CN105085848A - Preparation method for modified phenolic resin - Google Patents
Preparation method for modified phenolic resin Download PDFInfo
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- CN105085848A CN105085848A CN201510547357.6A CN201510547357A CN105085848A CN 105085848 A CN105085848 A CN 105085848A CN 201510547357 A CN201510547357 A CN 201510547357A CN 105085848 A CN105085848 A CN 105085848A
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Abstract
The invention relates to the technical field of phenolic resin preparation, in particular relates to a preparation method for modified phenolic resin, comprising the following steps of 1) adding phenol into a reactor, heating, stirring, then adding alkali liquor, adjusting the pH, continuously adding formaldehyde and polyving akohol into the reactor, heating, performing a thermal reaction, adding starch and melamine, performing the thermal reaction, stopping heating, cooling to the room temperature, adjusting the pH to neutral, discharging, and obtaining a condensation liquid; 2) carrying out atmospheric distillation dehydration on the condensation liquid until the water content of the condensation liquid is 4 to 9 wt%; 3) adding polytetrafluoroethylene into the dehydrated condensation liquid in step 2), stirring, and stopping stirring. The preparation method for the modified phenolic resin provided by the invention has the advantages that the method is simple; the operation is easy; the modified phenolic resin has high viscidity and the ageing resistance, the water resistance, the inoxidizability and the high-temperature resistance are improved; the brittleness of the phenolic resin is remarkably improved, and the toughness and the strength are improved.
Description
Technical field
The present invention relates to resol and prepare technical field, particularly the preparation method of modified phenolic resins.
Background technology
Resol is the class organic synthetic resin be made up through condensation reaction of phenol or its homologue and aldehydes.It is as one of three large resins (epoxy resin, resol, unsaturated polyester resin), because having good electrical insulation capability, mechanical property, ablation resistance, corrosion resistance nature and higher thermotolerance and good water tolerance, be widely used in the aspects such as electric, automobile making and mechanical industry.The character of phenolic resin self limits its application in a lot of field.The rigidity aromatic ring that the methylene radical closely piled up in such as its structure connects, makes resol show very large fragility; And there is phenolic hydroxyl group and the methylene radical of easily oxidation, reduce thermotolerance and the scale resistance of resol.In order to meet more and more higher performance requirement, the modification of resol becomes the large focus studied now.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of modified phenolic resins, and the method is simple, easy to operate, the modified phenolic resins excellent combination property prepared.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of modified phenolic resins, comprises following preparation process:
1) in reactor, add phenol, be warming up to 60 ~ 70 DEG C, stir 3 ~ 5min, add alkali lye again, regulate pH to 8.5 ~ 9.0, continue to add formaldehyde and polyvinyl alcohol, be warming up to 90 ~ 95 DEG C, after carrying out insulation reaction 50 ~ 100min, add starch, trimeric cyanamide, carry out insulation reaction 60 ~ 90min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 4 ~ 9wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 60 ~ 100min, stop stir.
Phenol of the present invention and formaldehyde mole ratio are 1:0.65 ~ 1.05.Select the optimum proportioning of phenol and aldehyde, reduce free phenol and free formaldehyde content to greatest extent.
The NaOH solution of alkali lye of the present invention to be mass concentration be 1mol/L.NaOH solution uses as catalyzer, adds fast response, saves time, and reduces costs.
The mixture of the dihydroxyphenyl propane of phenol of the present invention to be mol ratio be 1 ~ 3:2 ~ 4:3 ~ 5, cresols and Resorcinol.
Polyvinyl alcohol add-on of the present invention is 3 ~ 8wt% of phenol.The polyvinyl alcohol added can reduce resol fragility, improves toughness, also can improve tack and ageing resistance simultaneously.
The add-on of starch of the present invention is 2 ~ 6wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.May there is hydrolytic action in starch in resol building-up process, generate various dextrin etc., because starch relative molecular mass is very large, after dissolving, viscosity is also very large, effectively can improve the viscosity of resol, hydroxyl simultaneously on starch molecular chain, methylol and the aldehyde radical etc. produced because of hydrolysis may participate in the building-up reactions of resol, not only increase tack, and bonding strength and stability in storage are also improved.Described trimeric cyanamide can improve the water tolerance of resol effectively.
The add-on of tetrafluoroethylene of the present invention is 3 ~ 9wt% of phenol.Carry out modification with tetrafluoroethylene, the high thermal resistance of resin, ageing resistance and oxidation-resistance can be improved.
Step 3 of the present invention) described in tetrafluoroethylene be nano level.
