CN103130972B - Thermoplastic phenolic resin and preparation method thereof - Google Patents
Thermoplastic phenolic resin and preparation method thereof Download PDFInfo
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- CN103130972B CN103130972B CN201110383687.8A CN201110383687A CN103130972B CN 103130972 B CN103130972 B CN 103130972B CN 201110383687 A CN201110383687 A CN 201110383687A CN 103130972 B CN103130972 B CN 103130972B
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Abstract
The invention relates to thermoplastic phenolic resin. The thermoplastic phenolic resin is prepared from a component A and a component B through condensation polymerization. The component A comprises phenolic compound, lignin, acid catalyst and products obtained by a denaturation phenolate reaction of sulfide. The component B comprises aldehyde compound. The invention further relates to a preparation method of the thermoplastic phenolic resin. By means of addition of the sulfide, reactivity of the lignin and the substitution rate of the lignin for phenol are improved, and various lignin can be used for preparation of the thermoplastic phenolic resin.
Description
Technical field
The present invention relates to a kind of novolac resin, particularly relate to the novolac resin of lignin modification, also relate to the preparation method of this resin.
Background technology
Novolac resin reacts when under an acidic catalyst effect, phenol and formaldehyde are greater than 1 with mol ratio to make.Novolac resin (or claiming two-step approach resol), for light color is to dun brittle solid, is dissolved in ethanol, acetone equal solvent, has solvable meltability for a long time.Novolac resin can be used for manufacturing the friction materialss such as each disc-like type sheet, drum-type sheet, frictionshoe, clutch surface, brake band, brake-shoe for train.But phenol is a kind of industrial chemicals obtained from resources such as oil, along with reducing gradually and the rise of oil price of petroleum resources, the price of phenol rises steadily, therefore find a kind of can the material of Some substitute or completely alternative phenol extremely urgent.
The research substituting phenol synthesis resol with xylogen receives people's attention day by day.Xylogen is a kind of natural polyphenol family macromolecule polymkeric substance, there is more aldehyde radical and hydroxyl in its structure, wherein hydroxyl with alcoholic extract hydroxyl group and phenolic hydroxyl group two kinds of forms.With the reaction of phenol and formaldehyde novolak resin, not only xylogen can provide aldehyde radical but also can provide hydroxyl, reduces the consumption of phenol and formaldehyde.At occurring in nature, the reserves of xylogen are only second to Mierocrystalline cellulose, and all regenerate with the speed of 50,000,000,000 tons every year.Pulp and paper industry will isolate about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen byproduct of about 5,000 ten thousand tons simultaneously, but up to now, xylogen more than 95% still directly enters rivers with " black liquor " or burns after concentrating, seldom be utilized effectively, if after using lignin portion to replace phenol, can production cost be reduced.
Investigator has carried out some researchs in this respect, in CN101891933A, such as disclose the novel method that rub resistance material prepared by a kind of modifying solvent type lignin raw material, the method uses modifying solvent type lignin resol as resin glue, prepares friction-resistant composite material with fortifying fibre, frictional property regulator and solidifying agent.The advantage of the method: on the one hand due to natural high moleculer eompound that xylogen is three-dimensional structure, again containing abundant polar group, the resol of lignin modification is used to have stronger interaction than other components of traditional resol and friction materials, obtain more uniform friction materials compound fit, the friction materials that performance is more excellent can be obtained; Reduce the consumption of phenol on the other hand, reduce production cost and decrease environmental pollution.Because lignin molecule is large, the steric hindrance on aromatic ring is large, no matter xylogen and phenol, formaldehyde reaction, or and reactive modified phenolic resin, its reactive behavior is obviously not enough, and the substitution rate of xylogen Pyrogentisinic Acid is low.
Summary of the invention
For this reason, when first object of the present invention is phenolic resin modified in prior art, the problem that the reactive behavior of xylogen is low, the substitution rate of xylogen Pyrogentisinic Acid is low.For this reason, the invention provides a kind of novolac resin.
Second object of the present invention is to provide a kind of method preparing novolac resin.
The invention provides a kind of novolac resin, described novolac resin is prepared from through polycondensation by component A and B component:
Component A: phenolic compound, xylogen, an acidic catalyst and sulfide are obtained by reacting product through the phenolate of modification;
B component: aldehyde compound.
