CN101880365A - Foaming phenolic resin preparation method and phenolic resin foam - Google Patents
Foaming phenolic resin preparation method and phenolic resin foam Download PDFInfo
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- CN101880365A CN101880365A CN 201010242812 CN201010242812A CN101880365A CN 101880365 A CN101880365 A CN 101880365A CN 201010242812 CN201010242812 CN 201010242812 CN 201010242812 A CN201010242812 A CN 201010242812A CN 101880365 A CN101880365 A CN 101880365A
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Abstract
The invention discloses a foaming phenolic resin preparation method. The method comprises the following steps: A, phenol, aldehyde and alkali catalyst are added into a reactor, the mole ratio is 1 : 1-3 : 0.01-0.1, and the components are stirred for 5 to 8 hours at 70 to 90 degrees centigrade; B, the temperature of reaction liquid in step A is reduced to 50 to 60 degrees centigrade, acid is added and stirred until the pH value is 6.0 to 8.0; and C, the reaction liquid in step B is decompressed and dehydrated to 60 to 70 degrees centigrade and 2500 to 7000 m Pa.s viscosity. The invention further discloses phenolic resin foam made of the phenolic resin. The invention makes the foaming phenolic resin which can gel quickly have low free monomer content and high curing activity through controlling the synthesis technology condition accurately. The aperture of the prepared phenolic foam body is only 50 to 60 microns. The structure of the micro holes of the foam body is regular and the foam holes are fine and compact. The prepared phenolic foam body does not need any toughening modifier and no residue falls.
Description
Technical field
The present invention relates to the preparation of resol, especially a kind of preparation method of foamed phenolic resin, and the phenol formaldehyde foam that comprises this resol.
Background technology
Phenol formaldehyde foam is a kind of porous plastics that is obtained by foaming by resol.Compare with materials such as the polystyrene foam that accounts for the market dominant position in early days, polyvinyl chloride foam, polyurethane foams, it has special good victory energy aspect fire-retardant, and it is in light weight, rigidity is big, dimensional stability is good, resistance to chemical attack, good heat resistance, difficult combustion, from putting out, hang down smog, flame resistant penetrates, meeting fire does not have unrestrained thing, cheap; Therefore be comparatively ideal insulation heat-insulation and heat-preservation materials of industries such as electrical equipment, instrument, building, petrochemical complex, be subjected to people's extensive attention.At present, phenol formaldehyde foam has become one of kind with fastest developing speed in the porous plastics, and consumption constantly increases, and range of application constantly enlarges, and research and development is all quite active both at home and abroad.
Yet because the aperture is bigger in the existing phenol formaldehyde foam, phenolic foamed plastics enbrittles greatly, intensity and toughness is relatively poor, the shortcoming of high opening rate, in use easily comes off, and holes and falls slag when cutting easily.In addition, the resol free monomers content that is used to foam is bigger than normal, causes the phenolic foams smell big, all can cause certain influence to environment and human body in processing and application process.In addition, the phenol formaldehyde foam percentage of open area is higher, easily suction.These shortcomings have all limited the application of phenol formaldehyde foam.Therefore, but many in the world countries have all carried out the correlative study of relevant foamed phenolic resin modification.
Improving phenol formaldehyde foam flexible method generally is to adopt to add toughness reinforcing component in the resol foaming process, though the adding of various toughness reinforcing components improves to foamy toughness, has but reduced the performances such as flame retardant resistance of phenol formaldehyde foam.The adding of a large amount of toughness reinforcing components also can influence the foam microtexture, and foam percentage of open area, aperture are increased, and thermal conductivity increases, thereby has influence on the foamy heat-proof quality.
Summary of the invention
The present invention is directed to deficiency, propose a kind of preparation method of foamed phenolic resin, free monomer content is low, and gel time is short; The foam that adopts this resol to make has the little characteristics in aperture, need not add plasticized modifier, and phenol formaldehyde foam toughness is better.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of preparation method of foamed phenolic resin may further comprise the steps:
A, add phenol, aldehyde and alkaline catalysts in reactor, three's mol ratio is 1: 1～3: 0.01～0.1; At 70～90 ℃, stirred 5～8 hours;
Reaction solution is cooled to 50～60 ℃ among b, the step a, and adding acid, to be stirred to the pH value be 6.0～8.0;
The reaction solution decompression dehydration of c, step b, to 60～70 ℃ of following viscosity be 2500～7000mPa.s.
