CN102757618B - Modified phenol formaldehyde resin and preparation method thereof - Google Patents
Modified phenol formaldehyde resin and preparation method thereof Download PDFInfo
- Publication number
- CN102757618B CN102757618B CN201210237722.XA CN201210237722A CN102757618B CN 102757618 B CN102757618 B CN 102757618B CN 201210237722 A CN201210237722 A CN 201210237722A CN 102757618 B CN102757618 B CN 102757618B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde resin
- temperature
- phenol formaldehyde
- lignin
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a modified phenol formaldehyde resin and a preparation method thereof, relating to the field of phenol formaldehyde resins. The preparation method comprises the following steps: reacting 100 parts of phenol, 10-200 parts of lignin and 1-20 parts of acidic catalyst at 80-200 DEG C for 2-8 hours to form a reaction liquid; regulating the temperature of the reaction liquid to 60-110 DEG C, adding 50-200 parts of formaldehyde and 2-20 parts of composite catalyst, and reacting for 1-5 hours to form a sticky matter; washing the sticky matter in 60-70 DEG C water 2-5 times, and dehydrating to obtain a lignin phenol formaldehyde resin; and pulverizing the lignin phenol formaldehyde resin to 200 meshes, and evenly mixing with 2-20 parts of powder nitrile-butadiene rubber to obtain the modified phenol formaldehyde resin. The free phenol content of the modified phenol formaldehyde resin is 2-5%, the thermal decomposition temperature is 400-490 DEG C, the toughness and strength are high, and the friction material prepared from the modified phenol formaldehyde resin has high adhesive property and frictional property.
Description
Technical field
The present invention relates to resol field, be specifically related to a kind of modified phenolic resins and preparation method thereof.
Background technology
Synvaren is a kind of tackiness agent of being made by resol.Existing resol is general main to be made by phenol and formaldehyde reaction, but because phenol price is higher and environmental pollution is larger, synvaren industry attempts to find a kind of renewable, raw material that performance is high always, to replace phenol to prepare synvaren.Xylogen has cheap and reproducible feature, xylogen can replace most of phenol and formaldehyde reaction to prepare resol, not only can reduce resol and manufacture this, and the synvaren prepared of resol can recycling, relatively environmental protection.
But existing resol has the following disadvantages while preparing synvaren:
The comparison of ingredients of xylogen is complicated, the chemical reactivity of himself is lower, and molecular weight is higher, and xylogen is because itself space steric effect is difficult to participate in the polymerization of resol, in order to allow xylogen can be relatively easy to participate in the polymerization of resol, need to carry out modification to xylogen.But after modification, in the molecular structure of xylogen, contain a large amount of benzene ring structures, thereby make toughness and the intensity of the resol that the xylogen after modification makes lower, adhesiveproperties and the frictional behaviour of the synvaren that resol is made are poor.Therefore, adhesiveproperties and the frictional behaviour of the friction materials that synvaren is made are poor, and friction materials can only be applied to adhesiveproperties and frictional behaviour to require in lower field, and range of application is more single.
Summary of the invention
For the defect existing in prior art, the object of the present invention is to provide a kind of modified phenolic resins and preparation method thereof, not only free phenol content is lower, heat decomposition temperature is higher for the modified phenolic resins that adopts preparation method of the present invention to make, and toughness and intensity higher; Adhesiveproperties and the frictional behaviour of the synvaren that modified phenolic resins is made are better, adhesiveproperties and the frictional behaviour of the friction materials that synvaren is made are better, in the field that friction materials can be applied to adhesiveproperties and frictional behaviour to have relatively high expectations, range of application is more extensive.
