CN1065077A - Modified phenolic foam - Google Patents
Modified phenolic foam Download PDFInfo
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- CN1065077A CN1065077A CN 92106124 CN92106124A CN1065077A CN 1065077 A CN1065077 A CN 1065077A CN 92106124 CN92106124 CN 92106124 CN 92106124 A CN92106124 A CN 92106124A CN 1065077 A CN1065077 A CN 1065077A
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Abstract
A kind of PREPARATION OF PHENOLIC FOAM method of modification, be characterized in: react under certain condition with a certain amount of phenol and formaldehyde earlier, add a certain amount of a kind of non-resol monomer again after adding an amount of alkali, the pH value is adjusted with acid in the reaction back, just can obtain the heat-reactive phenolic resin after the modification behind the decompression dehydration, get a certain amount of resin, add an amount of equal infusion again, whipping agent, strengthening agent and another kind of non-resol monomer, under the katalysis of acid through the post-foaming that stirs, in baking oven, just can obtain uniform micro behind the crosslinking curing, good ultimate compression strength, thermal conductivity is little and fire-retardant, weathering resistance and erosion resistance are good, and lagging material with low cost.
Description
The invention belongs to technical field of organic synthesis, specifically a kind of preparation method of phenol formaldehyde foam modification.
The phenol formaldehyde foam of Chu Xianing is based on heat-reactive phenolic resin in the market, under all multiple auxiliary agent such as infusion, whipping agent cooperates, after catalyst action and forming process, make, its low thermal conductivity and hard polyurethane foam are very approaching, so its heat-insulating property excellence, remove this and also have good chemical stability, advantages such as workability, sound-proofing properties are also good, also possesses the unexistent flame retardant resistance of other organic foam simultaneously, that phenol formaldehyde foam has is significantly fire-retardant, low toxicity, characteristics such as smokeless and high temperature resistant, is a kind of very ideal lagging material.Therefore phenol formaldehyde foam has replaced hard polyurethane foam already and has been widely used in fields such as petrochemical complex, communications and transportation, freezing, refrigeration, building and military project as materials such as pipeline, basin and insulations abroad.Although phenol formaldehyde foam has so advantage, because cost is higher, up to the present, phenol formaldehyde foam also can't also can't be competed with other mineral-type lagging material on covil construction industry, the lagging material of doing body of wall and roof and price mutually in application.
The purpose of this invention is to provide a kind of cheap phenolic resin manufacture method, and make cheap and good-quality modified phenolic foam therefrom to replace existing urethane and polystyrene foam.
The object of the present invention is achieved like this: its preparation method is:
(1), the preparation of modified phenolic resins: with phenol and formaldehyde mole ratio is 1: under the 2-4 condition, Dropwise 5 0% sodium hydroxide solution, the dropping time is 10-20 minute, temperature remains on 36-45 ℃, slowly be warmed up to about 60 ℃ after alkali lye adds, keep slowly being raised to 80-100 ℃ again after 1 hour, when question response formaldehyde content to reaction solution reaches among the 7-10%, begin to be cooled to about 50 ℃, is 0.2-0.5 with second kind of non-resol monomer and phenol by the mol proportioning: 1 adds gradually, and reaction is 2 hours under 50 ℃ of conditions of maintenance, adjusts pH value to 7.5-8.0 with acid, decompression dehydration is to proper viscosity, just can obtain the heat-reactive phenolic resin after the modification;
(2), the preparation of modified phenolic foam: in 100 parts in the resol that will calculate by solid content, add the equal infusion of 1.5-3 part, the whipping agent of 15-20 part, 1-10 part as first kind of non-resol monomer of properties-correcting agent and the strengthening agent of 5-30 part, behind abundant stirring and evenly mixing, add the tosic acid made by 50: 50 proportionings and ethylene glycol solution 9-12 part of xylene monosulfonic acid mixing acid, through the post-foaming that stirs, the crosslinking curing modified phenolic foam that gets product about 15 minutes in 90 ℃ of baking ovens then;
Above-mentioned first kind of non-resol monomer is HO-CH
2-R, HO-CH
2-R-CH
2-OH(R is the fragrant same clan, olefines), second kind of non-resol monomer is urea element, cresol, dihydroxyphenyl propane residue and phynol residues.
