CN103087345A - Preparation method of phenolic foam - Google Patents
Preparation method of phenolic foam Download PDFInfo
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Abstract
The invention provides a preparation method of phenolic foam. The preparation method comprises the following steps of: mixing 90-100 parts by weight of liquid A-stage phenolic resin, 4-15 parts by weight of a foaming agent, 2-6 parts by weight of an emulsifier, 2-8 parts by weight of a toughening agent and 10-30 parts by weight of an organic acid curing agent, foaming and curing so as to obtain a mixture product; and carrying out aftertreatment on the mixture product so as to obtain the phenolic foam. In the process of preparing the phenolic foam, on one hand, as the curing speed of the organic acid curing agent is slow, the heat is slowly released in the condensation polymerization process when the phenolic foam is catalyzed, the foaming agent slowly functions, and less steam is generated, so that foam pores have better toughness, and on the other hand, due to the constant temperature and constant humidity aftertreatment condition, the foam pores of the phenolic foam are complete and have better strength, and the problem that the moisture is lost too rapidly is avoided, so that the phenolic foam has better toughness and is more stable in property along with the change of environment.
Description
Technical field
The present invention relates to the lagging material technical field, relate in particular to the preparation method of phenol formaldehyde foam.
Background technology
The main component of phenolic foamed plastics is resol, formed by petrochemical industry based raw material phenol and formaldehyde addition polycondensation, it is a class novel foamed plastic that grew up in recent years, so that its flame resistivity is good, the amount of being fuming is low, good heat preservation performance, stable performance, adiabatic heat insulation, sound insulation, easy-formation processing and weather resistance and rank the prostatitis of all porous plastics preferably, be called as " the emerging lagging material of the third generation ".Because phenolic foamed plastics has heat-insulating property preferably, and be widely used in heat-insulating heat-preserving material, be mainly used in the industries such as building, petrochemical complex, electric, instrument.
External thermal insulation system is the energy-saving technological measure that present China construction wall is most widely used in energy-conservation, and the whole nation is universal on a large scale, has made huge contribution aspect building energy conservation.Phenolic foamed plastics is as a kind of heat insulating material, and by the market recognition and acceptance, so phenolic foam heat insulation plate is widely used in exterior wall heat-preserving system.In field of heat insulating materials, to compare with other lagging materials such as urethane, polyphenyl, phenol formaldehyde foam has good thermal insulation, is also that other material is incomparable aspect fire-retardant simultaneously.But the disadvantage of phenol formaldehyde foam is poor toughness, easily falls slag, and unstable properties, thereby has limited to a certain extent the development of phenol formaldehyde foam.
Prior art adds inorganic acid catalyst to promote curing and the foaming of phenol formaldehyde foam in the process of preparation phenol formaldehyde foam, mineral acid solidify short, foaming inductive phase rapidly, solidify thoroughly, difficult generation is collapsed and is steeped and the unsettled defective of size, but because foaming is rapid, formed abscess has the phenomenons such as pinprick and cracking; And after curing and foaming, the phenol formaldehyde foam abscess toughness of formation is not enough, can make the performance reduction of phenol formaldehyde foam sheet material along with the variation of the conditions such as envrionment temperature and humidity.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of toughness better and the phenol formaldehyde foam of stable performance and preparation method thereof.
In view of this, the invention provides a kind of preparation method of phenol formaldehyde foam, comprise the following steps:
The liquid A step phenolic resin of 90 ~ 100 weight parts, the whipping agent of 4 ~ 15 weight parts, the emulsifying agent of 2 ~ 6 weight parts, the toughner of 2 ~ 8 weight parts are mixed with the organic acid solidifying agent of 10 ~ 30 weight parts, obtain mix products after foaming and curing;
Described mix products is carried out aftertreatment under the condition of fixed temperature and humidity, obtain phenol formaldehyde foam.
Preferably, described liquid phenol-formaldehyde resin is 7000 ~ 20000mpa.s the viscosity of 25 ℃, and moisture is 3% ~ 8%.
Preferably, described whipping agent is one or more in methylene dichloride, Skellysolve A, iso-pentane, normal hexane, isopropyl chloride, pentamethylene and carbonic acid gas.
