CN102643512A - 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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- CN102643512A CN102643512A CN2012101432874A CN201210143287A CN102643512A CN 102643512 A CN102643512 A CN 102643512A CN 2012101432874 A CN2012101432874 A CN 2012101432874A CN 201210143287 A CN201210143287 A CN 201210143287A CN 102643512 A CN102643512 A CN 102643512A
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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 are main with foam materialss such as urethane, PS mainly, their shortcoming be inflammable, smog is big, in case presence of fire, the people's personal safety of life and property will face very big threat.And phenol formaldehyde foam is a kind of thermal insulation, fire retardant material of excellent performance; It is in light weight, rigidity is big, dimensional stability is good, chemical resistance is good, good heat resistance, difficult fire, put out certainly, low smog, flame resistant penetrates, meets fiery no dropping, cheap, is the sound insulation of industry ideal, lagging materials such as building, petrochemical complex.
The advantage of resol is outstanding; But shortcoming is obvious too, one of them very big shortcoming be exactly the curing of phenol formaldehyde foam because of under acidic conditions, carrying out, so just making that the phenol formaldehyde foam curing molding is wherein residual later on has a large amount of acid; Cause phenol formaldehyde foam itself to have very strong corrodibility; Be easy to corrode the material that contacts with it, such as the aluminium foil that overlays on the 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 to disclose a kind of reduction foam materials corrodibility method among the CN200910015329.4.This method is at first removed volatile matter in the moulding product with vacuum method when making solidifying agent with hydrochloric acid, use NH again
3Neutralization is removed remaining acid or with 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 manufacturingization, and increase cost.4122045 of U.S. Pat disclose a kind of sodium tetraborate that utilizes and have reduced phenol formaldehyde foam tart method.Though this method is claimed can reduce the acidity of phenol formaldehyde foam through adding sodium tetraborate, do not provide the effect data after the reduction.The inventor verifies it, finds that sour effect and not obvious, the foam acidity of preparation still more intense (pH is 2-3) falls in this method.
Summary of the invention
The objective of the invention is problem, a kind of low acid phenolic resin foam is provided to the prior art existence.Another object of the present invention provides above-mentioned low acidic phenol urea formaldehyde foamy preparation method.
Low acid phenolic resin foam provided by the invention, it is characterized in that this foam by mass parts be by following component through the foamed solidification gained:
And this foamy pH value is 4～6.
Contained expandable phenolic resin both can adopt commercially availablely in the above foam, also can adopt by following method synthetic, preferably by following method synthetic.The process step of compound method is: the NaOH solution of 100 parts of phenol and 20 part 20% is joined in the there-necked flask, stir while heat; After temperature is elevated to 80 ℃, divide 4 batches to add 57 parts of solid formaldehydes again, the interval is 15 minutes between every batch; Add afterreaction 3.0h, gained resol is cooled to after the room temperature is neutralized to neutral getting final product with acetic acid again.
Contained tensio-active agent is a tween series in the above foam, silicone oil is serial or the TX10 series of surfactants in any.Preferred tween 80 or op-10 tensio-active agent.
Contained filler is that its particle diameter is 40～160 orders by lower melting point organic cpds and basic oxide or oxyhydroxide or the formed coating of carbonate powder in the above foam.Wherein the lower melting point organic cpds is any in solid paraffin, Triple Pressed Stearic Acid or the stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in Natural manganese dioxide, Marinco H, magnesiumcarbonate, quicklime, lime carbonate, volatile salt or the bicarbonate of ammonia powder.Preferred Natural manganese dioxide and quicklime.The concrete preparation method of this filler is:
Be that the lower melting point organic cpds of 1:1～3 joins stirring fast in the high-speed mixer with basic oxide or hydroxide powder earlier with mass ratio; Constantly raise along with stirring built-in temperature; The lower melting point organic cpds gradually fusion and be coated to basic oxide or oxyhydroxide on; Cooling, then its crushing screening being got particle diameter is 40～160 purpose fillers.
