CN102887982B - Phenolic resin for glass reinforced plastic extrusion technology and preparation method of phenolic resin - Google Patents
Phenolic resin for glass reinforced plastic extrusion technology and preparation method of phenolic resin Download PDFInfo
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- CN102887982B CN102887982B CN201210396881.4A CN201210396881A CN102887982B CN 102887982 B CN102887982 B CN 102887982B CN 201210396881 A CN201210396881 A CN 201210396881A CN 102887982 B CN102887982 B CN 102887982B
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Abstract
The invention discloses a phenolic resin which is used for a glass reinforced plastic extrusion technology and has excellent erosion resistance and a preparation method of the phenolic resin, wherein the preparation method comprises the following steps of: if calculated in parts by weight, taking 100 parts of phenol, 130 -150 parts of liquid formaldehyde, 50 -70 parts of boric acid, 5 -10 parts of modified expanded graphite and 30 parts of toluene; putting the phenol, boric acid and toluene weighed according to the weight parts into a reaction kettle, after evenly stirring the materials, adding a catalyst to adjust a pH value to be 8-10, and then stirring the mixture for 30 minutes to begin heating, and then slowly heating up the mixture, after performing a reaction for 2 -3 hours at a temperature of 85-90 DEG C, carrying out vacuum dehydrating on the mixture, wherein the content of water after vacuum dehydrating is no more than 0.01%, after the product is dehydrated, adding 37% of liquid formaldehyde or paraformaldehyde, heating up to a temperature of 90-100 DEG C, and then performing reaction for 2-3 hours, adding the modified expanded graphite, when the liquid formaldehyde is added, decompressing and dehydrating the mixture to obtain the black red liquid resin with a viscosity (mpa.s/25 DEG C) of 2000-3000.
Description
Technical field
The present invention relates to a kind of resol and preparation method thereof, relate in particular to a kind of crowded resol of steel technique and preparation method thereof of cutting a piece of glass of difficult combustion of producing.
Background technology
Along with the development of national economy, people, to the demand of glass fiber reinforced plastics composite material, approximately come larger.The raw material of current domestic glass reinforced plastic production use mainly contains unsaturated polyester resin, vinyl ester resin, phthalic acid diallyl ester resin, butadiene styrene resin, polybutadiene, epoxy resin, resol, urethane resin etc.At present, along with new standard < < material of construction and goods classification system for fire performance > > implement, the fire resistance of matrix material has been proposed to higher technical requirements, and at present a lot of resins can not meet its service requirements.Resol becomes the preferred resin of flame-proof composite material in the future with its good flame retardant properties, but at present a lot of resol has met fire-retardant requirement and lost corresponding processing performance, therefore a kind of resol that not only can meet the fire resistance of matrix material but also can meet formed by extrusion and tension explained hereafter is very important.
Summary of the invention
The object of this invention is to provide the resol for the crowded steel technique of cutting a piece of glass that a kind of ablation resistance is good.
The preparation method who the object of this invention is to provide the resol for the crowded steel technique of cutting a piece of glass that a kind of ablation resistance is good.
For achieving the above object, the technical solution used in the present invention is: a kind of for squeezing the resol of the steel technique of cutting a piece of glass, it is characterized in that: meter by weight, 30 parts of 100 parts of phenol, liquid formaldehyde 130-150 part or paraformaldehyde 48.5-55.5 part, boric acid 50-70 part, modified expanded graphite 5-10 part, toluene.
In this raw material, count by weight 100 parts of phenol, 140 parts of liquid formaldehyde, 60 parts of boric acid, 8 parts of modified expanded graphites, 30 parts of toluene.
In this raw material, liquid formaldehyde is the formaldehyde solution of content 37%-36%; Described paraformaldehyde is the solid formaldehyde of content 95% polymerization degree 8-12.
A kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: take by weight phenol, boric acid and toluene are put in reactor, after stirring, add catalyzer to adjust Ph value to 8-10, then stir and within 30 minutes, start heating, slowly heat up, in temperature, it is 85-90 ℃ of reaction final vacuum dehydration in 2-3 hour, after vacuum hydro-extraction, water content is no more than 0.01%, 37% liquid formaldehyde or the paraformaldehyde that after dehydration, add aforementioned proportion, be warming up to 90-100 ℃, react again 2-3 hour, add modified expanded graphite, decompression dehydration when adding liquid formaldehyde, take off to viscosity (mPa.s/25 ℃) for 2000-3000 dark red liquid resin.
In this preparation method, described vacuum hydro-extraction temperature is no more than 70 ℃; Described catalyzer is a kind of or several mixing arbitrarily in sodium hydroxide, hydrated barta, sodium carbonate or ammoniacal liquor.
