CN103087280B - Method for synthesizing phenolic resins by using paraformaldehyde - Google Patents
Method for synthesizing phenolic resins by using paraformaldehyde Download PDFInfo
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- CN103087280B CN103087280B CN201310029204.3A CN201310029204A CN103087280B CN 103087280 B CN103087280 B CN 103087280B CN 201310029204 A CN201310029204 A CN 201310029204A CN 103087280 B CN103087280 B CN 103087280B
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Abstract
The invention belongs to the technical field of phenolic resin synthesis, and discloses a method for synthesizing phenolic resins by using paraformaldehyde. The method comprises the following steps: opening a reaction kettle stirring mechanism, pumping preheated phenol into a reaction kettle in a reduced pressure state, then pumping recycled phenol containing wastewater into the reaction kettle and carrying out vacuum removal on the reaction kettle, and putting paraformaldehyde into the reaction kettle to uniformly heat at normal pressure so as to heat the obtained mixture to be boiled; after the boiling reaction is completed, cooling the obtained mixture, and adding an oxalic acid solution into the reaction kettle; after the obtained mixture is heated to be boiled and the pressure-reduced dehydration temperature rises to 150 DEG C, carrying out slow vacuum enrichment and then emptying on the obtained product so as to obtain phenolic resins, wherein the proportion of macromolecular weights of the phenolic resins is less than 6%, and the proportion of middle molecular weights of the phenolic resins is more than 80%. The phenolic resins prepared by using the method disclosed by the invention have high fluidity, and have a higher bonding strength when being taken as a binder under the condition that the resin adding amount is less.
Description
Technical field
The invention belongs to the synthetic technical field of resol, disclose a kind of method with paraformaldehyde novolak resin.
Background technology
Increasing research work in recent years shows the performance of distribution influence resol of the molecular size range, particularly molecular weight of resol.The more resol of middle molecular weight distribution is compared with common resol, and the former has lower softening temperature, longer degree of mobilization and compared with the curing action of homogeneous, in the situation that resol add-on is less, performance is significantly improved.
The common method that method that molecular weight narrows down is included in react in organic solvent and by the low-molecular-weight resol of removing of vapor distillation and solution washing, this procedure is complicated, produce a large amount of organic solvent and waste water, greatly polluted environment, and production cost improves.
Kurimoto etc. are in US Patent No. 6,001, and 949, US5,929,191 and US5,859, thus a kind of method that adopts tartrate, citric acid etc. to carry out the resol of catalysis of phenol and formaldehyde preparation narrow molecular weight distributions is disclosed in 168.Because organic acid consumption is high, the method has increased the cost of resol.
Rahman etc. are in US Patent No. 6,045,966, US5,977,288, US5,928,836 and US5, in 853,953, disclose the method that adopts the mixture of water soluble organic polar solvent/water to precipitate in batches phenol formaldehyde (PF) condensation product resol has been carried out to classification, thereby reached the object of resol molecular weight distribution.But the method has been prepared resol progressively classification afterwards, has increased preparation section, has consumed a large amount of organic solvents, has increased contaminated wastewater, from resol polycondensation, itself does not control the distribution of molecular weight.
Japanese Patent JP01-036618 and JP63-286424 have described the narrow distribution resol that a kind of epoxy curing agent is used, it is prepared in two steps, the first step phenol, formaldehyde, NaOH are that under 1:3:1, room temperature reaction obtains 2 in one week in mol ratio, 4,6 tri hydroxy methyl phenols, second 2,4,6 tri hydroxy methyl phenols and phenol obtain linear phenolic resin with phenol reactant under an acidic catalyst.The method NaOH consumption is large, and the reaction times is long, is difficult to realize suitability for industrialized production.In Chinese patent 00135829.4, introduced the improvement technique of above operational path, although reduced the reaction times, after first alkali, the technique controlling difficulty of acid is large, is difficult to realize suitability for industrialized production.