Preferably, described emulsifying agent is one or more in polydimethylsiloxane, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan stearate and castor oil polyoxyethylene ether.
Preferably, described organic acid solidifying agent is one or more in tosic acid, acid dimethyl and sulfocarbolic acid.
Preferably, described toughner is one or more in ethylene glycol, polyoxyethylene glycol, the pure and mild polyvinylpyrrolidone of polyester polyols.
Preferably, the temperature of described curing is 60 ~ 80 ℃, and the time of described curing is 10 ~ 15min.
Preferably, the temperature of described aftertreatment is 40 ℃ ~ 60 ℃, and the humidity of described aftertreatment is 30% ~ 90%.
Preferably, the temperature of described aftertreatment is 50 ℃, and the humidity of described aftertreatment is 50% ~ 70%.
The invention provides a kind of preparation method of phenol formaldehyde foam, comprise the following steps: the liquid A step phenolic resin of 90 ~ 100 weight parts, the whipping agent of 4 ~ 15 weight parts, the emulsifying agent of 2 ~ 6 weight parts, the toughner of 2 ~ 8 weight parts are mixed with the organic acid solidifying agent of 10 ~ 30 weight parts, obtain mix products after foaming and curing; Described mix products is carried out aftertreatment, obtain phenol formaldehyde foam.The present invention in the process of preparation phenol formaldehyde foam, because organic acid solidifying agent curing speed is slower, in the catalysed phenolic resin polycondensation process heat release slow, whipping agent plays a role slowly, water vapor generation less, the toughness of abscess is better; On the other hand, due to the post-treatment condition of fixed temperature and humidity, make the abscess of phenol formaldehyde foam complete and have intensity preferably, avoided the too fast problem of moisture loss, thereby made phenol formaldehyde foam have toughness preferably, and along with the environmental evolution performance is more stable.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The present invention also provides the preparation method of phenol formaldehyde foam, comprises the following steps:
The liquid A step phenolic resin of 90 ~ 100 weight parts, the whipping agent of 4 ~ 15 weight parts, the emulsifying agent of 2 ~ 6 weight parts, the toughner of 2 ~ 8 weight parts are mixed with the organic acid solidifying agent of 10 ~ 30 weight parts, obtain mix products after foaming and curing;
Described mix products is carried out aftertreatment under the condition of fixed temperature and humidity, obtain phenol formaldehyde foam.
According to the present invention, described liquid A step phenolic resin is the method preparation of the disclosed resol of Chinese patent of CN102199266A according to publication number, can prepare by the following method:
Melting phenol, alkaline catalysts are mixed with alkali lignin, be warming up to 170 ℃ ~ 300 ℃ back flow reaction, described alkali lignin is to have farm crop to extract the alkali lignin that obtains; Add formaldehyde in reaction solution, continue back flow reaction after being cooled to 60 ℃ ~ 90 ℃, obtain liquid A step phenolic resin.
Described alkaline catalysts is preferably one or more in sodium hydroxide, hydroxide agent and ammoniacal liquor.The mass ratio of described phenol and alkali lignin is preferably 100:(10 ~ 50), 100:(20 ~ 40 more preferably).The mass ratio of described phenol and described alkaline catalysts is 100:(1 ~ 10), 100:(2 ~ 8 more preferably); The time that described melting phenol and alkali lignin carry out back flow reaction is preferably 30min ~ 150min, more preferably 50min ~ 120min
Described liquid A step phenolic resin can also prepare by the following method:
Phenol, alkaline catalysts and formaldehyde are reacted under 60 ℃ ~ 90 ℃; Add alkali lignin in reaction solution, obtain resol after stirring, the alkali lignin of described resol for being obtained by extraction in farm crop.
Described alkaline catalysts is preferably one or more in sodium hydroxide, hydroxide agent and ammoniacal liquor.The mass ratio of described phenol and described formaldehyde is preferably 100:100 ~ 170, more preferably 100:104 ~ 168; The mass ratio of described phenol and described alkaline catalysts is preferably 100:(1 ~ 10), 100:(2 ~ 8 more preferably).The time that described formaldehyde and described phenol react is preferably 90min ~ 180min, more preferably 100min ~ 160min.