In this preparation method, a kind of or several mixing arbitrarily in described sodium hydroxide 1-3 part, hydrated barta 2-4 part, sodium carbonate 7-9 part or ammoniacal liquor 12-16 part.
In this preparation method, described modified expanded graphite is that expanded graphite and organic silicon surfactant are by the mixed paste liquid of the mass ratio of 2:1 ball milling in ball mill.
Advantageous effect of the present invention is: because the present invention has adopted these raw materials and preparation method, the boric acid modified ablation resistance that improves resin for the present invention, also added modified expanded graphite, so improved resin when improving flame retardant properties, squeezing the production technique performance of drawing while producing, result of use is good.
Embodiment
For squeezing a resol for the steel technique of cutting a piece of glass, it is characterized in that: meter by weight, 30 parts of 100 parts of phenol, liquid formaldehyde 130-150 part or paraformaldehyde 48.5-55.5 part, boric acid 50-70 part, modified expanded graphite 5-10 part, toluene; In the present embodiment, count by weight 100 parts of phenol, 140 parts of liquid formaldehyde, 60 parts of boric acid, 8 parts of modified expanded graphites, 30 parts of toluene; In the present embodiment, liquid formaldehyde is the formaldehyde solution of content 37%-36%; Described paraformaldehyde is the solid formaldehyde of content 95% polymerization degree 8-12.A kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: take by weight phenol, boric acid and toluene are put in reactor, after stirring, add catalyzer to adjust Ph value to 8-10, then stir and within 30 minutes, start heating, slowly heat up, in temperature, it is 85-90 ℃ of reaction final vacuum dehydration in 2-3 hour, after vacuum hydro-extraction, water content is no more than 0.01%, 37% liquid formaldehyde or the paraformaldehyde that after dehydration, add aforementioned proportion, be warming up to 90-100 ℃, react again 2-3 hour, add modified expanded graphite, decompression dehydration when adding liquid formaldehyde, take off to viscosity (mPa.s/25 ℃) for 2000-3000 dark red liquid resin, in the present embodiment, described vacuum hydro-extraction temperature is no more than 70 ℃, described catalyzer is a kind of or several mixing arbitrarily in sodium hydroxide, hydrated barta, sodium carbonate or ammoniacal liquor, in the present embodiment, a kind of or several mixing arbitrarily in described sodium hydroxide 1-3 part, hydrated barta 2-4 part, sodium carbonate 7-9 part or ammoniacal liquor 12-16 part, in the present embodiment, described modified expanded graphite is that expanded graphite and organic silicon surfactant are by the mixed paste liquid of the mass ratio of 2:1 ball milling in ball mill.
Embodiment 1: wash after reactor, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the sodium hydroxide of 1 part, test Ph value is 8, stir after 30 minutes and start to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%.Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 5 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2000 mPa.s/25 ℃.
Embodiment 2: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the sodium hydroxide of 1 part, test Ph value is 8, stir after 30 minutes and start to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 5 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2000 mPa.s/25 ℃.
Embodiment 3: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the sodium carbonate of 8 parts, test Ph value is 8, stir after 30 minutes and start to heat up, be warmed up to 90 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 7 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2500 mPa.s/25 ℃.
Embodiment 4: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the ammoniacal liquor of 12 parts, test Ph value is 8, stir after 30 minutes and start to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 5 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2000 mPa.s/25 ℃.
Embodiment 5: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the sodium hydroxide of 1 part, test Ph value is 8, stir after 30 minutes and start to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the solid formaldehyde that 49 parts of content are 95%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 5 parts of modified expanded graphites, obtain viscosity and be the dark red liquid resin of 2500 mPa.s/25 ℃.
Embodiment 6: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, add the sodium hydroxide of 2 parts, test Ph value is 9, stir after 30 minutes and start to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the solid formaldehyde that 50 parts of content are 95%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 7 parts of modified expanded graphites, obtain viscosity and be the dark red liquid resin of 3000 mPa.s/25 ℃.
Toluene used in the present invention is not participated in reaction, is mainly to slough the water of reaction generation and the water in liquid formaldehyde.
The said resol of the present invention is to utilize phenol, formaldehyde and boric acid by special process flow process, to be synthesized under alkaline condition.The expanded graphite that adds modification, make resol have higher flame retardant properties and squeeze in drawing production process more smooth and easy.
By processing condition of the present invention and modified formula, produce a kind of resol with ablation resistance, can be applicable to formed by extrusion and tension explained hereafter matrix material.
