitudinous sugared type polyether glycols
10 parts of phthalic anhydride, glycol ether type polyester polyols
3 parts of silicon foams stablizers
4 parts of trolamines
3 parts of triethylene diamines (33% dipropylene glycol solution)
2 parts of potassium oleates
30 parts of HCFC141b
12 parts of TCEP
6 parts of DMMP
0.5 part in water
The A component is the many phenyl diisocyanate of polymethine, with the B component by weight 1:1 directly be sprayed on the basal plane through the high pressure painting machine.3 second foam rise form uniform thermal insulation layer.
Embodiment 2
B component: reclaim 70 parts of grease polyvalent alcohols
30 parts of quadrol type polyether glycols
3 parts of Diethylene Glycols
4 parts of silicon foams stablizers
5 parts of DMMP
12 parts of TCEP
5 parts of trolamines
0.5 part in two lauric acid diisobutyl tin
1 part of dimethylcyclohexylamine
25 parts of HCFC141b
1 part in water
The A component is the many phenyl diisocyanate of polymethine, with the B component by weight 1:1 directly be sprayed on the basal plane through the high pressure painting machine.3 second foam rise form uniform thermal insulation layer.
Embodiment 3
B component: reclaim 60 parts of grease polyvalent alcohols
10 parts of sorb acid type polyether glycols
3 parts of propylene glycol
30 parts of phthalic anhydride, glycerol type polyester polyols
1 part of potassium oleate
3 parts of triethylamines
35 parts of HCFC141b
5 parts of silicon foams stablizers
3 parts of triethylene diamines (33% dipropylene glycol solution)
6 parts of DMMP
11 parts of TCEP
The A component is '-diphenylmethane diisocyanate repeatedly, with the B component by weight 1:1 directly be sprayed on the basal plane through the high pressure painting machine.3 second foam rise form uniform thermal insulation layer.
Being preferred embodiment of the present invention only in sum, is not to be used for limiting practical range of the present invention.Be that all equivalences of doing according to the content of patent claim of the present invention change and modification, all should be technology category of the present invention.
Claims (7)
1, a kind of with reclaiming the method that the grease polyvalent alcohol prepares polyurethane foamed material, it is characterized in that, with A component and B component is that the excessive proportioning of the relative B component of 1:1 or A component is mixed fully by weight, then mixture is sprayed or casts on the basal plane, foaming formation thermal insulation layer;
Described A component is an isocyanic ester;
Described B component comprises polyhydric alcohol polymer and auxiliary agent, and wherein, the weight percent that recovery grease polyvalent alcohol accounts for this polyhydric alcohol polymer is 30%～90%.
2, the method for preparing polyurethane foamed material according to claim 1 is characterized in that, described isocyanic ester is one or both in '-diphenylmethane diisocyanate or the polymethine polyphenyl polyisocyanate; Described auxiliary agent comprises linking agent, suds-stabilizing agent, catalyzer, whipping agent, fire retardant; Described polyhydric alcohol polymer comprises one or more in recovery grease polyvalent alcohol, oil polyether glycol, the polyester polyol.
3, the method for preparing polyurethane foamed material according to claim 2 is characterized in that, described oil polyether glycol is selected from one or more in cane sugar type polyether glycol, sorbyl alcohol type polyether glycol, the quadrol type polyether glycol.
4, the method for preparing polyurethane foamed material according to claim 2 is characterized in that, described polyester polyol adopts one or more in phthalic anhydride, glycol ether type polyester polyol, the glycerol type polyester polyol.
5, the method for preparing polyurethane foamed material according to claim 2 is characterized in that, described linking agent is selected from one or more in glycol ether, propylene glycol, the trolamine; Described catalyzer is selected from one or more in triethylene diamine, dimethyl cyclohexyl amine, two lauric acid diisobutyl tin, potassium oleate, the triethylamine; Described suds-stabilizing agent is an organic silicon surfactant; Described whipping agent is one or more in fluoro trichloromethane, a fluorine ethylene dichloride, the pentamethylene; Described fire retardant is selected from one or more in dimethyl methyl phosphonate, three (chloro isopropyl) phosphoric acid ester, three (β-chloroethyl) phosphoric acid ester.
6, the method for preparing polyurethane foamed material according to claim 1 is characterized in that, the weight percent that described recovery grease polyvalent alcohol accounts for described polyhydric alcohol polymer is 50%～70%.