Be in lower melting point organic cpds and the basic oxide or the hydroxide powder adding container of 1:1～3 earlier perhaps with mass ratio; And container inserted the limit heating edge constantly stirs in 80 ℃ the water-bath; Up to the lower melting point organic cpds gradually fusion and be coated to basic oxide or oxyhydroxide on; Cooling, then its grinding and sieving being got particle diameter is 40～160 purpose fillers.
Contained whipping agent is any in Skellysolve A, hexane, pentamethylene or the sherwood oil in the above foam; Solidifying agent is at least a in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and the phosphoric acid.
Above-mentioned low acidic phenol urea formaldehyde foamy preparation method provided by the invention; It is characterized in that this method is after earlier 4～10 parts of 100 parts of expandable phenolic resins, 2～8 parts in tensio-active agent, 2～6 parts of fillers, whipping agent being stirred; Added 8～15 parts of restir of solidifying agent then 1～3 minute; Thereafter being heated to foams under 60～80 ℃ and solidify got final product in 10～30 minutes, and the umber of used material is mass parts.
Used expandable phenolic resin both can adopt commercially availablely in the above method, also can adopt by following method synthetic, preferably by following method synthetic.The process step of compound method is: the NaOH solution of 100 parts of phenol and 20 part 20% is joined in the there-necked flask, stir while heat; After temperature is elevated to 80 ℃, divide 4 batches to add 57 parts of solid formaldehydes again, the interval is 15 minutes between every batch; Add afterreaction 3.0h, gained resol is cooled to after the room temperature is neutralized to neutral getting final product with acetic acid again.
Used tensio-active agent is a tween series in the above method, silicone oil is serial or the TX10 series of surfactants in any.Preferred tween 80 or op-10 tensio-active agent.Whipping agent is any in Skellysolve A, hexane, pentamethylene or the sherwood oil; Solidifying agent is at least a in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and the phosphoric acid.
Used filler is that its particle diameter is 40～160 orders by lower melting point organic cpds and basic oxide or oxyhydroxide or the formed coating of carbonate powder in the above method.Wherein the lower melting point organic cpds is any in solid paraffin, Triple Pressed Stearic Acid or the stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in Natural manganese dioxide, Marinco H, magnesiumcarbonate, quicklime, lime carbonate, volatile salt or the bicarbonate of ammonia powder.Preferred Natural manganese dioxide and quicklime.The concrete preparation method of this filler is:
Be that the lower melting point organic cpds of 1:1～3 joins stirring fast in the high-speed mixer with basic oxide or hydroxide powder earlier with mass ratio; Constantly raise along with stirring built-in temperature; The lower melting point organic cpds gradually fusion and be coated to basic oxide or oxyhydroxide on; Cooling, then its crushing screening being got particle diameter is 40～160 purpose fillers.
Be in lower melting point organic cpds and the basic oxide or the hydroxide powder adding container of 1:1～3 earlier perhaps with mass ratio; And container inserted the limit heating edge constantly stirs in 80 ℃ the water-bath; Up to the lower melting point organic cpds gradually fusion and be coated to basic oxide or oxyhydroxide on; Cooling, then its grinding and sieving being got particle diameter is 40～160 purpose 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 lower melting point organic cpds coating alkaline powder filler; It can discharge at leisure with acid at solidified process neutral and alkali powder filler and carry out neutralization reaction; Thereby the acid in the foams of its gained will reduce in a large number, and this will reduce the corrodibility of phenolic resin foam to its contact material greatly.
2, because the sour filler that falls that the present invention selects for use all is by some wide material sources; The compound of less expensive is formed; The filler processing is also comparatively simple in addition, and it can reduce the consumption of a part of resol after adding, thereby can not bring influence to the cost of phenolic resin foam.
3, owing to used filler in the inventive method only need pass through the watery fusion blend, crushing screening is handled, and just can participate in the preparation phenolic resin foam together directly with other components, do not need other specific step, thereby technology is simple, easy handling.
4, owing to acid process of reduction and solidification process in the inventive method carry out simultaneously; Thereby both can under the situation that does not influence resin solidification, significantly reduce the acidity of phenolic resin foam; And simplified operation steps again, the problem of having avoided prior art to exist.
Embodiment
Provide embodiment below the present invention is done more detailed explanation; It is important to point out that following examples can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
What be worth explanation is that the used umber of following examples reaction mass is mass parts.