Sulfide in described component A is one or more in sodium sulphite, potassium sulphide, hydrogen sulfide, Sodium sulfhydrate and potassium bisulfide.
The mass ratio of described phenolic compound, xylogen, sulfide and an acidic catalyst is 1: (0.01 ~ 0.4): (0.001 ~ 0.04): (0.001 ~ 0.08): (0.15 ~ 0.32), and described phenolic compound and aldehyde compound mol ratio are 1: (0.47 ~ 1).
Described phenolate reaction for this area be that phenolate well known in the art is reacted, namely there is phenolate and react in xylogen and phenolic compound under an acidic catalyst effect; The phenolate reaction of described modification is reacted for xylogen and phenolic compound, under an acidic catalyst and sulfide effect, phenolate occurs; In the phenolate reaction of xylogen, add sulfide can play the effect removing methoxyl group in xylogen, be conducive to increasing lignin reaction active, make that xylogen to be identified oneself with in the polycondensation of synthetic thermoplastic resol more, thus improve the substitution rate of xylogen Pyrogentisinic Acid.
In the present invention, described phenolic compound can be the phenolic compound that this area routine uses, described phenolic compound is one or more in phenol, cresols, tert-butyl phenol, amino phenol, nitrophenol, naphthols, chlorophenol, ortho-cresol, meta-cresol, Resorcinol, Phloroglucinol or pyrocatechol, preferred phenol.
In the present invention, described xylogen can be the xylogen that this area routine uses, as being one or more in the xylogen of ligninsulfonate, hydrochloric acid xylogen, enzymolysis xylogen, high-boiling alcohol lignin, the xylogen extracted from black liquid, organic solvent extraction, cuprammonium xylogen, Milled wood lignin, natural lignin, dioxane lignin, Periodic acid xylogen and Thiovanic acid xylogen, in the preferred case, xylogen can be ligninsulfonate, enzymolysis xylogen, the xylogen that extracts from papermaking night.
In the present invention, described an acidic catalyst can be an acidic catalyst that this area routine uses, as being one or more in mineral acid, organic acid or acid salt.In the preferred case, described mineral acid can be one or more in sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid and phosphoric acid; Described organic acid can be one or more in formic acid, acetic acid, phenylformic acid, oxalic acid, succinic acid, tosic acid and oxalic acid; Described acid salt can be one or more in sodium pyrosulfate, S-WAT, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, ammonium chloride, ammonium sulfate, monoammonium sulfate, ammonium bisulfite, ammonium hydrogen phosphate and primary ammonium phosphate.Under further preferable case, described organic acid can be sulfuric acid, hydrochloric acid.
In the present invention, described aldehyde compound can be the aldehyde compound that this area routine uses, and described aldehyde compound is one or more in formaldehyde, acetaldehyde, propionic aldehyde and paraformaldehyde, is preferably formaldehyde.
Present invention also offers a kind of preparation method of novolac resin, the method comprises the following steps:
A phenolic compound, xylogen, an acidic catalyst and sulfide mix and stir by (), and carry out the phenolate reaction of modification;
B mixture that step (a) obtains by () adds aldehyde compound, then carries out polycondensation;
C polycondensate that step (b) obtains by () carries out underpressure distillation, obtains thermoplastic phenolic aldehyde resin.
Described sulfide is one or more in sodium sulphite, potassium sulphide, hydrogen sulfide, Sodium sulfhydrate and potassium bisulfide.
In described step (a), the temperature of the phenolate reaction of described modification is 100 ~ 180 DEG C.
In described step (a), the time of the phenolate reaction of described modification is 0.5 ~ 6h.
The temperature obtained to step (c) is add described an acidic catalyst and aldehyde compound in the mixture of 60 ~ 90 DEG C.
In described step (b), the temperature of described polycondensation is 90 ~ 100 DEG C.
In described step (b), the time of described polycondensation is 1 ~ 10h.
In described step (c), described underpressure distillation is the technology that those skilled in the art's routine uses, underpressure distillation is carried out to the product that step (b) obtains, to remove moisture, free phenol and small-molecule substance, when its free phenol content lower than 8.0% time, blowing while hot, obtains the novolac resin of lignin modification, the temperature of described underpressure distillation can be 90 ~ 190 DEG C, and the vacuum tightness of underpressure distillation can be 0.0013 ~ 0.1013MPa.
