CN101659780A - Compositely modified thermosetting phenol-formaldehyde resin powder - Google Patents
Compositely modified thermosetting phenol-formaldehyde resin powder Download PDFInfo
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- CN101659780A CN101659780A CN200810141127A CN200810141127A CN101659780A CN 101659780 A CN101659780 A CN 101659780A CN 200810141127 A CN200810141127 A CN 200810141127A CN 200810141127 A CN200810141127 A CN 200810141127A CN 101659780 A CN101659780 A CN 101659780A
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- formaldehyde resin
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- thermosetting phenol
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Abstract
The invention discloses thermosetting phenol-formaldehyde resin powder compositely modified by organic rubber, organic montmorillonoid or inorganic modified montmorillonoid, and a production method thereof. The known thermosetting phenol-formaldehyde resin powder is prepared by a suspension condensation process, and needs to be prepared by means of chemical plants such as a specific reaction kettle with high-speed stirring, a centrifugal machine or a filter, a fluidized bed or an air-flow drier and the like. The thermosetting phenol-formaldehyde resin powder of the invention is prepared only by a common reaction kettle (the conventional 2132 thermosetting phenol-formaldehyde resin powder production equipment). The production method has the core characteristics of the suspension condensation process, and prepares the thermosetting phenol-formaldehyde resin powder with high temperature resistance, strong wear resistance, long storage period and excellent comprehensive performance throughsimplified equipment. The process is possibly more suitable to be promoted and applied by medium and small-sized manufacturing plants. The product can be widely used for phenolic moulding materials,abrasives, friction materials, heat insulating materials and the like, and is an upgraded substitute product of the conventional phenol-formaldehyde resin.
Description
Technical field
The present invention relates to a kind of thermosetting phenol-formaldehyde resin powder and manufacture craft of utilizing organic rubber and organo montmorillonite or inorganic modified montmorillonite Composite modification.
Background technology
By the suspension polycondensating process (PTS) of the resol of U.S. combinating carbide company exploitation, be synthesis technique more advanced in the world today, have simply, easily control need not pulverized the thermosetting phenol-formaldehyde resin powder that can directly obtain good fineness.This thermosetting phenol-formaldehyde resin powder has been broken in the solid phenolic resin field, the dominance of thermal plastic phenolic resin's powder.Thermosetting phenol-formaldehyde resin powder has overcome the easy moisture absorption conglomeration of novolac resin powder, can not long-term storage, and need add solidifying agent could solidify, and has a large amount of obnoxious flavoures to overflow in curing, easily causes the product bubbling, the shortcoming of crackle; Have nonhygroscopicly, do not lump, deposit under the normal temperature and can store 2 years, heat-resisting height, intensity is big, need not add advantages such as solidifying agent, at automobile, space flight and aviation, electron device, fields such as extraordinary grinding materials and grinding tool obtain widespread use.Chinese patent ZL03112025 just reflects this technology technical progress at home.Resol is cheap owing to its cost of material, mature production technology, and equipment is simple, product is heat-resisting, chemical-resistant stability height, advantage such as mechanical property is good, be widely applied to more than 30 field, opened in many high-tech areas and play very important and irreplaceable effect.Also resol is proposed to make the more optimal requirement of performance simultaneously.And that the single pure phenolic resin of composition shows fragility is big, and toughness is low, and shortcoming such as easily decompositions of being heated under comparatively high temps, is difficult to the job requirement of suitable particular surroundings.Simultaneously, the suspension polycondensating process requires to have the special reactor of high-speed stirring, vacuum filter or whizzer, and dry the need with floatingization bed dryer or pneumatic drier, these equipment are different fully with traditional phenol-formaldehyde resin powder production unit.The numerous middle-size and small-size resol factory of China just means and must drop into very big fund as wanting to adopt the technology of suspension polycondensation, sets up another the kitchen range stove.This may be that the suspension polycondensating process is promoted a very slow reason for a long time in China.
Summary of the invention
Purpose of the present invention is intended to overcome the limitation of prior art, provides a kind of performance excellent more, the simple thermosetting phenol-formaldehyde resin powder of manufacture craft.A kind of heat-reactive phenolic resin production technique that can make full use of the prior art equipment is provided simultaneously.
The present invention realizes by following technical proposals.
Will be by 100～115 parts of by weight phenol or phenols homologues; 100～115 parts in formaldehyde, 6～12 parts of urotropines, 50～100 parts in water, 0.5～5 part of protective colloid; 0.5～5 part of still release agent, 2～10 parts of paracrils, 2～10 parts of organic modification montmonrillonite or inorganic modified polynites be through reacting by heating, polycondensation; dehydration, drying, pulverizing forms.
Make the processing method of above-mentioned thermosetting phenolic powder, the steps include:
A). feed intake: with the phenols raw material, formaldehyde, water, urotropine, protective colloid, still release agent, organic rubber, organo montmorillonite or inorganic modified polynite drop in the reactor, fully stir, then heat temperature raising.
B) polycondensation: when above-mentioned material rises to 65 ℃ of left and right sides, stop heating, allow material slowly rise to 70～90 ℃, close observation when material in reactor becomes turbid, picks up counting insulation reaction 60～120 minutes.
C) separate: stop to stir, static 5～20 minutes, open the blowing bottom valve, thermal material is put into charging tray, cooling.Upper water is stayed in the reactor, carries out wastewater treatment while hot.(concrete technology is declared patent separately).
D) drying: charging tray is put into moisture eliminator or vacuum drier, behind the removal residual water-content, take out cooling.
E) will cool off finished product block and pulverize, packing with pulverizer.
The present invention has added the properties-correcting agent paracril in material.Paracril is by divinyl and vinyl cyanide synthetic organic rubber, has good springiness, heat-resisting height, advantage such as oil resistant is good.After rubber-like rubber ion is distributed in the resol, resol there is significant toughness reinforcing enhancement, played the same effect of steel alloy.Have document to prove, the resol anti-impact force that adds 2% paracril has improved 100%.
The present invention has added organic modification montmonrillonite or inorganic modified polynite in material, improved the resistance to elevated temperatures of resol.Nano composite polymer-montmorillonoid material is a big focus of nearly more than ten years materialogy research.This class material often combines the advantage of inorganic materials and macromolecular material, shows excellent mechanical property, thermal property, and barrier properties for gases and flame retardant resistance have wide application prospect.
The present invention has added the still release agent sodium lauryl sulphate in material, overcome the sticking still phenomenon of big area that occurs during Chinese patent ZL 03112025 implements.
The protective colloid that the present invention adds in material is polyvinyl alcohol or gum arabic, any one in the sodium cellulosate.
Because entire reaction course is carried out in low viscous water all the time, therefore got rid of heat dissipation problem and bumping phenomenon in the general substance law polycondensation process, temperature of reaction is low, and easily control is energy-conservation, safety.The main drawback of resol is that cured article is more crisp.By organic rubber, the blending and modifying of organo montmorillonite makes it toughness reinforcing, and is heat-resisting, and wear-resisting and processing characteristics is improved simultaneously.
Regular suspension polycondensating process need rely on high-speed stirring to control the particle diameter of spherical product, after polycondensation is finished under the help of water and protective colloid; cool off fast with frozen water, avoid the mutual adhesion of spherical product, so that separate moisture with filter; dry with floatingization bed at last, finish technology.The present invention only need lean on the stirring on the common response still to finish the mixing of material, after polycondensation is finished, stops to stir, and material AUTOMATIC ZONING immediately in the reactor, water layer is last, and the heat-reactive phenolic resin layer is down.Pause static after, open baiting valve at the bottom of the still, while hot material is put into charging tray.After changing hot charging tray over to vacuum drying oven again and removing remaining moisture, cooling is finished last manufacture craft with the pulverizer of routine.The finished product of two kinds of suspension polycondensating process are (regular handicraft product is spherical, and product of the present invention is irregular powdery because of mechanical disintegration) except shape is had any different slightly, its product colour, and inner quality, effect is just the same.Product performance of the present invention are better than 2123 general phenol-formaldehyde resin powders, and technology is better than traditional substance law, and the more known again suspension polycondensating process of producing apparatus is simple, and is inexpensive, has the excellent development prospect.The technology of the present invention's narration may be more suitable for medium and small factory and apply.
Below in conjunction with embodiment technical solution of the present invention is explained further.
Specific embodiments
Embodiment 1
In the 1000L enamel reaction still, add 200Kg phenol, 210Kg37% formaldehyde, 160Kg water, gum arabic 2Kg, K121Kg, urotropine 16Kg behind the DK2 3kg, starts stirring, slowly be warming up to 65 ℃～70 ℃, stop heating, reaction is carried out automatically, when temperature rises between 78 ℃～90 ℃, material picked up counting in the time of can becoming turbid, and the insulation polycondensation stopped to stir after 60 minutes.After static 5～20 minutes, open baiting valve at the bottom of the still, material is put into charging tray, in time change loft drier over to, after removing the residue small amount of moisture, take out and be cooled to piece, break into pieces, mix with common 2123 resin mass of some amount, put into pulverizer and pulverize, obtain faint yellow no ammonia phenol-formaldehyde resin powder product.Product is used for certain electrical equipment moulding material, and after tested, free ammonia is less than 80PPm.