7, the method for preparing polyurethane foamed material according to claim 2, it is characterized in that, by weight calculating, described recovery grease polyvalent alcohol: oil polyether glycol: polyester polyol: linking agent: suds-stabilizing agent: catalyzer: whipping agent: fire retardant: the ratio of water is 50～80:10～60:0～30:0～10:2～5:0.5～20:10～50:6～20:0～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710046114XA CN101392047A (en) | 2007-09-19 | 2007-09-19 | Method for preparing polyurethane foam material by using polyatomic alcohol made by reclaimed grease |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710046114XA CN101392047A (en) | 2007-09-19 | 2007-09-19 | Method for preparing polyurethane foam material by using polyatomic alcohol made by reclaimed grease |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101392047A true CN101392047A (en) | 2009-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200710046114XA Pending CN101392047A (en) | 2007-09-19 | 2007-09-19 | Method for preparing polyurethane foam material by using polyatomic alcohol made by reclaimed grease |
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| CN (1) | CN101392047A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040725A (en) * | 2010-11-09 | 2011-05-04 | 烟台德邦电子材料有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN102336901A (en) * | 2011-08-03 | 2012-02-01 | 句容宁武新材料发展有限公司 | Method for preparing polyurethane polyether polyol by waste oil |
| CN102453224A (en) * | 2011-07-15 | 2012-05-16 | 上海高裕海绵制品有限公司 | Technology for producing sponge from plant oil polyether |
| CN102559032A (en) * | 2010-12-20 | 2012-07-11 | 上海抚佳精细化工有限公司 | Low-temperature spraying combination material, and preparation method and application of low-temperature spraying combination material |
| CN102977586A (en) * | 2012-09-29 | 2013-03-20 | 北京东方雨虹防水技术股份有限公司 | Degradation resistance fire retardation type rigid polyurethane foam material and preparation method thereof |
| CN103059712A (en) * | 2011-10-21 | 2013-04-24 | 湖南晟通科技集团有限公司 | Single-component polyurethane coating |
| CN106519167A (en) * | 2016-12-13 | 2017-03-22 | 江苏久久防水保温隔热工程有限公司 | Preparation method and application of spraying polyurethane semi-rigid foam |
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
| WO2023109869A1 (en) * | 2021-12-17 | 2023-06-22 | 海尔智家股份有限公司 | Thermal insulation material, and refrigerator, refrigerated storage, or freezer using same |
-
2007
- 2007-09-19 CN CNA200710046114XA patent/CN101392047A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040725A (en) * | 2010-11-09 | 2011-05-04 | 烟台德邦电子材料有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN102040725B (en) * | 2010-11-09 | 2012-11-21 | 烟台德邦科技有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN102559032A (en) * | 2010-12-20 | 2012-07-11 | 上海抚佳精细化工有限公司 | Low-temperature spraying combination material, and preparation method and application of low-temperature spraying combination material |
| CN102559032B (en) * | 2010-12-20 | 2014-05-07 | 上海抚佳精细化工有限公司 | Low-temperature spraying combination material, and preparation method and application of low-temperature spraying combination material |
| CN102453224A (en) * | 2011-07-15 | 2012-05-16 | 上海高裕海绵制品有限公司 | Technology for producing sponge from plant oil polyether |
| CN102336901A (en) * | 2011-08-03 | 2012-02-01 | 句容宁武新材料发展有限公司 | Method for preparing polyurethane polyether polyol by waste oil |
| CN103059712A (en) * | 2011-10-21 | 2013-04-24 | 湖南晟通科技集团有限公司 | Single-component polyurethane coating |
| CN103059712B (en) * | 2011-10-21 | 2016-08-03 | 湖南晟通科技集团有限公司 | A kind of one-can urethane coating |
| CN102977586A (en) * | 2012-09-29 | 2013-03-20 | 北京东方雨虹防水技术股份有限公司 | Degradation resistance fire retardation type rigid polyurethane foam material and preparation method thereof |
| CN102977586B (en) * | 2012-09-29 | 2014-12-17 | 北京东方雨虹防水技术股份有限公司 | Degradation resistance fire retardation type rigid polyurethane foam material and preparation method thereof |
| CN106519167A (en) * | 2016-12-13 | 2017-03-22 | 江苏久久防水保温隔热工程有限公司 | Preparation method and application of spraying polyurethane semi-rigid foam |
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
| CN109627746B (en) * | 2018-11-23 | 2021-04-06 | 贵州航天天马机电科技有限公司 | Large negative pressure polyurethane front end fragile protective cover and forming method thereof |
| WO2023109869A1 (en) * | 2021-12-17 | 2023-06-22 | 海尔智家股份有限公司 | Thermal insulation material, and refrigerator, refrigerated storage, or freezer using same |
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Open date: 20090325 |