CN102675821A - Preparation method of low-acidity phenolic foam - Google Patents
Preparation method of low-acidity phenolic foam Download PDFInfo
- Publication number
- CN102675821A CN102675821A CN2012101878141A CN201210187814A CN102675821A CN 102675821 A CN102675821 A CN 102675821A CN 2012101878141 A CN2012101878141 A CN 2012101878141A CN 201210187814 A CN201210187814 A CN 201210187814A CN 102675821 A CN102675821 A CN 102675821A
- Authority
- CN
- China
- Prior art keywords
- acid
- phenol formaldehyde
- parts
- formaldehyde foam
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to low-acidity phenolic foam and a preparation method thereof. The low-acidity phenolic foam is prepared from the following raw materials in parts by weight: 100 parts of foamable phenolic resin, 2-8 parts of a surfactant, 5-10 parts of a foaming agent, 10-40 parts of an acid-acceptor and 10-20 parts of a curing agent. The phenolic foam has low acidity, is 5-6 in pH, has superior fire-proofing and heat-preserving properties, and can be widely applied to outer wall outer heat-preserving materials.
Description
Technical field
The present invention relates to high molecular foam material, be specifically related to a kind of phenol formaldehyde foam and preparation method thereof.
Background technology
Phenolic foam material is a kind of fire prevention, heat insulation, sound insulation, lightweight, the superior building material of energy-efficient performance.The phenolic foam material thermal conductivity is low; And difficult combustion degree significantly is superior to polystyrene foam and polyurethane foam that present construction industry is used; Phenol formaldehyde foam meet fire do not burn, indeformable, do not distribute toxic gas, no dropping;, be the excellent lagging material of a kind of fire resistance only, be expected to replace traditional organic polymer lagging materials such as polyurethane foam, polystyrene foam in superficial charring.
At present,, require energy-saving and emission-reduction, especially the external wall heat insulating material for external is required not only heat insulation effect excellence, more require material to have the good flame fire resistance for material of construction.Yet; Because the main strong acid catalysis realization curing molding that relies in the phenol formaldehyde foam sheet material manufacturing processed, the remaining acidic cpd of meeting in the foam article is during as external-wall heat-insulation material; In case there is water to penetrate into thermal insulation layer; Will produce acidic liq, body of wall and bar construction are produced corrosion, thus the potential safety hazard of bringing.
Therefore, for phenol formaldehyde foam, urgent hope reduces its cloudy acidity, thereby improves safety in utilization and expanded application scope.
At present, about reducing phenol formaldehyde foam tart relevant report.For example, it is a kind of through the mixing novolac resin of hot-rolling, heat-reactive phenolic resin and the solid-state whipping agent of pyrolysated that US7605189 provides, mixing even post-heating; Solid-state whipping agent decomposes and generates gas, thereby obtains phenol formaldehyde foam, forms HS, light weight and low tart phenol formaldehyde foam through 170 ℃ high-temperature heat treatment at last; But its solidification value is higher; Requirement to equipment is high, and energy consumption is big, is unfavorable for suitability for industrialized production.
JP2010285496 provides a kind of method for preparing phenol formaldehyde foam through resol, Skellysolve A, organosilicon, lime carbonate and xylene monosulfonic acid.The prepared phenolic aldehyde bubble of this method pH reaches 6.0.But, need in this method to use expensive organosilicon, cost is too high.
CN101748811 discloses a kind of highly flame-resistant external wall heat preservation material and production technique thereof; With the low hydroxyl resol of modification is raw material; Low acid cure production high flame retardant HS external-wall heat-insulation material adopts with heating under the condition of alkali after the acid formerly of phenol, formaldehyde, properties-correcting agent and chopped glass fiber and is condensed into the modified phenolic resins with low hydroxyl through copolymerization.But, this method can obtain the low hydroxyl resol of low tart midbody-modification, but the external-wall heat-insulation material-foamed phenolic resin that uses the low hydroxyl resol of this modification to make still has very high acidity, has corrodibility.