Wherein, described step c is specially: the reaction solution of step b is stopped dehydration at vacuum tightness 0.080～0.082MPa, 60～70 ℃ of water-bath decompression dehydrations during to viscosity 2500～7000mPa.s, be cooled to 52 ℃.
Compared with prior art, the present invention is by accurate control synthetic technological condition, as proportionlity and the temperature of reaction and the time of reactant, guarantees that sufficient reacting finishes, and reduced the product free monomers; Control product pH value is 6.0～8.0, and when guaranteeing product storage period, control product alkalescence has the characteristic of PhastGel in the assurance product foaming process under same sour consumption situation, make the foams aperture tiny.Free phenol is 2～3wt% in the resol that finally makes, and free aldehyde is 1～2wt%; Water-content is 5～12wt%; Gel time is 80～400s; Solid content is 75～90wt%.Therefore, such resol has the characteristic of PhastGel, and is because free monomer is few, so smell is little, little to the influence of environment and human body simultaneously.
The present invention is after furtheing investigate the key factor of the foamex that influences phenolic foams foam structure and pore size, with the research of raw material resol as focus, but determined the synthesis technique of the foamed phenolic resin of PhastGel, core is to have realized reaching the purpose that accurate control prepares the phenolic foams of diverse microcosmic appearance by adjusting resin synthesis condition control resin key index.
The present invention also provides a kind of phenolic resin foam, and by the 100 weight parts resol, the tensio-active agent of 1～6 weight part, the whipping agent of 1～25 weight part and the acid as curing agent of 5～25 weight parts that obtain of preparation method as mentioned above, the mixing foaming is made.
Since use can PhastGel resol make phenol formaldehyde foam, cause the aperture of this phenol formaldehyde foam to have only 50～60 microns, thereby foamy microporous structure rule, abscess are fine and smooth fine and close.Because the aperture is little, the toughness of phenol formaldehyde foam is better, is difficult for falling slag.
Embodiment
A kind of preparation method of foamed phenolic resin may further comprise the steps:
1. in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenolic compound, formalin and alkaline catalysts successively by proportioning, heating in water bath is kept and is reflected at 70～90 ℃ of internal condensations reactions, total about 5～8 hours of condensation reaction times spent under stirring;
2. system is cooled to 50～60 ℃, adds acid and be neutralized to pH value 6.0～8.0;
3. resin system is stopped dehydration during to viscosity 2500～7000mPa.s at vacuum tightness 0.080～0.082MPa, 60～70 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings.
Preferably, described phenol be selected from cresols, xylenol, to alkylphenol, Resorcinol.Described aldehyde is selected from formaldehyde, acetaldehyde.Described basic catalyst is selected from potassium hydroxide, sodium hydroxide, hydrated barta.The mol ratio of described phenol, aldehyde and alkaline catalysts is 1: 1.4～2.5: 0.03～0.08.
Adopt above-mentioned phenol, aldehyde and alkaline catalysts, and the mol ratio between the three, more help the complete of reactive modified phenolic resin, make and contain lower residual monomer in the resin that makes, as free phenol, free aldehyde etc., help foaming in the generation of follow-up phenol formaldehyde foam early stage steadily and sufficient nucleation, the foamy hole gauge is then tiny.
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 25 weight parts and sodium hydroxide 0.3 weight part, heating in water bath is kept and is reflected at 70 ℃ of internal condensations reactions, total about 7 hours of condensation reaction times spent under stirring; System is cooled to 60 ℃, adds acid and be neutralized to pH value 7.5; Resin system is stopped dehydration during to viscosity 4000mPa.s at vacuum tightness 0.080～0.082MPa, 70 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain Resin A, its performance index are listed in the table 1.