Before carrying out described underpressure distillation, optionally carry out alkali neutralization and separating step, to remove the acid in product.If do not remove acid, an acidic catalyst can residue in final resol.
The mass ratio of described phenolic compound, xylogen, sulfide and an acidic catalyst is 1: (0.01 ~ 0.4): (0.001 ~ 0.04): (0.001 ~ 0.08), and described phenolic compound and aldehyde compound mol ratio are 1: (0.47 ~ 1).
Described phenolic compound, described xylogen, described an acidic catalyst and described aldehyde compound as hereinbefore, do not repeat them here.
A kind of novolac resin prepared by described method.
The application of medium sulphide content is reacted in the phenolate preparing novolac resin.
Above-mentioned technology of the present invention compared with prior art has the following advantages:
(1) in the phenolate reaction of xylogen, sulfide is added, improve the reactive behavior of xylogen and the substitution rate of xylogen Pyrogentisinic Acid, various types of xylogen can be adopted to prepare novolac resin, thus part replace phenolic compound, reduces production cost.
(2) the present invention adopts phenolic compound, xylogen, an acidic catalyst and sulfide to carry out the phenolate reaction of modification, and then carry out the advantage of polycondensation with aldehyde compound, sulfide can play the effect removing methoxyl group in xylogen, thus lignin reaction's activity is increased, being conducive to xylogen participates in the reaction of thermoplastic resin, range of choice like this for expansion xylogen is favourable, makes the not tolerant amount of synthesized resol in alcohol reduce simultaneously.
(3) the present invention adopts phenolic compound, xylogen, acid catalyst and sulfide at 100 ~ 180 DEG C to carry out the advantage of reacting, at ambient pressure, within the scope of this temperature section, can promote that sulfide is to the replacement of the methoxyl group on xylogen, and along with temperature rising, the degree of replacement and speed of reaction also can increase thereupon.
(4) the present invention adopts in step (b), the temperature of the described product that described step (a) obtains when adding aldehyde compound is the advantage of 60 ~ 90 DEG C, because the reaction of phenolic compound, aldehyde compound is in temperature comparatively Gao Shiyi generation implode, wayward, therefore select to add under the temperature condition of 60 ~ 90 DEG C.
Embodiment
(1) raw material used in the present invention and model: ligninsulfonate; Alkali lignin; Chromite (325 order), Brown Alundum iron powder (1200 order), slicker solder breeze (325 order), carbon black (model N330), graphite (10-30 order), sodium aluminum fluoride (325 order), water-ground limestone (325 order), coke powder (20-40 order) and iron oxide red (325 order) are all derive from Wujin, Changzhou friction materials company limited; Steel fiber (steel wool D0-160) derives from Dezhou dragon celebrating steel wool fiber mailbox company etc.
(2) plant and instrument is used in the present invention:
Softening temperature testing tool: Hong Yu plant and instrument company limited of Hebei province, INSTRUMENT MODEL;
Softening temperature testing tool: Hong Yu plant and instrument company limited of Hebei province;
Reactor: Wuxi City airing of views biochemical equipment company limited;
Four-hole bottle: upper marine rich glassware company limited;
Electric mixer: Shanghai Sheng Hai electric apparatus company limited;
Heating jacket: Shanghai Peng Yi Instrument Ltd.;
(3) testing method of resol performance:
The mensuration of the viscosity of resol: carry out according to GB-T9571.1-2008;
The mensuration of resol free phenol: carry out according to ISO 8974:2002;
The mensuration of phenolic resin gel time: carry out according to ISO 9396:1997;
The mensuration of resol softening temperature: carry out according to GB-T 8146-2003;
The mensuration of resol degree of mobilization: carry out according to ISO 8619:2003;
Resol gathers the mensuration of speed: carry out according to YB-T4131-2005.
(4) testing method of Properties of Friction Materials:
The shear strength of friction materials, the test of 300 DEG C of performances such as frictional coefficient, 350 DEG C of frictional coefficient, 350 DEG C of wear rates carry out according to national standard (GB5763-2008);
The test of flexural strength: carry out according to standard GB/T 1449-2005;
The test of surface hardness: carry out according to standard GB/T5766-2007;
The test of shock strength: carry out according to standard GB/T 1451-2005.
Below will the invention will be further described by specific embodiment.