At present, demand urgently and need put method with less cost, the low acid phenolic aldehyde foamy of simple explained hereafter.
Summary of the invention
For smolderability and the peracidity problem that solves phenol formaldehyde foam, the inventor has carried out research with keen determination, and the result finds: when producing phenol formaldehyde foam; When synthetic foamable resol as raw material is synthetic, in reaction mass, add basic oxide or hydroxide solids particle as neutralizing agent, like this; In the phenol formaldehyde condensation polymerization process, generate basic oxide or the hydroxide particles that resol coats, the foamable resol that is coated with neutralizing agent in use adds neutralizing agent when foaming shape phenol formaldehyde foam; Especially, the amine-containing polymer particle that adds glutaraldehyde cross-linking is as acid-acceptor, and the neutralizing agent particle can neutralize with residual acid in the foam after foaming; Crosslinked amine-containing polymer particle can pass through the amido protonation reaction; Residual free acid in the slow absorbing phenolic foam, residual sour composition is eliminated in the release of remaining acidic components thus when reducing phenol formaldehyde foam chance water; Reduce the acidity of phenol formaldehyde foam, thereby accomplish the present invention.
The object of the present invention is to provide following aspect:
(1) a kind of low acid phenol formaldehyde foam, this low acid phenol formaldehyde foam is by comprising that following materials of weight proportions processes:
100 parts in foamable resol;
2～8 parts in tensio-active agent;
5～10 parts of whipping agents;
Neutralizing agent 10-50 part
10～20 parts in solidifying agent;
The pH of this phenol formaldehyde foam is 5～6;
Wherein, foamable resol adds the neutralizing agent solid particulate through phenol and formaldehyde and obtains in polycondensation process, and the neutralizing agent consumption is 1～15wt% of phenol usage;
Wherein, tensio-active agent is to be selected among Tween-40, tween-80, AK8812 and the L5440 one or more;
Whipping agent is to be selected from sherwood oil, pentane, normal hexane, methylene dichloride, trichloromethane and the tetracol phenixin one or more;
Neutralizing agent is to be selected from solid granular hydrated barta, white lake, Marinco H, Natural manganese dioxide, quicklime and the hydrotalcite one or more;
Solidifying agent is mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid and Witco 1298 Soft Acid.
(2) the low acid phenol formaldehyde foam described in above-mentioned (1), this low acid phenol formaldehyde foam is by comprising that following materials of weight proportions processes:
100 parts in foamable resol;
2～8 parts in tensio-active agent;
5～10 parts of whipping agents;
Neutralizing agent 10-50 part
1～5 part of acid-acceptor;
10～20 parts in solidifying agent;
Wherein, acid-acceptor is the amino-contained polymer beads of glutaraldehyde cross-linking, and it prepares through following method: the amino-contained polymer dissolution in water, is dripped LUTARALDEHYDE under high-speed stirring, reaction, the amino-contained polymer beads of acquisition glutaraldehyde cross-linking.
(3) the low acid phenol formaldehyde foam described in above-mentioned (2), wherein, said amino-contained polymkeric substance is selected from: polymine, alkylation polymine, polyvinylamine and alkylation polyvinylamine.
(4) the low acid phenol formaldehyde foam described in above-mentioned (2) or (3), wherein, the reaction times is 2-6 hour.
(5) like above-mentioned low acid phenol formaldehyde foam described in each, wherein, based on the foamable resol of 100 weight parts, tensio-active agent is the 3-4 weight part.
(6) like above-mentioned low acid phenol formaldehyde foam described in each, wherein, based on the foamable resol of 100 weight parts, whipping agent is the 5-8 weight part.
(7) like above-mentioned low acid phenol formaldehyde foam described in each, wherein, based on the foamable resol of 100 weight parts, neutralizing agent is the 10-20 weight part.