The preparation method of modified phenolic resins provided by the invention, comprise the following steps: by mass fraction, 100 parts of phenol, 10～200 parts of xylogen and 1～20 part of an acidic catalyst are added in reactor, at the temperature of 80 ℃～200 ℃, isothermal reaction is 2～8 hours, forms reaction solution; Keep the temperature of described reaction solution between 60 ℃～110 ℃, gradation accumulation adds 50～200 parts of formaldehyde solutions, adds 2～20 parts of composite catalysts, and isothermal reaction 1～5 hour forms dope; After described dope is washed to 2～5 times in the water of 60 ℃～70 ℃, dehydrate, obtain lignin phenol formaldehyde resin; After being crushed to 200 orders, described lignin phenol formaldehyde resin adds 2～20 parts of Powdered acrylonitrile-butadiene rubber, and even in stirrer for mixing, obtain modified phenolic resins.
On the basis of technique scheme, the separating-purifying from extract of xylogen described in steps A obtains, and described extract is bagasse, cornstalk or straw stalk.
On the basis of technique scheme, the process of described separating-purifying is: the ethanolic soln that is 50% by described extract, an acidic catalyst and concentration constant temperature back flow reaction 8 hours at the temperature of 200 ℃, filters out residue.
On the basis of technique scheme, xylogen described in steps A is black liquid concentrated solution, high-boiling alcohol lignin, sodium lignosulfonate, calcium lignin sulphonate or alkali lignin.
On the basis of technique scheme, an acidic catalyst described in steps A is at least one in hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, oxalic acid, acetic acid and p-methyl benzenesulfonic acid.
On the basis of technique scheme, composite catalyst described in step B is at least two kinds in potassium hydroxide, sodium hydroxide, hydrated barta, magnesium hydroxide, inorganic salt and oxide compound, described inorganic salt and oxide compound all contain manganese, magnesium, copper and calcium in a kind of element.
On the basis of technique scheme, the fineness of Powdered acrylonitrile-butadiene rubber described in step D is 100～300 orders.
On the basis of technique scheme, the process dehydrating described in step C is: in vacuum drying oven, first at the temperature of 120 ℃～150 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.05Mpa～0.1Mpa, the temperature of 110 ℃～140 ℃, decompression dehydration is dry.
Modified phenolic resins provided by the invention, adopts the method described in arbitrary claim in claim 1 to 8 to make.
On the basis of technique scheme, the free phenol content of described modified phenolic resins is 2%～5%, heat decomposition temperature is 400 ℃～490 ℃.
Beneficial effect of the present invention is:
(1) when the present invention prepares modified phenolic resins, add Powdered acrylonitrile-butadiene rubber, improved toughness and the intensity of modified phenolic resins.Therefore, adhesiveproperties and the frictional behaviour of the synvaren of being made by the present invention are better, adhesiveproperties and the frictional behaviour of the friction materials that synvaren is made are better, can reach the standard of resol > > for GB/T 24411-2009 < < friction materials, in the field that friction materials can be applied to adhesiveproperties and frictional behaviour to have relatively high expectations, range of application is more extensive.
(2) the present invention has optimized the consumption of the required an acidic catalyst of the temperature of reaction of phenol and xylogen and phenol and lignin reaction, phenol can be relatively easy to and lignin reaction, so the reactive behavior of the product hydroxyl that obtains of phenol and lignin reaction is higher.
(3) the present invention has added composite catalyst when xylogen and phenol reactant, so the product after xylogen and phenol reactant is easier and formaldehyde reaction, thereby makes modified phenolic resins have lower free phenol content and higher heat decomposition temperature.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The preparation method of modified phenolic resins in the embodiment of the present invention, comprise the following steps: by mass fraction, 100 parts of phenol, 10～200 parts of xylogen and 1～20 part of an acidic catalyst are added in reactor, at the temperature of 80 ℃～200 ℃, isothermal reaction is 2～8 hours, forms reaction solution; Keep the temperature of described reaction solution between 60 ℃～110 ℃, gradation accumulation adds 50～200 parts of formaldehyde solutions, adds 2～20 parts of composite catalysts, and isothermal reaction 1～5 hour forms dope; Dope is washed 2～5 times in the water of 60 ℃～70 ℃, in vacuum drying oven, first at the temperature of 120 ℃～150 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.05Mpa～0.1Mpa, the temperature of 110 ℃～140 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin; Lignin phenol formaldehyde resin is crushed to to add 2～20 parts of fineness after 200 orders be 100～300 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain modified phenolic resins.
