CN105001386A - High-activity phenolic compound modified expandable phenolic resin and preparation method thereof - Google Patents
High-activity phenolic compound modified expandable phenolic resin and preparation method thereof Download PDFInfo
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- CN105001386A CN105001386A CN201510323268.3A CN201510323268A CN105001386A CN 105001386 A CN105001386 A CN 105001386A CN 201510323268 A CN201510323268 A CN 201510323268A CN 105001386 A CN105001386 A CN 105001386A
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Abstract
The invention relates to a preparation method for high-activity phenolic compound modified expandable phenolic resin. Raw materials of the resin comprises, by weight, 35 to 55 parts of phenol, 0.5 to 10 parts of high-activity phenolic compound, 15 to 40 parts of aldehyde compound, 0.5 to 5 parts of basic catalyst and 10 to 30 parts of water. The high-activity phenolic compound modified expandable phenolic resin is prepared through step-by-step condensation polymerization technology, the phenol, the basic catalyst, the water and parts of the aldehyde compound are added into a four-opening flask, reaction is conducted for a period of time, the residual aldehyde compound is added in batches, and reaction is conducted continuously; the temperature is lowered to 55 to 75 DEG C, the high-activity phenolic compound is added, reaction is conducted continuously for a period of time, and the high-activity expandable phenolic resin is prepared. According to the preparation method for the high-activity phenolic compound modified expandable phenolic resin, part of phenol is replaced by the high-activity phenolic compound, the activity of the resin is improved, and at the same time, the free formaldehyde content of the resin, and the dosage of the curing agent and the curing temperature of the resin are lowered; in addition, no waste water is generated in the preparation process of the resin, and the environmental pollution and energy waste due to dehydration are avoided.
Description
Technical field
The present invention relates to the preparation field of high active phenolic resin, be specifically related to the preparation method of high reactivity phenolic compound modification expandability large arch dam resol.
Background technology
Heat-reactive phenolic resin is the superpolymer being reacted preparation by phenolic compound and aldehyde compound under the catalysis of basic catalyst by condensation polymerization.Foam materials can be obtained through overcuring at a certain temperature after the auxiliary agents such as heat-reactive phenolic resin, tensio-active agent, whipping agent and solidifying agent mix, this foam materials has the advantages such as insulation, flame retardant properties, resistance to elevated temperatures and sound insulation, is widely used in the fields such as building, automobile, boats and ships, air material, petroleum pipe line.More in the research of phenol formaldehyde foam in phenolic foam material at present.CN 103897125 A provides a kind of Nitrogen-containing Phenolic Resins of modified by cardanol, both cardanol side base had been comprised in the phenolic resin structure that this technology is produced, again containing N element, overcome the fragility of resol, improve the resistance to elevated temperatures of resol, flexibility and shock resistance.CN 102936325A provides a kind of large arch dam expandability urea modified phenolic resin and preparation method thereof, this technology adopts urea modified phenolic resin, reduce free formaldehyde content, instead of part phenol adding of urea simultaneously, reduce the free phenol content in production of resins cost and resin.CN 103214642 A provides one and prepares foaming at normal temp phenolic resins, this technology aminated compounds (urea or urea) modified phenolic resins, obtained low viscosity, highly active resol, solidify 8-10 minute obtained high-performance fireproof heat preservation plate in the resol of this modification and tensio-active agent, whipping agent, Alcoholic modifier, rubber powder, polystyrene foam particles, solidifying agent normal temperature environment.
But the most of phenol resin active produced at present is lower, and the acid curing agent needed during curing molding is many and solidification value is high, and set time is long.The emphasis that the activity improving resol will be research.High reactivity phenolic compound modified phenolic resins introduces high reactivity phenolic compound in resol molecule.CN 102633968 A and CN 103146015 A improves a kind of preparation technology of high reactivity phenolic monomers modified phenolic foam, this technique is by shaping to resol, high reactivity phenols (Resorcinol, Phloroglucinol and Resorcinol etc.) and the blended even post-foaming of frothing aid, the method prepares the phenol formaldehyde foam of low density, high closed pore, low acidity, but because the high reactivity phenol normal temperature used is solid, directly and resin alloy, lack of homogeneity.
High reactivity phenolic compound adds in the polycondensation later stage by the present invention, reacts under alkaline condition with the methylol that generates in early stage, while also can with the aldehyde reaction of remnants.The introducing of high reactivity phenolic compound, not only can improve the activity of resol, and the free formaldehyde content in resin significantly declines.Obtained high active phenolic resin prepares phenolic aldehyde foam thermal insulation material through curing reaction under low acid as curing agent, low temperature, reduces phenolic foam material acid curing agent in use to the corrosion of construction wall, petroleum pipe line etc., and save energy.
Summary of the invention
The technical problem solved is low in order to solve the phenol resin active existed in prior art, the acid curing agent needed during curing molding is many, the problems such as solidification value is high, the present invention utilizes high reactivity phenolic compound Substitute For Partial phenol to prepare resol, improve the activity of resol, reduce hardener dose, solidification value and set time simultaneously, reduce phenolic foam material acid curing agent to the corrosion of construction wall, petroleum pipe line etc., and save energy.
