Background technology
Grinding wheel base body is for support grinding layer and on machine tool chief axis, is installed fixing, it has determined grinding tool dynamically and static strength, through long-term test and on probation, present general employing resistance shock stability is superior, perfect heat-dissipating, and the glass that physical strength is high strengthens grinding wheel base body, and the production of this matrix is generally the webbed grid cloth that is first interweaved, in grid cloth, be coated with one deck resol again, through heating, baking, cooling and system.Traditional resol is due to the defect of self, and its goods occur that fragility is large, the problem that intensity is low, and the grid cloth making is also difficult to reach the requirement of making ultrathin section emery wheel.
Chinese Patent Application No. is that 200710129850.1 application for a patent for invention discloses and in a kind of glass fiber impregnated phenolic resin, enumerated several resol toughner, be respectively nylon 66, adjacent benzene vitamin A acid dibutyl ester, diheptyl phthalate, Di Iso Decyl Phthalate, dimixo-octyl phthalate, PVB, PEG etc., these toughner add the toughness of greatly having improved resol, the grid cloth making has met the requirement of ultrathin section emery wheel.But its toughness reinforcing mode is outer toughness reinforcing, when grid cloth is produced, toughner not only dissolves more difficultly, and its dispersiveness more can not be guaranteed.Phenol-formaldehyde A and the bakelite B in above-mentioned patent application " glass fiber impregnated phenolic resin ", made are all to produce by liquid formaldehyde, later stage vacuum hydro-extraction meeting produces a large amount of waste water, deal with need to be very large expense, do not process and cause environmental pollution.
Summary of the invention
Object of the present invention is just to provide and a kind of adopt solid formaldehyde to produce resol and adopt intrinsic toughening, in resin building-up process, add toughner, has guaranteed its solvability and dispersed and make it the poly ethyldiol modified resol and the preparation technology thereof that react with resol.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of poly ethyldiol modified resol, is characterized in that being made by the raw material of following weight part:
Phenol: 100
Solid formaldehyde: 25-27
PEG1000:1.5—4
More than 98% industrial ethanedioic acid of content: 1.1-1.5
Acid containing phenol water: 15-40
In addition, in described component, also comprise the silane coupling agent of 0.2-1 weight part.
The method of preparing above-mentioned poly ethyldiol modified resol is:
Open stirring, then under the decompression state that is-0.06MPa--0.08MPa at pressure, the phenol that is preheating to 50-60 ℃ is pumped in reactor, then 14%-40% restored acid phenolic wastewater is pumped in reactor, the oxalic acid adding, make the pH value of system 1-2, then heat temperature raising, when temperature reaches 85 ± 2 ℃, the solid formaldehyde adding; Add after formaldehyde, make its boiling that heats up, and keep seething with excitement 150-180 minutes, after add PEG1000, and decompression dehydration is warming up to 145 ℃, adopt reduced steam washing free phenol, viscosity reaches/160 ℃ of 9 pool/160 ℃-18 pools, then add silane coupling agent, blowing obtains poly ethyldiol modified resol.
Wherein, in above-mentioned preparation method,
---the pH value of described acid phenolic wastewater is 1-2, containing phenol concentration, is 4%-6%;
---described in add 3-5 batches of solid formaldehyde time-divisions to add;
---described in add the time that is warming up to boiling after formaldehyde and be controlled at 60-80 minutes;
---described in add after PEG1000 and the pressure range of decompression dehydration is controlled at-0.03--0.08MPa.