Xylogen can be selected black liquid concentrated solution, high-boiling alcohol lignin, sodium lignosulfonate or calcium lignin sulphonate or alkali lignin; Xylogen also can obtain by separating-purifying in extract (bagasse, cornstalk or straw stalk).The process that extract separating-purifying obtains xylogen is: the ethanolic soln that is 50% by extract, an acidic catalyst and concentration constant temperature back flow reaction 8 hours at the temperature of 200 ℃, filters out residue.An acidic catalyst is at least one in hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, oxalic acid, acetic acid and p-methyl benzenesulfonic acid.Composite catalyst is at least two kinds in potassium hydroxide, sodium hydroxide, hydrated barta, magnesium hydroxide, inorganic salt and oxide compound, in described inorganic salt and oxide compound, all contain manganese, magnesium, copper and calcium in a kind of element.
Below by eight embodiment, be specifically described.
Embodiment 1: select sodium lignosulfonate according to above-mentioned preparation method prepare that free phenol content is 2.0%, heat decomposition temperature is the modified phenolic resins of 400 ℃.
By 100.0g phenol, 50.0g fineness, be that 200 object sodium lignosulfonates and an acidic catalyst that is comprised of the 1.0g vitriol oil (an acidic catalyst is 1.0g altogether) are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 150 ℃, isothermal reaction is 4 hours, forms reaction solution.Reaction solution is cooled to after 80 ℃, adding 40.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 1.0g sodium hydroxide, 0.5g magnesium sulfate, 0.5g manganous sulfate (composite catalyst is 2.0g altogether), be warming up to 100 ℃ after isothermal reaction 20min; Then adding 100.0g concentration is 37% formaldehyde solution, isothermal reaction 20min at the temperature of 100 ℃; Adding 60.0g concentration is 37% formaldehyde solution again, be warming up to 110 ℃ after isothermal reaction 20min (formaldehyde solution is 200.0g altogether, totally 1 hour isothermal reaction time), obtain sorrel emulsus dope.After sorrel emulsus dope is washed to 3 times in 60 ℃ of water, put into vacuum drying oven, first at the temperature of 120 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.05Mpa, the temperature of 110 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 10.0g fineness after 200 orders be 100 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 2.0%, heat decomposition temperature is the modified phenolic resins of 400 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.35～0.49, and wear rate is between 0.19%～0.38%.
Embodiment 2: select high-boiling alcohol lignin according to above-mentioned preparation method prepare that free phenol content is 3.6%, heat decomposition temperature is the modified phenolic resins of 417 ℃.
100.0g phenol, 10.0g high-boiling alcohol lignin and an acidic catalyst that is comprised of the 5.0g vitriol oil and 3.0g phosphoric acid (an acidic catalyst is 8.0g altogether) are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 150 ℃, isothermal reaction is 2 hours, forms reaction solution.Reaction solution is cooled to after 70 ℃, adding 27.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 2.0g sodium hydroxide, 2.0g potassium hydroxide, 1.0g copper sulfate (composite catalyst is 5.0g altogether), isothermal reaction 120min after being slowly warming up to 80 ℃, then adding 27.0g concentration is 37% formaldehyde solution, isothermal reaction 120min after being warming up to 90 ℃, adding 27.0g concentration is 37% formaldehyde solution again, (formaldehyde solution is 81.0g altogether for isothermal reaction 60min after being warming up to 100 ℃, totally 5 hours isothermal reaction time), obtain sorrel emulsus dope.After sorrel emulsus dope is washed to 4 times in 65 ℃ of water, put into vacuum drying oven, first at the temperature of 130 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.07Mpa, the temperature of 120 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 7.0g fineness after 200 orders be 300 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 3.6%, heat decomposition temperature is the modified phenolic resins of 417 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.38～0.45, and wear rate is between 0.25%～0.32%.