Beneficial effect of the present invention is:
1, the present invention adds polyvinyl alcohol, starch, trimeric cyanamide in novolak resin process, by after synthetic condensation agent liquid with polytetrafluoroethylblended blended, can greatly improve phenolic resin modified performance.
2, adjust ph to 8.5 ~ 9.0 of the present invention are optimal ph, and reactant has best reactive behavior in this pH value range, can significantly improve speed of response, reduce the reaction times, reduce and produce power consumption and production cost.
3, the present invention controls water content is 4 ~ 9wt%, and moisture reduces, and can extend the shelf time of modified phenolic resins, resol can be prevented mouldy simultaneously, can also improve the over-all properties of modified phenolic resins.
4, the inventive method is simple, easy to operate, can significantly reduce product preparation cycle.
5, by the modified phenolic resins that the inventive method prepares, viscosity is higher, and ageing resistance, water tolerance, oxidation-resistance and high thermal resistance are improved, and significantly improves the fragility of resol, improves toughness and intensity.Test-results shows, the modified phenolic resins that the present invention prepares, and free formaldehyde is less than 0.08wt%, viscosity 19000 ~ 26000mp.s/20 DEG C, and the shelf time is greater than 1 year, and softening temperature 180 ~ 205 DEG C/SP, acid number is less than 18.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to these embodiments.
Embodiment 1
1) in reactor, add phenol, be warming up to 60 DEG C, stir 3min, add alkali lye again, regulate pH to 8.5, continue to add formaldehyde and polyvinyl alcohol, be warming up to 95 DEG C, after carrying out insulation reaction 50min, add starch, trimeric cyanamide, carry out insulation reaction 90min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 9wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 100min, stop stir.
Described phenol and formaldehyde mole ratio are 1:1.05.
The NaOH solution of described alkali lye to be mass concentration be 1mol/L.
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 1:4:5, cresols and Resorcinol.
Described polyvinyl alcohol is nano level, and add-on is the 8wt% of phenol.
The add-on of described starch is the 2wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.
The add-on of described tetrafluoroethylene is the 9wt% of phenol.
Embodiment 2
1) in reactor, add phenol, be warming up to 63 DEG C, stir 5min, add alkali lye again, regulate pH to 8.6, continue to add formaldehyde and polyvinyl alcohol, be warming up to 94 DEG C, after carrying out insulation reaction 60min, add starch, trimeric cyanamide, carry out insulation reaction 85min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 8wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 90min, stop stir.
Described phenol and formaldehyde mole ratio are 1:0.95.
The NaOH solution of described alkali lye to be mass concentration be 1mol/L.
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 2:4:4, cresols and Resorcinol.
Described polyvinyl alcohol is nano level, and add-on is the 6wt% of phenol.
The add-on of described starch is the 3wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.
The add-on of described tetrafluoroethylene is the 8wt% of phenol.
Embodiment 3
1) in reactor, add phenol, be warming up to 65 DEG C, stir 4min, add alkali lye again, regulate pH to 8.7, continue to add formaldehyde and polyvinyl alcohol, be warming up to 93 DEG C, after carrying out insulation reaction 75min, add starch, trimeric cyanamide, carry out insulation reaction 75min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 6wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 80min, stop stir.
Described phenol and formaldehyde mole ratio are 1:0.85.
The NaOH solution of described alkali lye to be mass concentration be 1mol/L.
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 2:3:4, cresols and Resorcinol.
Described polyvinyl alcohol is nano level, and add-on is the 5wt% of phenol.
The add-on of described starch is the 4wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.
The add-on of described tetrafluoroethylene is the 6wt% of phenol.
Embodiment 4
1) in reactor, add phenol, be warming up to 68 DEG C, stir 4min, add alkali lye again, regulate pH to 8.8, continue to add formaldehyde and polyvinyl alcohol, be warming up to 92 DEG C, after carrying out insulation reaction 85min, add starch, trimeric cyanamide, carry out insulation reaction 70min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 5wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 70in, stop stir.
Described phenol and formaldehyde mole ratio are 1:0.75.
The NaOH solution of described alkali lye to be mass concentration be 1mol/L.
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 3:2:3, cresols and Resorcinol.
Described polyvinyl alcohol is nano level, and add-on is the 4wt% of phenol.
The add-on of described starch is the 5wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.
The add-on of described tetrafluoroethylene is the 4wt% of phenol.
Embodiment 5
1) in reactor, add phenol, be warming up to 70 DEG C, stir 3min, add alkali lye again, regulate pH to 9.0, continue to add formaldehyde and polyvinyl alcohol, be warming up to 90 DEG C, after carrying out insulation reaction 100min, add starch, trimeric cyanamide, carry out insulation reaction 60min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 4wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 60min, stop stir.