(8) like above-mentioned low acid phenol formaldehyde foam described in each, wherein, based on the foamable resol of 100 weight parts, acid-acceptor is 1-2 part.
(9) above-mentioned each said low acid phenol formaldehyde foam; It mixes through foamable resol, tensio-active agent, whipping agent, neutralizing agent and the optional acid-acceptor with said weight proportion; The solidifying agent that adds said weight proportion then foams, solidifies and make.
According to phenol formaldehyde foam provided by the invention, significantly reduced acidic components residual volume and the burst size in the phenolic foam material, pH reaches 5～6, has obviously reduced the corrosion risk of phenolic aldehyde foam thermal insulation material to construction wall.
Embodiment
Describe the present invention below, characteristics of the present invention and advantage will become more clear, clear and definite along with these descriptions.
According to the present invention, a kind of low acid phenol formaldehyde foam is provided, this low acid phenol formaldehyde foam is by comprising that following materials of weight proportions processes:
100 parts in foamable resol;
2～8 parts in tensio-active agent;
5～10 parts of whipping agents;
Neutralizing agent 10-50 part
10～20 parts in solidifying agent;
The pH of this phenol formaldehyde foam is 5～6;
Wherein, foamable resol adds the neutralizing agent solid particulate through phenol and formaldehyde and obtains in polycondensation process, and the neutralizing agent consumption is 1～15wt% of phenol usage;
Wherein, tensio-active agent is to be selected among Tween-40, tween-80, AK8812 and the L5440 one or more;
Whipping agent is to be selected from sherwood oil, pentane, normal hexane, methylene dichloride, trichloromethane and the tetracol phenixin one or more;
Neutralizing agent is to be selected from solid granular hydrated barta, white lake, Marinco H, Natural manganese dioxide, quicklime and the hydrotalcite one or more;
Solidifying agent is mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid and Witco 1298 Soft Acid.
In the present invention, foamable resol adds the neutralizing agent solid particulate through phenol and formaldehyde and obtains in polycondensation process, and in a preferred embodiment, foamable resol can prepare through following method:
(1) phenol, solid formaldehyde and softening water are added in the reactor drum, open and stir and prolong, keeping temperature of charge is 30 ℃～40 ℃, and wherein, the consumption of solid formaldehyde is 38%～65% of a phenol quality, and the consumption of softening water is 40%～70% of a phenol quality;
(2) add catalyzer, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 2～4h, wherein, catalyst consumption is 0.5%～2% of a phenol quality;
(3) add neutralizing agent, its consumption is 1～15% of a phenol quality;
(4) vacuumize dehydration, vacuum tightness-0.08～-0.1MPa, when system viscosity reaches 2000mPaS～10000mPaS, cooling discharging;
Wherein, said catalyzer is one or more in sodium hydroxide, ammoniacal liquor, yellow soda ash, the salt of wormwood;
Said neutralizing agent is to be selected from solid granular hydrated barta, white lake, Marinco H, Natural manganese dioxide, quicklime and the hydrotalcite one or more.
Be suitable for preparing low acid phenol formaldehyde foam according to foamable resol provided by the invention; This be because; These neutralizing agent particles are coated by the resol that is generated in the phenol formaldehyde condensation polymerization process; The neutralizing agent particle that these are coated resol after foaming forms foam can with the acid generation neutralization reaction retained in the foam, thereby consume the acid of retaining in the foam materials.
In low acid phenol formaldehyde foam according to the present invention; Said tensio-active agent is selected from Tween-40, tween-80, AK8812 (a kind of siloxanes-copolyether tensio-active agent) and L5440 (a kind of silicon oil surface activity agent), can use wherein one or more.Based on the foamable resol of 100 weight parts, tensio-active agent is the 2-8 weight part.If dosage of surfactant is lower than 2 weight parts, then can cause and can't foam owing to consumption is low excessively, otherwise, if dosage of surfactant is higher than 8 weight parts, then can cause foaming effect bad owing to consumption is too high.In preferred embodiment, based on the foamable resol of 100 weight parts, tensio-active agent 3-4 weight part.