Embodiment 1
Be that Triple Pressed Stearic Acid and the magnesium oxide powder of 1:1 put into container with mass ratio earlier, the limit heating edge constantly stirs in 80 ℃ water-bath, up to Triple Pressed Stearic Acid fusion and being coated on the magnesium oxide powder gradually, cools off, and then its grinding and sieving being got particle diameter is 80 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 4 parts of op-10,5 part of 80 purpose Natural manganese dioxide/Triple Pressed Stearic Acid filler; Add at normal temperatures mix in the impeller after; 4 parts of Skellysolve As addings are continued to mix; Again 12 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 1 minute and pour in the good mould of preheating, place 70 ℃ environment foaming and solidified 10 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Embodiment 2
Be that Triple Pressed Stearic Acid and the magnesium oxide powder of 1:1 put into container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to Triple Pressed Stearic Acid fusion and being coated on the magnesium oxide powder gradually, cooling, then its grinding and sieving being got particle diameter is 160 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 2 parts of op-10,2.5 part of 160 purpose Natural manganese dioxide/Triple Pressed Stearic Acid filler; Add at normal temperatures mix in the impeller after; 6 parts of pentamethylene addings are continued to mix; Again 12 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 2 minutes and pour in the good mould of preheating, place 80 ℃ environment foaming and solidified 20 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Embodiment 3
Be that solid paraffin and the nano-calcium carbonate calcium powder of 1:1 joins in the container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to solid paraffin fusion and being coated on the nano-calcium carbonate calcium powder gradually, cooling, then its grinding and sieving being got particle diameter is 40 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 8 parts of tween-80s, 6 part of 40 purpose solid paraffin/pearl filler; Add at normal temperatures mix in the impeller after; 6 parts of pentamethylene addings are continued to mix; Again 8 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 1 minute and pour in the good mould of preheating, place 60 ℃ baking oven foaming and solidified 30 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Embodiment 4
Be that Triple Pressed Stearic Acid and the magnesium hydroxide powder of 1:1 joins in the container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to Triple Pressed Stearic Acid fusion and being coated on the magnesium hydroxide powder gradually, cooling, then its grinding and sieving being got particle diameter is 80 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 5 parts of polyether modified siloxanes (BD-3086), 4 part of 80 purpose Triple Pressed Stearic Acid and Marinco H filler; Add at normal temperatures mix in the impeller after; 6 parts of pentamethylene addings are continued to mix; Again the mixing acid of 15 parts of methylsulphonic acids and phosphoric acid (5: 1) is added to stir fast and be about to mixture in 3 minutes and pour in the good mould of preheating, place 70 ℃ baking oven foaming and solidified 30 minutes.
Dip in the water test foamy pH value 4 that takes a morsel with the wide pH value test paper.
Embodiment 5
Be that Triple Pressed Stearic Acid and the lime powder of 1:1.5 joins in the container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to Triple Pressed Stearic Acid fusion and being coated on the lime powder gradually, cooling, then its grinding and sieving being got particle diameter is 80 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 4 parts of tween-80s, 5 part of 80 purpose Triple Pressed Stearic Acid and quicklime filler; Add at normal temperatures mix in the impeller after; 10 parts of sherwood oils addings are continued to mix; Again 12 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 1 minute and pour in the good mould of preheating, place 75 ℃ baking oven foaming and solidified 10 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Embodiment 6
Be that stearyl alcohol and the magnesium oxide powder of 1:3 joins in the container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to stearyl alcohol fusion and being coated on the magnesium oxide powder gradually, cooling, then its grinding and sieving being got particle diameter is 40 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 4 parts of tween-80s, 2 part of 40 purpose stearyl alcohol and magnesium hydroxide filler; Add at normal temperatures mix in the impeller after; 6 parts of Skellysolve As addings are continued to mix; Again 10 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 2 minutes and pour in the good mould of preheating, place 60 ℃ baking oven foaming and solidified 25 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Embodiment 7
Be that solid paraffin and the magnesium oxide powder of 1:1 joins in the container earlier with mass ratio; The limit heating edge constantly stirs in 80 ℃ water-bath; Up to solid paraffin fusion and being coated on the magnesium oxide powder gradually, cooling, then its grinding and sieving being got particle diameter is 40 purpose fillers.