In Chinese patent 00131050.X, adopt organic phosphoric acid as catalyzer, to prepare the resol of narrow molecular weight distributions, in reaction, need to add a large amount of catalyzer, and need washing that catalyzer is removed, this had both increased cost, increased again wastewater flow rate, if do not wash, the residual a large amount of catalyzer of meeting in resin, thus reduce resin property.
What in Chinese patent CN200710129851.6, adopt is composite catalyst, and catalyzer add-on is larger, and cost is high, and what in producing, use is liquid formaldehyde, and the waste water of generation is also more.
Summary of the invention
Object of the present invention is just to provide a kind of method with paraformaldehyde novolak resin.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A method with paraformaldehyde novolak resin, is characterized in that being made by the raw material of following weight part:
Open reactor stirring mechanism, under the decompression state that is-0.06MPa ~-0.08Mpa at pressure, the phenol of 100 weight parts of preheating is pumped in reactor, the phenolic wastewater of the recovery that is then 1 ~ 2 by the pH value of 10 ~ 30 weight parts, is 5% ~ 6% containing phenol amount is pumped in described reactor removes vacuum, under normal pressure, the paraformaldehyde of 25 ~ 27 weight parts is dropped into homogeneous heating in reactor, make its 30-40 minute be warming up to boiling; After boiling reaction 1.5-2.5 hour, be cooled to 70 ℃, add oxalic acid solution; The extremely boiling at intensification 30-40 minute; Boiling reaction 2-4 hour, be decompressed to-0.06MPa ~-0.08MPa dehydration, when dehydration temperaturre rises to 150 ℃, while slowly increasing vacuum to-0.09Mpa, then blowing can obtain the resol that macromolecule proportion is less than 8%, middle molecular weight proportion is greater than 80%.
Method with paraformaldehyde novolak resin provided by the present invention compared with prior art, have the following advantages: one, employing paraformaldehyde is raw material, add a small amount of processing wastewater, in the situation that not adding catalyzer, by paraformaldehyde depolymerization, after depolymerization, be cooled to 70 ℃, the catalyzer that adds minute quantity, the linear phenolic resin of deferred reaction synthetic macromolecule amount proportion < 8%, middle molecular weight proportion > 80%, it is for the tackiness agent of refractory materials dry materials, and its performance can improve greatly; They are two years old, because paraformaldehyde shifts to an earlier date depolymerization, can not concentrate reaction, concentrate heat release, in reaction process, reduced the severe degree of reaction, reaction is easily controlled, and in the situation that the add-on of catalyzer greatly reduces, make that generated middle molecular weight proportion is more, the less linear phenolic resin of macromolecule proportion, and slowed down the severe degree of reaction; Its four, employing paraformaldehyde is raw material, has greatly reduced the generation of processing wastewater, the operating process that makes to produce easily controls, simple.
accompanying drawing explanation:
Fig. 1 is the GPC spectrogram of resol in the embodiment of the present invention 1;
Fig. 2 is the GPC spectrogram of resol in the embodiment of the present invention 2;
Fig. 3 is the GPC spectrogram of resol in the embodiment of the present invention 3;
Fig. 4 is the GPC spectrogram of resol in comparative example 1 of the present invention;
Fig. 5 is the GPC spectrogram of resol in comparative example 1 of the present invention.
Embodiment
Below in conjunction with specific embodiment, the method with paraformaldehyde novolak resin provided by the present invention and preparation thereof are described in further detail.
Embodiment 1:
Open stirring, then under decompression state, (pressure is-0.06MPa) is pumped into preheated phenol 400kg in reactor, and the phenolic wastewater then 100kg being reclaimed (pH value, 2, is 5.5% containing phenol amount) is pumped in reactor, removes vacuum.Under normal pressure, 104kg paraformaldehyde (content is 96%) is dropped in reactor, heat temperature raising then, homogeneous heating, is warming up to boiling for 30-40 minute.Boiling reaction 2 hours.Then be cooled to 70 ℃, add 2kg oxalic acid solution, heat up and within 30 minutes, be warming up to boiling.Boiling reaction 2 hours, decompression dehydration, while dewatering to 150 ℃, slowly increases vacuum to 0.09MPa, and then blowing obtains High Performance Phenolic Resins.
