CN101544736A - Rigid polyurethane water-blown foam material - Google Patents
Rigid polyurethane water-blown foam material Download PDFInfo
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- CN101544736A CN101544736A CN200810035314A CN200810035314A CN101544736A CN 101544736 A CN101544736 A CN 101544736A CN 200810035314 A CN200810035314 A CN 200810035314A CN 200810035314 A CN200810035314 A CN 200810035314A CN 101544736 A CN101544736 A CN 101544736A
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Abstract
The invention relates to a rigid polyurethane water-blown foam material, which consists of 100 portions of comprehensive polyether and polyester polyol, 1 to 3 portions of silicon oil, 1 to 5 portions of comprehensive catalyst, 1 to 5 portions of water and 100 to 150 portions of isocyanate; and the comprehensive polyether and polyester polyol consists of benzoic anhydride polyester polyol which introduces benzene ring structures in molecular structures, increases the benzene ring content in polyurethane chains, and has high strength, good toughness, low heat conductivity, excellent hydrolytic resistance, and excellent thermal stability and primary hydroxyl characteristics, and polyether polyol taking sucrose glycerin and sorbierite as an initiator. The rigid polyurethane water-blown foam material has the advantages of increasing the fluidity, reducing the difference between the whole density and the central density, being capable of obviously improving the dimension stability of rigid foam, decreasing pore diameter of cells, and reducing the transparency of the walls of the cells so as to made up for the deficiency of improved thermal conductivity caused by water blowing.
Description
Technical field
The present invention relates to a kind of rigid polyurethane water-blown foam material.
Background technology
Urethane foam is in the highest flight a big kind in the polyurethane synthetic material; urethane foam is the rich and influential family who consumes CFC and HCFC series whipping agent; well-known CFC series product are to the destruction of atmospheric ozone layer tool; form Greenhouse effect; global temperature is got warm again after a cold spell; skin carcinoma patient increases, so the human ozonosphere of depending on for existence of protection is very urgent.
(China had participated in international Montreal Convention in 1991, was Montreal Protocol on Substances that Deplete the Ozone Layer signatory state, limited and ban use of CFC-11 to become policy measure of China.)
2007 No. 45 file of State Environmental Protection Administration " about banning use of the bulletin of Chlorofluorocarbons (CFCs) CFCs material as whipping agent " announced to ban use of CFCs as whipping agent from January 1st, 2008.The production and consumption of HCFC simultaneously will be frozen in the level of 2009 and 2010 in advance.
The statistics of protecting general bureau's foreign economic cooperation office according to ball, HCFC series product production and consumption every year is to surpass 20% speed increase behind the CFC products substitution.Therefore the production and consumption of HCF series product freezes in advance, hard polyurethane foam industry to high speed development remains an acid test, therefore the substitute of researching and developing HCFC-141B is the important topic of foam industry in for some time from now on, develop moderate cost, excellent thermal insulation performance, do not need equipment is carried out large-scale redevelopment, alternative whipping agent or the alternative foaming system of the low GWP (greenhouse gases index) of zero odp safe in utilization (depletion of the ozone layer index) are the problems that the technician will solve.
Summary of the invention
The technical issues that need to address of the present invention have provided a kind of rigid polyurethane water-blown foam material, are intended to solve the above problems.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The present invention is made up of comprehensive polyether polyester polyvalent alcohol, silicone oil, integrated catalyst, water, isocyanic ester; Wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, 1～3 part of silicone oil, integrated catalyst 1～～5 part, water 1～～5 part, isocyanic ester 100～～150 part; Described comprehensive polyether polyester polyvalent alcohol is by introducing benzene ring structure in the molecular structure, having increased the forming as the polyether glycol of initiator by the benzoic anhydride polyester polyol of low, the excellent resistance to hydrolysis of intensity height, good toughness, thermal conductivity, excellent thermostability and primary hydroxyl feature and by sucrose glycerine, sorbyl alcohol of tool of the phenyl ring content in the polyurethane chain;
Described silicone oil be stable by the hydrolysis chemical property, can reduce the silicone oil of silicon-carbon structure that intermolecular surface tension plays a kind of polysiloxane-copolyether of stable and uniform abscess effect;
Described integrated catalyst by the stronger amino catalyzer of a spot of alkalescence, can be dissolved in water and general organic Chemical Composition, to provide balance to rise to send out reaction and gel reaction, low viscosity again be the catalyst for trimerization of triazines organism gentleness.
