CN103897125A - Method for preparing thermosetting phenol resin - Google Patents
Method for preparing thermosetting phenol resin Download PDFInfo
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- CN103897125A CN103897125A CN201410126017.1A CN201410126017A CN103897125A CN 103897125 A CN103897125 A CN 103897125A CN 201410126017 A CN201410126017 A CN 201410126017A CN 103897125 A CN103897125 A CN 103897125A
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title abstract description 20
- 229920001187 thermosetting polymer Polymers 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 phenol compound Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 43
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 23
- 150000002989 phenols Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000013517 stratification Methods 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001896 cresols Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003739 xylenols Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 42
- 239000011347 resin Substances 0.000 abstract description 42
- 230000018044 dehydration Effects 0.000 abstract description 18
- 238000006297 dehydration reaction Methods 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 235000013904 zinc acetate Nutrition 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a method for preparing a thermosetting phenol resin. The method comprises the following steps: mixing a phenol compound, an aldehyde compound, an amine compound and a catalyst to have a reaction, standing, layering, dehydrating in vacuum, thus obtaining the thermosetting phenol resin. Compared with the prior art, the method has the advantages that the added amine compound participates in the reaction, the polarity of the resin can be reduced by the reaction products, which is beneficial to separation of the resin layer from the water layer; therefore, the dehydration time at the later stage is reduced, the solid thermosetting phenol resin with stable quality is favorably prepared; and the method is simple in operation and easy to control.
Description
Technical field
The invention belongs to phenolic resins field, relate in particular to a kind of preparation method of heat-reactive phenolic resin.
Background technology
Resol is to realize the earliest in the world industrialized synthetic resins, the history of existing last 100 years, because its raw material is easy to get, cheap so far, production technique and equipment are simple, the more important thing is that its properties of having a mind to has been widely used in the every field of daily life.
Resol can be divided into thermosetting resin and thermoplastic resin, heat-reactive phenolic resin is owing to there being a large amount of active groups in resin structure, cannot use comparatively high temps that the moisture in resin is removed, therefore, heat-reactive phenolic resin is all generally to exist with liquid form, form solid form and generally will use special dehydration and reaction unit, and the generative process of resin is wayward.
The patent No. be JP2005194354 Japanese Patent Publication a kind of preparation technology of solid thermosetting phenolic resin, be elder generation's Heat of Formation plastic resin under acidic conditions, then, under alkaline condition, add aldehyde reaction, under reaction final vacuum condition, dewater, form solid resin.But the late phase reaction of this patent is difficult to control, be difficult for generating stable resin, and the resin softening point of preparation is low.
The patent No. be JP2002201245A Japanese Patent Publication a kind of preparation technology of powdery thermoset phenolic resin.Technological process is as follows: first Heat of Formation solid-liquid resin under alkaline condition, then under vacuum condition, dewater, and the paste resin that contains certain moisture is pulverized at low temperatures, finally by the high temperature fluidized bed dehydration of powdered resin process after pulverizing.Whole preparation process is high to the stability requirement of equipment and process condition.
Application number is that the Chinese patent of CN201110124374 discloses another kind of preparation process: after Heat of Formation solid-liquid resol, add non-proton organic solvent, it is resin-phase, water and solvent phase that resin is divided into three-phase.By this three phase separation, the direct cooling crush of resin-phase, solvent phase recycles and reuses.But in reaction process, the use of a large amount of solvents has increased the factor of environmental influence and dangerous possibility, and in resin, still has many moisture, and the use in resin later stage is still existed to larger impact.
The Chinese patent that other patent is CN200910023149 as application number, the Japanese Patent that the patent No. is JP58074709A have all been made explanation to other preparation methods of thermosetting solid phenolic resin, but have all been had the influence factor of the aspects such as equipment and technology stability.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of heat-reactive phenolic resin, and the method can obtain solid thermosetting phenolic resin and be easy to controlling.
The preparation method who the invention provides a kind of heat-reactive phenolic resin, comprising:
Phenolic compound, aldehyde compound, aminated compounds are reacted with catalyst mix, then carry out, after stratification and vacuum hydro-extraction, obtaining heat-reactive phenolic resin.
