CN108546320B - The preparation method of phenolic resin - Google Patents
The preparation method of phenolic resin Download PDFInfo
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- CN108546320B CN108546320B CN201810327311.7A CN201810327311A CN108546320B CN 108546320 B CN108546320 B CN 108546320B CN 201810327311 A CN201810327311 A CN 201810327311A CN 108546320 B CN108546320 B CN 108546320B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention discloses a kind of preparation method of phenolic resin, the following steps are included: 1) part by weight, 70~100 parts of phenol, 50~80 parts of formaldehyde and catalyst are added into reaction kettle, heating, react 4-6H, 10~15 parts of organic matter phosphorus, 10~20 parts of expansile graphite is added, 12-24H is reacted in heating；2) vacuum oven dehydrating and curing is used after reaction, and for temperature control when solidification at 120~160 DEG C, curing time is 60~90S.Composite catalyst that the present invention uses utilizes the synergistic effect of double alkyl methyl tertiary amines and barium hydroxide, prepare the lower water soluble phenol resin of free phenol content and free formaldehyde content, the cost of material that this method uses is low, easy to operate, the addition of expansile graphite increases the intensity and wearability of phenolic resin.
Description
Technical field
The present invention relates to macromolecule resin preparation fields, and in particular to a kind of preparation method of phenolic resin.
Background technique
Phenolic resin is also bakelite, also known as phenolic moulding powder, is originally colourless or yellowish-brown transparency, and market sale often adds coloring
Agent and in the colors such as red, yellow, black, green, brown, blue, have particle, powdered, because selecting the difference of catalyst, phenolic resin can be divided into
Two class of thermosetting property and thermoplasticity.Phenolic resin has good acid resistance, mechanical property, heat resistance, therefore is answered extensively
For fields such as anticorrosion engineering, adhesive, fire proofings.
The fire-retardant of resin generally is improved by the way that halogen flame is added during prepared by phenolic resin in the prior art
Performance, but the halogen flame especially fire retardant containing bromine can generate poisonous gas under high temperature or burning condition,
It pollutes the environment, influences human health.In addition, single catalysis is generally used in the manufacturing process of phenolic resin at present
Agent is catalyzed, and such as uses barium hydroxide excellent catalytic effect, but free phenol and free formaldehyde also increase, and influence environment, use is weak
Basic catalyst catalytic action is gentle, influences the quality of resin.
Summary of the invention
The present invention provides a kind of preparation method of phenolic resin, and the resins fire retardant prepared is high and to free of air pollution.
To achieve the goals above, the invention adopts the following technical scheme: a kind of preparation method of phenolic resin, including with
Lower step:
1) part by weight, is added 70~100 parts of phenol, 50~80 parts of formaldehyde and catalyst into reaction kettle, heating, instead
4-6H is answered, 10~15 parts of organic matter phosphorus, 10~20 parts of expansile graphite is added, 12-24H is reacted in heating；
2) vacuum oven dehydrating and curing is used after reaction, and temperature when solidification controls the solidification at 120~160 DEG C
Time is 60~90S.
Further, organic matter phosphorus described in step 1) is microencapsulated powder oil.Common red phosphorus is oxidizable in air,
Moisture absorption, and high temperature is inflammable, it is poor with high molecular material intermiscibility the defects of, application range is restricted.The present invention uses micro- glue
Encapsulated red phosphorus, microencapsulated powder oil have efficiently in addition to overcoming the intrinsic drawback of red phosphorus, and low cigarette, work in-process does not generate
Toxic gas, dispersibility, physics, mechanical performance, thermal stability and flame retardant property are improved and improve.
Further, catalyst described in step 1) is composite catalyst, and the composite catalyst includes double alkyl
Methyl tertiary amine and barium hydroxide, 5~10 parts of double alkyl methyl tertiary amines, 0.2~1 part of barium hydroxide.Pass through double alkyl methyl tertiary amines
Concerted catalysis with barium hydroxide acts on, and prepares the lower water soluble phenolic resin of free phenol content and free formaldehyde content
Rouge.
Further, temperature is first heated 80~100 DEG C in step 1), reacts 4-6H, organic matter phosphorus and dilatancy is added
Graphite is heated to 100~110 DEG C, reacts 6-8H, is heated to 120~160 DEG C of reaction 12-24H.
Preferably, 70~100 parts of phenol, 50~80 parts of formaldehyde, catalyst, organic matter phosphorus are added into reaction kettle for step 1)
10~15 parts, 10~20 parts of expansile graphite are uniformly mixed and are heated to 120-160 DEG C of temperature, react 12-24H.