Technical scheme high reactivity phenolic compound modification expandability large arch dam resol, resin raw material formula, in mass parts, consists of: phenol 35 ~ 55 parts, high reactivity phenolic compound 0.5 ~ 10 part, aldehyde compound 15 ~ 40 parts, basic catalyst 0.5 ~ 5 part, 10 ~ 30 parts, water.
Described high reactivity phenolic compound modification expandability large arch dam resol, is characterized in that described high reactivity phenolic compound is any one in meta-cresol, p-cresol, ortho-cresol, 3,5-xylenols or Resorcinol.
Described high reactivity phenolic compound modification expandability large arch dam resol, is characterized in that described aldehyde compound is any one in paraformaldehyde, acetaldehyde, furfural or salicylic aldehyde.
Described high reactivity phenolic compound modification expandability large arch dam resol, is characterized in that described basic catalyst is any one in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or calcium oxide.
Described high reactivity phenolic compound modification expandability large arch dam resol, step is:
(1) 35 ~ 55 parts of phenol, 0.5 ~ 5 part of basic catalyst, 10 ~ 30 parts of water are joined in the four-hole boiling flask with prolong, be warming up to 70 ~ 90 DEG C, add 4 ~ 10 parts of aldehyde compound reactions 10 ~ 30 minutes;
(2) add remaining aldehyde compound in the mixed solution reacted to (1), point to add for 3 ~ 4 times, control temperature of reaction 70 ~ 90 DEG C, react 30 ~ 60 minutes;
(3) be cooled to 55 ~ 75 DEG C, add 0.5 ~ 10 part of high reactivity phenolic compound and continue reaction 20 ~ 60 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of high reactivity compounds modification.
Described high reactivity phenolic compound modification expandability large arch dam resol, it is characterized in that, the solids content of the high active phenolic resin of preparation is 70% ~ 85%.
Beneficial effect
1. the present invention's high reactivity phenolic compound Substitute For Partial phenol, the resol methylol group content of preparation increases, and resin activity is improved;
2. the phenolic resin curative consumption that prepared by the present invention reduces, and solidification value reduces, and set time shortens;
3. the present invention prepare in resol process resin preparation process without waste water produce, avoid environmental pollution and energy dissipation.
Embodiment
Basic catalyst sodium hydroxide in the embodiment of the present invention, potassium hydroxide, hydrated barta are the aqueous solution that mass concentration is 30wt%.
Below in conjunction with concrete example, illustrate the solution of the present invention and effect further, the number described in following embodiment is mass fraction.
Embodiment 1
(1) 35g phenol, 0.5g calcium oxide, 10g water are joined in the four-hole boiling flask with prolong, be warming up to 70 DEG C of reactions, add 4g polyformaldehyde reaction 10 minutes;
(2) add paraformaldehyde 11g in the mixed solution reacted to (1), point to add for 3 times, control temperature of reaction 70 DEG C, copolycondensation 30 minutes;
(3) be cooled to 55 DEG C, add 0.5g meta-cresol and continue reaction 20 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of meta-cresol modification.
Resin fundamental property and curing process condition see attached list 1.
Embodiment 2
(1) by 55g phenol, 16.5g 30% (wt) Ba (OH)
2solution, 20g water join in the four-hole boiling flask with prolong, are warming up to 90 DEG C, add 10g furfural reaction 30 minutes;
(2) add furfural 30g in the mixed solution reacted to (1), point to add for 3 times, control temperature of reaction 90 DEG C, copolycondensation 60 minutes;
(3) be cooled to 75 DEG C, add 10g p-cresol and continue reaction 60 minutes, being cooled to 40 DEG C of dischargings, preparing the expandable phenolic resin to adding phenol modification.
Resin fundamental property and curing process condition see attached list 1.
Embodiment 3
(1) 45g phenol, 7.5g 30% (wt) NaOH solution, 10g water are joined in the four-hole boiling flask with prolong, be warming up to 85 DEG C, add 6g polyformaldehyde reaction 20 minutes;
(2) add paraformaldehyde 24g in the mixed solution reacted to (1), point to add for 4 times, control temperature of reaction 85 DEG C, copolycondensation 40 minutes;
(3) be cooled to 65 DEG C, add 5g Resorcinol and continue reaction 35 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of Resorcinol modification.
Resin fundamental property and curing process condition see attached list 1.
Embodiment 4
(1) 50g phenol, 3g sodium carbonate, 15g water are joined in the four-hole boiling flask with prolong, be warming up to 75 DEG C, add 8g acetaldehyde and react 15 minutes;
(2) add acetaldehyde 30g in the mixed solution reacted to (1), point to add for 4 times, control temperature of reaction 80 DEG C, copolycondensation 50 minutes;
(3) be cooled to 60 DEG C, add 8g ortho-cresol and continue reaction 40 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of ortho-cresol modification.