The parameter of this resol as shown in Figure 1,
| Sequence number | Title | Retention time (minute) | Mn | Area | % area |
| 1 | Peak 2 | 12.000 | 16211 | 17697 | 4.14 |
| 2 | Wide distribution | 15.300 | 1567 | 351087 | 82.03 |
| 3 | Peak 4 | 17.558 | 355 | 26836 | 6.27 |
| 4 | Peak 5 | 18.348 | 189 | 32364 | 7.56 |
Also,
1, molecular weight to be greater than 11650 region 1(be also the region that the B that is 11650 from spring of curve A to molecular weight in coordinate forms) molecular-weight average be that Mn1 is 16211, shared region area is 17697, accounts for 4.14% of the total area;
2, molecular weight is also the region that C that the B that is 11650 from molecular weight in coordinate is 380 to molecular weight forms at 11650-380 region 2() molecular-weight average be that Mn1 is 1567, shared region area is 351087, accounts for 82.03% of the total area;
3, molecular weight is also the region that D that the C that is 380 from molecular weight in coordinate is 290 to molecular weight forms at 380-290 region 3() molecular-weight average be that Mn1 is 355, shared region area is 26836, accounts for 6.27% of the total area;
4, molecular weight is also the region that E that the D that is 290 from molecular weight in coordinate is 202 to molecular weight forms at 290-202 region 4() molecular-weight average be that Mn1 is 189, shared region area is 32364, accounts for 7.56% of the total area.
Embodiment 2:
Open stirring, then under decompression state, (pressure is-0.07MPa) is pumped into preheated phenol 400kg in reactor, and the phenolic wastewater then 80kg being reclaimed (pH value, 1, is 6% containing phenol amount) is pumped in reactor, removes vacuum.Under normal pressure, 108kg paraformaldehyde (content is 96%) is dropped in reactor, heat temperature raising then, homogeneous heating, is warming up to boiling for 30-40 minute.Boiling reaction 2 hours.Then be cooled to 70 ℃, add 3kg oxalic acid solution, heat up and within 30 minutes, be warming up to boiling.Boiling reaction 3 hours, decompression dehydration, while dewatering to 150 ℃, slowly increases vacuum to 0.09MPa, and then blowing obtains High Performance Phenolic Resins.
The performance perameter of this resol as shown in Figure 2,
| Sequence number | Title | Retention time (minute) | Mn | Area | % area |
| 1 | Peak 2 | 12.000 | 15328 | 11732 | 2.70 |
| 2 | Wide distribution | 15.067 | 1532 | 358178 | 82.31 |
| 3 | Peak 4 | 17.592 | 352 | 29477 | 6.77 |
| 4 | Peak 5 | 18.383 | 183 | 35745 | 8.21 |
Also,
1, molecular weight to be greater than 11650 region 1(be also the region that the B that is 11650 from spring of curve A to molecular weight in coordinate forms) molecular-weight average be that Mn1 is 15328, shared region area is 11732, accounts for 2.70% of the total area;
2, molecular weight is also the region that C that the B that is 11650 from molecular weight in coordinate is 371 to molecular weight forms at 11650-371 region 2() molecular-weight average be that Mn1 is 1532, shared region area is 358178, accounts for 82.31% of the total area;
3, molecular weight is also the region that D that the C that is 371 from molecular weight in coordinate is 284 to molecular weight forms at 371-284 region 3() molecular-weight average be that Mn1 is 352, shared region area is 26836, accounts for 6.77% of the total area;
4, molecular weight is also the region that E that the D that is 284 from molecular weight in coordinate is 197 to molecular weight forms at 284-197 region 4() molecular-weight average be that Mn1 is 183, shared region area is 35745, accounts for 8.21% of the total area.