The Phenylsulfonic acid of the pentane of the polysiloxane of 100 parts by weight resin A, 1 weight part, 25 weight parts and 5 weight parts behind 20 ℃ of following thorough mixing, 70 ℃ of foaming down, and is carried out after fixing in 70 ℃, prepare phenolic foams A-F, apparent density 70kg/m
3, the foam index is listed in the table 2.
Embodiment 2
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 21 weight parts and sodium hydroxide 0.3 weight part, heating in water bath is kept and is reflected at 90 ℃ of internal condensations reactions, total about 8 hours of condensation reaction times spent under stirring; System is cooled to 50 ℃, adds acid and be neutralized to pH value 7.0; Resin system is stopped dehydration during to viscosity 6000mPa.s at vacuum tightness 0.082MPa, 60 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain resin B, its performance index are listed in the table 1.
With the xylene monosulfonic acid of the hexane of the polyoxyethylene of 100 parts by weight resin B, 6 weight parts and polyoxypropylene three's segmented copolymer, 5 weight parts and butane and 25 weight parts behind 20 ℃ of following thorough mixing, 60 ℃ of foaming down, and carry out after fixing in 70 ℃, prepare phenolic foams B-F, apparent density 52kg/m
3, the foam index is listed in the table 2.
Embodiment 3
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 25 weight parts and sodium hydroxide 0.5 weight part, heating in water bath is kept and is reflected at 80 ℃ of internal condensations reactions, total about 6.5 hours of condensation reaction times spent under stirring; System is cooled to 55 ℃, adds acid and be neutralized to pH value 6.5; Resin system is stopped dehydration during to viscosity 4800mPa.s at vacuum tightness 0.081MPa, 65 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain resin C, its performance index are listed in the table 1.
With the sulfocarbolic acid of the Trimethylmethane of the polysorbate of 100 parts by weight resin C, 3 weight parts, 10 weight parts and 15 weight parts and sulfuric acid behind 20 ℃ of following thorough mixing, 65 ℃ of foaming down, and carry out after fixing in 70 ℃, prepare phenolic foams C-F, apparent density 57kg/m
3, the foam index is listed in the table 2.
1 reaction times of Comparative Examples less than 5 hours
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 25 weight parts and sodium hydroxide 0.3 weight part, heating in water bath is kept and is reflected at 80 ℃ of internal condensations reactions, total about 3.5 hours of condensation reaction times spent under stirring; System is cooled to 56 ℃, adds acid and be neutralized to pH value 6.5; Resin system is stopped dehydration during to viscosity 5000mPa.s at vacuum tightness 0.081MPa, 67 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain resin D, its performance index are listed in the table 1.
The tosic acid of the hexane of the polyethenoxy ether of 100 parts by weight resin D, 4 weight parts, 15 weight parts and 9 weight parts behind 20 ℃ of following thorough mixing, 63 ℃ of foaming down, and is carried out after fixing in 70 ℃, prepare phenolic foams D-F, apparent density 60kg/m
3, the foam index is listed in the table 2.
Since the polycondensation reaction time deficiency, Comparative Examples 1 resin D free monomer content height, gel is slow, and foam D-F aperture is big.
Comparative Examples 2 phenolic molar ratios are than on the low side
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 18 weight parts and sodium hydroxide 0.3 weight part, heating in water bath is kept and is reflected at 79 ℃ of internal condensations reactions, total about 3.5 hours of condensation reaction times spent under stirring; System is cooled to 54 ℃, adds acid and be neutralized to pH value 6.7; Resin system is stopped dehydration during to viscosity 4400mPa.s at vacuum tightness 0.082MPa, 64 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain resin E, its performance index are listed in the table 1.
With Phenylsulfonic acid, tosic acid and the xylene monosulfonic acid of pentane, hexane and the butane of the polysorbate of 100 parts by weight resin E, 5 weight parts, 5 weight parts and 20 weight parts behind 20 ℃ of following thorough mixing, 70 ℃ of foaming down, and carry out after fixing in 70 ℃, prepare phenolic foams E-F, apparent density 59kg/m
3, the foam index is listed in the table 2.