The technical problem that the present invention solves is by introduce polyoxyethylene glycol in resol building-up process, under acidic conditions, an OH of polyoxyethylene glycol can be combined by the OH in resol on the one hand, an OH in an OH and resin in polyoxyethylene glycol also can forming section hydrogen bond on the other hand, make to import in resol the flexible ether chain of length, thereby play toughness reinforcing effect.Resol resin adds part silane coupling agent post-synthesis phase, can greatly improve the cementability of resol and inorganics, thereby reaches resol and be used in the effect of toughness reinforcing enhancing in grid cloth.And there is following characteristics:
(1) the toughness reinforcing mode of resol of existing grid cloth being used is improved, and takes resol intrinsic toughening, and the solvability of toughner and dispersiveness have obtained good guarantee, and toughening effect is obviously better than outer toughness reinforcing.Resin adds silane coupling agent post-synthesis phase, can greatly increase the cohesiveness of resin and inorganics.By these two kinds of improvement, its ultrathin section emery wheel cutting ratio of making is significantly improved.
(2) production technique of resol is also adjusted, and adopts paraformaldehyde to produce, and the waste water of generation can recycle.
Embodiment
Below in conjunction with specific embodiment, poly ethyldiol modified resol provided by the present invention and preparation thereof are described in further detail.
Embodiment 1
Open stirring, then at pressure, be-decompression state of 0.06MPa under, the 400Kg phenol that is preheating to 55 ℃ is pumped in reactor, then by 120Kg restored acid phenolic wastewater, (pH value is 1, containing phenol concentration, be 4%) be pumped in reactor, add the industrial ethanedioic acid of 6Kg, make the pH value of system 1, then heat temperature raising, when temperature reaches 85 ℃, evenly point add 108Kg solid formaldehyde (content 96%) for 4 times, within 80 minutes, add, and control temperature in reactor not higher than 85 ℃; Add after formaldehyde, and utilize 50 minutes time chien shih its be slowly warming up to 100 ℃ of boilings, keep boiling 150 minutes, add the PEG1000 of 15 kilograms, under decompression state, (pressure is-0.04MPa) dehydration, to 145 ℃ (along with its temperature of minimizing of moisture raises), adopts reduced steam washing free phenol, and viscosity reaches 9 pool/160 ℃, then add the Silane coupling agent KH550 of 2.5 kilograms, stir blowing after 40 minutes and get final product to obtain the PEG modified phenolic resins of 408 kilograms.
Embodiment 2
Open stirring, then at pressure, be-the phenol 400Kg that is preheating to 50 ℃ is pumped in reactor under 0.07MPa decompression state, then 90Kg restored acid phenolic wastewater (pH value, 1.5, is 5% containing phenol amount) is pumped in reactor, adds 5.5Kg oxalic acid, make the pH value of system 1.5, heat temperature raising, when temperature reaches 85 ℃, evenly divides and adds 108Kg solid formaldehyde (content 96%) for 3 times, within 80 minutes, add, and control temperature in reactor in 85 ℃.Add after formaldehyde, make it utilize 60 minutes and be slowly warming up to boiling, keep boiling 140 minutes, add PEG1000 16Kg, under decompression state, (pressure is-0.04MPa) dewaters to 145 ℃, adopts reduced steam washing free phenol, and viscosity reaches 15 pool/160 ℃, then add the Silane coupling agent KH550 of 2Kg, stir 30 minutes blowings and get final product to obtain the PEG modified phenolic resins of 410 kilograms.
Embodiment 3
Open stirring, then at pressure, be-decompression state of 0.08MPa under, the 400Kg phenol that is preheating to 60 ℃ is pumped in reactor, then by 60Kg restored acid phenolic wastewater, (pH value is 2, containing phenol concentration, be 5%) be pumped in reactor, add the industrial ethanedioic acid of 4.4Kg, make the pH value of system 2, then heat temperature raising, when temperature reaches 87 ℃, evenly point add 106Kg solid formaldehyde (content 96%) for 5 times, within 90 minutes, add, and control temperature in reactor not higher than 87 ℃; Add after formaldehyde, and utilize time chien shih its boiling that slowly heats up of 80 minutes, keep boiling 180 minutes, add the PEG1000 of 13 kilograms, under decompression state, (pressure is-0.08MPa) dewaters to 145 ℃, adopts reduced steam washing free phenol, and viscosity reaches 18 pool/160 ℃, then add the silane coupling agent KH560 of 3 kilograms, stir blowing after 40 minutes and get final product to obtain the PEG modified phenolic resins of 416 kilograms.