Embodiment 3: select black liquid concentrated solution according to above-mentioned preparation method prepare that free phenol content is 5.0%, heat decomposition temperature is the modified phenolic resins of 440 ℃.
An acidic catalyst (an acidic catalyst is 15.0g altogether) that 100.0g phenol, concentration are 30% black liquid concentrated solution 150.0g and the sulfuric acid 5.0g that is 60% by concentration, 10.0g p-methyl benzenesulfonic acid forms is added in reactor and (in reactor, has thermometer, stirring and reflux condensate device), after being slowly warming up to 80 ℃, isothermal reaction is 6 hours, forms reaction solution.Reaction solution is cooled to after 60 ℃, adding 20.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 5.0g sodium hydroxide, 5.0g hydrated barta, 5.0g calcium oxide (composite catalyst is 15.0g altogether), isothermal reaction 60min after being warming up to 80 ℃, then adding 20.0g concentration is 37% formaldehyde solution, isothermal reaction 120min after being warming up to 90 ℃, adding 10.0g concentration is 37% formaldehyde solution again, (formaldehyde solution is 50.0g altogether for isothermal reaction 60min after being warming up to 100 ℃, totally 4 hours isothermal reaction time), obtain chocolate emulsus dope.After chocolate emulsus dope is washed to 5 times in 70 ℃ of water, put into vacuum drying oven, first at the temperature of 140 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.1Mpa, the temperature of 130 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 15.0g fineness after 200 orders be 200 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 5.0%, heat decomposition temperature is the modified phenolic resins of 440 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.39～0.45, and wear rate is between 0.18%～0.30%.
Embodiment 4: select calcium lignin sulphonate according to above-mentioned preparation method prepare that free phenol content is 4.9%, heat decomposition temperature is the modified phenolic resins of 458 ℃.
By 100.0g phenol, by 50.0g fineness, be that 200 object calcium lignin sulphonates and an acidic catalyst that is comprised of 6.0g oxalic acid, 8.0g trifluoroacetic acid, 6.0g acetic acid (an acidic catalyst is 20.0g altogether) are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 120 ℃, isothermal reaction is 8 hours, forms reaction solution.Reaction solution is cooled to after 90 ℃, and adding 35.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 1.0g magnesium oxide, 2.0g manganese oxide (composite catalyst is 3.0g altogether), be warming up to 100 ℃ after isothermal reaction 30min; Then adding 35.0g concentration is 37% formaldehyde solution, isothermal reaction 30min at the temperature of 100 ℃; Adding 35.0g concentration is 37% formaldehyde solution again, be warming up to 110 ℃ after isothermal reaction 30min (formaldehyde solution is 105.0g altogether, totally 1.5 hours isothermal reaction time) obtain chocolate emulsus dope.After chocolate emulsus dope is washed to 4 times in 65 ℃ of water, put into vacuum drying oven, first at the temperature of 150 ℃, lower normal pressure dehydrates, and at vacuum pressure, is then that at 0.1Mpa, the temperature of 130 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 2.0g fineness after 200 orders be 200 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 4.9%, the modified phenolic resins of 458 ℃ of heat decomposition temperatures.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), with the brake facing that this modified phenolic resins is made, there is larger noise, its frictional coefficient is between 0.29～0.39, and wear rate is between 0.29%～0.37%.
Embodiment 5: select alkali lignin according to above-mentioned preparation method prepare that free phenol content is 2.5%, heat decomposition temperature is the modified phenolic resins of 490 ℃.