Because phenolic molar ratio is than on the low side, Comparative Examples 2 resin E free phenol content height, thermal discharge is big early stage during foaming, is unfavorable for nucleation, and foam cell is thick, and fragility is big.
In Comparative Examples 3 resins and insufficient
In the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed, add phenol 15 weight parts successively by proportioning, 37% concentration formalin, 25 weight parts and sodium hydroxide 0.3 weight part, heating in water bath is kept and is reflected at 90 ℃ of internal condensations reactions, total about 3.5 hours of condensation reaction times spent under stirring; System is cooled to 60 ℃, adds acid and be neutralized to pH value 8.5; Resin system is stopped dehydration during to viscosity 6000mPa.s at vacuum tightness 0.080MPa, 70 ℃ of water-bath decompression dehydrations, be cooled to 52 ℃ of dischargings, obtain resin F, its performance index are listed in the table 1.
The phosphoric acid of the butane of the polyoxyethylene of 100 parts by weight resin F, 6 weight parts, 2 weight parts and 22 weight parts behind 20 ℃ of following thorough mixing, 60 ℃ of foaming down, and is carried out after fixing in 70 ℃, prepare phenolic foams F-F, apparent density 50kg/m
3, the foam index is listed in the table 2.
Because the resin degree of neutralization is not enough, Comparative Examples 3 resin F foaming activities are low, and foams F-F aperture is big.
Table 1
| Resin | Solid content/% | Water-content/% | Viscosity/mPa.s | Gel time/s | Free phenol/% | Free aldehyde/% | The pH value |
| ??A | ??83.65 | ??12.67 | ??5500 | ??212 | ??2.63 | ??1.75 | ??6.5 |
| ??B | ??79.08 | ??11.56 | ??4200 | ??329 | ??2.98 | ??0.69 | ??7.0 |
| ??C | ??79.57 | ??11.40 | ??4800 | ??202 | ??2.38 | ??2.09 | ??6.5 |
| ??D | ??83.31 | ??11.52 | ??4100 | ??414 | ??4.53 | ??2.29 | ??6.5 |
| ??E | ??79.02 | ??8.79 | ??4300 | ??492 | ??10.51 | ??0.45 | ??6.5 |
| ??F | ??81.6 | ??12.58 | ??6600 | ??185 | ??2.19 | ??1.88 | ??8.6 |
Table 2
| Foam | ??A-F | ??B-F | ??C-F | ??D-F | ??E-F | ??F-F |
| Apparent density/kg/m 3 | ??53.2 | ??56.1 | ??61.2 | ??60.9 | ??59.6 | ??67.0 |
| Mean pore size/μ m | ??55.36 | ??50.07 | ??56.09 | ??101.11 | ??134.6 | ??87.30 |
As shown in table 1: 1 reaction times of Comparative Examples less than 5 hours, since the polycondensation reaction time deficiency, Comparative Examples 1 resin D free monomer content height, gel is slow, and foam D-F aperture is big.Comparative Examples 2 phenolic molar ratios are than on the low side, resin E free phenol content height, and thermal discharge is big early stage during foaming, is unfavorable for nucleation, and foam cell is thick, and fragility is big.With insufficient, resin F foaming activity is low in Comparative Examples 3 resins, and foams F-F aperture is big.
Attached: the resol testing method
1. solid content
Measure according to HG/T2711: the conventional determining of resol non-volatile matter.
2. viscosity
Measure according to HG/T2712: the mensuration of liquid state and solution shape resol viscosity.
3. free phenol
Measure according to HG5 1342: free phenol content measuring method in the resol.
4. free aldehyde
Measure according to HG5 1343: free formaldehyde content measuring method in the resol.
5 gel times
Measure according to HG5 1338: resol polymerization velocity test method.
6 water-contents
Measure according to HG5 1341: determination of moisture method in the resol.
7.pH value
Measure according to HG/T 2501: the mensuration of resol pH value.