Compared with prior art, the invention has the beneficial effects as follows: flowability is increased, dwindled the difference of global density and center density, can improve the dimensional stability of hard bubbling significantly, reduced the abscess aperture and reduced the transparency of cell wall, like this to since the thermal conductivity rising phenomenon that the water foaming causes remedy to some extent.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
The present invention is made up of comprehensive polyether polyester polyvalent alcohol, silicone oil, integrated catalyst, water, isocyanic ester; Wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, silicone oil 1～～3 part, 1～5 part of integrated catalyst, water 1～～5 part, isocyanic ester 100～～150 part; Described comprehensive polyether polyester polyvalent alcohol is by introducing benzene ring structure in the molecular structure, what increased the phenyl ring content in the polyurethane chain has intensity height, good toughness, low, an excellent resistance to hydrolysis of thermal conductivity, the excellent thermostability and the benzoic anhydride polyester polyol of primary hydroxyl feature.There is amine to condense and is difficult for soon producing hydrostomia, and formed as the polyether glycol of initiator by sucrose, glycerine, sorbyl alcohol as having of initiator.Can mate according to different purposes.
Described silicone oil is stable by the hydrolysis chemical property, can reduce the silicone oil of silicon-carbon structure that intermolecular surface tension plays a kind of polysiloxane-copolyether of stable and uniform abscess effect.Make foam obtain the closed pore of uniform and smooth and the stability of optimum size.
Described integrated catalyst is by the stronger amino class catalyzer of a spot of alkalescence, and the catalyst for trimerization that to be dissolved in water and general organic Chemical Composition be the organic gentleness of triazines can provide balance to rise again and send out a reaction and a gel reaction, low viscosity.The catalyzer that can be dissolved in water fully and can use with the Ya Xi of polymerized polyalcohol, carbon fluoride can be regulated in combined polyether according to different purposes.
Embodiment 1
Be used as low density sheet material basic recipe: 100 parts of comprehensive polyethers
Silicone oil 1～～2 part
Integrated catalyst 1～～2 part
Water 3～～5 part
Isocyanic ester 100～～130 part
Spray bubble prescription: 100 parts of comprehensive polyethers
Silicone oil 1～～2 part
Integrated catalyst 3～～5 part
Water 3～～5 part
Isocyanic ester 100～～130 part
Be used as the high-density plate material formula: 100 parts of comprehensive polyethers
Silicone oil 1～～2 part
Integrated catalyst 2～～5 part
Water 1～～2 part
Isocyanic ester 100～～120
Though the present domestic full water foamed project that has, but only rest on upward (referring to Linkage's urethane-the foundation information-All-Water Blown Polyurethane Foam brief introduction 2007---10-30 derive from Zibo Lianchuang Polyurethane Co., Ltd) on probation (the emerging urethane of benefit demonstration plant, Shenyang City, product introduction of full water polyethers) of soft bubble and tubing.
Owing to adopt full water foamed new technology, novel process to replace traditional foam process, just must solve a series of problems that occurred in the new technology, rather than simply replace process, the material system viscosity of hard bubbling by the water foaming is big, and mobile poor, abscess is thick, the thermal conductivity height, foam is more crisp poor with substrate bonding, and in box foaming, water and MDI reaction generate allophanate and cause foam surface to send out shortcake, embrittlement, the unequal problem of abscess.
The performance of urethane foam, the structure that depends on polyethers or polyester polyol to a great extent, a traditional multitudinous sugared glycerin polyether is to solve these difficult points for the full water foamed foam on basis, selected the polyester polyol of the full water polyethers of Shenyang urethane and Changxing chemical industry company limited in the present invention, the polyether glycol in Shanghai Gaoqiao chemical plant, the new raw material system that combines, concrete composition is as follows:
Full water polyethers 50～～80 parts
Polyester polyol 5～～30 part
Polyether glycol 20～～45 part
New material system increases flowability, dwindled the difference of global density and center density, can improve the dimensional stability of hard bubbling significantly, reduce the abscess aperture and reduced the transparency of cell wall, like this to since the thermal conductivity rising phenomenon that the water foaming causes remedy to some extent.
Suds-stabilizing agent has certain influence to foaming system and flowability with the foam thermal conductance, and when other raw material was identical, foam density then equated substantially, but owing to suds-stabilizing agent kind difference, foamy thermal conductivity difference is bigger, and mobile difference is also big.
Suds-stabilizing agent is commonly called as silicone oil, is one of key assistant that generates hard polyurethane foam, and its consumption only accounts for about 1% of foam total amount, but its effect is very big, excellent property, and the silicone oil that has good quality should have following three functions:
1., foamy is stablized nucleogenesis---and reduce the surface tension of abscess, generate evenly the closed-cell foam of microporeization.