The selected strengthening agent of the present invention is meant the flue dust after perlite powder, pumice sand, pure aluminium silicate and the acidifying, and flue dust is the flue dust after the phosphoric acid acidifying.What all infusion was selected for use is Dow Corning DC-193 and Si-C type closed pore silicone oil.Adjust the acid of pH value and preferably select phosphoric acid and acetic acid for use.
The present invention mainly divides two steps to implement from technique scheme as can be seen: promptly utilize the monomer modified resol of non-resol, to reduce the resin cost, also use cheap filler with reinforcement foamy ultimate compression strength simultaneously.Existing division is as follows:
1, with the monomer modified resol of non-resol
The non-resol monomer that the present invention uses is divided into two types: first kind is to have the monomer of active hydroxyl such as methylol benzene, xylenediol, vinylcarbinol, 1,2-dihydroxymethyl ethene, furfuralcohol, 2,5-dihydroxymethyl furans etc.These monomers all have one or two HO-CH
2Therefore-C=C-structural unit under the protonic acid effect, is sloughed hydroxyl easily and is formed the carbonium ion group; Though second kind of monomer itself do not have active hydroxyl such as urea element, cyanamid dimerization, trimeric cyanamide (pyramine), cresylol and dihydroxyphenyl propane residue and phynol residues etc., it is under the base catalysis condition and formaldehyde generation hydroxymethylation, and resultant is similar in appearance to first kind of non-resol monomer structure feature.One or two HO-CH is arranged like this
2-N-C=structural unit under the protonic acid effect, also is easy to slough hydroxyl and forms the carbonium ion gene.The non-resol monomer basis of above-mentioned two classes is characteristic separately, in the different steps adding of preparation resol, through meeting after the foaming technique processing the crosslinked of complex construction takes place, thereby reaches the modification purpose of phenol formaldehyde foam.After second section mixing as xylenediol and heat-reactive phenolic resin, under the acid catalysis effect, the foam of the crosslinked generation of foaming can increase hydrophobicity, helps water-intake rate and descends.If the urea element is joined when first section in the resol of preparation, the hydrogen in the urea molecule can be replaced by methylol, and its reaction is represented with following formula:
This class heat-reactive phenolic resin mixture is handled by foaming technique, can reduce cost significantly, therefore helps developing cheap lagging material, as: the production of body of wall or roof foam heat-insulating board.
2, filler reinforcement porous plastics
Phenol formaldehyde foam generally is to add with an acidic catalyst to contain whipping agent and equal heat-reactive phenolic resins of infusion, the plastics through foaming and obtaining after crosslinked.The present invention adds cheap strengthening agent to reduce cost and to increase foamy ultimate compression strength when making phenol formaldehyde foam.That strengthening agent commonly used has is that the power station discharges, the flue dust after peracid treatment, perlite powder, pumice sand.In sum, the phenol formaldehyde foam that the present invention produced has with low cost, and technology is simple, and condition relaxes, foam ultimate compression strength height, and flame retardant properties is good, has effectively utilized pollutent (flue dust), thereby has supported national environmental protection work indirectly.
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The resol preparation that the modification foam is used: have electric work whipping appts, prolong, thermometer and dropping funnel at one, capacity is in three mouthfuls of reaction flasks of 1 liter, add 95.9 gram phenol (98%) and 317 gram formaldehyde (35%) respectively, the mole ratio of its phenol and aldehyde is 1: 3.7,50% sodium hydroxide solution, 8.3 grams that will configure then, in 10 minutes, be added drop-wise in the reaction flask while stirring by dropping funnel.Be reflected under the thermostatic control of electric heating bag and carry out, remain on about 40 ℃ adding alkaline solution elementary reaction temperature always, can slowly rise to 60 ℃ after alkali lye adds.And keep slowly being warmed up to 80 ℃ more afterwards in 1 hour, after under refluxad keeping 2-3 hour, the formaldehyde content of analytical reaction liquid, when reaching 8% left and right sides, begin to cool to 50 ℃, add 36 gram urea elements in the reaction mixture in two batches, keep temperature of reaction about 50 ℃, reacted 2 hours, and adjusted pH value to 7.5-8.0 with 85% phosphoric acid, decompression dehydration can obtain the heat-reactive phenolic resin of needs to the proper viscosity.