In low acid phenol formaldehyde foam according to the present invention, whipping agent is selected from sherwood oil, pentane, normal hexane, methylene dichloride, trichloromethane and tetracol phenixin, can use wherein one or more.Based on the foamable resol of 100 weight parts; Foaming agent consumption is 5～10 weight parts, if the consumption of whipping agent is lower than 5 weight parts, can cause foaming degree not enough owing to foaming agent consumption is not enough; Otherwise; If the consumption of whipping agent is higher than 10 weight parts, then can cause gained quality, froth deterioration owing to the excessive abscess that cause in the gained foam of foaming dosage is excessive.In preferred embodiment, based on the foamable resol of 100 weight parts, whipping agent is the 5-8 weight part.
In low acid phenol formaldehyde foam according to the present invention, neutralizing agent is solid basic oxide or hydroxide particles, like particulate state hydrated barta, white lake, Marinco H, Natural manganese dioxide, quicklime and hydrotalcite etc., can use wherein one or more.Based on the foamable resol of 100 weight parts; The consumption of neutralizing agent is the 10-50 weight part, if the neutralizing agent consumption is lower than 10 weight parts, in being difficult to foam in remaining sour composition; The gained foamy is acid strong; Otherwise, if the neutralizing agent consumption is higher than 50 weight parts, because the excessive gained quality, froth deterioration that makes of its consumption.In preferred embodiment, based on the foamable resol of 100 weight parts, neutralizing agent is the 10-20 weight part.
In low acid phenol formaldehyde foam according to the present invention, solidifying agent is mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid and Witco 1298 Soft Acid.Can use any one or more mixture wherein.Preferably, solidifying agent is tosic acid or tosic acid and vitriolic mixture.Can use wherein any one or more.Based on the foamable resol of 100 weight parts, hardener dose is 10～20 weight parts.If hardener dose is lower than 10 weight parts, because crossing to hang down, hardener dose can cause the foam curing degree not enough, otherwise, if hardener dose is higher than 20 weight parts, because the too high curing speed that causes of hardener dose is too fast, gained foamy quality badness.
According to low acid phenol formaldehyde foam of the present invention; In preferred embodiment; In the low acid phenolic aldehyde foamy raw material of preparation, comprise amino-contained polymer beads,, can absorb the free acid in the gained phenol formaldehyde foam for a long time, lentamente because the amino-contained polymer beads of glutaraldehyde cross-linking can absorb the free proton through the protonation reaction of amido as the glutaraldehyde cross-linking of acid-acceptor; And; Owing to contain a large amount of amidos in the amino-contained polymer beads of glutaraldehyde cross-linking, so its ability or capacity of absorbing free acid are high, thereby further reduce the acidity of phenol formaldehyde foam.Comparatively speaking, neutralizing agent can be eliminated the residual sour composition in the gained phenol formaldehyde foam fast through the acid-base neutralisation reaction, but; Because phenol formaldehyde foam can constantly discharge free acid; Free acid can't effectively be removed with neutralizing agent, and through using the amino-contained polymer beads of glutaraldehyde cross-linking, can constantly slowly absorb the free acid that from phenol formaldehyde foam, constantly discharges; Thereby the removing free acid is avoided or the acid risk that increases when reducing phenol formaldehyde foam and meeting water.Through neutralizing agent and the collaborative effect of eliminating sour composition of acid-acceptor, the acidity of gained phenol formaldehyde foam of the present invention is extremely low, also can not demonstrate strongly-acid even place when meeting water for a long time, and construction wall is not had corrosion basically.