Preferably, described phenolic compound is selected from one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, propylphenol, ethylphenol and cardanol.
Preferably, described aldehyde compound is selected from one or more in formaldehyde, acetaldehyde, butyraldehyde, polyoxymethylene and furfural.
Preferably, described aminated compounds is primary amine compounds.
Preferably, described catalyzer is one or more in divalent metal salt, bivalent metal oxide and an alkali metal salt.
Preferably, described catalyzer is selected from one or more in sodium carbonate, zinc oxide, magnesium oxide, calcium oxide and zinc acetate.
Preferably, the mol ratio of described phenolic compound, aldehyde compound and aminated compounds is 1:(1～3): (0.1～1).
Preferably, the quality of described catalyzer is 0.05%～8% of phenolic compound quality.
Preferably, the temperature of described reaction is 60 DEG C～100 DEG C, and the reaction times is 1～6h.
Preferably, also comprise:
After stratification, wash with water.
The preparation method who the invention provides a kind of heat-reactive phenolic resin, comprising: phenolic compound, aldehyde compound, aminated compounds are reacted with catalyst mix, then carry out, after stratification and vacuum hydro-extraction, obtaining heat-reactive phenolic resin.Compared with prior art, the present invention adds aminated compounds and participates in reaction, reaction product can reduce the polarity of resin, contribute to separating of resin layer and water layer, thereby the time that reduces later stage dehydration, contributes to the stable solid thermosetting phenolic resin of preparation quality, and, the present invention is simple to operate, is easy to control.
Embodiment
The invention provides a kind of heat-reactive phenolic resin, comprising:
Phenolic compound, aldehyde compound, aminated compounds are reacted with catalyst mix, then carry out, after stratification and vacuum hydro-extraction, obtaining heat-reactive phenolic resin.
Wherein, the present invention does not have special restriction to the source of all raw materials, for commercially available.
Described phenolic compound is phenolic compound well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, propylphenol, ethylphenol and cardanol, more preferably phenol.
Described aldehyde compound is aldehyde compound well known to those skilled in the art, there is no special restriction, is preferably one or more in formaldehyde, acetaldehyde, butyraldehyde, polyoxymethylene and furfural in the present invention.
Described aminated compounds is preferably one or more in primary amine compounds, secondary-amine compound and tertiary amine compounds, more preferably primary amine compounds, then be preferably one or more in aniline, quadrol and diethylenetriamine.
Described catalyzer is preferably one or more in divalent metal salt, bivalent metal oxide and an alkali metal salt, more preferably one or more in magnesium salts, magnesium oxide, zinc salt, zinc oxide, calcium salt, calcium oxide and sodium salt, be preferably again one or more in sodium carbonate, zinc oxide, magnesium oxide, calcium oxide and zinc acetate, most preferably be magnesium oxide and/or zinc acetate.
Phenolic compound, aldehyde compound, aminated compounds are reacted with catalyst mix.Wherein, described phenolic compound, aldehyde compound are preferably 1:(1～3 according to mol ratio with aminated compounds): the ratio of (0.1～1) is mixed, more preferably 1:(1.2～2.7): (0.2～0.8); The quality optimization of described catalyzer is 0.05%～8% of phenolic compound quality, more preferably 0.1%～6%; The temperature of described reaction is preferably 60 DEG C～100 DEG C, more preferably 80 DEG C～100 DEG C; The time of described reaction is preferably 1～6h, more preferably 1～4h, then be preferably 1～2h.
After hybrid reaction, carry out stratification, separate the water that takes out upper strata.
According to the present invention, after stratification, preferably wash with water, have neither part nor lot in phenolic compound and the aldehyde compound of reaction with remove portion.
Then carry out vacuum hydro-extraction, remove unnecessary moisture, obtain heat-reactive phenolic resin.The present invention preferably heats and dewaters under vacuum.
The present invention adds aminated compounds and participates in reaction, and reaction product can reduce the polarity of resin, contributes to separating of resin layer and water layer, thereby the time that reduces later stage dehydration, contributes to the stable solid thermosetting phenolic resin of preparation quality, and, the present invention is simple to operate, is easy to control; Meanwhile, the resol of aminated compounds modification can react to larger molecular weight.