2., the emulsifying effect of material---make the interior each component of material system that good intermiscibility be arranged, the clarified liq that becomes homogeneous has long storage period.
3., it is good that the mold filling effect---the foamed time material fluidity is good, it is even that the foam physical efficiency is full of in the die cavity each position density equably.
Adopted full water foamed after, variation has taken place in the material system, the silicone oil of former use can not satisfy the requirement of foam thermal conductivity and technical indicator, must seek the new variety silicone oil that is fit to this foamed system for this reason, has selected two kinds of silicone oil of import and home-made among the present invention.Each component has good intermiscibility in this silicone oil and the material, can reduce abscess surface tension, generate evenly, the closed-cell foam of microporeization, material fluidity is good in the time of making foaming, the foam physical efficiency is full of each position in the die cavity equably, density is even.
Catalyst system is meant and uses several different catalyzer, Da Pei composition by a certain percentage, and the reactive behavior that must have when guaranteeing the urethane generation is to use any catalyzer reactive behavior that all is beyond one's reach.
The effect of catalyzer when hard polyurethane foam generates is very important, it not only directly has influence on the foamy physical performance index, and can adapt to seeing important to all types of production lines, the generation of polyurethane foam is the process of a complexity, its existing chemical reaction has physical change again, and existing crosslinking reaction has the venting reaction again; Existing heat-producing chemical reaction has the heat absorption physical process again, and everything all is to finish in the extremely short time, is controlled at perfect condition in order to make above-mentioned variation, just must regulate realization by catalysis system.
Because full water foamed poly-nitrogen ester hard bubbles and compares with original hard bubbling, in the body material system, significant change all takes place in plurality of raw materials such as whipping agent suds-stabilizing agent, original catalysis system is obviously inapplicable, filter out basic catalyst, amines catalyst, the agent of triazine catalytic organism, four kinds of catalyzer of tin class catalyzer among the present invention, determine best amount ranges, four kinds of catalyst consumption are respectively: 1～～2 part; 2～～3 parts; 0.2～～0.5 part; 0.05～～0.2 part (based on 100 parts of comprehensive polyethers) regulate four kinds of catalyst levels ratios, the dynamic technique parameter when can control foam generating is with the manufacturing technique requirent of the polyurethane products that satisfy different purposes.
Claims (4)
1. a rigid polyurethane water-blown foam material is made up of comprehensive polyether polyester polyvalent alcohol, silicone oil, integrated catalyst, water, isocyanic ester; Wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, silicone oil 1～～3 part, integrated catalyst 1～～5 part, water 1～～5 part, isocyanic ester 100～～150 part; Described comprehensive polyether polyester polyvalent alcohol is by introducing benzene ring structure in the molecular structure, having increased the forming as the polyether glycol of initiator by the benzoic anhydride polyester polyol of low, the excellent resistance to hydrolysis of intensity height, good toughness, thermal conductivity, excellent thermostability and primary hydroxyl feature and by sucrose glycerine, sorbyl alcohol of tool of the phenyl ring content in the polyurethane chain;
Described silicone oil be stable by the hydrolysis chemical property, can reduce the silicone oil of silicon-carbon structure that intermolecular surface tension plays a kind of polysiloxane-copolyether of stable and uniform abscess effect;
Described integrated catalyst by the stronger amino catalyzer of a spot of alkalescence, can be dissolved in water and general organic Chemical Composition, to provide balance to rise to send out reaction and gel reaction, low viscosity again be the catalyst for trimerization of triazines organism gentleness.
2. rigid polyurethane water-blown foam material according to claim 1, wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, silicone oil 1～～2 part, integrated catalyst 1～～2 part, water 3～～5 part, isocyanic ester 100～～130 part.
3. rigid polyurethane water-blown foam material according to claim 1, wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, silicone oil 1～～2 part, integrated catalyst 3～～5 part, water 3～～5 part, isocyanic ester 100～～130 part.