Compared with prior art, the present invention uses composite catalyst utilizes double alkyl methyl tertiary amines and barium hydroxide
Synergistic effect, prepares the lower water soluble phenol resin of free phenol content and free formaldehyde content, and fire retardant uses micro- glue
Encapsulated red phosphorus overcomes outside the intrinsic drawback of red phosphorus, and has efficiently, and low cigarette, work in-process does not generate toxic gas, dispersion
Property, physics, mechanical performance, thermal stability and flame retardant property be improved and improve, reduce the pollution to environment.This method uses
Cost of material it is low, easy to operate, the addition of expansile graphite increases the intensity and wearability of phenolic resin.
Specific embodiment
The present invention is explained in detail combined with specific embodiments below.
Embodiment 1
70 parts of phenol, 50 parts of formaldehyde, 5 parts of double alkyl methyl tertiary amines, barium hydroxide are added into reaction kettle for part by weight
0.2 part, 80 DEG C are warming up to, reacts 4H, 10 parts of microencapsulated powder oil, 10 parts of expansile graphite is added, is warming up to 100 DEG C, reaction
6H continues to be heated to 120 DEG C, reacts 12H, uses vacuum oven dehydrating and curing after reaction, temperature control when solidification
At 120 DEG C, solids phenol-formaldehyde resin is obtained, test result is shown in Table 1.
Embodiment 2
100 parts of phenol, 80 parts of formaldehyde, 10 parts of double alkyl methyl tertiary amines, hydroxide are added into reaction kettle for part by weight
1 part of barium, 100 DEG C are warming up to, reacts 6H, 15 parts of microencapsulated powder oil, 20 parts of expansile graphite is added, is warming up to 110 DEG C, high speed
It is stirred to react 8H, continues to be heated to 160 DEG C, reacts 24H, uses vacuum oven dehydrating and curing after reaction, when solidification
Temperature is controlled at 160 DEG C, obtains solids phenol-formaldehyde resin, test result is shown in Table 1.
Embodiment 3
85 parts of phenol, 65 parts of formaldehyde, 7 parts of double alkyl methyl tertiary amines, barium hydroxide are added into reaction kettle for part by weight
0.6 part, 90 DEG C are warming up to, reacts 5H, 12 parts of microencapsulated powder oil, 15 parts of expansile graphite is added, is warming up to 105 DEG C, reaction
7H continues to be heated to 140 DEG C, reacts 18H, uses vacuum oven dehydrating and curing after reaction, temperature control when solidification
At 140 DEG C, solids phenol-formaldehyde resin is obtained, test result is shown in Table 1.
Embodiment 4
70 parts of phenol, 50 parts of formaldehyde, 5 parts of double alkyl methyl tertiary amines, barium hydroxide are added into reaction kettle for part by weight
It 0.2 part, stirs evenly, 10 parts of microencapsulated powder oil, 10 parts of expansile graphite is added, be warming up to 120 DEG C, react 12H, reaction knot
Vacuum oven dehydrating and curing is used after beam, 120 DEG C of solidification temperature, obtains solids phenol-formaldehyde resin, test result is shown in Table 1.
Embodiment 5
100 parts of phenol, 80 parts of formaldehyde, 10 parts of double alkyl methyl tertiary amines, hydroxide are added into reaction kettle for part by weight
It 1 part of barium, stirs evenly, 15 parts of microencapsulated powder oil, 20 parts of expansile graphite is added, be warming up to 160 DEG C, react 24H, reaction knot
Vacuum oven dehydrating and curing is used after beam, 160 DEG C of solidification temperature, obtains solids phenol-formaldehyde resin, test result is shown in Table 1.
Embodiment 6
85 parts of phenol, 65 parts of formaldehyde, 7 parts of double alkyl methyl tertiary amines, barium hydroxide are added into reaction kettle for part by weight
It 0.6 part, stirs evenly, 12 parts of microencapsulated powder oil, 15 parts of expansile graphite is added, be warming up to 140 DEG C, react 18H, reaction knot
Vacuum oven dehydrating and curing is used after beam, temperature when solidification is controlled at 140 DEG C, obtains solids phenol-formaldehyde resin, test result is shown in
Table 1.
Comparative example 1
85 parts of phenol, 65 parts of formaldehyde, 7 parts of double alkyl methyl tertiary amines, barium hydroxide are added into reaction kettle for part by weight
0.6 part, stir evenly, be added alkalinity or acidic catalyst it is any, be warming up to 140 DEG C, after reaction dehydrating and curing, obtain
Solids phenol-formaldehyde resin, test result are shown in Table 1.
Table 1
| Solid content (%) | Free phenol (%) | Free aldehyde (%) | Moisture (%) | |
| Embodiment 1 | 85.37 | 2.78 | 0.21 | 10.13 |
| Embodiment 2 | 84.68 | 3.03 | 0.19 | 9.97 |
| Embodiment 3 | 85.79 | 2.65 | 0.25 | 10.22 |
| Embodiment 4 | 85.62 | 2.59 | 0.17 | 10.47 |
| Embodiment 5 | 86.02 | 2.70 | 0.22 | 10.33 |
| Embodiment 6 | 86.12 | 2.55 | 0.17 | 10.19 |
| Comparative example 1 | 84.07 | 6.07 | 1.25 | 10.98 |
Basic principles and main features and the features of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement is both fallen in the range of claimed invention, the scope of protection of present invention is by appended claims
And its equivalent thereof.
Claims (1)
1. a kind of preparation method of phenolic resin, it is characterised in that: the following steps are included:
1) part by weight, 70~100 parts of phenol, 50~80 parts of formaldehyde and catalyst are added into reaction kettle, and 4- is reacted in heating
10~15 parts of organic matter phosphorus, 10~20 parts of expansile graphite, heating is added in 6h；
2) vacuum oven dehydrating and curing is used after reaction, and temperature control when solidification is at 120~160 DEG C, curing time
For 60~90s；
Organic matter phosphorus described in step 1) is microencapsulated powder oil；
Catalyst described in step 1) is composite catalyst, and the composite catalyst is selected from double alkyl methyl tertiary amines and hydrogen-oxygen
Change barium, 5~10 parts of double alkyl methyl tertiary amines, 0.2~1 part of barium hydroxide；
Temperature is first heated 80~100 DEG C in step 1), reacts 4-6h, organic matter phosphorus and expansile graphite is added, is heated to
100~110 DEG C, 6-8h is reacted, 120~160 DEG C of reaction 12-24h are heated to.
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| CN201810327311.7A CN108546320B (en) | 2018-04-12 | 2018-04-12 | The preparation method of phenolic resin |
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| CN201810327311.7A CN108546320B (en) | 2018-04-12 | 2018-04-12 | The preparation method of phenolic resin |
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| CN108546320A CN108546320A (en) | 2018-09-18 |
| CN108546320B true CN108546320B (en) | 2019-07-26 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524609A (en) * | 2003-09-18 | 2004-09-01 | 武汉理工大学 | Composite material comprising expandable graphite and phenolic resin group active carbon |
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN103724664A (en) * | 2012-10-16 | 2014-04-16 | 南京理工大学 | Novel fire retardant microencapsulated red phosphorus and preparation method thereof |
| CN104449500A (en) * | 2014-12-15 | 2015-03-25 | 济南圣泉集团股份有限公司 | Modified phenolic resin adhesive, preparation method thereof and tire rubber |
| CN105566588A (en) * | 2015-11-26 | 2016-05-11 | 陕西启源科技发展有限责任公司 | Phenolic resin preparation method |
| CN106633897A (en) * | 2016-12-31 | 2017-05-10 | 铜陵华科电子材料有限公司 | Formula of halogen-free flame-retardant aid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075937A (en) * | 2003-09-01 | 2005-03-24 | Sumitomo Bakelite Co Ltd | Manufacturing process of novolac type phenolic resin |
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2018
- 2018-04-12 CN CN201810327311.7A patent/CN108546320B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524609A (en) * | 2003-09-18 | 2004-09-01 | 武汉理工大学 | Composite material comprising expandable graphite and phenolic resin group active carbon |
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN103724664A (en) * | 2012-10-16 | 2014-04-16 | 南京理工大学 | Novel fire retardant microencapsulated red phosphorus and preparation method thereof |
| CN104449500A (en) * | 2014-12-15 | 2015-03-25 | 济南圣泉集团股份有限公司 | Modified phenolic resin adhesive, preparation method thereof and tire rubber |
| CN105566588A (en) * | 2015-11-26 | 2016-05-11 | 陕西启源科技发展有限责任公司 | Phenolic resin preparation method |
| CN106633897A (en) * | 2016-12-31 | 2017-05-10 | 铜陵华科电子材料有限公司 | Formula of halogen-free flame-retardant aid |
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