Embodiment 1
By 1.0kg phenol, 0.3kg ligninsulfonate solid, 0.015kg potassium sulphide, 0.02kg sulfuric acid adds in reactor successively, then the temperature in reactor is adjusted to 150 DEG C, stirs 2 hours at a constant temperature; And then be cooled to 70 DEG C, then in reactor, add 0.431kg formaldehyde (formaldehyde solution of 37%), the mol ratio of phenol and formaldehyde is 1: 0.5, is warming up to 100 DEG C after adding formaldehyde, at a constant temperature polycondensation 5 hours; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-180 DEG C, and underpressure distillation pressure is 0.0013 ~ 0.1013MPa; After tested, the free phenol content in product reaches 5%, blowing, obtains 1.151kg novolac resin, and yield is 1.15.
Method of calculation: yield=M/m.
M: after reflection, the weight of the novolac resin of weighing;
M: the weight of the phenolic compound added.
The index of novolac resin prepared by the present embodiment: free phenol content is 4.8%, softening temperature is 110 DEG C, and degree of mobilization is 27mm, and poly-speed is 49s.
Embodiment 2
By 1.0kg phenol, 0.4kg ligninsulfonate solid, 0.001kg sodium sulphite, 0.01kg sulfuric acid adds in reactor successively, then the temperature in reactor is adjusted to 180 DEG C, stirs 0.5 hour at a constant temperature; And then be cooled to 80 DEG C, then add 0.863kg formaldehyde (formaldehyde solution of 37%) to reactor, the mol ratio of phenol and formaldehyde is 1: 1, and after adding formaldehyde, degree of intensification is to 100 DEG C, at a constant temperature polycondensation 4 hours; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance again, the temperature of underpressure distillation reaches 190 DEG C, controlling distillation pressure is 0.0013 ~ 0.1013MPa, after tested, the free phenol content in product reaches 7%, blowing, obtain 1.168kg novolac resin, yield is 1.17.
The index of novolac resin prepared by the present embodiment: free phenol content is 6.7%, softening temperature is 113 DEG C, and degree of mobilization is 35mm, and poly-speed is 55s.
Embodiment 3
By 1.0kg phenol, 0.7kg ligninsulfonate solution (wherein content of lignin is 50%), 0.04kg Sodium sulfhydrate, 0.02kg sulfuric acid, add successively in reactor, again the temperature in reactor is adjusted to 100 DEG C, stirs 4 hours at a constant temperature, and then be cooled to 60 DEG C, reactor adds 0.604kg formaldehyde (formaldehyde solution of 37%) again, the mol ratio of phenol and formaldehyde is 1: 0.7, adjusts the temperature to 90 DEG C after adding formaldehyde, constant temperature polycondensation 9 hours; After reaction terminates, carry out underpressure distillation dehydration and removing small-molecule substance, underpressure distillation reaches 90-170 DEG C to temperature, controlling distillation pressure is 0.0013 ~ 0.1013MPa, and after tested, the free phenol content in product reaches 3%, blowing, obtains 1.162kg novolac resin, and yield is 1.16.
The index of novolac resin prepared by the present embodiment: free phenol content is 2.9%, softening temperature is 115 DEG C, and degree of mobilization is 20mm, and poly-speed is 40s.
Embodiment 4
By 1.0kg phenol, 0.01kg enzymolysis xylogen, 0.04kg potassium sulphide, 0.08kg oxalic acid, adds in reactor successively, then the temperature in reactor is adjusted to 160 DEG C, stirs 2 hours at a constant temperature; And then be cooled to 90 DEG C, then add 0.351kg acetaldehyde to reactor, the mol ratio of phenol and acetaldehyde is 1: 0.75, adjusts the temperature to 95 DEG C after adding acetaldehyde, constant temperature polycondensation 1 hour; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation reaches 180 DEG C, controlling distillation pressure is 0.0013 ~ 0.1013MPa, and after tested, the free phenol content in product reaches 4%, blowing, obtains 1.14kg novolac resin, and yield is 1.14.
The index of novolac resin prepared by the present embodiment: free phenol content is 3.9%, softening temperature is 107 DEG C, and degree of mobilization is 22mm, and poly-speed is 45s.