100.0g phenol, 10.0g alkali lignin and an acidic catalyst that is comprised of the 5.0g vitriol oil and 5.0g phosphoric acid (an acidic catalyst is 10.0g altogether) are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 150 ℃, isothermal reaction is 4 hours, forms reaction solution.Reaction solution is cooled to after 80 ℃, adding 30.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 2.0g sodium hydroxide, 2.0g potassium hydroxide, 1.0g cupric oxide (composite catalyst is 5.0g altogether), isothermal reaction 120min at the temperature of 80 ℃, then adding 30.0g concentration is 37% formaldehyde solution, isothermal reaction 120min after being warming up to 90 ℃, adding 40.0g concentration is 37% formaldehyde solution again, (formaldehyde solution is 100.0g altogether for isothermal reaction 60min after being warming up to 100 ℃, totally 5 hours isothermal reaction time), obtain sorrel emulsus dope.After sorrel emulsus dope is washed to 4 times in 65 ℃ of water, put into vacuum drying oven, first at the temperature of 130 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.07Mpa, the temperature of 120 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 8.0g fineness after 200 orders be 300 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin powder and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 2.5%, heat decomposition temperature is the modified phenolic resins of 490 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.37～0.45, and wear rate is between 0.25%～0.32%.
Embodiment 6: select bagasse according to above-mentioned preparation method prepare that free phenol content is 4.7%, heat decomposition temperature is the modified phenolic resins of 421 ℃.
By 50.0g fineness, be that 200 object bagasse, the 50.0g concentration ethanolic soln that is 50% and an acidic catalyst (an acidic catalyst is 6.0g altogether) that is comprised of 3.0g oxalic acid, 3.0g concentrated hydrochloric acid are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 200 ℃, constant temperature back flow reaction is 8 hours, after filtering out residue, add 100.0g phenol, and isothermal reaction 4 hours at the temperature of 200 ℃, form reaction solution.Reaction solution is cooled to after 95 ℃, adding 25.0g concentration is 36% formaldehyde solution and by 5.0g sodium hydroxide, 10.0g magnesium hydroxide, 1.0g calcium oxide, the composite catalyst that 4.0g manganous sulfate is composited (composite catalyst is 20.0g altogether), isothermal reaction 30min at the temperature of 95 ℃, then adding 25.0g concentration is 36% formaldehyde solution, isothermal reaction 60min after being slowly warming up to 100 ℃, adding 25.0g concentration is 36% formaldehyde solution again, (formaldehyde solution is 75.0g altogether for isothermal reaction 120min after being slowly warming up to 100 ℃, totally 3.5 hours isothermal reaction time), obtain chocolate emulsus dope.After chocolate emulsus dope is washed to 2 times in 60 ℃ of water, put into vacuum drying oven, first at the temperature of 150 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.08Mpa, the temperature of 140 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 20.0g fineness after 200 orders be 200 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 4.7%, heat decomposition temperature is the modified phenolic resins of 421 ℃.(touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.35～0.40, and wear rate is between 0.20%～0.34%.
Embodiment 7: select cornstalk according to above-mentioned preparation method prepare that free phenol content is 3.2%, heat decomposition temperature is the modified phenolic resins of 466 ℃.
By 100.0g fineness, be that 200 object cornstalks, the 70g concentration ethanolic soln that is 50% and an acidic catalyst (an acidic catalyst is 8.0g altogether) that is comprised of 3.0g oxalic acid, 3.0g concentrated hydrochloric acid, the 2.0g vitriol oil are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 200 ℃, constant temperature back flow reaction is 8 hours, after filtering out residue, add 100.0g phenol, and isothermal reaction 4 hours at the temperature of 200 ℃, form reaction solution.Reaction solution is cooled to after 110 ℃, adding 25.0g concentration is 36% formaldehyde solution and by 5.0g sodium hydroxide, 10.0g magnesium hydroxide, 1.0g calcium oxide, the composite catalyst that 4.0g manganous sulfate is composited (composite catalyst is 20.0g altogether), isothermal reaction 30min after being cooled to 95 ℃, then adding 25.0g concentration is 36% formaldehyde solution, isothermal reaction 60min after being warming up to 100 ℃, adding 25.0g concentration is 36% formaldehyde solution again, (formaldehyde solution is 75g altogether for isothermal reaction 120min at the temperature of 100 ℃, totally 3.5 hours isothermal reaction time), obtain chocolate emulsus dope.After chocolate emulsus dope is washed to 2 times in 70 ℃ of water, put into vacuum drying oven, first at the temperature of 150 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.08Mpa, the temperature of 140 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is broken to to add 20.0g fineness after 200 orders be 200 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin powder and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 3.2%, heat decomposition temperature is the modified phenolic resins of 466 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.37～0.40, and wear rate is between 0.25%～0.34%.