Embodiment 4
Open stirring, then at pressure, be-the phenol 400Kg that is preheating to 55 ℃ is pumped in reactor under the decompression state of 0.07MPa, then 100Kg restored acid phenolic wastewater (pH value, 1, is 6% containing phenol concentration) is pumped in reactor, adds 4.8Kg oxalic acid, make the pH value of system 1.5, heat temperature raising, when temperature reaches 86 ℃, divides and adds 106Kg solid formaldehyde (content 96%) for 3 times, within 95 minutes, add, and control temperature in reactor not higher than 86 ℃.Add after formaldehyde, and utilize time chien shih its boiling that slowly heats up of 60 minutes, keep boiling 150 minutes, add PEG1000 14Kg, under decompression state, (pressure is-0.05MPa) dewaters to 145 ℃, adopts reduced steam washing free phenol, and viscosity reaches 12 pool/160 ℃, then add silane coupling agent KH560 3.5Kg, stir 30 minutes blowings and get final product to obtain the PEG modified phenolic resins of 412 kilograms.
Embodiment 5
Open stirring, then at pressure, be-decompression state of 0.06MPa under, the 400Kg phenol that is preheating to 50 ℃ is pumped in reactor, then by 80Kg restored acid phenolic wastewater, (pH value is 1.5, containing phenol concentration, be 6%) be pumped in reactor, add the industrial ethanedioic acid of 5.0Kg, make the pH value of system 1.5, then heat temperature raising, when temperature reaches 85 ℃, evenly point add 104Kg solid formaldehyde (content 96%) for 4 times, within 100 minutes, add, and control temperature in reactor not higher than 95 ℃; Add after formaldehyde, and utilize time chien shih its boiling that slowly heats up of 60 minutes, keep boiling 200 minutes, add the PEG1000 of 15 kilograms, under decompression state, (pressure is-0.06MPa) dewaters to 145 ℃, adopts reduced steam washing free phenol, and viscosity reaches 15 pool/160 ℃, then add the silane coupling agent KH560 of 4 kilograms, stir blowing after 40 minutes and get final product to obtain the PEG modified phenolic resins of 412 kilograms.
Embodiment 6
Open stirring, then at pressure, be-the phenol 400Kg that is preheating to 60 ℃ is pumped in reactor under the decompression state of 0.08MPa, then 90Kg restored acid phenolic wastewater (pH value, 2, is 4% containing phenol amount) is pumped in reactor, adds 5Kg oxalic acid, make the pH value of system 1, heat temperature raising, when temperature reaches 85 ℃, divides and adds 104Kg solid formaldehyde (content 96%) for 5 times, within 85 minutes, add, and control temperature in reactor not higher than 85 ℃.Add after formaldehyde, utilize 180 minutes time chien shih its be slowly warming up to boiling, keep boiling 200 minutes, add PEG1000 12Kg, under decompression state, (pressure is-0.06MPa) dewaters to 145 ℃, adopt reduced steam washing free phenol, viscosity reaches 15 pool/160 ℃, and blowing gets final product to obtain the PEG modified phenolic resins of 408 kilograms.
In the poly ethyldiol modified resol and preparation technology thereof of present patent application
---the abbreviation of the polyoxyethylene glycol that PEG1000 molecular weight is 1000;
---embodiment 6 is for not adding the PEG modified phenolic resins of silane coupling agent, just in use relative poor with the composite effect of fiber, but this PEG modified phenolic resins can reach object of the present invention equally;
---poly ethyldiol modified resol viscosity can be brought up to 18 pool/160 ℃ by 9 pool/160 ℃ along with the prolongation in formaldehyde, industrial ethanedioic acid and reaction times.