In preferred embodiment; Amino-contained polymer beads as the glutaraldehyde cross-linking of acid-acceptor prepares through following method: with the amino-contained polymer dissolution in water; Under high-speed stirring, drip LUTARALDEHYDE, reaction, the amino-contained polymer beads of acquisition glutaraldehyde cross-linking.Said amino-contained polymkeric substance is selected from: polymine, alkylation polymine such as methyl polyethylene imines, ethyl polymine etc., polyvinylamine and alkylation polyvinylamine such as methyl polyethylene amine, ethyl polyvinylamine etc.Can use any one or more amino-contained polymkeric substance wherein.As the amino-contained polymer beads of glutaraldehyde cross-linking, cause polymer beads toxicity low owing to LUTARALDEHYDE toxicity is low on the one hand, on the other hand, can play toughening effect after LUTARALDEHYDE and amine-containing polymer are crosslinked, therefore be suitable for use among the present invention.
Low acid phenol formaldehyde foam according to the present invention prepares through following method: foamable resol, tensio-active agent, whipping agent, neutralizing agent and the optional acid-acceptor of said weight proportion are mixed; The solidifying agent that adds said weight proportion then foams, solidifies and make.
One preferred embodiment in; Foamable resol, tensio-active agent, whipping agent, neutralizing agent and optional acid-acceptor joined in the reaction kettle together stir; Add solidifying agent again and stir fast together, pour into fast in the mould that is preheated to 30～40 ℃ after mixing, the baking oven of putting into 60～80 ℃ foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment
Embodiment 1
Synthesizing of foamable resol:
600g phenol, 228g solid formaldehyde and 240g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 3g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 4h; Add 6g trimeric cyanamide and 30g white lake, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 2000mPaS, cooling discharging obtained foamable resol.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 3g tween-80,10g aluminum hydroxide particles; The 5g pentane joins together and stirs 3min in the reaction kettle; Add the 11g tosic acid again and stir fast together, pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 60～80 ℃ the baking oven 7min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment 2
Synthesizing of foamable resol:
600g phenol, 345g solid formaldehyde and 375g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 4.2g Natural manganese dioxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 12gPEG-1000 and 75 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 4000mPaS, cooling discharging obtained foamable resol.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 3g Tween-40,20g aluminum hydroxide particles; 5g spun glass, 7g pentane join together and stir 3min in the reaction kettle, add 7g sulfuric acid and 3g tosic acid again and stir fast together; Pour in the mould that is preheated to 40 ℃ after mixing fast; Put into 60～80 ℃ the baking oven 15min that foams, take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment 3
Synthesizing of foamable resol:
600g phenol, 268g solid formaldehyde and 290g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 6g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 12g urea, 15g Marinco H and 15g white lake, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 4000mPaS, cooling discharging obtained foamable resol.
The preparation of acid-acceptor:
The 5g polymine is dissolved in the 10g water, under high-speed stirring, drips the 6g LUTARALDEHYDE, reacted 4 hours, obtain the amine based polymer particle of glutaraldehyde cross-linking, as acid-acceptor.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 3g L5440,15g white lake; The 5g calcium oxide particle, the above-mentioned gained acid-acceptor of 1g, the 7g pentane joins together and stirs 3min in the reaction kettle; Add the 11g tosic acid again and stir fast together, pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 60～80 ℃ the baking oven 10min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment 4
Synthesizing of foamable resol:
600g phenol, 306g solid formaldehyde and 330g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 9g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 12g urea, 12g trimeric cyanamide and 60 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 5000mPaS, cooling discharging obtained foamable resol.