Embodiment 8: select straw stalk according to above-mentioned preparation method prepare that free phenol content is 3.5%, heat decomposition temperature is the modified phenolic resins of 478 ℃.
The ethanolic soln that 200.0g fineness is 200 object straw stalks, 65g concentration is 50% and an acidic catalyst that is comprised of 3.0g oxalic acid, the 2.0g vitriol oil (an acidic catalyst is 5.0g altogether) are added in reactor and (in reactor, have thermometer, stirring and reflux condensate device), after being slowly warming up to 200 ℃, constant temperature back flow reaction is 8 hours, after filtering out residue, add 100.0g phenol, and isothermal reaction 4 hours at the temperature of 200 ℃, form reaction solution.Reaction solution is cooled to after 95 ℃, adding 25.0g concentration is 36% formaldehyde solution and by 5.0g sodium hydroxide, 10.0g magnesium hydroxide, 1.0g calcium chloride, the composite catalyst that 4.0g manganous sulfate is composited (composite catalyst is 20.0g altogether), isothermal reaction 30min at the temperature of 95 ℃, then adding 25.0g concentration is 36% formaldehyde solution, isothermal reaction 60min after being warming up to 100 ℃, adding 25.0g concentration is 36% formaldehyde solution again, (formaldehyde solution is 75g altogether for isothermal reaction 120min at the temperature of 100 ℃, totally 3.5 hours isothermal reaction time), obtain chocolate emulsus dope.After chocolate emulsus dope is washed to 2 times in 65 ℃ of water, put into vacuum drying oven, first at the temperature of 150 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.08Mpa, the temperature of 140 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin.Lignin phenol formaldehyde resin is crushed to to add 20.0g fineness after 200 orders be 200 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin powder and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 3.5%, heat decomposition temperature is the modified phenolic resins of 478 ℃.Draw after tested (touchstone is GB5763-2008 < < brake spacer for automobile > >), the brake facing frictional coefficient made from this modified phenolic resins is between 0.29～0.40, and wear rate is between 0.27%～0.34%.
The modified phenolic resins that the embodiment of the present invention provides, adopts above-mentioned preparation method to be prepared from, and the free phenol content of the modified phenolic resins of preparing free phenol content between 2%～5% is less; Heat decomposition temperature is between 400 ℃～490 ℃, and heat decomposition temperature is higher, utilizes the brake facing (friction materials) that this modified phenolic resins is made not only to have higher frictional coefficient and lower wear rate, and adhesiveproperties and frictional behaviour better.