The present invention adopts following methods to test the heat-reactive phenolic resin obtaining
Polymerization velocity testing method: the heat-reactive phenolic resin of getting 1 ± 0.2g, be placed in above the flat board of 150 ± 0.2 DEG C, stir with scraper, use manual time-keeping simultaneously, in the time that resin agitating can not pull thread, be designated as terminal, this period is the polymerization velocity of heat-reactive phenolic resin at 150 DEG C.
Dissolve viscosity test method: heat-reactive phenolic resin is mixed with to the spirituous solution of resin according to the mass ratio of 1:1, with the soltion viscosity at 25 DEG C of rotational viscosimeter method tests.
Softening temperature testing method is ring and ball method test; In resin, the testing method of free phenol is vapor-phase chromatography; In resin, the test of moisture content adopts karl Fischer method.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of heat-reactive phenolic resin provided by the invention is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
The quadrol of the calcium oxide of the formaldehyde of 940 weight part phenol, 1090 weight parts 44%, 9.4 weight parts and 120 weight parts is added to there is thermometer, in the 3000ml reaction vessel of whipping appts, reflux exchanger, heating 1.5h is warming up to after 100 DEG C of reaction 4h, leave standstill 20min, isolate 489 weight parts waters, remaining resin layer is heated up and the vacuum pressure of keep-0.095MPa under dewater, control dehydration temperaturre below 95 DEG C, utilize the softening temperature of ring and ball method test resin to reach 81 DEG C, obtain the heat-reactive phenolic resin of 1128 weight parts.
The heat-reactive phenolic resin obtaining in embodiment 1 is carried out to Performance Detection, obtain the results are shown in Table 1.
Embodiment 2
By 940 weight part phenol, the formaldehyde of 1227 weight parts 44%, the zinc oxide of 3 weight parts is added to has thermometer, whipping appts, in the 3000ml reaction vessel of reflux exchanger, heating 1.5h is warming up to after 100 DEG C of reaction 2.5h, be cooled to 55 DEG C, add the diethylenetriamine of 206 weight parts, be heated to 70 DEG C of reaction 2h, leave standstill 20min, isolate 1028 weight parts waters, 55 DEG C of washings of water by remaining resin layer with 500 weight parts, divide water outlet 476 weight parts, then resin is heated up and the vacuum pressure of keep-0.095MPa under dewater, control dehydration temperaturre below 95 DEG C, utilize the softening temperature of ring and ball method test resin to reach 85 DEG C, obtain the heat-reactive phenolic resin of 1316 weight parts.
The heat-reactive phenolic resin obtaining in embodiment 2 is carried out to Performance Detection, obtain the results are shown in Table 1.
Embodiment 3
By 2280 weight part dihydroxyphenyl propanes, the formaldehyde of 886 weight parts 44%, the quadrol of the zinc acetate of 34 weight parts and 120 weight parts is added to has thermometer, whipping appts, in the 5000ml reaction vessel of reflux exchanger, heating 1.5h is warming up to after 100 DEG C of reaction 3h, leave standstill 20min, isolate 506 weight parts waters, water washing by remaining resin layer with 500 weight parts, separate the water of 489 weight parts, then resin is heated up and the vacuum pressure of keep-0.095MPa under dewater, control dehydration temperaturre below 95 DEG C, utilize the softening temperature of ring and ball method test resin to reach 93 DEG C, obtain the heat-reactive phenolic resin of 2736 weight parts.
The heat-reactive phenolic resin obtaining in embodiment 3 is carried out to Performance Detection, obtain the results are shown in Table 1.
Embodiment 4
By 1880 weight part phenol, the paraformaldehyde of 1304 weight parts 92%, the aniline of the zinc acetate of 9.4 weight parts and 470 weight parts is added to has thermometer, whipping appts, in the 3000ml reaction vessel of reflux exchanger, heating 2h is warming up to after 100 DEG C of reaction 2h, leave standstill 20min, isolate 188 weight parts waters, water washing by remaining resin layer with 700 weight parts, separate the water of 657 weight parts, then resin is heated up and the vacuum pressure of keep-0.098MPa under dewater, control dehydration temperaturre below 98 DEG C, utilize the softening temperature of ring and ball method test resin to reach 88 DEG C, obtain the heat-reactive phenolic resin of 2444 weight parts.