Embodiment 3:
Open stirring, then under decompression state, (pressure is-0.08MPa) is pumped into preheated phenol 400kg in reactor, and the phenolic wastewater then 80kg being reclaimed (pH value, 1.5, is 5% containing phenol amount) is pumped in reactor, removes vacuum.Under normal pressure, 106kg paraformaldehyde (content is 96%) is dropped in reactor, heat temperature raising then, homogeneous heating, is warming up to boiling for 30-40 minute.Boiling reaction 2 hours.Then be cooled to 70 ℃, add 4kg oxalic acid solution, heat up and within 30 minutes, be warming up to boiling.Boiling reaction 4 hours, decompression dehydration, while dewatering to 150 ℃, slowly increases vacuum to 0.09MPa, and then blowing obtains High Performance Phenolic Resins.
The performance perameter of this resol as shown in Figure 3,
| Sequence number | Title | Retention time (minute) | Mn | Area | % area |
| 1 | Peak 2 | 12.000 | 16330 | 26607 | 5.85 |
| 2 | Wide distribution | 15.100 | 1568 | 368527 | 81.02 |
| 3 | Peak 4 | 17.600 | 336 | 25636 | 5.64 |
| 4 | Peak 5 | 18.393 | 179 | 34078 | 7.49 |
Also,
1, molecular weight to be greater than 11650 region 1(be also the region that the B that is 11650 from spring of curve A to molecular weight in coordinate forms) molecular-weight average be that Mn1 is 16330, shared region area is 26607, accounts for 5.85% of the total area;
2, molecular weight is also the region that C that the B that is 11650 from molecular weight in coordinate is 368 to molecular weight forms at 11650-368 region 2() molecular-weight average be that Mn1 is 1568, shared region area is 368527, accounts for 81.02% of the total area;
3, molecular weight is also the region that D that the C that is 368 from molecular weight in coordinate is 280 to molecular weight forms at 368-280 region 3() molecular-weight average be that Mn1 is 336, shared region area is 25636, accounts for 5.64% of the total area;
4, molecular weight is also the region that E that the D that is 280 from molecular weight in coordinate is 196 to molecular weight forms at 280-196 region 4() molecular-weight average be that Mn1 is 179, shared region area is 34078, accounts for 7049%. of the total area
Comparative example 1:
Open stirring, then under decompression state, (pressure is-0.06MPa ~-0.08MPa) is pumped in reactor by preheated phenol 400kg, 8kg oxalic acid gradually, within 30-40 minute, be warming up to 88-90 ℃, start to drip liquid formaldehyde and (be total to 281kg, content 37%), per minute drips 4.6kg, within 1 hour, drips off.After dripping off, be naturally warming up to boiling, boiling reaction 3 hours, decompression dehydration, while dewatering to 150 ℃, slowly increases vacuum to 0.09MPa, and then blowing obtains resol.
The performance perameter of this resol as shown in Figure 4,
| Sequence number | Title | Retention time (minute) | Mn | Area | % area |
| 1 | Peak 2 | 11.950 | 16012 | 58835 | 10.02 |
| 2 | Wide distribution | 14.300 | 1736 | 459314 | 78.21 |
| 3 | Peak 4 | 17.582 | 349 | 32348 | 5.51 |
| 4 | Peak 5 | 18.367 | 184 | 36786 | 6.26 |
Comparative example 2:
Open stirring, then under decompression state, (pressure is-0.06MPa ~-0.08MPa) is pumped in reactor by preheated phenol 400kg, 6kg oxalic acid gradually, within 30-40 minute, be warming up to 88-90 ℃, start to drip liquid formaldehyde and (be total to 289kg, content 37%), per minute drips 4.8kg, within 1 hour, drips off.After dripping off, be naturally warming up to boiling, boiling reaction 2 hours, decompression dehydration, while dewatering to 150 ℃, slowly increases vacuum to 0.09MPa, and then blowing obtains resol.