The present invention is not limited to above-mentioned embodiment, for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, within these improvements and modifications are also considered as protection scope of the present invention.The content not being described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (1)
1. a preparation method for modified phenolic resins, is characterized in that, comprises the following steps:
A, by 100.0g phenol, 50.0g fineness, be that 200 object sodium lignosulfonates and an acidic catalyst that is comprised of the 1.0g vitriol oil are added in reactor, be warming up to 150 ℃ after isothermal reaction 4 hours, form reaction solution;
B, reaction solution is cooled to after 80 ℃, adding 40.0g concentration is 37% formaldehyde solution and the composite catalyst that is composited by 1.0g sodium hydroxide, 0.5g magnesium sulfate, 0.5g manganous sulfate, be warming up to 100 ℃ after isothermal reaction 20min; Then adding 100.0g concentration is 37% formaldehyde solution, isothermal reaction 20min at the temperature of 100 ℃; Adding 60.0g concentration is 37% formaldehyde solution again, be warming up to 110 ℃ after isothermal reaction 20min, obtain sorrel emulsus dope;
C, put into vacuum drying oven after sorrel emulsus dope is washed to 3 times in 60 ℃ of water, first at the temperature of 120 ℃, normal pressure dehydrates, and at vacuum pressure, is then that at 0.05MPa, the temperature of 110 ℃, decompression dehydration is dry, obtains lignin phenol formaldehyde resin;
D, lignin phenol formaldehyde resin is crushed to to add 10.0g fineness after 200 orders be 100 object Powdered acrylonitrile-butadiene rubber, lignin phenol formaldehyde resin and Powdered acrylonitrile-butadiene rubber are mixed in homogenizer, obtain free phenol content and be 2.0%, heat decomposition temperature is the modified phenolic resins of 400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237722.XA CN102757618B (en) | 2012-07-11 | 2012-07-11 | Modified phenol formaldehyde resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237722.XA CN102757618B (en) | 2012-07-11 | 2012-07-11 | Modified phenol formaldehyde resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102757618A CN102757618A (en) | 2012-10-31 |
| CN102757618B true CN102757618B (en) | 2014-10-08 |
Family
ID=47052292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210237722.XA Active CN102757618B (en) | 2012-07-11 | 2012-07-11 | Modified phenol formaldehyde resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102757618B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030759B (en) * | 2012-12-19 | 2015-01-14 | 山东圣泉新材料股份有限公司 | Lignin phenol resin prepolymer and preparation method thereof, lignin phenol resin and preparation method thereof |
| CN103131022B (en) * | 2013-03-15 | 2015-06-17 | 中国科学院化学研究所 | Method for degrading lignin by phenolation |
| CN103641967B (en) * | 2013-12-27 | 2016-03-02 | 山东圣泉新材料股份有限公司 | A kind of modified phenolic resins |
| CN103709349B (en) * | 2013-12-27 | 2016-08-24 | 山东圣泉新材料股份有限公司 | A kind of phenol-formaldehyde resin modified |
| CN103864535B (en) * | 2014-04-02 | 2015-04-29 | 山东农业大学 | Modified phenol-formaldehyde resin coated controlled-release fertilizer and preparation method thereof |
| CN105018011B (en) * | 2015-08-21 | 2017-05-10 | 广西星岛科技发展有限公司 | Adhesive synthesized by using papermaking black liquor as raw material and production method thereof |
| CN105171886B (en) * | 2015-08-21 | 2017-07-28 | 广西星岛科技发展有限公司 | A kind of production method of ultra micro residual formaldehyde amount fiberboard |
| CN106810653B (en) * | 2017-01-23 | 2018-11-06 | 广西科学院 | A kind of method and its application of biorefinery Bagasse Lignin base phenolic resin |
| CN108794711B (en) * | 2017-04-27 | 2021-03-12 | 东北林业大学 | Technology for repairing organic pesticide soil pollution by polyphenol lignin low-crosslinking polymer |
| CN107200994A (en) * | 2017-06-10 | 2017-09-26 | 唐沫容 | A kind of preparation method of the composite modified phenol formaldehyde resin of anacardol and nitrile rubber |
| CN107216603A (en) * | 2017-06-21 | 2017-09-29 | 东莞市联洲知识产权运营管理有限公司 | Attapulgite modified lignin phenol formaldehyde resin of a kind of metal/nanometer and preparation method thereof |