Liquid A step phenolic resin of the present invention is preparation according to the method described above preferably, and functional group is more due to alkali lignin, and resol is carried out accessing activity resol preferably after modification.Described liquid A step phenolic resin is preferably high viscosity low moisture resol, and its viscosity in the time of 25 ℃ is preferably 7000 ~ 20000mpa.s, and moisture is 3% ~ 8%.The content of described liquid A step phenolic resin is 90 ~ 100 weight parts, more preferably 92 ~ 98 weight parts.
According to the present invention, also contain the organic acid solidifying agent in described phenol formaldehyde foam, described organic acid solidifying agent curing speed is slow, heat release is slow in the catalysed phenolic resin polycondensation process, whipping agent plays a role slowly, and the bubble of water vapour generation is less, makes the abscess good toughness; Organic group in the organic acid solidifying agent is present in and has toughness reinforcing effect in phenol formaldehyde foam on the other hand.Described organic acid solidifying agent is preferably one or more in tosic acid, acid dimethyl and sulfocarbolic acid, more preferably tosic acid and sulfocarbolic acid.The content of described organic acid solidifying agent is 10 ~ 30 weight parts, more preferably 15 ~ 20 weight parts.
Also contain the whipping agent that can form pore in described phenol formaldehyde foam, described whipping agent is preferably one or more in methylene dichloride, Skellysolve A, iso-pentane, normal hexane, isopropyl chloride, pentamethylene and carbonic acid gas, and wherein carbonic acid gas is preferably introduced by high-tension unit.Described whipping agent is pentamethylene and iso-pentane more preferably.The content of described whipping agent is preferably 4 ~ 15 weight parts, is preferably 8 ~ 12 weight parts.
According to the present invention, also contain emulsifying agent in described phenol formaldehyde foam, described emulsifying agent can promote the dispersiveness of each component in phenol formaldehyde foam.Described emulsifying agent is preferably one or more in polydimethylsiloxane, polyoxyethylene, polyoxyethylene-sorbitan mono-oleate (tween 80), polyoxyethylene sorbitan stearate (polysorbate60), castor oil polyoxyethylene ether and silicone oil DC193.Wherein silicone oil DC193 is the water-soluble silicon oil that organo-siloxane and allyl polyether reaction form.Described emulsifying agent is silicone oil DC193 more preferably.The content of described emulsifying agent is 2 ~ 6 weight parts, is preferably 3 ~ 5 weight parts.
In order further to improve the toughness of phenol formaldehyde foam, also contain toughner in the raw material of described phenol formaldehyde foam, described toughner is preferably one or more in ethylene glycol, polyoxyethylene glycol, polyester polyol, glycol ether and polyvinylpyrrolidone.The content of described toughner is 2 ~ 8 weight parts, is preferably 3 ~ 5 weight parts.
According to the present invention, in order to make phenol formaldehyde foam have stability preferably, the preparation process of described mix products is preparation by the following method preferably: with the liquid A step phenolic resin of 90 ~ 100 weight parts, the whipping agent of 4 ~ 15 weight parts, the emulsifying agent of 2 ~ 6 weight parts and the toughner of 2 ~ 8 weight parts, turn with 1000 ~ 1500 and stirred 30 ~ 40 seconds, temperature control to 15 ℃ ~ 20 ℃, then add the organic acid solidifying agent of 10 ~ 30 weight parts, stirred 20 ~ 30 seconds, foaming and curing tentatively obtain phenol formaldehyde foam.The temperature of described curing is preferably 60 ~ 80 ℃, and the time of described curing is 10 ~ 15min.
The phenol formaldehyde foam that then will tentatively obtain carries out aftertreatment in the environment of fixed temperature and humidity, make the slaking of powder foam; The temperature of described aftertreatment is preferably 40 ~ 60 ℃, and more preferably 50 ℃, humidity is preferably 30% ~ 90%, and more preferably 50% ~ 70%.Under the condition of fixed temperature and humidity, the abscess intensity enhancing of phenol formaldehyde foam sheet material, the moisture of polycondensation can not cause abscess the phenomenon of pin hole or crackle to occur rapidly because the variation of humidity is lost.To carry out the phenol formaldehyde foam of aftertreatment under working conditions, because the abscess intensity of sheet material improves, abscess is more complete, and the dimensional stability of sheet material is better, and physical and chemical index is also very stable.