The preparation of acid-acceptor:
The 5g polyvinylamine is dissolved in the 10g water, under high-speed stirring, drips the 10g LUTARALDEHYDE, reacted 6 hours, obtain the amine based polymer particle of glutaraldehyde cross-linking, as acid-acceptor.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 3g AK8812,15g aluminum hydroxide particles; The 5g quicklime, 4g terepthaloyl moietie, the above-mentioned gained acid-acceptor of 2g; The 7g pentane joins together and stirs 3min in the reaction kettle, adds the 13g tosic acid again and stirs fast together, pours in the mould that is preheated to 40 ℃ after mixing fast; Put into 60～80 ℃ the baking oven 12min that foams, take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment 5
Synthesizing of foamable resol:
600g phenol, 383g solid formaldehyde and 415g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 1.2g sodium hydroxide and 3.0g Natural manganese dioxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 18g urea and 90 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 5000mPaS, cooling discharging obtained foamable resol.
The preparation of acid-acceptor:
The 5g polymine is dissolved in the 15g water, under high-speed stirring, drips the 8g LUTARALDEHYDE, reacted 2 hours, obtain the amine based polymer particle of glutaraldehyde cross-linking, as acid-acceptor.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 4g tween-80,20g aluminum hydroxide particles; The 2g flame retardant polyether polyol, 2g amine-containing polymer, 7g pentane join together and stir 3min in the reaction kettle; Add 7g sulfuric acid and 3g tosic acid again and stir fast together, pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 60～80 ℃ the baking oven 20min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment 6
Synthesizing of foamable resol:
600g phenol, 306g solid formaldehyde and 330g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add the 9g sodium hydrate particle, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add the waste and old phenol formaldehyde foam chip of 30g and 90 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reached 10000mPaS, cooling discharging obtained foamable resol.
PREPARATION OF PHENOLIC FOAM:
With the resol of 100g expandability bubble, 4g tween-80,50g aluminum hydroxide particles; The 8g pentane joins together and stirs 3min in the reaction kettle; Add 7g sulfuric acid and 3g tosic acid again and stir fast together, pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 60～80 ℃ the baking oven 12min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Comparative Examples 1
Synthesizing of foamable resol:
600g phenol, 345g solid formaldehyde and 375g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 4.2g Natural manganese dioxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Vacuumize dehydration, vacuum tightness-0.08～-0.1MPa, when system viscosity reaches 4000mPaS; Cooling discharging obtains foamable resol.
PREPARATION OF PHENOLIC FOAM:
With the foamable resol of 100g, 3g Tween-40,5g spun glass; The 7g pentane joins together and stirs 3min in the reaction kettle; Add 7g sulfuric acid and 3g tosic acid again and stir fast together, pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 60～80 ℃ the baking oven 15min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Test Example
The pH pH-value determination pH of phenol formaldehyde foam
With the surface of the smooth cleaning of the moistening phenol formaldehyde foam sample of deionized water, cover a slice pH value scope and be 1～14 test paper, place observation in 1 minute, measure the pH value, the result is shown in the following table 1.
The pH pH-value determination pH result of table 1 phenol formaldehyde foam
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 1 |
| The pH value | 5 | 5.5 | 5.5 | 5.5 | 6 | 6 | 2 |
More than through specific embodiment the present invention is further specified, but these embodiment only are exemplary, protection scope of the present invention are not constituted any restriction.It will be appreciated by those skilled in the art that under the situation that does not exceed spirit of the present invention and protection domain can carry out multiple replacement of equal value, modify or improve technical scheme of the present invention and embodiment thereof, these all should fall in protection scope of the present invention.Protection scope of the present invention is as the criterion with appended claim.
All documents of mentioning in the literary composition are incorporated herein by reference at this in full.
Claims (9)
1. one kind low acid phenol formaldehyde foam, this low acid phenol formaldehyde foam is by comprising that following materials of weight proportions processes:
100 parts in foamable resol;
2～8 parts in tensio-active agent;
5～10 parts of whipping agents;
Neutralizing agent 10-50 part;
10～20 parts in solidifying agent;
The pH of this phenol formaldehyde foam is 5～6;
Wherein, foamable resol adds the neutralizing agent solid particulate through phenol and formaldehyde and obtains in polycondensation process, and the neutralizing agent consumption is 1～15wt% of phenol usage;
Wherein, tensio-active agent is to be selected among Tween-40, tween-80, AK8812 and the L5440 one or more;
Whipping agent is to be selected from sherwood oil, pentane, normal hexane, methylene dichloride, trichloromethane and the tetracol phenixin one or more;
Neutralizing agent is to be selected from solid granular hydrated barta, white lake, Marinco H, Natural manganese dioxide, quicklime and the hydrotalcite one or more;
Solidifying agent is mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid and Witco 1298 Soft Acid.