4. rigid polyurethane water-blown foam material according to claim 1, wherein: 100 parts of comprehensive polyether polyester polyvalent alcohols, silicone oil 1～～2 part, integrated catalyst 1～～5 part, water 1～～2 part, isocyanic ester 100～～120 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810035314A CN101544736A (en) | 2008-03-28 | 2008-03-28 | Rigid polyurethane water-blown foam material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810035314A CN101544736A (en) | 2008-03-28 | 2008-03-28 | Rigid polyurethane water-blown foam material |
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| CN101544736A true CN101544736A (en) | 2009-09-30 |
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| CN200810035314A Pending CN101544736A (en) | 2008-03-28 | 2008-03-28 | Rigid polyurethane water-blown foam material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093527A (en) * | 2010-12-30 | 2011-06-15 | 上海东大聚氨酯有限公司 | Composite polyether, polyurethane rigid foam as well as raw material composition and usage thereof |
| CN102399437A (en) * | 2010-09-11 | 2012-04-04 | 烟台彤祥化工科技有限公司 | DVD high-density PU plate special for automobile interior decoration |
| CN103012711A (en) * | 2011-09-21 | 2013-04-03 | 绍兴市恒丰聚氨酯实业有限公司 | Hard polyurethane molding foam negative pressure foaming raw material formula and hard polyurethane molding foam negative pressure foaming production method |
| CN103319997A (en) * | 2013-02-05 | 2013-09-25 | 扬中市天正合成材料研究中心 | High-fire-retardant water-blown polyurethane exterior-wall spray coating and preparation method thereof |
| CN104725587A (en) * | 2013-12-18 | 2015-06-24 | 上海东大聚氨酯有限公司 | Polyurethane thermal-insulation layer repair agent, applications and use method thereof |
| CN104987482A (en) * | 2015-08-06 | 2015-10-21 | 深圳市桑得特实业发展有限公司 | Full-water type flame-resistant rigid polyurethane foam, composite heat insulation board and preparation method therefor |
| CN110790884A (en) * | 2019-11-20 | 2020-02-14 | 上海东大聚氨酯有限公司 | Combined polyether for block foam, polyurethane raw material composition, polyurethane block foam and preparation method thereof |
| CN111269453A (en) * | 2020-01-20 | 2020-06-12 | 广州城市职业学院 | Polyurethane hard foam roof waterproof and heat-insulating process |
| CN113754877A (en) * | 2021-09-10 | 2021-12-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low thermal conductivity coefficient |
-
2008
- 2008-03-28 CN CN200810035314A patent/CN101544736A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399437A (en) * | 2010-09-11 | 2012-04-04 | 烟台彤祥化工科技有限公司 | DVD high-density PU plate special for automobile interior decoration |
| CN102399437B (en) * | 2010-09-11 | 2013-03-27 | 烟台正海汽车内饰件有限公司 | DVD high-density PU plate special for automobile interior decoration |
| CN102093527B (en) * | 2010-12-30 | 2012-07-25 | 上海东大聚氨酯有限公司 | Composite polyether, polyurethane rigid foam as well as raw material composition and usage thereof |
| CN102093527A (en) * | 2010-12-30 | 2011-06-15 | 上海东大聚氨酯有限公司 | Composite polyether, polyurethane rigid foam as well as raw material composition and usage thereof |
| CN103012711A (en) * | 2011-09-21 | 2013-04-03 | 绍兴市恒丰聚氨酯实业有限公司 | Hard polyurethane molding foam negative pressure foaming raw material formula and hard polyurethane molding foam negative pressure foaming production method |
| CN103319997B (en) * | 2013-02-05 | 2016-05-25 | 扬中市天正合成材料研究中心 | Full water foamed polyurethane exterior wall spray paint of a kind of high flame retardant and preparation method thereof |
| CN103319997A (en) * | 2013-02-05 | 2013-09-25 | 扬中市天正合成材料研究中心 | High-fire-retardant water-blown polyurethane exterior-wall spray coating and preparation method thereof |
| CN104725587A (en) * | 2013-12-18 | 2015-06-24 | 上海东大聚氨酯有限公司 | Polyurethane thermal-insulation layer repair agent, applications and use method thereof |
| CN104987482A (en) * | 2015-08-06 | 2015-10-21 | 深圳市桑得特实业发展有限公司 | Full-water type flame-resistant rigid polyurethane foam, composite heat insulation board and preparation method therefor |
| CN110790884A (en) * | 2019-11-20 | 2020-02-14 | 上海东大聚氨酯有限公司 | Combined polyether for block foam, polyurethane raw material composition, polyurethane block foam and preparation method thereof |
| CN111269453A (en) * | 2020-01-20 | 2020-06-12 | 广州城市职业学院 | Polyurethane hard foam roof waterproof and heat-insulating process |
| CN113754877A (en) * | 2021-09-10 | 2021-12-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low thermal conductivity coefficient |
| CN113754877B (en) * | 2021-09-10 | 2023-09-22 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low heat conductivity coefficient |
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Open date: 20090930 |