Embodiment 5
By 1.0kg phenol, the xylogen solid that 0.27kg extracts from papermaking wastewater, 0.03kg potassium sulphide, 0.001kgkg sulfuric acid adds in reactor successively, then the temperature in reactor is adjusted to 140 DEG C, stirs 3 hours at a constant temperature; Be cooled to 80 DEG C again, then add 0.561kg formaldehyde (formaldehyde solution of 37%) to reactor, the mol ratio of phenol and formaldehyde is 1: 0.65, is warming up to 100 DEG C after adding formaldehyde, constant temperature polycondensation 10 hours; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-190 DEG C, controlling distillation pressure is 0.0013 ~ 0.1013MPa, after tested, the free phenol content in product reaches 5%, blowing, obtain 1.16kg novolac resin, yield is 1.16.
The index of novolac resin prepared by the present embodiment: free phenol content is 4.7%, softening temperature is 112 DEG C, and degree of mobilization is 25mm, and poly-speed is 50s.
Embodiment 6
By 2.0kg tert-butyl phenol, 0.5kg papermaking wastewater (wherein content of lignin is 50%), 0.3kg potassium sulphide, 0.04kg sulfuric acid adds in reactor successively, then the temperature in reactor is adjusted to 100 DEG C, stirs 6 hours at a constant temperature; Be cooled to 90 DEG C again, then add 0.6125kg formalin (concentration 37%) to reactor, wherein the mol ratio of tert-butyl phenol and formaldehyde is 1: 0.8, after adding formaldehyde, polycondensation 5 hours at 90 DEG C of temperature; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-190 DEG C, controlling distillation pressure is 0.0013 ~ 0.1013MPa, after tested, the free phenol content in product reaches 6.5%, blowing, obtain 2.36kg novolac resin, yield is 1.18.
The index of novolac resin prepared by the present embodiment: free phenol content is 6.2%, softening temperature is 113 DEG C, and degree of mobilization is 24mm, and poly-speed is 46s.
Comparative example 1
This comparative example, for illustration of the situation of not adding xylogen, is formed with embodiment 3 and contrasts
By 1.0kg phenol, 0.604kg formaldehyde (formaldehyde solution of 37%), 0.02kg sulfuric acid, add successively in reactor, wherein the mol ratio of phenol and formaldehyde is 1: 0.7, then the temperature in reactor is adjusted to 100 DEG C, constant temperature 4 hours, continues temperature adjustment to 90 DEG C, constant temperature 9 hours; After isothermal reaction terminates, carry out underpressure distillation dehydration and removing small-molecule substance, underpressure distillation to temperature is 90-170 DEG C, controlling distillation pressure is 0.0013 ~ 0.1013MPaMPa, after tested, the free phenol content in product reaches 3%, blowing, obtain 1.21kg novolac resin, yield is 1.21.
The index of novolac resin prepared by the present embodiment: free phenol content is 2.9%, softening temperature is 113 DEG C, and degree of mobilization is 19mm, and poly-speed is 39s.
Comparative example 2
This comparative example, for illustration of the situation of not adding sulfide, is formed with embodiment 1 and contrasts
By 1.0kg phenol, 0.3kg ligninsulfonate, 0.02kg sulfuric acid adds in reactor successively, then the temperature in reactor is adjusted to 150 DEG C, stirs 2 hours at a constant temperature; Be cooled to 70 DEG C again, then in reactor, add 0.431kg formaldehyde (formaldehyde solution of 37%), the mol ratio of phenol and formaldehyde is 1: 0.5, is warming up to 100 DEG C after adding formaldehyde, constant temperature polycondensation 5 hours; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-180 DEG C, and underpressure distillation pressure is 0.0013 ~ 0.1013MPa; After tested, the free phenol content in product reaches 6%, blowing, obtains 1.148kg novolac resin, and yield is 1.148.
The index of novolac resin prepared by the present embodiment: free phenol content is 5.7%, softening temperature is 95 DEG C, and degree of mobilization is 40mm, and poly-speed is 60s.
Comparative example 3
This comparative example, for illustration of the situation of not adding sulfide, is formed with embodiment 4 and contrasts.
By the phenol of 1.0kg, the enzymolysis xylogen of 0.01kg, the oxalic acid of 0.08kg drops in reactor successively, then adjusts the temperature to 160 DEG C, stirs 2 hours at a constant temperature; And then be cooled to 90 DEG C, then 0.351kg acetaldehyde is added in reactor, the mol ratio of phenol and acetaldehyde is 1: 0.75, adjusts the temperature to 95 DEG C after adding acetaldehyde, constant temperature polycondensation 1 hour; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-180 DEG C, and underpressure distillation pressure is 0.0013 ~ 0.1013MPa; After tested, the free phenol content in product reaches 5.5%, blowing, obtains 1.13kg novolac resin, and yield is 1.13.