The preparation of modified phenolic foam: with 100 parts of resins (pressing the resin solid content calculates) of above-mentioned production, add 2 parts of equal infusions of Dow Corning DC-193,20 parts of whipping agents of FREON11,3 parts of properties-correcting agent of xylenediol and 25 portions of strengthening agents of flue dust etc. are through after fully stirring, add 10 parts of the tosic acid blended ethylene glycol solutions made by 50: 50 proportionings, through the post-foaming that stirs, crosslinking curing just can obtain uniform micro in 15 minutes in 90 ℃ of baking ovens, good ultimate compression strength, thermal conductivity is little and fire-retardant, the lagging material that weathering resistance and erosion resistance are good.
Embodiment 2
The resol preparation that modified phenolic foam is used: in the experimental assembly of embodiment 1, add 60 gram phenol and 242 gram formaldehyde (35%) respectively, the mole ratio of its phenol and aldehyde is 1: 2.8,40% sodium hydroxide, 3 grams that will configure then, in 5 minutes, be added drop-wise in the reaction flask by dropping funnel.Be reflected under the thermostatic control of electric heating bag and carry out, temperature remains on about 40 ℃ when adding alkaline solution, and temperature progressively rises to 60 ℃ then, keeps rising to 80 ℃ again after 1 hour, refluxes 2 hours.After beginning to cool to 50 ℃, divide two batches of addings with 20 gram ureas are plain, reaction is 2 hours under 50 ℃ of conditions, add acetic acid (50-60%) and adjust pH value about 7.5, the beginning decompression dehydration get final product to the proper viscosity the thermosetting resin that needs.
The preparation of modified phenolic foam: with 50 parts of resins (pressing the resin solid content calculates) of above-mentioned preparation, add 1.5 parts of equal infusions of DC-193,8 parts of whipping agents of F11,1.5 parts of properties-correcting agent of xylenediol and 10 portions of strengthening agents of perlite powder etc. are through after fully stirring, add 5 parts of the tosic acid blended ethylene glycol solutions made by 50: 50 proportionings, through the post-foaming that stirs, crosslinking curing just can obtain uniform micro in 15 minutes in 90 ℃ of baking ovens, good ultimate compression strength, the lagging material that thermal conductivity is little.
Claims (5)
1, a kind of preparation method of modified phenolic foam is characterized in that:
(1), the preparation of modified phenolic resins: with phenol and formaldehyde mole ratio is 1: under the 2-4 condition, Dropwise 5 0% sodium hydroxide solution, the dropping time is 5-20 minute, temperature remains on 36-45 ℃, slowly be warmed up to about 60 ℃ after alkali lye adds, keep slowly being raised to 80-100 ℃ again after 1 hour, when question response formaldehyde content to reaction solution reaches among the 7-10%, begin to be cooled to about 50 ℃, is 0.2-0.5 with second kind of non-resol monomer and phenol by the mol proportioning: 1 adds gradually, and reaction is 2 hours under 50 ℃ of conditions of maintenance, adjusts pH value to 7.5-8.0 with acid, decompression dehydration is to proper viscosity, just can obtain the heat-reactive phenolic resin after the modification;
(2), the preparation of modified phenolic foam: in 100 parts in the resol that will calculate by solid content, add the equal infusion of 1.5-3 part, the whipping agent of 15-20 part, 1-10 part as first kind of non-resol monomer of properties-correcting agent and the strengthening agent of 5-30 part, behind abundant stirring and evenly mixing, add the tosic acid made by 50: 50 proportionings and ethylene glycol solution 9-12 part of xylene monosulfonic acid mixing acid, through the post-foaming that stirs, the crosslinking curing modified phenolic foam that gets product about 15 minutes in 90 ℃ of baking ovens then;
Above-mentioned first kind of non-resol monomer is HO-CH2-R, HO-CH2-R-CH2-OH (R is the fragrant same clan, olefines), and second kind of non-resol monomer is urea element, cresol, dihydroxyphenyl propane residue, phynol residues.
2, preparation method according to claim 1 is characterized in that the flue dust after selected strengthening agent is meant perlite powder, pumice sand, pure aluminium silicate and acidifying.