2. according to the low acid phenol formaldehyde foam described in the claim 1, this low acid phenol formaldehyde foam is by comprising that following materials of weight proportions processes:
100 parts in foamable resol;
2～8 parts in tensio-active agent;
5～10 parts of whipping agents;
Neutralizing agent 10-50 part
1～5 part of acid-acceptor;
10～20 parts in solidifying agent;
Wherein, acid-acceptor is the amino-contained polymer beads of glutaraldehyde cross-linking, and it prepares through following method: the amino-contained polymer dissolution in water, is dripped LUTARALDEHYDE under high-speed stirring, reaction, the amino-contained polymer beads of acquisition glutaraldehyde cross-linking.
3. according to the low acid phenol formaldehyde foam described in the claim 2, wherein, said amino-contained polymkeric substance is selected from: polymine, alkylation polymine, polyvinylamine and alkylation polyvinylamine.
4. according to the low acid phenol formaldehyde foam described in claim 2 or 3, wherein, the reaction times is 2-6 hour.
5. according to each described low acid phenol formaldehyde foam among the claim 1-4, wherein, based on the foamable resol of 100 weight parts, tensio-active agent is the 3-4 weight part.
6. according to each described low acid phenol formaldehyde foam among the claim 1-5, wherein, based on the foamable resol of 100 weight parts, whipping agent is the 5-8 weight part.
7. according to each described low acid phenol formaldehyde foam among the claim 1-6, wherein, based on the foamable resol of 100 weight parts, neutralizing agent is the 10-20 weight part.
8. according to each described low acid phenol formaldehyde foam among the claim 1-7, wherein, based on the foamable resol of 100 weight parts, acid-acceptor is 1-2 part.
9. according to each described low acid phenol formaldehyde foam among the claim 1-8; It mixes through foamable resol, tensio-active agent, whipping agent, neutralizing agent and the optional acid-acceptor with said weight proportion; The solidifying agent that adds said weight proportion then foams, solidifies and make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210187814 CN102675821B (en) | 2012-06-08 | 2012-06-08 | Preparation method of low-acidity phenolic foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210187814 CN102675821B (en) | 2012-06-08 | 2012-06-08 | Preparation method of low-acidity phenolic foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102675821A true CN102675821A (en) | 2012-09-19 |
| CN102675821B CN102675821B (en) | 2013-10-23 |
Family
ID=46808404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210187814 Expired - Fee Related CN102675821B (en) | 2012-06-08 | 2012-06-08 | Preparation method of low-acidity phenolic foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102675821B (en) |
Cited By (8)
| 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 |
| CN103554830A (en) * | 2013-10-25 | 2014-02-05 | 林百川 | Phenolic foam material with low coefficient of thermal conductivity and preparation method thereof |
| CN105085972A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Method for preparing foamable phenolic resin through acidity reducing phenolic vacuum foaming |
| CN105086350A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Toughened phenolic foamed resin with long carbon chains and preparation method thereof |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN105199312A (en) * | 2015-11-05 | 2015-12-30 | 北京莱恩斯高新技术有限公司 | Neutral phenolic foam plastic and preparation method thereof |
| CN108587056A (en) * | 2018-04-24 | 2018-09-28 | 谢新昇 | A kind of preparation method of fire prevention vapor-permeable type sound insulation felt material |
| CN113956608A (en) * | 2021-10-22 | 2022-01-21 | 山东北理华海复合材料有限公司 | Neutral low-thermal-conductivity phenolic foam material for building thermal insulation 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 |
| 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 |
-
2012