The index of novolac resin prepared by the present embodiment: free phenol content is 5.2%, softening temperature is 98 DEG C, and degree of mobilization is 38mm, and poly-speed is 55s.
Comparative example 4
This comparative example, for illustration of the situation of not adding sulfide, is formed with embodiment 6 and contrasts
By 2.0kg tert-butyl phenol, 0.5kg alkali lignin, 0.04kg sulfuric acid drops in reactor successively, then adjusts the temperature to 100 DEG C, stirs 6 hours; Mixture is cooled to 90 DEG C, then in reactor, adds 0.6125kg formaldehyde (formaldehyde solution of 37%), the mol ratio of tert-butyl phenol and formaldehyde is 1: 0.8, after regulating, carries out polycondensation 5 hours at 90 DEG C of temperature after adding formaldehyde; After polycondensation terminates, carry out underpressure distillation dehydration and removing small-molecule substance, the temperature of underpressure distillation is 90-190 DEG C, and underpressure distillation pressure is 0.0013 ~ 0.1013MPa; After tested, in product, free phenol content reaches 6.8%, blowing, obtains 2.356kg novolac resin, and yield is 1.178.
The index of novolac resin prepared by the present embodiment: free phenol content is 6.5%, softening temperature is 96 DEG C, and degree of mobilization is 42mm, and poly-speed is 63s.
Test case 1
The novolac resin of embodiment 1-6 and comparative example 1-4 synthesis is accurately taken 10g with analytical balance respectively, dissolves respectively in 50g alcohol, after fully dissolving, filter insolubles, weigh, calculate, result is as follows:
Table 1
| Sequence number | Resin quality | Ethanol quality | Insolubles quality | Insolubles accounts for resin ratio |
| Embodiment 1 | 9.9863 | 50.01 | 0.2796 | 2.7998％ |
| Embodiment 2 | 10.0021 | 49.98 | 0.2908 | 2.9074％ |
| Embodiment 3 | 9.9991 | 50.00 | 0.2888 | 2.8883％ |
| Embodiment 4 | 9.9897 | 50.03 | 0.2787 | 2.7899％ |
| Embodiment 5 | 10.0010 | 50.10 | 0.2931 | 2.9307％ |
| Embodiment 6 | 10.0018 | 49.97 | 0.2868 | 2.8675％ |
| Comparative example 1 | 10.0009 | 49.89 | 0.2109 | 2.1088％ |
| Comparative example 2 | 10.0003 | 50.05 | 0.6401 | 6.4008％ |
| Comparative example 3 | 9.9979 | 50.07 | 0.6511 | 6.5124％ |
| Comparative example 4 | 9.9985 | 49.94 | 0.6379 | 6.3800％ |
As can be seen from Table 1, in the building-up process of lignin modification resol, after adding sulfide, the alcohol-insoluble substance of synthesized resin is obviously reduced.Because novolac resin is soluble in ethanol, and xylogen is insoluble in ethanol, therefore the most of xylogen in known embodiment 1-6 and phenol, formaldehyde there occurs reaction, and the insolubles of comparative example 2-4 increases relatively, more xylogen does not react with phenol, formaldehyde, what can prove sulfide thus adds the effect serving and improve lignin reaction's activity
Test case 2
Above-described embodiment 1-6, comparative example 1-4 are under equal conditions carried out batch mixing, compacting according to table 1 formula respectively, and obtain the sample strip of friction materials, the component of sample is in table 2, and test result is as following table 3.