The invention provides a kind of preparation method of phenol formaldehyde foam, in the process of preparation phenol formaldehyde foam, because the organic acid solidifying agent solidifies slower, heat release is slow in the catalysed phenolic resin polycondensation process, whipping agent plays a role slowly, and it is less that water vapor produces, and the toughness of abscess is better, the existence of organic acid organic group, have toughness reinforcing effect simultaneously; On the other hand, due to the post-treatment condition of fixed temperature and humidity, make the abscess of phenol formaldehyde foam complete and intensity is arranged, avoided the too fast problem of moisture loss, thereby made phenol formaldehyde foam have toughness preferably, and stable performance.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of phenol formaldehyde foam provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Resol used herein is the JQPM series plastics that Jinan, Shandong Province holy well chemical inc is produced, and its leading indicator sees Table 1, and table 1 is the performance index of the resol of embodiment of the present invention employing.Other raw materials in embodiment are the commercially available prod.
Table 1 liquid A step phenolic resin performance index
Embodiment 1
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and polyvinylpyrrolidone (PVPK15) that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1 and glycol ether mixed solution 5 weight parts and emulsifying agent DC1935 weight part, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, do not do aftertreatment.
Embodiment 2
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify after 10 minutes and take out, and continue slaking 40h under 50 ℃.
Embodiment 3
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 50 ℃/30% humidity.
Embodiment 4
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 50 ℃/50% humidity.
Embodiment 5
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 50 ℃/70% humidity.
Embodiment 6
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 50 ℃/90% humidity.
Embodiment 7
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 60 ℃/70% humidity.
Embodiment 8
In the above-mentioned resole of 100 weight parts, adding mass ratio is the pentamethylene of 6:4 and PVPK15 and glycol ether mixed solution 5 weight parts and the emulsifying agent DC1935 weight part that iso-pentane mixed solution 8.5 weight parts, mass ratio are 3:1, turn with 1000 ~ 1500 and stirred 30 seconds, temperature control to 15 ℃, then pour tosic acid that mass ratio is 7:3 and mixed solution 20 weight parts of sulfocarbolic acid into, and continue to stir 20 seconds, pour at last in the 30cm*30cm*4cm mould, 60 ℃ solidify taking-up after 10 minutes, continue slaking 40h under 40 ℃/70% humidity.
Table 1JQPM series index
The foam of table 2 embodiment 1 ~ 7 preparation detects index
The foam of continued 2 embodiment 1 ~ 7 preparations detects index
From above-mentioned data as can be known: aftertreatment plays very important effect to foaming properties stable.And select a suitable post-processing temperature and humidity very crucial: if excess Temperature (embodiment 7) can cause foam inside moisture sharply to scatter and disappear, and then cause holes, rate of closed hole to descend; Temperature too low (embodiment 8), outside temperature are not enough to support the power that the deformation of foam inside abscess produces, and then cause the bubble phenomenon of collapsing, and rate of closed hole is descended; If humidity too low (embodiment 2,3) can cause the interior moisture content of foam so that speed is lost faster, easily cause the perforation phenomenon; Humidity too high (embodiment 6) can make foam excessively absorb water, and causes the mechanical propertys such as compression and drawing to descend.Can reach a conclusion from these several groups experiments: in 50 ℃/50% ~ 70%(temperature/humidity) descend the phenol formaldehyde foam of aftertreatment can have more stable performance, rate of closed hole is steady in a long-term, and thermal conductivity is good.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. the preparation method of a phenol formaldehyde foam comprises the following steps:
The liquid A step phenolic resin of 90 ~ 100 weight parts, the whipping agent of 4 ~ 15 weight parts, the emulsifying agent of 2 ~ 6 weight parts, the toughner of 2 ~ 8 weight parts are mixed with the organic acid solidifying agent of 10 ~ 30 weight parts, obtain mix products after foaming and curing;
Described mix products is carried out aftertreatment under the condition of fixed temperature and humidity, obtain phenol formaldehyde foam.
2. preparation method according to claim 1, is characterized in that, described liquid phenol-formaldehyde resin is 7000 ~ 20000mpa.s the viscosity of 25 ℃, and moisture is 3% ~ 8%.