3, preparation method according to claim 2 is characterized in that flue dust is the flue dust after the phosphoric acid acidifying.
4, preparation method according to claim 1, what it is characterized in that equal infusion selects for use is Dow Corning DC-193 and Si-C type closed pore silicone oil.
5, preparation method according to claim 1 is characterized in that the acid of adjusting pH value preferably selects phosphoric acid and acetic acid for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106124 CN1065077A (en) | 1992-04-10 | 1992-04-10 | Modified phenolic foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106124 CN1065077A (en) | 1992-04-10 | 1992-04-10 | Modified phenolic foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1065077A true CN1065077A (en) | 1992-10-07 |
Family
ID=4941818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92106124 Pending CN1065077A (en) | 1992-04-10 | 1992-04-10 | Modified phenolic foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1065077A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300228C (en) * | 2003-11-05 | 2007-02-14 | 厦门新风机实业有限公司 | Sealed cell toughening foamed material and preparation thereof |
| CN100419009C (en) * | 2006-03-13 | 2008-09-17 | 覃强 | Process for producing phenolic foam capable of improving flame-retarding property |
| CN101781393A (en) * | 2009-01-19 | 2010-07-21 | 济南圣泉集团股份有限公司 | Resin for high-flame-retardant phenol formaldehyde foam and production method thereof |
| CN101274976B (en) * | 2007-03-30 | 2011-10-26 | 上海友存实业有限公司 | Preparation for multicomponent copolycondensation phenolic resin |
| CN102303978A (en) * | 2011-06-03 | 2012-01-04 | 清华大学 | Method for preparing porous silicon carbide ceramic with high strength |
| CN101768326B (en) * | 2010-01-15 | 2012-11-07 | 上海虞城新型建材有限公司 | Preparation method of modified phenolic resin and application thereof |
| CN106589792A (en) * | 2016-12-22 | 2017-04-26 | 河北建筑工程学院 | Composite phenolic foam insulation material and preparation method thereof |
| CN106589796A (en) * | 2016-12-22 | 2017-04-26 | 河北建筑工程学院 | Pumice phenolic resin compound foam material and preparation method thereof |
| CN106750534A (en) * | 2016-12-23 | 2017-05-31 | 河北建筑工程学院 | A kind of pumice concrete phenolic resin composite foam material and preparation method thereof |
-
1992
- 1992-04-10 CN CN 92106124 patent/CN1065077A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300228C (en) * | 2003-11-05 | 2007-02-14 | 厦门新风机实业有限公司 | Sealed cell toughening foamed material and preparation thereof |
| CN100419009C (en) * | 2006-03-13 | 2008-09-17 | 覃强 | Process for producing phenolic foam capable of improving flame-retarding property |
| CN101274976B (en) * | 2007-03-30 | 2011-10-26 | 上海友存实业有限公司 | Preparation for multicomponent copolycondensation phenolic resin |
| CN101781393A (en) * | 2009-01-19 | 2010-07-21 | 济南圣泉集团股份有限公司 | Resin for high-flame-retardant phenol formaldehyde foam and production method thereof |
| CN101768326B (en) * | 2010-01-15 | 2012-11-07 | 上海虞城新型建材有限公司 | Preparation method of modified phenolic resin and application thereof |
| CN102303978A (en) * | 2011-06-03 | 2012-01-04 | 清华大学 | Method for preparing porous silicon carbide ceramic with high strength |
| CN106589792A (en) * | 2016-12-22 | 2017-04-26 | 河北建筑工程学院 | Composite phenolic foam insulation material and preparation method thereof |
| CN106589796A (en) * | 2016-12-22 | 2017-04-26 | 河北建筑工程学院 | Pumice phenolic resin compound foam material and preparation method thereof |
| CN106589792B (en) * | 2016-12-22 | 2019-10-29 | 河北建筑工程学院 | A kind of composite phenol formaldehyde cellular insulant and preparation method thereof |
| CN106750534A (en) * | 2016-12-23 | 2017-05-31 | 河北建筑工程学院 | A kind of pumice concrete phenolic resin composite foam material and preparation method thereof |
| CN106750534B (en) * | 2016-12-23 | 2019-01-22 | 河北建筑工程学院 | A kind of pumice concrete phenolic resin composite foam material and preparation method thereof |
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