The heat-reactive phenolic resin obtaining in embodiment 4 is carried out to Performance Detection, obtain the results are shown in Table 1.
Embodiment 5
By 1410 weight part phenol, the formaldehyde of 1304 weight parts 44%, the quadrol of the zinc acetate of 7 weight parts and 141 weight parts is added to has thermometer, whipping appts, in the 5000ml reaction vessel of reflux exchanger, be warming up to after 100 DEG C of reaction 2h, leave standstill 20min, isolate 720 weight parts waters, water washing by remaining resin layer with 700 weight parts, separate the water of 657 weight parts, then resin is heated up and the vacuum pressure of keep-0.098MPa under dewater, control dehydration temperaturre below 95 DEG C, utilize the softening temperature of ring and ball method test resin to reach 83 DEG C, obtain the heat-reactive phenolic resin of 1833 weight parts.
The heat-reactive phenolic resin obtaining in embodiment 5 is carried out to Performance Detection, obtain the results are shown in Table 1.
Comparative example 1
The potassium hydroxide of the formaldehyde of 940 weight part phenol, 1229 weight parts 37% and 40 weight parts 47% is added to there is thermometer, in the 3000ml reaction vessel of whipping appts, reflux condensate device, be heated to 70 DEG C, after 1h, be warming up to 85 DEG C of isothermal reactions, after reaction 1h, dehydration heats up under vacuum-0.09MPa, control dehydration temperaturre below 90 DEG C, resin is at 30min after coagulation.
Comparative example 2
940 weight part phenol, 94 weight part dihydroxyphenyl propanes, the formaldehyde of 1229 weight parts 37% and the ammoniacal liquor of 75 weight parts 25% are added to there is thermometer, in the 3000ml reaction vessel of whipping appts, reflux condensate device, be heated to 65 DEG C, after 1h, be warming up to 80 DEG C of isothermal reactions, after reaction 1h, dehydration heats up under vacuum-0.09MPa, control dehydration temperaturre below 100 DEG C, detect the polymerization velocity of resin, polymerization velocity is after 165s/150 DEG C, rapidly blowing, obtains heat-reactive phenolic resin after cooling.
The heat-reactive phenolic resin obtaining in comparative example 2 is carried out to Performance Detection, obtain the results are shown in Table 1.
Comparative example 3
By 940 weight part phenol, the ammoniacal liquor of the formaldehyde of 1229 weight parts 37% and 75 weight parts 25% is added to has thermometer, whipping appts, in the 3000ml reaction vessel of reflux condensate device, be heated to 70 DEG C, after 1h, be warming up to 90 DEG C of isothermal reactions, after reaction 2h, dehydration heats up under vacuum-0.09MPa, keep under this vacuum condition, dehydration temperaturre reaches 60 DEG C, resin is put into vacuum drying oven, dehydrate, resin thickness is less than 5mm, the temperature of baking oven is 80 DEG C, vacuum tightness is-0.085MPa, after dry 1h, take out, after cooling, obtain heat-reactive phenolic resin.
The heat-reactive phenolic resin obtaining in comparative example 3 is carried out to Performance Detection, obtain the results are shown in Table 1.
Comparative example 4
The formaldehyde of 940 weight part phenol, 1229 weight parts 37% and 9.4 weight part zinc acetates are added to there is thermometer, in the 3000ml reaction vessel of whipping appts, reflux condensate device, after 2h, be warming up to 90 DEG C of isothermal reactions, after reaction 1h, be warming up to 100 DEG C, continue isothermal reaction 4h, then dehydration heats up under vacuum-0.09MPa, control dehydration temperaturre below 100 DEG C, detect the polymerization velocity of resin, polymerization velocity is after 125s/150 DEG C, rapidly blowing, obtains heat-reactive phenolic resin after cooling.
The heat-reactive phenolic resin obtaining in comparative example 4 is carried out to Performance Detection, obtain the results are shown in Table 1.
Table 1 heat-reactive phenolic resin performance test results
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 (10)
1. a preparation method for heat-reactive phenolic resin, is characterized in that, comprising:
Phenolic compound, aldehyde compound, aminated compounds are reacted with catalyst mix, then carry out, after stratification and vacuum hydro-extraction, obtaining heat-reactive phenolic resin.