Claims (8)
1. one kind for squeezing the resol of the steel technique of cutting a piece of glass, it is characterized in that: count by weight, 30 parts of 100 parts of phenol, liquid formaldehyde 130-150 part or paraformaldehyde 48.5-55.5 part, boric acid 50-70 part, modified expanded graphite 5-10 part, toluene, liquid formaldehyde is the formaldehyde solution of content 37%-36%, described paraformaldehyde is the solid formaldehyde of content 95% polymerization degree 8-12, take by weight phenol, boric acid and toluene are put in reactor, after stirring, add catalyzer to adjust pH value to 8-10, then stir and within 30 minutes, start heating, slowly heat up, in temperature, it is 85-90 ℃ of reaction final vacuum dehydration in 2-3 hour, after vacuum hydro-extraction, water content is no more than 0.01%, 37% liquid formaldehyde or the paraformaldehyde that after dehydration, add aforementioned proportion, be warming up to 90-100 ℃, react again 2-3 hour, add modified expanded graphite, decompression dehydration when adding liquid formaldehyde, take off to viscosity be 2000-3000mPas/25 ℃ of dark red liquid resin.
2. according to claim 1 a kind of for squeezing the resol of the steel technique of cutting a piece of glass, count by weight 100 parts of phenol, 140 parts of liquid formaldehyde, 60 parts of boric acid, 8 parts of modified expanded graphites, 30 parts of toluene.
3. according to claim 1 and 2 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: take by weight phenol, boric acid and toluene are put in reactor, after stirring, add catalyzer to adjust pH value to 8-10, then stir and within 30 minutes, start heating, slowly heat up, in temperature, it is 85-90 ℃ of reaction final vacuum dehydration in 2-3 hour, after vacuum hydro-extraction, water content is no more than 0.01%, 37% liquid formaldehyde or the paraformaldehyde that after dehydration, add aforementioned proportion, be warming up to 90-100 ℃, react again 2-3 hour, add modified expanded graphite, decompression dehydration when adding liquid formaldehyde, take off to viscosity be 2000-3000mPas/25 ℃ of dark red liquid resin.
4. according to claim 3 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: described vacuum hydro-extraction temperature is no more than 70 ℃; Described catalyzer is a kind of or several mixing arbitrarily in sodium hydroxide, hydrated barta, sodium carbonate or ammoniacal liquor.
5. according to claim 4 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: a kind of or several mixing arbitrarily in described sodium hydroxide 1-3 part, hydrated barta 2-4 part, sodium carbonate 7-9 part or ammoniacal liquor 12-16 part.
6. according to claim 5 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: described modified expanded graphite is that expanded graphite and organic silicon surfactant are by the mixed paste liquid of the mass ratio of 2:1 ball milling in ball mill.
7. according to claim 6 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, the sodium hydroxide that adds 1 part, test pH value is 8, stirs after 30 minutes and starts to heat up, be warmed up to 85 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 5 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2000 mPas/25 ℃.
8. according to claim 6 a kind of for squeezing the preparation method of the resol of the steel technique of cutting a piece of glass, it is characterized in that: after cleaning reaction still, add 100 parts of phenol, the boric acid of 65 parts, 30 parts of toluene, the sodium carbonate that adds 8 parts, test pH value is 8, stirs after 30 minutes and starts to heat up, be warmed up to 90 ℃ of reactions 2.5 hours, start decompression dehydration, controlling dehydration temperaturre is 65 ℃, and test resin water content is 0.01%; Be parked in vacuum, add the liquid formaldehyde that 130 parts of content are 37%, continue to be warmed up to 90 ℃ of reactions 2 hours, add 7 parts of modified expanded graphites, decompression dehydration, obtains viscosity and is the dark red liquid resin of 2500mPas/25 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210396881.4A CN102887982B (en) | 2012-10-18 | 2012-10-18 | Phenolic resin for glass reinforced plastic extrusion technology and preparation method of phenolic resin |
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| CN201210396881.4A CN102887982B (en) | 2012-10-18 | 2012-10-18 | Phenolic resin for glass reinforced plastic extrusion technology and preparation method of phenolic resin |
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| CN102887982A CN102887982A (en) | 2013-01-23 |
| CN102887982B true CN102887982B (en) | 2014-03-19 |
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| CN103951933A (en) * | 2014-04-24 | 2014-07-30 | 三棵树涂料股份有限公司 | Cardanol modified phenolic resin for glass fiber reinforced plastic laminated materials and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
| CN102604020A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Boron modified phenolic resin and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805435A (en) * | 2010-04-19 | 2010-08-18 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
| CN102604020A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Boron modified phenolic resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 膨胀石墨/酚醛树脂复合材料双极板研究;陈惠等;《中南大学学报(自然科学版)》;20111126;第42卷(第11期);3326-3330 * |
| 陈惠等.膨胀石墨/酚醛树脂复合材料双极板研究.《中南大学学报(自然科学版)》.2011,第42卷(第11期),3326-3330. |
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