3. preparation method according to claim 1, is characterized in that, described whipping agent is one or more in methylene dichloride, Skellysolve A, iso-pentane, normal hexane, isopropyl chloride, pentamethylene and carbonic acid gas.
4. preparation method according to claim 1, is characterized in that, described emulsifying agent is one or more in polydimethylsiloxane, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan stearate and castor oil polyoxyethylene ether.
5. preparation method according to claim 1, is characterized in that, described organic acid solidifying agent is one or more in tosic acid, acid dimethyl and sulfocarbolic acid.
6. preparation method according to claim 1, is characterized in that, described toughner is one or more in ethylene glycol, polyoxyethylene glycol, the pure and mild polyvinylpyrrolidone of polyester polyols.
7. preparation method according to claim 1, is characterized in that, the temperature of described curing is 60 ~ 80 ℃, and the time of described curing is 10 ~ 15min.
8. preparation method according to claim 1, is characterized in that, the temperature of described aftertreatment is 40 ℃ ~ 60 ℃, and the humidity of described aftertreatment is 30% ~ 90%.
9. preparation method according to claim 8, is characterized in that, the temperature of described aftertreatment is 50 ℃, and the humidity of described aftertreatment is 50% ~ 70%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104307428A (en) * | 2014-09-10 | 2015-01-28 | 山东圣泉新材料股份有限公司 | Surfactant, application thereof and phenolic resin foam board using surfactant |
| CN104370569A (en) * | 2013-11-22 | 2015-02-25 | 江深 | High and low temperature composite heat insulation foaming material |
| CN106009490A (en) * | 2016-07-08 | 2016-10-12 | 江南大学 | Heterogeneous nucleating agent toughening-modified phenolic resin foam and preparation method thereof |
| CN106280231A (en) * | 2016-08-12 | 2017-01-04 | 河南科技大学 | A kind of sports equipment toughening modifying phenolic foam and preparation method thereof |
| CN109929216A (en) * | 2019-04-15 | 2019-06-25 | 天津鹏安数讯消防设备工程有限公司 | A kind of resol low-temp foaming preparation process |
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| CN102199266A (en) * | 2011-04-02 | 2011-09-28 | 山东圣泉化工股份有限公司 | Method for preparing phenolic resin and phenolic resin foaming body |
| CN102838770A (en) * | 2012-09-10 | 2012-12-26 | 山东圣泉化工股份有限公司 | Preparation method of phenolic foam boards |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199266A (en) * | 2011-04-02 | 2011-09-28 | 山东圣泉化工股份有限公司 | Method for preparing phenolic resin and phenolic resin foaming body |
| CN102838770A (en) * | 2012-09-10 | 2012-12-26 | 山东圣泉化工股份有限公司 | Preparation method of phenolic foam boards |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370569A (en) * | 2013-11-22 | 2015-02-25 | 江深 | High and low temperature composite heat insulation foaming material |
| CN104307428A (en) * | 2014-09-10 | 2015-01-28 | 山东圣泉新材料股份有限公司 | Surfactant, application thereof and phenolic resin foam board using surfactant |
| CN104307428B (en) * | 2014-09-10 | 2016-03-16 | 山东圣泉新材料股份有限公司 | Surfactant, its purposes and use its phenolic resin foamed board |
| CN106009490A (en) * | 2016-07-08 | 2016-10-12 | 江南大学 | Heterogeneous nucleating agent toughening-modified phenolic resin foam and preparation method thereof |
| CN106009490B (en) * | 2016-07-08 | 2018-06-19 | 江南大学 | A kind of phenolic resin foam of heterogeneous nucleation agent toughening modifying and preparation method thereof |
| CN106280231A (en) * | 2016-08-12 | 2017-01-04 | 河南科技大学 | A kind of sports equipment toughening modifying phenolic foam and preparation method thereof |
| CN106280231B (en) * | 2016-08-12 | 2018-05-01 | 河南科技大学 | A kind of sports equipment toughening modifying phenolic foam and preparation method thereof |
| CN109929216A (en) * | 2019-04-15 | 2019-06-25 | 天津鹏安数讯消防设备工程有限公司 | A kind of resol low-temp foaming preparation process |
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