| CN111115640B (en) * | 2020-01-03 | 2022-05-31 | 吉林大学 | Method for preparing natural nano silicon dioxide and comprehensively utilizing rice hulls |
| CN112011020A (en) * | 2020-10-10 | 2020-12-01 | 黄石金朝阳粉末材料有限责任公司 | Preparation process of friction-resistant high-temperature-resistant modified phenolic resin |
| CN115073684B (en) * | 2022-08-11 | 2024-06-07 | 江苏大学 | Preparation method of daidzein biomass-based phenolic resin |
| CN117229462B (en) * | 2023-11-14 | 2024-05-31 | 山东永创材料科技有限公司 | Phenolic resin for molding compound and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241802A (en) * | 2011-04-28 | 2011-11-16 | 北京化工大学 | Comprehensive utilization of phenol-containing wastewater |
| CN102516911A (en) * | 2011-12-14 | 2012-06-27 | 黄石金朝阳粉末材料有限责任公司 | Modified phenolic resin adhesive for friction material and preparation method for modified phenolic resin adhesive |
-
2012
- 2012-07-11 CN CN201210237722.XA patent/CN102757618B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241802A (en) * | 2011-04-28 | 2011-11-16 | 北京化工大学 | Comprehensive utilization of phenol-containing wastewater |
| CN102516911A (en) * | 2011-12-14 | 2012-06-27 | 黄石金朝阳粉末材料有限责任公司 | Modified phenolic resin adhesive for friction material and preparation method for modified phenolic resin adhesive |
Non-Patent Citations (4)
| Title |
|---|
| 方红霞等.高性能环保型木质素基酚醛胶粘剂的制备.《复旦学报( 自然科学版)》.2009,第48卷(第3期),第295-300页. |
| 谢建军等.高邻位羟甲基含量的酚醛胶粘剂制备及其性能研究.《湘潭大学自然科学学报》.2012,第34卷(第2期),第66-69页. |
| 高性能环保型木质素基酚醛胶粘剂的制备;方红霞等;《复旦学报( 自然科学版)》;20090630;第48卷(第3期);第295-300页 * |
| 高邻位羟甲基含量的酚醛胶粘剂制备及其性能研究;谢建军等;《湘潭大学自然科学学报》;20120630;第34卷(第2期);第66-69页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102757618A (en) | 2012-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102757618B (en) | Modified phenol formaldehyde resin and preparation method thereof | |
| CN102516911B (en) | Modified phenolic resin adhesive for friction material and preparation method for modified phenolic resin adhesive | |
| CN101260283B (en) | Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof | |
| CN101942068B (en) | Preparation method of lignin phenolic resin | |
| CN102936323A (en) | Preparation method of lignin-phenol-formaldehyde resin and preparation method of lignin-phenol-formaldehyde resin foam | |
| CN107337774A (en) | A kind of preparation method of furfural modified lignin resin base phenolic resin adhesive | |
| CN105504191A (en) | Preparation method of eutectic ionic liquid modified lignin-phenolic resin | |
| CN102114432A (en) | Composite solid acid catalyst | |
| CN106947419A (en) | A kind of synvaren of alkali lignin self-catalysis synthesis in situ and preparation method thereof | |
| CN106750179A (en) | A kind of preparation method of enzymolysis xylogen base epoxy | |
| CN104194257B (en) | A kind of fiberglass reinforced moulding compound of heat resistant type Environmental protection phenol formaldehyde resin | |
| CN100537164C (en) | Method for liquefying wood | |
| CN103113840A (en) | Method for producing wood adhesive by using papermaking black liquor | |
| CN103450420A (en) | Preparation method of enzymolysis lignin modified phenolic resin | |
| CN103467683A (en) | Preparation method for thermosetting phenolic resin and thermosetting phenolic resin prepared with method | |
| CN105315936A (en) | Preparing method for phenolic resin adhesive for wood | |
| CN102633967B (en) | A kind of preparation technology of bamboo lignin modified phenolic resins | |
| CN103739801A (en) | Raw materials of resin adhesive for sympodial bamboo integrated profile and preparation method of resin adhesive | |
| CN103497333B (en) | Containing the Preparation method and use of benzoxazine-maleinamide resin compound | |
| CN102887982A (en) | Phenolic resin for glass reinforced plastic extrusion technology and preparation method of phenolic resin | |
| CN103450263A (en) | Preparation method of phosphorus-modified phenolic resin | |
| CN103319686A (en) | High-performance polyisocyanate adhesive production process | |
| CN103396649B (en) | Preparation method of alkynylated cardanol phenolic resin/titanium dioxide composite material | |
| CN105694111B (en) | A kind of preparation method of cellulose montmorillonite Composite hydrogel | |
| CN103450265A (en) | Preparation method of phosphorus-modified phenolic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |