CN102643512B - Low-acid phenolic resin foam and preparation method thereof - Google Patents
Low-acid phenolic resin foam and preparation method thereof Download PDFInfo
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- CN102643512B CN102643512B CN201210143287.4A CN201210143287A CN102643512B CN 102643512 B CN102643512 B CN 102643512B CN 201210143287 A CN201210143287 A CN 201210143287A CN 102643512 B CN102643512 B CN 102643512B
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Abstract
The invention discloses a low-acid phenolic resin foam, which is characterized in that the foam is prepared by foaming and curing the following components, by mass: 100 parts of expandable phenolic resin, 2-8 parts of surface active agents, 2-6 parts of fillers, 4-10 parts of foaming agents and 8-15 parts of curing agents. The potential of hydrogen (pH) value of the foam is 4-6. The invention further discloses a preparation method of the low-acid phenolic resin foam. Due to the fact that the low-acid phenolic resin foam contains alkaline powder fillers coated by low-melting-point organic compounds, the coated alkaline powder fillers are released slowly in the curing process of the low-acid phenolic resin foam to perform neutral reaction with acid, thereby greatly reducing acidity in a foam body and then reducing corrosion of the phenolic resin foam on materials contacted with the phenolic resin foam. Additionally, due to the fact that the acidity reduction process and the curing process are performed simultaneously, thereby simplifying operation steps and avoiding problems in the prior art.
Description
Technical field
The invention belongs to phenolic resin foam and preparing technical field thereof, relate in particular to a kind of low acid phenolic resin foam and preparation method thereof.
Background technology
Existing sound insulation, lagging material mainly be take the foam materialss such as urethane, polystyrene as main, their shortcoming be inflammable, smog is large, once presence of fire, the people's personal safety of life and property will face great threat.And phenol formaldehyde foam is a kind of thermal insulation, fire retardant material of excellent performance, it is lightweight, rigidity is large, good stability of the dimension, chemical resistance are good, good heat resistance, difficultly fire, certainly put out, low smog, flame resistant penetrate, meet fiery without dropping, cheap, are desirable sound insulation, the lagging materials of industry such as building, petrochemical complex.
The advantages of resol, but shortcoming is obvious too, one of them very large shortcoming is exactly the curing because carrying out under acidic conditions of phenol formaldehyde foam, so just make phenol formaldehyde foam curing molding wherein remain a large amount of acid later, cause phenol formaldehyde foam itself to there is very strong corrodibility, be easy to the material that corrosion contacts with it, such as the aluminium foil overlaying on phenol formaldehyde foam, this has limited the widespread use of phenol formaldehyde foam undoubtedly.In order to address this problem, number of patent application is in CN200910015329.4, to disclose a kind of reduction foam materials corrodibility method.The method, when making solidifying agent with hydrochloric acid, is first removed volatile matter in moulding product with vacuum method, then uses NH
3neutralization is removed remaining acid or by product thermal treatment under 80-130 ℃ of condition, or adds neutralizing agent etc. at resin formula.Though these methods can reduce the acidity of product to a certain extent, can increase production link undoubtedly, make complex manufacturing, and increase cost.4122045 of US Patent No. disclose a kind of method of utilizing sodium tetraborate to reduce phenol formaldehyde foam acidity.Though the method claims by adding sodium tetraborate can reduce the acidity of phenol formaldehyde foam, does not provide the effect data after reduction.The inventor verifies it, finds the method deacidification effect not obvious, and the foam acidity of preparation is more intense (pH is 2-3) still.
Summary of the invention
The object of the invention is the problem existing for prior art, a kind of low acid phenolic resin foam is provided.Another object of the present invention is to provide the preparation method of above-mentioned low acid phenolic resin foam.
Low acid phenolic resin foam provided by the invention, it is characterized in that this foam by mass parts be by following component through foamed solidification gained:
And the pH value of this foam is 4～6.
In above foam, contained expandable phenolic resin both can adopt commercially availablely, also can adopt by the following method synthetic, preferably synthetic by the following method.The processing step of synthetic method is: the NaOH solution of 100 parts of phenol and 20 part 20% is joined in there-necked flask, while heat, stir; When temperature is elevated to after 80 ℃, then divide 4 batches to add 57 parts of solid formaldehydes, between every batch, interval is 15 minutes; Add rear reaction 3.0h, by gained resol be cooled to acetic acid, be neutralized to again after room temperature neutral.
In above foam, contained tensio-active agent is tween series, silicone oil is serial or alkylphenol polyoxyethylene series of surfactants in any.Preferred tween 80 or op-10 tensio-active agent.
In above foam, contained filler is that its particle diameter is 40～160 orders by low melting point organic compound and basic oxide or oxyhydroxide or the formed coating of carbonate powder.Wherein low melting point organic compound is any in solid paraffin, stearic acid or stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, volatile salt or bicarbonate of ammonia powder.Preferential oxidation magnesium and calcium oxide.The concrete preparation method of this filler is:
The low melting point organic compound that is first 1:1～3 by mass ratio and basic oxide or hydroxide powder join rapid stirring in high-speed mixer, along with stirring built-in temperature, constantly raise, low melting point organic compound gradually melting and be coated to basic oxide or oxyhydroxide on, cooling, then pulverized and sieved to such an extent that particle diameter is 40～160 object fillers.
Or the low melting point organic compound that is first 1:1～3 by mass ratio and basic oxide or hydroxide powder add in container, and container is inserted to limit heating edge in the water-bath of 80 ℃ and constantly stir, until low melting point organic compound gradually melting and be coated to basic oxide or oxyhydroxide on, cooling, then its grinding and sieving being obtained to particle diameter is 40～160 object fillers.
In above foam, contained whipping agent is any in Skellysolve A, hexane, pentamethylene or sherwood oil; Solidifying agent is at least one in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and phosphoric acid.
The preparation method of above-mentioned low acid phenolic resin foam provided by the invention, it is characterized in that the method is after first 4～10 parts of 100 parts of expandable phenolic resins, 2～8 parts, tensio-active agent, 2～6 parts of fillers, whipping agent being stirred, then add 8～15 parts, solidifying agent to stir again 1～3 minute, thereafter be heated to and at 60～80 ℃, foam and solidify 10～30 minutes, the umber of material used is mass parts.
In above method, expandable phenolic resin used both can adopt commercially availablely, also can adopt by the following method synthetic, preferably synthetic by the following method.The processing step of synthetic method is: the NaOH solution of 100 parts of phenol and 20 part 20% is joined in there-necked flask, while heat, stir; When temperature is elevated to after 80 ℃, then divide 4 batches to add 57 parts of solid formaldehydes, between every batch, interval is 15 minutes; Add rear reaction 3.0h, by gained resol be cooled to acetic acid, be neutralized to again after room temperature neutral.
In above method, tensio-active agent used is tween series, silicone oil is serial or alkylphenol polyoxyethylene series of surfactants in any.Preferred tween 80 or op-10 tensio-active agent.Whipping agent is any in Skellysolve A, hexane, pentamethylene or sherwood oil; Solidifying agent is at least one in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and phosphoric acid.
In above method, filler used is that its particle diameter is 40～160 orders by low melting point organic compound and basic oxide or oxyhydroxide or the formed coating of carbonate powder.Wherein low melting point organic compound is any in solid paraffin, stearic acid or stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, volatile salt or bicarbonate of ammonia powder.Preferential oxidation magnesium and calcium oxide.The concrete preparation method of this filler is:
The low melting point organic compound that is first 1:1～3 by mass ratio and basic oxide or hydroxide powder join rapid stirring in high-speed mixer, along with stirring built-in temperature, constantly raise, low melting point organic compound gradually melting and be coated to basic oxide or oxyhydroxide on, cooling, then pulverized and sieved to such an extent that particle diameter is 40～160 object fillers.
Or the low melting point organic compound that is first 1:1～3 by mass ratio and basic oxide or hydroxide powder add in container, and container is inserted to limit heating edge in the water-bath of 80 ℃ and constantly stir, until low melting point organic compound gradually melting and be coated to basic oxide or oxyhydroxide on, cooling, then its grinding and sieving being obtained to particle diameter is 40～160 object fillers.
The present invention compared with prior art, has following positively effect:
1, because phenolic resin foam provided by the invention contains a kind of by the coated alkaline powder filler of low melting point organic compound, it can discharge at leisure with acid and carry out neutralization reaction at curing process neutral and alkali powder filler, thereby the acid in the foams of its gained will reduce in a large number, this will reduce the corrodibility of phenolic resin foam to its contact material greatly.
2, the deacidification filler of selecting due to the present invention is all by some wide material sources, the compound of less expensive forms, in addition filler processing is also comparatively simple, and it can reduce the consumption of a part of resol after adding, thereby can not bring impact to the cost of phenolic resin foam.
3, because filler used in the inventive method only need to pass through watery fusion blend, pulverize and sieve processing, just can participate in directly and prepare phenolic resin foam together with other components, do not need other specific step, thereby technique is simple, easy handling.
4, owing to reducing acid process and solidification process in the inventive method, carry out simultaneously, thereby both can in the situation that not affecting resin solidification, significantly reduce the acidity of phenolic resin foam, and simplified again operation steps, the problem of having avoided prior art to exist.
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to the invention described above content and adjustment still belong to protection scope of the present invention.
What deserves to be explained is, following examples reaction mass umber used is mass parts.
Embodiment 1
The stearic acid and the magnesium oxide powder that by mass ratio, are first 1:1 are put into container, and in the water-bath of 80 ℃, limit heating edge constantly stirs, until stearic acid melting being coated on magnesium oxide powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 80 object fillers.
Preceding method synthetic 100 parts of expandable phenolic resins, 4 parts of op-10,5 part of 80 object magnesium oxide/stearic acid filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 4 parts of Skellysolve As are added and continue to be uniformly mixed, 12 parts of concentrated hydrochloric acids are added rapid stirring within 1 minute, to be about to mixture again and pour in preheated mould, the environment that is placed in 70 ℃ foams and solidifies 10 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Embodiment 2
The stearic acid and the magnesium oxide powder that by mass ratio, are first 1:1 are put into container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until stearic acid melting being coated on magnesium oxide powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 160 object fillers.
Preceding method synthetic 100 parts of expandable phenolic resins, 2 parts of op-10,2.5 part of 160 object magnesium oxide/stearic acid filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 6 parts of pentamethylene are added and continue to be uniformly mixed, 12 parts of concentrated hydrochloric acids are added rapid stirring within 2 minutes, to be about to mixture again and pour in preheated mould, the environment that is placed in 80 ℃ foams and solidifies 20 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Embodiment 3
The solid paraffin that is first 1:1 by mass ratio and nano-calcium carbonate calcium powder join in container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until solid paraffin melting being coated on nano-calcium carbonate calcium powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 40 object fillers.
Preceding method synthetic 100 parts of expandable phenolic resins, 8 parts of tween-80s, 6 part of 40 object solid paraffin/pearl filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 6 parts of pentamethylene are added and continue to be uniformly mixed, 8 parts of concentrated hydrochloric acids are added rapid stirring within 1 minute, to be about to mixture again and pour in preheated mould, the baking oven that is placed in 60 ℃ foams and solidifies 30 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Embodiment 4
The stearic acid that is first 1:1 by mass ratio and magnesium hydroxide powder join in container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until stearic acid melting being coated on magnesium hydroxide powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 80 object fillers.
100 parts of synthetic expandable phenolic resins of preceding method, 5 parts of polyether modified siloxanes (BD-3086), 4 part of 80 object stearic acid and magnesium hydroxide filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 6 parts of pentamethylene are added and continue to be uniformly mixed, the mixing acid of 15 parts of methylsulphonic acids and phosphoric acid (5: 1) is added rapid stirring within 3 minutes, to be about to mixture again and pour in preheated mould, the baking oven that is placed in 70 ℃ foams and solidifies 30 minutes.
With wide pH value test paper, dip the pH value 4 of a small amount of water test foam.
Embodiment 5
The stearic acid that is first 1:1.5 by mass ratio and lime powder join in container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until stearic acid melting being coated on lime powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 80 object fillers.
100 parts of synthetic expandable phenolic resins of preceding method, 4 parts of tween-80s, 5 part of 80 object stearic acid and calcium oxide filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 10 parts of sherwood oils are added and continue to be uniformly mixed, 12 parts of concentrated hydrochloric acids are added rapid stirring within 1 minute, to be about to mixture again and pour in preheated mould, the baking oven that is placed in 75 ℃ foams and solidifies 10 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Embodiment 6
The stearyl alcohol that is first 1:3 by mass ratio and magnesium oxide powder join in container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until stearyl alcohol melting being coated on magnesium oxide powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 40 object fillers.
100 parts of synthetic expandable phenolic resins of preceding method, 4 parts of tween-80s, 2 part of 40 object stearyl alcohol and magnesium hydroxide filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 6 parts of Skellysolve As are added and continue to be uniformly mixed, 10 parts of concentrated hydrochloric acids are added rapid stirring within 2 minutes, to be about to mixture again and pour in preheated mould, the baking oven that is placed in 60 ℃ foams and solidifies 25 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Embodiment 7
The solid paraffin that is first 1:1 by mass ratio and magnesium oxide powder join in container, in the water-bath of 80 ℃, limit heating edge constantly stirs, until solid paraffin melting being coated on magnesium oxide powder gradually, cooling, then its grinding and sieving being obtained to particle diameter is 40 object fillers.