Embodiment 2
In the 1000L enamel reaction still, add 200kg phenol, 210kg formaldehyde, 160kg water, polyvinyl alcohol 2kg is behind the urotropine 7kg.Start stirring, slowly be warming up to 65-70 ℃, stop heating, when temperature rises between 75-85 ℃, material picked up counting when becoming turbid, and the insulation polycondensation stopped to stir after 55 minutes, leave standstill 10-20 minute after, open the bottom baiting valve.Material is put into charging tray, change vacuum drying oven over to, after the removal small amount of moisture, take out and be cooled to piece.With this thermosetting resin piece, replace 70% urotropine, with 30% urotropine, a certain amount of 2123 resin mass mix, and pulverize, and must hang down the ammonia phenol-formaldehyde resin powder.Product is used for non-woven mat, and free ammonia reaches the export techniques index less than 200ppm..
Embodiment 3
In the 1000L stainless steel cauldron, add 200Kg phenol, 206Kg37% formaldehyde, 180Kg water, PVA 2Kg, K12 1Kg, urotropine 14Kg, behind the lithium base montmorillonite 8Kg, start stirring, slowly be warming up to 65 ℃～70 ℃, stop heating, when temperature rises between 78 ℃～90 ℃, when material becomes turbid, pick up counting, after the insulation reaction 70 minutes, stop to stir. after static 10 minutes, open baiting valve, material is put to charging tray, in time change loft drier over to, after removing residual moisture, be cooled to piece, crushing packing.Product is used for certain structure glue, has stood 192 hours high temperature tests, has satisfied special technical requirement.
Embodiment 4
In the 1000L stainless steel cauldron, add 200Kg phenol, 202Kg formaldehyde, 170Kg water, PVA 1Kg, K12 1Kg behind the urotropine 14Kg ni montmorillonite 6Kg, starts stirring, slowly be warming up to 65-70 ℃, stop heating, when temperature rises between 75 ℃-85 ℃, when cloud point occurring.Pick up counting, be incubated after 80 minutes, stop to stir, open the still bottom valve, blowing changes vacuum drying oven over to, removes the residual moisture postcooling and becomes piece, crushing packing.Product is used for the grinding materials and grinding tool industry, and product cutting degree is improved greatly.，
Embodiment 5
In the 1000L stainless steel cauldron, add 200Kg phenol, 204Kg formaldehyde, 160Kg water, urotropine 14Kg, PVA 1Kg, K12 1Kg, NBR4Kg behind the DK5 4Kg, starts stirring, slowly is warming up to 65 ℃～70 ℃, stops heating.When material between 75 ℃～85 ℃, when becoming turbid, pick up counting, insulation reaction stopped to stir after 80 minutes. after static 5～20 minutes, open the bed material valve, material put into charging tray, in time change loft drier over to, remove residual moisture, be cooled to piece, crushing packing.Product is used for certain superhard material grinding tool. and this grinding tool has higher line speed and grinding efficiency, and durability has significantly raising, and processing work has surface gloss preferably.
Claims (8)
1, a kind of composite modified thermosetting phenol-formaldehyde resin powder.It is characterized in that: will be by 100～115 parts of by weight phenol or phenols homologues; 100～115 parts in formaldehyde, 6～14 parts of urotropines, 50～100 parts in water, 0.5～5 part of protective colloid; 0.5～5 part of still release agent, 2～10 parts of paracrils, 2～10 parts of organic modification montmonrillonite or inorganic modified polynites be through reacting by heating, polycondensation; dehydration, drying, pulverizing forms.
Described phenols homologue is a cresols, any one in the phenol.
Described organic rubber is divinyl and vinyl cyanide synthetic paracril.
Described protective colloid is polyvinyl alcohol or gum arabic, any one in the sodium cellulosate.
Described organic modification montmonrillonite is the modified product of organic active agent to inorganic polynite.
Described inorganic modified polynite is the modified product of the inorganic polynite of inorganic metal ion.
Described still release agent is a sodium lauryl sulphate.
2, its preparation process of manufacturing claim is as follows:
A). feed intake: with the phenols raw material, formaldehyde, water, urotropine, protective colloid, still release agent, paracril, organo montmorillonite or inorganic polynite drop in the reactor, fully stir, then heat temperature raising.
B) polycondensation: when above-mentioned material rises to 65 ℃ of left and right sides, stop heating, allow material slowly rise to 70～90 ℃, close observation when material in reactor becomes turbid, picks up counting insulation reaction 60～120 minutes.
C) separate: stop to stir, static 5～20 minutes, open the blowing bottom valve, while hot material is put into charging tray, cooling.Upper water is stayed in the reactor, carries out wastewater treatment while hot.
D) drying: charging tray is put into moisture eliminator or vacuum drier, behind the removal residual water-content, take out cooling.