Will be by 100 parts of expandable phenolic resins of preceding method synthetic, 4 parts of tween-80s, 5 part of 40 purpose solid paraffin and magnesium hydroxide filler; Add at normal temperatures mix in the impeller after; 6 parts of Skellysolve As addings are continued to mix; Again 12 parts of concentrated hydrochloric acids are added to stir fast and be about to mixture in 1 minute and pour in the good mould of preheating, place 60 ℃ baking oven foaming and solidified 30 minutes.
Dip in the water test foamy pH value 5～6 that takes a morsel with the wide pH value test paper.
Claims (10)
1. one kind low acid phenolic resin foam, it is characterized in that this foam by mass parts be by following component through the foamed solidification gained:
And this foamy pH value is 4～6.
2. low acid phenolic resin foam according to claim 1, it is characterized in that tensio-active agent contained in this foam is a tween series, silicone oil is serial or the TX10 series of surfactants in any.
3. low acid phenolic resin foam according to claim 1 and 2 is characterized in that filler contained in this foam is that its particle diameter is 40～160 orders by lower melting point organic cpds and basic oxide or oxyhydroxide or the formed coating of carbonate powder.
4. low acid phenolic resin foam according to claim 3 is characterized in that lower melting point organic cpds contained in this foam is any in solid paraffin, Triple Pressed Stearic Acid or the stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in Natural manganese dioxide, Marinco H, magnesiumcarbonate, quicklime, lime carbonate, volatile salt or the bicarbonate of ammonia powder.
5. 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 the sherwood oil; Solidifying agent is at least a in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and the phosphoric acid.
6. low acid phenolic resin foam according to claim 4 is characterized in that whipping agent contained in this foam is any in Skellysolve A, hexane, pentamethylene or the sherwood oil; Solidifying agent is at least a in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and the phosphoric acid.
7. described low acidic phenol urea formaldehyde foamy preparation method of claim 1; It is characterized in that this method is after earlier 4～10 parts of 100 parts of expandable phenolic resins, 2～8 parts in tensio-active agent, 2～6 parts of fillers, whipping agent being stirred; Added 8～15 parts of restir of solidifying agent then 1～3 minute; Thereafter being heated to foams under 60～80 ℃ and solidify got final product in 10～30 minutes, and the umber of used material is mass parts.
8. low acidic phenol urea formaldehyde foamy preparation method according to claim 7, it is characterized in that tensio-active agent used in this method is a tween series, silicone oil is serial or the TX10 series of surfactants in any; Whipping agent is any in Skellysolve A, hexane, pentamethylene or the sherwood oil; Solidifying agent is at least a in methylsulphonic acid, tosic acid, oxalic acid, formic acid, methylsulphonic acid, concentrated hydrochloric acid and the phosphoric acid.
9. according to claim 7 or 8 described low acidic phenol urea formaldehyde foamy preparing methods; It is characterized in that filler used in this method is that its particle diameter is 40～160 orders by lower melting point organic cpds and basic oxide or oxyhydroxide or the formed coating of carbonate powder.
10. low acidic phenol urea formaldehyde foamy preparation method according to claim 9 is characterized in that lower melting point organic cpds used in this method is any in solid paraffin, Triple Pressed Stearic Acid or the stearyl alcohol; Basic oxide or oxyhydroxide or carbonate powder are any in Natural manganese dioxide, Marinco H, magnesiumcarbonate, quicklime, lime carbonate, volatile salt or the bicarbonate of ammonia powder.
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| CN201210143287.4A CN102643512B (en) | 2012-05-10 | 2012-05-10 | Low-acid phenolic resin foam and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194003A (en) * | 2013-04-02 | 2013-07-10 | 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 |
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| 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 |
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101305035A (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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2012
- 2012-05-10 CN CN201210143287.4A patent/CN102643512B/en not_active Expired - Fee Related
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 |
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101305035A (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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194003A (en) * | 2013-04-02 | 2013-07-10 | 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 |
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| CN102643512B (en) | 2014-04-09 |
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