Described phenol and formaldehyde mole ratio are 1:0.65.
The NaOH solution of described alkali lye to be mass concentration be 1mol/L.
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 1:2:3, cresols and Resorcinol.
Described polyvinyl alcohol is nano level, and add-on is the 3wt% of phenol.
The add-on of described starch is the 6wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1.
The add-on of described tetrafluoroethylene is the 3wt% of phenol.
Claims (2)
1. the preparation method of modified phenolic resins, is characterized in that, comprises following preparation process:
1) in reactor, add phenol, be warming up to 60 ~ 70 DEG C, stir 3 ~ 5min, add alkali lye again, regulate pH to 8.5 ~ 9.0, continue to add formaldehyde and polyvinyl alcohol, be warming up to 90 ~ 95 DEG C, after carrying out insulation reaction 50 ~ 100min, add starch, trimeric cyanamide, carry out insulation reaction 60 ~ 90min, stop heating, be cooled to room temperature, regulate pH to neutral, discharging, obtains condensated liquid;
2) condensated liquid being carried out air distillation dehydration, is 4 ~ 9wt% to water content;
3) to step 2) dehydration after condensated liquid add tetrafluoroethylene, stir 60 ~ 100min, stop stir;
Described phenol and formaldehyde mole ratio are 1:0.65 ~ 1.05;
The NaOH solution of described alkali lye to be mass concentration be 1mol/L;
The mixture of the dihydroxyphenyl propane of described phenol to be mol ratio be 1 ~ 3:2 ~ 4:3 ~ 5, cresols and Resorcinol;
Described polyvinyl alcohol add-on is 3 ~ 8wt% of phenol;
The add-on of described starch is 2 ~ 6wt% of phenol, and the mass ratio of starch and trimeric cyanamide is 2:1;
The add-on of described tetrafluoroethylene is 3 ~ 9wt% of phenol.
2. the preparation method of modified phenolic resins according to claim 1, is characterized in that: step 3) described in tetrafluoroethylene be nano level.
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| CN201510547357.6A CN105085848A (en) | 2015-08-31 | 2015-08-31 | Preparation method for modified phenolic resin |
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| CN201510547357.6A CN105085848A (en) | 2015-08-31 | 2015-08-31 | Preparation method for modified phenolic resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733178A (en) * | 2016-04-27 | 2016-07-06 | 桂林兴松林化有限责任公司 | Preparation method of abrasion-resistant and anti-aging resin |
| CN106750065A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of modified phenolic resin adhesive |
| CN106854263A (en) * | 2016-12-11 | 2017-06-16 | 钦州学院 | A kind of starch conversion phenolic resin and preparation method thereof |
| CN106947041A (en) * | 2017-03-31 | 2017-07-14 | 西京学院 | A kind of preparation method of modified phenolic fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102703007A (en) * | 2012-04-30 | 2012-10-03 | 苏州信邦绿色新材料科技有限公司 | Preparation method of polyvinyl alcohol modified phenolic resin adhesive |
| CN102964553A (en) * | 2012-11-27 | 2013-03-13 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of modified melamine formaldehyde resin |
| CN103601865A (en) * | 2013-11-27 | 2014-02-26 | 山东圣泉化工股份有限公司 | Starch modified phenolic resin and application thereof |
-
2015
- 2015-08-31 CN CN201510547357.6A patent/CN105085848A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703007A (en) * | 2012-04-30 | 2012-10-03 | 苏州信邦绿色新材料科技有限公司 | Preparation method of polyvinyl alcohol modified phenolic resin adhesive |
| CN102964553A (en) * | 2012-11-27 | 2013-03-13 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of modified melamine formaldehyde resin |
| CN103601865A (en) * | 2013-11-27 | 2014-02-26 | 山东圣泉化工股份有限公司 | Starch modified phenolic resin and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733178A (en) * | 2016-04-27 | 2016-07-06 | 桂林兴松林化有限责任公司 | Preparation method of abrasion-resistant and anti-aging resin |
| CN105733178B (en) * | 2016-04-27 | 2018-01-12 | 桂林兴松林化有限责任公司 | A kind of preparation method of wear-resisting anti-aging resin |
| CN106750065A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of modified phenolic resin adhesive |
| CN106854263A (en) * | 2016-12-11 | 2017-06-16 | 钦州学院 | A kind of starch conversion phenolic resin and preparation method thereof |
| CN106947041A (en) * | 2017-03-31 | 2017-07-14 | 西京学院 | A kind of preparation method of modified phenolic fiber |
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