8. mean pore size
With scanning electronic microscope (SEM) the foam square section is carried out 300 times and amplify to xerox,, this abscess number is removed straight length xeroxing the abscess number on the counting 30mm straight length on the photo, then average abscess chord length.Measure according to GB/T 12811 testing method.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (11)
1. the preparation method of a foamed phenolic resin may further comprise the steps:
A, add phenol, aldehyde and alkaline catalysts in reactor, three's mol ratio is 1: 1～3: 0.01～0.1; At 70～90 ℃, stirred 5～8 hours;
Reaction solution is cooled to 50～60 ℃ among b, the step a, and adding acid, to be stirred to the pH value be 6.0～8.0;
The reaction solution decompression dehydration of c, step b, to 60～70 ℃ of following viscosity be 2500～7000mPa.s.
2. preparation method according to claim 1, it is characterized in that: described step c is specially: the reaction solution of step b is stopped dehydration at vacuum tightness 0.080～0.082MPa, 60～70 ℃ of water-bath decompression dehydrations during to viscosity 2500～7000mPa.s, be cooled to 52 ℃.
3. preparation method according to claim 1 and 2 is characterized in that: described phenol is selected from cresols, xylenol, to alkylphenol, Resorcinol.
4. preparation method according to claim 1 and 2 is characterized in that: described aldehyde is selected from formaldehyde, acetaldehyde.
5. preparation method according to claim 1 and 2 is characterized in that: the mol ratio of described phenol, aldehyde and alkaline catalysts is 1: 1.4～2.5: 0.03～0.08.
6. preparation method according to claim 1 and 2 is characterized in that: described basic catalyst is selected from potassium hydroxide, sodium hydroxide, hydrated barta.
7. resol of obtaining of preparation method according to claim 1, it is characterized in that: free phenol is 2～3wt% in this resol, free aldehyde is 1～2wt%; Water-content is 5～12wt%; Gel time is 80～400s; Solid content is 75～90wt%.
8. phenolic resin foam, as resol, the tensio-active agent of 1～6 weight part, the whipping agent of 1～25 weight part and the acid as curing agent of 5～25 weight parts as described in the claim 7, the mixing foaming is made by 100 weight parts.
9. phenolic resin foam according to claim 8 is characterized in that: described tensio-active agent is selected from polysiloxane, polyoxyethylene and polyoxypropylene three's segmented copolymer, polyoxyethylene, polyethenoxy ether, polysorbate.
10. phenolic resin foam according to claim 8 is characterized in that: described whipping agent is selected from one or more in pentane, hexane, butane and their isomer.
11. phenolic resin foam according to claim 8 is characterized in that: described acid as curing agent is selected from one or more in Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, sulfocarbolic acid, sulfuric acid, the phosphoric acid.
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| CN102002207A (en) * | 2010-11-16 | 2011-04-06 | 山东大学 | Preparation process of phenolic resin porous material |
| CN102127197A (en) * | 2010-12-01 | 2011-07-20 | 山东圣泉化工股份有限公司 | Preparation method for phenolic resin for magnesia-carbon brick |
| CN102212245A (en) * | 2011-05-11 | 2011-10-12 | 山东圣泉化工股份有限公司 | Phenolic resin foaming body |
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| CN103146015B (en) * | 2013-03-15 | 2014-11-26 | 中国科学院化学研究所 | Low-acidity phenolic foam and preparation method thereof |
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| CN105001386A (en) * | 2015-06-09 | 2015-10-28 | 中国林业科学研究院林产化学工业研究所 | High-activity phenolic compound modified expandable phenolic resin and preparation method thereof |
| CN105175989A (en) * | 2015-09-29 | 2015-12-23 | 天津科技大学 | Method for preparing shrimp and crab shell modified phenolic foam |
| CN110289139A (en) * | 2019-06-25 | 2019-09-27 | 红旗集团江西铜业有限公司 | A kind of processing technology for copper enameled wire |
| CN113278121A (en) * | 2021-04-26 | 2021-08-20 | 中国科学院化学研究所 | Method for preparing special phenolic resin with narrow distribution and wide processing window in expansion mode, production device and stability evaluation method |
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Application publication date: 20101110 |