The performance perameter of this resol as shown in Figure 4,
| Sequence number | Title | Retention time (minute) | Mn | Area | % area |
| 1 | Peak 2 | 11.862 | 16340 | 61441 | 10.26 |
| 2 | Wide distribution | 14.600 | 1677 | 465481 | 77.72 |
| 3 | Peak 4 | 17.610 | 338 | 34123 | 5.70 |
| 4 | Peak 5 | 18.402 | 177 | 37898 | 6.33 |
In the above embodiments 1-3 and comparative example 1,2, preheated phenol refers to the liquefied carbolic acid that Phenol,Solid is heated to 50-60 ℃ of formation.
By the GPC(gel liquid chromatography to above-mentioned three embodiment and two comparative examples) spectrogram (respectively corresponding Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5) carries out after area integral, obtains molecular size range and distribution situation relatively in Table 1:
The data sheet of table 1 embodiment 1-3 and comparative example 1-2
As can be seen from Table 1, adopt the synthetic resol of this production method compared with common resol, macromolecule proportion can significantly reduce, and middle molecule proportion can effectively improve, this is conducive to improve the degree of mobilization of resol, in the situation that resin amount is few, play higher intensity.
In the specification sheets of present patent application:
---macromolecule proportion refers to that molecular size range is the shared ratio of resin of >10633;
---middle molecular weight proportion refers to the shared ratio of the resin of molecular weight ranges in (10633 ~ 441);
---in table, Mn refers to number-average molecular weight.
Claims (1)
1. by a method for paraformaldehyde novolak resin, comprise the following steps:
Open reactor stirring mechanism, under the decompression state that is-0.06MPa ~-0.08MPa at pressure, the phenol of 100 weight parts of preheating is pumped in reactor, the phenolic wastewater of the recovery that is then 1 ~ 2 by the pH value of 10 ~ 30 weight parts, is 5% ~ 6% containing phenol amount is pumped in described reactor removes vacuum, under normal pressure, the paraformaldehyde of 25 ~ 27 weight parts is dropped into homogeneous heating in reactor, make its 30-40 minute be warming up to boiling; After boiling reaction 1.5-2.5 hour, be cooled to 70 ℃, add oxalic acid solution; The extremely boiling at intensification 30-40 minute; Boiling reaction 2-4 hour, be decompressed to-0.06MPa ~-0.08MPa dehydration, when dehydration temperaturre rises to 150 ℃, while slowly increasing vacuum to-0.09MPa, the resol that then blowing can obtain that molecular weight is greater than that 10633 macromolecule proportion is less than 8%, molecular weight is greater than 80% at the middle molecular weight proportion of 10633 ~ 441 scopes.
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| CN105199063B (en) * | 2015-10-28 | 2018-01-19 | 山东永汇新材料股份有限公司 | The preparation method of paraformaldehyde novolak resin |
| CN106496471B (en) * | 2016-10-11 | 2018-08-24 | 洛阳双瑞橡塑科技有限公司 | The preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system |
| CN106750061B (en) * | 2017-03-13 | 2020-01-24 | 河北泽田化工有限公司 | High-water-resistance phenolic resin and preparation process thereof |
| CN107083217B (en) * | 2017-05-26 | 2020-05-15 | 山东宇世巨化工有限公司 | Poly (arylene ether nitrile) modified phenolic resin adhesive and preparation method thereof |
| CN107141432A (en) * | 2017-07-05 | 2017-09-08 | 郑州振东科技有限公司 | A kind of production method of phenolic resin |
| CN107987237B (en) * | 2017-12-12 | 2021-03-02 | 济南鲁东耐火材料有限公司 | Preparation method of phenolic resin for refractory material |
| CN110330613A (en) * | 2019-07-18 | 2019-10-15 | 河北泽田化工有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof |
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| CN101724133B (en) * | 2009-12-18 | 2011-07-13 | 湖南中野高科技特种材料有限公司 | Method for producing phenolic resin by utilizing paraformaldehyde |
| CN101885818B (en) * | 2010-07-02 | 2012-06-20 | 北京化工大学 | Method for synthesizing expandable phenolic resin |
| CN102241802A (en) * | 2011-04-28 | 2011-11-16 | 北京化工大学 | Comprehensive utilization of phenol-containing wastewater |
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