2. preparation method according to claim 1, is characterized in that, described phenolic compound is selected from one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, propylphenol, ethylphenol and cardanol.
3. preparation method according to claim 1, is characterized in that, described aldehyde compound is selected from one or more in formaldehyde, acetaldehyde, butyraldehyde, polyoxymethylene and furfural.
4. preparation method according to claim 1, is characterized in that, described aminated compounds is primary amine compounds.
5. preparation method according to claim 1, is characterized in that, described catalyzer is one or more in divalent metal salt, bivalent metal oxide and an alkali metal salt.
6. preparation method according to claim 1, is characterized in that, described catalyzer is selected from one or more in sodium carbonate, zinc oxide, magnesium oxide, calcium oxide and zinc acetate.
7. preparation method according to claim 1, is characterized in that, the mol ratio of described phenolic compound, aldehyde compound and aminated compounds is 1:(1～3): (0.1～1).
8. preparation method according to claim 1, is characterized in that, the quality of described catalyzer is 0.05%～8% of phenolic compound quality.
9. preparation method according to claim 1, is characterized in that, the temperature of described reaction is 60 DEG C～100 DEG C, and the reaction times is 1～6h.
10. preparation method according to claim 1, is characterized in that, also comprises:
After stratification, wash with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410126017.1A CN103897125A (en) | 2014-03-31 | 2014-03-31 | Method for preparing thermosetting phenol resin |
Applications Claiming Priority (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN108503758A (en) * | 2017-02-27 | 2018-09-07 | 阿瓦隆工业股份公司 | Method for producing thermosetting phenolic resin and pass through the available phenolic resin of this method |
| CN111875763A (en) * | 2020-07-13 | 2020-11-03 | 杭摩新材料集团股份有限公司 | A kind of aniline-modified solid thermosetting phenolic resin and preparation method thereof |
| CN111978497A (en) * | 2020-08-12 | 2020-11-24 | 北京化工大学 | Preparation method, product and application of semi-solid thermosetting phenolic resin |
| CN111995723A (en) * | 2020-07-13 | 2020-11-27 | 杭摩新材料集团股份有限公司 | Solid thermosetting phenolic resin and method for preparing same by adopting suspension method |
| JP2021004270A (en) * | 2019-06-25 | 2021-01-14 | 住友ベークライト株式会社 | Phenol resin |
| CN112321780A (en) * | 2021-01-04 | 2021-02-05 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
| CN112979492A (en) * | 2019-12-12 | 2021-06-18 | 中国石油天然气股份有限公司 | Poly-Mannich base and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108503758A (en) * | 2017-02-27 | 2018-09-07 | 阿瓦隆工业股份公司 | Method for producing thermosetting phenolic resin and pass through the available phenolic resin of this method |
| JP2021004270A (en) * | 2019-06-25 | 2021-01-14 | 住友ベークライト株式会社 | Phenol resin |
| CN112979492A (en) * | 2019-12-12 | 2021-06-18 | 中国石油天然气股份有限公司 | Poly-Mannich base and preparation method and application thereof |
| CN112979492B (en) * | 2019-12-12 | 2023-06-30 | 中国石油天然气股份有限公司 | Poly-Mannich base and preparation method and application thereof |
| CN111875763A (en) * | 2020-07-13 | 2020-11-03 | 杭摩新材料集团股份有限公司 | A kind of aniline-modified solid thermosetting phenolic resin and preparation method thereof |
| CN111995723A (en) * | 2020-07-13 | 2020-11-27 | 杭摩新材料集团股份有限公司 | Solid thermosetting phenolic resin and method for preparing same by adopting suspension method |
| CN111978497A (en) * | 2020-08-12 | 2020-11-24 | 北京化工大学 | Preparation method, product and application of semi-solid thermosetting phenolic resin |
| CN111978497B (en) * | 2020-08-12 | 2021-12-07 | 浙江自立高分子化工材料有限公司 | Preparation method, product and application of semi-solid thermosetting phenolic resin |
| CN112321780A (en) * | 2021-01-04 | 2021-02-05 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
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