Table 2
| Component | Weight (%) |
| Resin | 7 |
| Chromite | 9 |
| Brown Alundum | 0.5 |
| Iron powder | 2 |
| Slicker solder breeze | 3.5 |
| Carbon black | 2 |
| Graphite | 12 |
| Sodium aluminum fluoride | 5 |
| Water-ground limestone | 3.5 |
| Coke powder | 12 |
| Iron oxide red | 2 |
| Barium sulfate | 23 |
| Sulphur | 0.5 |
| Steel fiber | 13 |
| Frication powder | 2 |
Table 3
As can be seen from Table 3, known with the Data Comparison of comparative example 1, the resol of the lignin modification that this patent relates to, can find out by the application at friction materials the property indices substantially reaching phenolic resin, this also demonstrates being successfully prepared of lignin modification resol further; Known with the Data Comparison of comparative example 2,3 and 4, the surface hardness of the friction materials that the present invention is prepared by interpolation sulfide, shear strength, 300 DEG C of frictional coefficient, flexural strength, shock strengths are all greatly improved, and 300 DEG C of wear rates reduce, the resol of lignin modification prepared by the present invention is better than the resol of the lignin modification not adding sulfide, illustrate that adding sulfide improves the reactive behavior of xylogen, thus can the excellent resol of processability.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (12)
1. a novolac resin, is characterized in that: described novolac resin is prepared from through polycondensation by component A and B component:
Component A: phenolic compound, xylogen, an acidic catalyst and sulfide are obtained by reacting product through the phenolate of modification;
B component: aldehyde compound.
2., according to the novolac resin described in claim 1, it is characterized in that:
Sulfide in described component A is one or more in sodium sulphite, potassium sulphide, hydrogen sulfide, Sodium sulfhydrate and potassium bisulfide.
3., according to the novolac resin described in claim 1, it is characterized in that:
The mass ratio of described phenolic compound, xylogen, sulfide and an acidic catalyst is 1:(0.01 ~ 0.4): (0.001 ~ 0.04): (0.001 ~ 0.08): (0.15 ~ 0.32), described phenolic compound and aldehyde compound mol ratio are 1:(0.5 ~ 1).
4. prepare a method for novolac resin, it is characterized in that, comprise the following steps:
A phenolic compound, xylogen, an acidic catalyst and sulfide mix and stir by (), and carry out the phenolate reaction of modification;
Add aldehyde compound in b mixture that () obtains to step (a), then carry out polycondensation;
C polycondensation product that step (b) obtains by () carries out underpressure distillation, obtains novolac resin.
5. according to the method described in claim 4, it is characterized in that: described sulfide is one or more in sodium sulphite, potassium sulphide, hydrogen sulfide, Sodium sulfhydrate and potassium bisulfide.
6. the method according to claim 4 or 5, is characterized in that: in described step (a), the phenolate of described modification reaction temperature be 100 ~ 180 DEG C.
7. method according to claim 6, is characterized in that: in described step (a), and the time of the phenolate reaction of described modification is 0.5 ~ 6 hour.
8. method according to claim 7, is characterized in that: the temperature obtained to step (c) is add described an acidic catalyst and aldehyde compound in the mixture of 60 ~ 90 DEG C.
9. the method according to claim 7 or 8, is characterized in that: in step (b), and the temperature of described polycondensation is 90 ~ 100 DEG C.
10. method according to claim 9, is characterized in that: in step (b), and the time of described polycondensation is 1 ~ 10 hour.
11. methods according to claim 4,5,7,8 or 10, it is characterized in that: the mass ratio of described phenolic compound, xylogen, sulfide and an acidic catalyst is 1:(0.01 ~ 0.4): (0.001 ~ 0.04): (0.001 ~ 0.08), described phenolic compound and aldehyde compound mol ratio are 1:(0.5 ~ 1).
12. 1 kinds of novolac resins prepared by the method in claim 4-11 described in any one.
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| CN105111394B (en) * | 2015-08-18 | 2020-03-03 | 北京林业大学 | High-activity lignin phenolic resin adhesive and preparation method thereof |
| CN105754059B (en) * | 2016-05-18 | 2018-05-04 | 浙江大学 | A kind of thermoplastic phenolic resin synthesized by bamboo wood scrap material liquefied substance and preparation method and application |
| CN108864427B (en) * | 2017-05-08 | 2022-03-22 | 北京彤程创展科技有限公司 | Sulfur-containing phenolic resin and preparation method thereof |
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| CN101092472A (en) * | 2007-07-27 | 2007-12-26 | 中国林业科学研究院林产化学工业研究所 | Phenol-formaldehyde resin of lignin and biomass oil in use for moulding plastic material, and preparation method |
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| CN101092472A (en) * | 2007-07-27 | 2007-12-26 | 中国林业科学研究院林产化学工业研究所 | Phenol-formaldehyde resin of lignin and biomass oil in use for moulding plastic material, and preparation method |
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| 工业碱木素热化学转化制备酚类化学品;隋鑫金;《化工学报》;20110611;第62卷(第6期);第1763-1769页 * |
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