- 2012-06-08 CN CN 201210187814 patent/CN102675821B/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 (9)
| 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 |
| CN103554830A (en) * | 2013-10-25 | 2014-02-05 | 林百川 | Phenolic foam material with low coefficient of thermal conductivity and preparation method thereof |
| CN105085972A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Method for preparing foamable phenolic resin through acidity reducing phenolic vacuum foaming |
| CN105086350A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Toughened phenolic foamed resin with long carbon chains and preparation method thereof |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN105085972B (en) * | 2015-08-31 | 2017-11-14 | 沈阳化工大学 | One kind reduces acid phenolic aldehyde vacuum foam and prepares expandable phenolic resin method |
| CN105199312A (en) * | 2015-11-05 | 2015-12-30 | 北京莱恩斯高新技术有限公司 | Neutral phenolic foam plastic and preparation method thereof |
| CN108587056A (en) * | 2018-04-24 | 2018-09-28 | 谢新昇 | A kind of preparation method of fire prevention vapor-permeable type sound insulation felt material |
| CN113956608A (en) * | 2021-10-22 | 2022-01-21 | 山东北理华海复合材料有限公司 | Neutral low-thermal-conductivity phenolic foam material for building thermal insulation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102675821B (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102675821B (en) | Preparation method of low-acidity phenolic foam | |
| CN108706953B (en) | Homogeneous low thermally conductive inorganic heat-insulation board of one kind and preparation method thereof | |
| TW211021B (en) | ||
| CN101525465B (en) | Preparing method of toughening metlbond foam | |
| CN103333457B (en) | A kind of height presses down cigarette, high oxygen index phenolic fireproof insulating plate and preparation method thereof | |
| CN101735553A (en) | Material for manufacturing modified phenolic fireproof insulating plate | |
| CN103087344B (en) | Preparation method of hollow glass microbead-reinforced phenolic foam composite material | |
| CN102766243A (en) | Room-temperature foamable phenolic resin and method for preparing phenolic foams by same | |
| CA2610285A1 (en) | Expandable resol-type phenolic resin molding material and phenolic resin foam | |
| CN102838771B (en) | Preparation method of halogen-free environmental-friendly synergistic flame retardant phenolic foam composite material | |
| CN103450630A (en) | Preparation method of environment-friendly phenol aldehyde-inorganic composite heat insulating material | |
| CN104140512A (en) | Isocyanate-group-reinforced intumescent-flame-retardance rigid polyurethane foam panel and preparation method thereof | |
| CN103725236A (en) | Polystyrene foam and preparation method thereof | |
| CN103146015B (en) | Low-acidity phenolic foam and preparation method thereof | |
| CN102992802A (en) | Fireproof cement foam insulation board | |
| CN107257821A (en) | Thermoset foam and the manufacture method using reduced sugar and amine | |
| CN103848950A (en) | Method for modifying phenolic resin by adopting methylolurea and method for preparing foam by utilizing modified phenolic resin | |
| CA2749760C (en) | Expandable resol-type phenolic resin molding material, method for producing the same, and phenolic resin foam | |
| CN109666228B (en) | Graphene polystyrene board and preparation method thereof | |
| CN105001386A (en) | High-activity phenolic compound modified expandable phenolic resin and preparation method thereof | |
| US4001148A (en) | Process for the production of flame-resistant phenolic resin foam plastics | |
| CN102372832A (en) | Phthalonitrile-based etherified phenolic resin and preparation method thereof | |
| CN102532445A (en) | Foaming phenolic resin and phenolic foam with foaming phenolic resin | |
| CN102261137B (en) | Ultrathin stone polyurethane composite board and preparation method thereof | |
| CN101928442A (en) | Material for manufacturing modified phenolic fireproofing insulation board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131023 |