CN104164050A - Heatproof environmental protection phenolic resin and preparation method of its composite material - Google Patents
Heatproof environmental protection phenolic resin and preparation method of its composite material Download PDFInfo
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- CN104164050A CN104164050A CN201410330913.XA CN201410330913A CN104164050A CN 104164050 A CN104164050 A CN 104164050A CN 201410330913 A CN201410330913 A CN 201410330913A CN 104164050 A CN104164050 A CN 104164050A
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Abstract
The invention relates to a heatproof environmental protection phenolic resin and its composite material, which belongs to the technical field of synthetic resin treatment and production. The environmental protection phenolic resin comprises environmental protection phenolic resin, alkali-free glass fiber filament, a coupling agent KH-550, powdered steatile, a mold lubricant, a pigment, graphite, silica, industrial alcohol and silica. The above materials are processed through three steps of synthesis of phenolic resin, mixing and stirring, timely glue injection. The environmental protection phenolic resin has the advantages of reasonable method, clear ratio, low free phenol content and good weight reservation rate.
Description
Technical field:
The present invention relates to synthetic resins processing and fabricating technical field, be specifically related to the preparation method of a kind of heat resistant type environmental protection resol and matrix material thereof.
Background technology:
Resol is as one of three large thermosetting resins, the developing history of existing over one hundred year, its significant feature is cheap, heat-resisting, resistance to ablation, fire-retardant, during burning, be fuming few, along with electronics, machinery, the fast development of communications and transportation and national defense industry, resol and matrix material thereof are also developed rapidly, but the weakness of common resol is hydroxyl and methylene radical and is easily oxidized, phenolic hydroxyl group is not generally participated in chemical reaction in resin is synthetic, therefore in resol, there are many hydroxyls, phenolic hydroxyl group is a polar group, easily water suction makes the electrical property variation of Bakeland, physical strength is low, but phenolic hydroxyl group changes under heat or UV-irradiation, easily generate quinone or other structure, cause material variable color, the protection of phenolic hydroxyl group and methylene radical becomes phenolic resin modified main path, therefore by being carried out to modification, resol can improve its thermotolerance and antioxidative stabilizer.In resol structure after solidifying, because virtue is internuclear, only have methylene radical to be connected, fragility is larger, in order to change its fragility, need add therein toughness reinforcing component toughness reinforcing to it, different Application Areass can adopt corresponding toughening technology and means according to specific requirement, in order to meet self service requirements, but how many adding of toughening material all can affect its thermotolerance, how in toughness reinforcing, not reduce or to reduce less thermotolerance, trim point in the middle of finding, take into account toughness and resistance to elevated temperatures, expand its Application Areas, for national defence and civilian industry, machinery, electronics, building, the application important in inhibiting of the departments such as traffic.
Prepared by synthetic general phenol and the liquid formaldehyde (massfraction of liquid formaldehyde is 37～40%) of adopting of tradition resol, in production process, not only energy consumption is high, efficiency is low, and also can produce a large amount of phenolic wastewater in dehydration or drying process, according to statistics, one ton of novolac resin of every production produces waste water 500～600kg, one ton of heat-reactive phenolic resin of every production can produce 600～800kg waste water, manufacturer takes several different methods to process phenolic wastewater, received certain effect, but still can not tackle the problem at its root.Research shows, it is feasible adopting water-free solid formaldehyde to replace the liquid formaldehyde aqueous solution to produce resol, gained resin quality is higher than conventional production methods, in production process, without waste water, produce, can realize cleaner production, resin water content ranges is controlled by introducing the water yield, saves the operation of vacuum hydro-extraction.Certainly use solid formaldehyde to replace liquid formaldehyde to produce resol, because its technical difficulty is made slow progress greatly, we are through unremitting effort, with keen determination, have finally obtained success.The performance index of the environmental protection resol that the present invention produces are better than conventional ammonia phenolic aldehyde and ba phenolic resin, the mechanical property of the matrix material of preparing with it and thermotolerance are better than general phenolic resin-base composite, for resol and matrix material thereof, be undoubtedly important innovation.
Summary of the invention:
Technical problem to be solved by this invention is to overcome existing technological deficiency a kind of method is reasonable, proportioning is clear, free phenol content is low, weight retention rate is good a kind of heat resistant type environmental protection resol and the preparation method of matrix material thereof is provided.
Technical problem to be solved by this invention adopts following technical scheme to realize:
Heat resistant type environmental protection resol and a matrix material thereof, is characterized in that: comprise following composition:
Each component proportion is as follows in weight fraction,
Described releasing agent is happy auspicious solid 6290;
Described pigment is glossy black;
A preparation method for heat resistant type environmental protection resol and matrix material thereof, comprises the following steps,
Step 1, synthesizing environment-friendly resol: by phenol: the proportioning of aniline: solid formaldehyde=1:0.1～0.2:1.2～1.8mol, operation steps is as follows: 80～120g phenol is melted, add 1～5g magnesium oxide, stir 20min, add again aniline 1～10g, finally add solid formaldehyde and auxiliary agent 20～120g, stir, control temperature at 70～105 ℃, maintain reaction 1h, timing during 80 ℃ of temperature, after reaction 50min, start to sample the viscosity of assize fat, when resin is coated with 4# cup viscosity and reaches 28～30S at 50 ℃, stopped reaction, material temperature is down at 80 ℃, add the concentration of having dissolved at 10～20% PVB spirituous solution, stir lower reaction 1 hour, measure gel time in the time of 90～120S/150 ℃, qualified, discharging, obtain brown transparent environmental protection resol,
Step 2, mix and blend: after synthesizing environment-friendly resol is made, said ratio, by each component mix and blend 1h in kneader, naturally dried or dried, obtaining heat resistant type environmental protection resol and moulding compound thereof;
Step 3, timely injecting glue: the material after above-mentioned mix and blend is placed in colloidal mill and is mixed, and glue is poured glue groove into, starts adhesive applicator, controls gel content, dries, and rolling obtains heat-resisting toughening type environmental protection resol preimpregnation cloth.
Beneficial effect of the present invention is: resol is adopted solid formaldehyde and replaced liquid formaldehyde synthetic, not moisture in raw material, there is no processing wastewater, environmental protection and energy saving, increase the toughness of phenolic aldehyde, and made matrix material has good fluidity, and manufacturability is good, can adopt quick die press technology for forming preparation thermal insulation, heat insulation high strength composite goods.The inventive method is reasonable, proportioning is clear, free phenol content is low, weight retention rate is good.
Embodiment:
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below further set forth the present invention.
Heat resistant type environmental protection resol and a matrix material thereof, is characterized in that: comprise following composition:
Each component proportion is as follows in weight fraction,
Described releasing agent is happy auspicious solid 6290;
Described pigment is glossy black;
A preparation method for heat resistant type environmental protection resol and matrix material thereof, is characterized in that: comprises the following steps,
Step 1, synthesizing environment-friendly resol: by phenol: the proportioning of aniline: solid formaldehyde=1:0.1～0.2:1.2～1.8mol, operation steps is as follows: 80～120g phenol is melted, add 1～5g magnesium oxide, stir 20min, add again aniline 1～10g, finally add solid formaldehyde and auxiliary agent 20～120g, stir, control temperature at 70～105 ℃, maintain reaction 1h, timing during 80 ℃ of temperature, after reaction 50min, start to sample the viscosity of assize fat, when resin is coated with 4# cup viscosity and reaches 28～30S at 50 ℃, stopped reaction, material temperature is down at 80 ℃, add the concentration of having dissolved at 10～20% PVB spirituous solution, stir lower reaction 1 hour, measure gel time in the time of 90～120S/150 ℃, qualified, discharging, obtain brown transparent environmental protection resol,
Step 2, mix and blend: after synthesizing environment-friendly resol is made, said ratio, by each component mix and blend 1h in kneader, naturally dried or dried, obtaining heat resistant type environmental protection resol and moulding compound thereof;
Step 3, timely injecting glue: the material after above-mentioned mix and blend is placed in colloidal mill and is mixed, and glue is poured glue groove into, starts adhesive applicator, controls gel content, dries, and rolling obtains heat-resisting toughening type environmental protection resol preimpregnation cloth.
According to above-mentioned description, for the content's index of the free phenol of product of the present invention as following table 1,
Table 1
| Fundamental property | Outward appearance | Solids content (%) | Gel time (S) | Free phenol content (%) |
| Ammonia phenolic aldehyde | Brown liquid | 57-62 | 90-120 | ≤15 |
| Environmental protection resol | Brown transparent liquid | 56±2 | 90-120 | ＜12 |
The carbon residue rate of resol is to weigh an important indicator of resin resistance toheat, in general, the carbon residue rate of resin is higher, its resistance toheat is better, under rare gas element, the carbon residue rate that adopts thermogravimetric analysis to measure cured resin is a kind of simple, economy, the effective means of evaluation resin resistance toheat, and following table 2 is environmental protection resol and conventional ammonia phenolic aldehyde, the weight retention rate (%) of ba phenolic resin under differing temps
Table 2
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. heat resistant type environmental protection resol and a matrix material thereof, is characterized in that: comprise following composition:
Each component proportion is as follows in weight fraction,
2. a preparation method for heat resistant type environmental protection resol and matrix material thereof, is characterized in that: comprises the following steps,
Step 1, synthesizing environment-friendly resol: by phenol: the proportioning of aniline: solid formaldehyde=1:0.1～0.2:1.2～1.8mol, operation steps is as follows: 80～120g phenol is melted, add 1～5g magnesium oxide, stir 20min, add again aniline 1～10g, finally add solid formaldehyde and auxiliary agent 20～120g, stir, control temperature at 70～105 ℃, maintain reaction 1h, timing during 80 ℃ of temperature, after reaction 50min, start to sample the viscosity of assize fat, when resin is coated with 4# cup viscosity and reaches 28～30S at 50 ℃, stopped reaction, material temperature is down at 80 ℃, add the concentration of having dissolved at 10～20% PVB spirituous solution, stir lower reaction 1 hour, measure gel time in the time of 90～120S/150 ℃, qualified, discharging, obtain brown transparent environmental protection resol,
Step 2, mix and blend: after synthesizing environment-friendly resol is made, said ratio, by each component mix and blend 1h in kneader, naturally dried or dried, obtaining heat resistant type environmental protection resol and moulding compound thereof;
Step 3, timely injecting glue: the material after above-mentioned mix and blend is placed in colloidal mill and is mixed, and glue is poured glue groove into, starts adhesive applicator, controls gel content, dries, and rolling obtains heat-resisting toughening type environmental protection resol preimpregnation cloth.
3. a kind of heat resistant type environmental protection resol according to claim 1 and matrix material thereof, is characterized in that: described releasing agent is happy auspicious solid 6290.
4. a kind of heat resistant type environmental protection resol according to claim 1 and matrix material thereof, is characterized in that: described pigment is glossy black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410330913.XA CN104164050B (en) | 2014-07-11 | 2014-07-11 | A kind of heat resistant type Environmental protection phenol formaldehyde resin and the preparation method of composite thereof |
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| CN201410330913.XA CN104164050B (en) | 2014-07-11 | 2014-07-11 | A kind of heat resistant type Environmental protection phenol formaldehyde resin and the preparation method of composite thereof |
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| CN104164050A true CN104164050A (en) | 2014-11-26 |
| CN104164050B CN104164050B (en) | 2016-11-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676321A (en) * | 2018-05-29 | 2018-10-19 | 安徽凯沃科技有限公司 | The method that polyvinyl butyral is modified magnesium phenolic aldehyde is prepared based on solid formaldehyde |
| CN111019289A (en) * | 2019-12-20 | 2020-04-17 | 湖南星鑫航天新材料股份有限公司 | Phenolic glass fiber composite material and preparation method thereof |
Citations (3)
| 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 |
| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
| CN103183907A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | High-temperature-resistant phenolic glass fibre reinforced plastic material |
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Patent Citations (3)
| 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 |
| CN103183907A (en) * | 2011-12-27 | 2013-07-03 | 常熟市亚美模特儿衣架有限公司 | High-temperature-resistant phenolic glass fibre reinforced plastic material |
| CN103013036A (en) * | 2012-12-14 | 2013-04-03 | 焦雷 | Preparation method of halogen-free flame retardant glass fiber reinforced material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676321A (en) * | 2018-05-29 | 2018-10-19 | 安徽凯沃科技有限公司 | The method that polyvinyl butyral is modified magnesium phenolic aldehyde is prepared based on solid formaldehyde |
| CN111019289A (en) * | 2019-12-20 | 2020-04-17 | 湖南星鑫航天新材料股份有限公司 | Phenolic glass fiber composite material and preparation method thereof |
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| CN104164050B (en) | 2016-11-09 |
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