100 parts of synthetic expandable phenolic resins of preceding method, 4 parts of tween-80s, 5 part of 40 object solid paraffin and magnesium hydroxide filler will be pressed, after adding at normal temperatures and being uniformly mixed in homogenizer, 6 parts of Skellysolve As are added and continue to be uniformly mixed, 12 parts of concentrated hydrochloric acids are added rapid stirring within 1 minute, to be about to mixture again and pour in preheated mould, the baking oven that is placed in 60 ℃ foams and solidifies 30 minutes.
With wide pH value test paper, dip the pH value 5～6 of a small amount of water test foam.
Claims (8)
1. a low acid phenolic resin foam, it is characterized in that this foam by mass parts be by following component through foamed solidification gained:
And the pH value of this foam is 4～6, wherein contained filler is that its particle diameter is 40～160 orders by low melting point organic compound and basic oxide or oxyhydroxide or the formed coating of carbonate powder.
2. low acid phenolic resin foam according to claim 1, it is characterized in that tensio-active agent contained in this foam is tween series, silicone oil is serial or alkylphenol polyoxyethylene series of surfactants in any.
3. low acid phenolic resin foam according to claim 1 and 2, is characterized in that low melting point organic compound contained in this foam is any in solid paraffin, stearic acid or stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, volatile salt or bicarbonate of ammonia powder.
4. low acid phenolic resin foam according to claim 1 and 2, is characterized in that whipping agent contained in this foam is any in Skellysolve A, hexane, pentamethylene or sherwood oil; Solidifying agent is at least one in methylsulphonic acid, tosic acid, oxalic acid, formic acid, concentrated hydrochloric acid and phosphoric acid.
5. the preparation method of a low acid phenolic resin foam claimed in claim 1, it is characterized in that the method is first by 100 parts of expandable phenolic resins, 2～8 parts, tensio-active agent, 2～6 parts of fillers, after 4～10 parts of whipping agents stir, then add 8～15 parts, solidifying agent to stir again 1～3 minute, be heated to and at 60～80 ℃, foam and solidify 10～30 minutes thereafter, the umber of material used is mass parts, wherein filler used is by low melting point organic compound and basic oxide or oxyhydroxide or the formed coating of carbonate powder, its particle diameter is 40～160 orders.
6. the preparation method of low acid phenolic resin foam according to claim 5, it is characterized in that tensio-active agent used in the method is tween series, silicone oil is serial or alkylphenol polyoxyethylene series of surfactants in any.
7. according to the preparation method of the low acid phenolic resin foam described in claim 5 or 6, it is characterized in that low melting point organic compound used in the method is any in solid paraffin, stearic acid or stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium carbonate, volatile salt or bicarbonate of ammonia powder.
8. according to the preparation method of the low acid phenolic resin foam described in claim 5 or 6, it is characterized in that whipping agent in the method is any in Skellysolve A, hexane, pentamethylene or sherwood oil; Solidifying agent is at least one in methylsulphonic acid, tosic acid, oxalic acid, formic acid, concentrated hydrochloric acid and phosphoric acid.
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| CN103194003B (en) * | 2013-04-02 | 2014-07-16 | 中国科学院化学研究所 | Low-acidity phenolic foam and preparation method thereof |
| CN104559044A (en) * | 2014-12-30 | 2015-04-29 | 陕西师范大学 | Non-corrosive, low-density and high-strength phenolic foam |
| CN113388224A (en) * | 2021-06-28 | 2021-09-14 | 湖北汽车工业学院 | Phenolic resin composite board and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563131A (en) * | 2004-04-12 | 2005-01-12 | 厦门高特高新材料有限公司 | Phenol-formaldehyde resin modified, preparation method, and application in preparing pheol formaldehyde foam |
| CN101305035A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101880365A (en) * | 2010-07-30 | 2010-11-10 | 山东圣泉化工股份有限公司 | Foaming phenolic resin preparation method and phenolic resin foam |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563131A (en) * | 2004-04-12 | 2005-01-12 | 厦门高特高新材料有限公司 | Phenol-formaldehyde resin modified, preparation method, and application in preparing pheol formaldehyde foam |
| CN101305035A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101880365A (en) * | 2010-07-30 | 2010-11-10 | 山东圣泉化工股份有限公司 | Foaming phenolic resin preparation method and phenolic resin foam |
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