E) will cool off finished product block and pulverize, packing with pulverizer.
3, make claim and comprise properties-correcting agent only with paracril or the heat-reactive phenolic resin product only produced with polynite.
4, make claim and comprise use production technique disclosed by the invention, but do not add the product of still release agent and properties-correcting agent.
5, make claim and comprise use composition disclosed by the invention, the product that utilizes the device fabrication of known suspension polycondensating process to go out.
6, make claim and comprise use composition disclosed by the invention, the product that utilizes the general chemical device fabrication to go out.
7, the manufacturing claim comprises the thermosetting phenol-formaldehyde resin powder that uses the present invention to produce and all and partly replaces urotropine, the no ammonia of production or few ammonia phenol-formaldehyde resin powder, phenolaldehyde moulding compound.
8, make claim and be not limited only to composition disclosed by the invention, but utilize the thermosetting phenol-formaldehyde resin powder of fabrication process of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810141127A CN101659780A (en) | 2008-08-26 | 2008-08-26 | Compositely modified thermosetting phenol-formaldehyde resin powder |
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|---|---|---|---|
| CN200810141127A CN101659780A (en) | 2008-08-26 | 2008-08-26 | Compositely modified thermosetting phenol-formaldehyde resin powder |
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| CN101659780A true CN101659780A (en) | 2010-03-03 |
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| CN200810141127A Pending CN101659780A (en) | 2008-08-26 | 2008-08-26 | Compositely modified thermosetting phenol-formaldehyde resin powder |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408670A (en) * | 2011-09-16 | 2012-04-11 | 无锡创达电子有限公司 | Ammonia-free phenolic molding compound and its preparation method |
| CN107363737A (en) * | 2017-08-23 | 2017-11-21 | 宁波大华砂轮有限公司 | A kind of rail polishing emery wheel |
| CN107414688A (en) * | 2017-08-23 | 2017-12-01 | 宁波大华砂轮有限公司 | A kind of rail polishing emery wheel |
| CN108067581A (en) * | 2017-11-30 | 2018-05-25 | 宁波新天阳新材料科技有限公司 | A kind of low foul smell type precoated sand |
| CN111871561A (en) * | 2020-08-04 | 2020-11-03 | 苏州兴业材料科技南通有限公司 | Method for preventing low-softening-point phenolic resin from caking |
| CN111995723A (en) * | 2020-07-13 | 2020-11-27 | 杭摩新材料集团股份有限公司 | Solid thermosetting phenolic resin and method for preparing same by adopting suspension method |
| CN115746807A (en) * | 2021-09-03 | 2023-03-07 | 中国石油化工股份有限公司 | Lignin-based channeling sealing agent and preparation method and application thereof |
-
2008
- 2008-08-26 CN CN200810141127A patent/CN101659780A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408670A (en) * | 2011-09-16 | 2012-04-11 | 无锡创达电子有限公司 | Ammonia-free phenolic molding compound and its preparation method |
| CN107363737A (en) * | 2017-08-23 | 2017-11-21 | 宁波大华砂轮有限公司 | A kind of rail polishing emery wheel |
| CN107414688A (en) * | 2017-08-23 | 2017-12-01 | 宁波大华砂轮有限公司 | A kind of rail polishing emery wheel |
| CN107363737B (en) * | 2017-08-23 | 2020-05-12 | 宁波大华砂轮有限公司 | Rail grinding wheel |
| CN107414688B (en) * | 2017-08-23 | 2020-05-12 | 宁波大华砂轮有限公司 | Rail grinding wheel |
| CN108067581A (en) * | 2017-11-30 | 2018-05-25 | 宁波新天阳新材料科技有限公司 | A kind of low foul smell type precoated sand |
| CN111995723A (en) * | 2020-07-13 | 2020-11-27 | 杭摩新材料集团股份有限公司 | Solid thermosetting phenolic resin and method for preparing same by adopting suspension method |
| CN111995723B (en) * | 2020-07-13 | 2021-12-07 | 杭摩新材料集团股份有限公司 | Solid thermosetting phenolic resin and method for preparing same by adopting suspension method |
| CN111871561A (en) * | 2020-08-04 | 2020-11-03 | 苏州兴业材料科技南通有限公司 | Method for preventing low-softening-point phenolic resin from caking |
| CN115746807A (en) * | 2021-09-03 | 2023-03-07 | 中国石油化工股份有限公司 | Lignin-based channeling sealing agent and preparation method and application thereof |
| CN115746807B (en) * | 2021-09-03 | 2024-02-13 | 中国石油化工股份有限公司 | Lignin-based channeling sealing agent and preparation method and application thereof |
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Open date: 20100303 |