Resin fundamental property and curing process condition see attached list 1.
Embodiment 5
(1) 40g phenol, 4g salt of wormwood, 25g water are joined in the four-hole boiling flask with prolong, be warming up to 82 DEG C, add 7g salicylic aldehyde and react 25 minutes;
(2) add 15g furfural in the mixed solution reacted to (1), point to add for 3 times, control temperature of reaction 90 DEG C, copolycondensation 55 minutes;
(3) be cooled to 62 DEG C, add 2g 3,5-xylenol and continue reaction 25 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of 3,5-xylenol modification.
Resin fundamental property and curing process condition see attached list 1.
Embodiment 6
(1) 38g phenol, 6g 30% (wt) KOH solution, 13g water are joined in the four-hole boiling flask with prolong, be warming up to 87 DEG C, add 5g polyformaldehyde reaction 17 minutes;
(2) add paraformaldehyde 20g in the mixed solution reacted to (1), point to add for 4 times, control temperature of reaction 78 DEG C, copolycondensation 45 minutes;
(3) be cooled to 72 DEG C, add 3.5g Resorcinol and continue reaction 45 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of Resorcinol modification.
Resin fundamental property and curing process condition see attached list 1.
The high reactivity expandable phenolic resin of subordinate list 1 different ingredients and curing process condition
The detection of above-mentioned resol and foam materials thereof: methylol group content detects by the regulation of GB/T14074-2006; Solids content detects by the regulation of GB/T14074-2006; Compressive strength specifies test by GB 8813-2008; Flexural strength specifies test by GB 8812-2007.
Claims (6)
1. high reactivity phenolic compound modification expandability large arch dam resol, it is characterized in that, resin raw material formula, in mass parts, consists of:
2. high reactivity phenolic compound modification expandability large arch dam resol according to claim 1, is characterized in that described high reactivity phenolic compound is any one in meta-cresol, p-cresol, ortho-cresol, 3,5-xylenols or Resorcinol.
3. high reactivity phenolic compound modification expandability large arch dam resol according to claim 1, is characterized in that described aldehyde compound is any one in paraformaldehyde, acetaldehyde, furfural or salicylic aldehyde.
4. high reactivity phenolic compound modification expandability large arch dam resol according to claim 1, is characterized in that described basic catalyst is any one in sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood or calcium oxide.
5. high reactivity phenolic compound modification expandability large arch dam resol according to claim 1, it is characterized in that, step is:
(1) 35 ~ 55 parts of phenol, 0.5 ~ 5 part of basic catalyst, 10 ~ 30 parts of water are joined in the four-hole boiling flask with prolong, be warming up to 70 ~ 90 DEG C, add 4 ~ 10 parts of aldehyde compound reactions 10 ~ 30 minutes;
(2) add remaining aldehyde compound in the mixed solution reacted to (1), point to add for 3 ~ 4 times, control temperature of reaction 70 ~ 90 DEG C, react 30 ~ 60 minutes;
(3) be cooled to 55 ~ 75 DEG C, add 0.5 ~ 10 part of high reactivity phenolic compound and continue reaction 20 ~ 60 minutes, be cooled to 40 DEG C of dischargings, prepare the expandable phenolic resin of high reactivity phenolic compound modification.
6. high reactivity phenolic compound modification expandability large arch dam resol according to claim 1, it is characterized in that, the solids content of the high active phenolic resin of preparation is 70% ~ 85%.
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Cited By (4)
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| CN106046283A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | High-ortho benzyl ether phenolic resin and preparation method thereof, and method for applying high-ortho benzyl ether phenolic resin to cold box binder |
| CN106220800A (en) * | 2016-08-31 | 2016-12-14 | 四川国能高科生物树脂有限公司 | A kind of fast curing type bio-oil phenol-formaldehyde resin modified and preparation method thereof |
| CN107629404A (en) * | 2017-09-18 | 2018-01-26 | 中国林业科学研究院林产化学工业研究所 | Silicon whisker phenol-formaldehyde resin modified and its preparation method and application |
| CN117467097A (en) * | 2023-12-28 | 2024-01-30 | 上海大学 | Phenol-formaldehyde resin capable of being cured at room temperature by using benzenediol, and preparation method and application thereof |
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| CN106046283A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | High-ortho benzyl ether phenolic resin and preparation method thereof, and method for applying high-ortho benzyl ether phenolic resin to cold box binder |
| CN106220800A (en) * | 2016-08-31 | 2016-12-14 | 四川国能高科生物树脂有限公司 | A kind of fast curing type bio-oil phenol-formaldehyde resin modified and preparation method thereof |
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| CN117467097A (en) * | 2023-12-28 | 2024-01-30 | 上海大学 | Phenol-formaldehyde resin capable of being cured at room temperature by using benzenediol, and preparation method and application thereof |
| CN117467097B (en) * | 2023-12-28 | 2024-04-05 | 上海大学 | Phenol-formaldehyde resin capable of being cured at room temperature by using benzenediol, and preparation method and application thereof |
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