CN106496471B - The preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system - Google Patents
The preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system Download PDFInfo
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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
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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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
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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
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
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Abstract
The preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system, it is related to the preparation method of phenolic resin, paraformaldehyde is cracked completely first and obtains formalin, then a certain amount of acetic acid is first added, adding phenol and zinc oxide makes reaction solution pH between 57, and 120 180min are reacted at 80 95 DEG C；Then other aldehydes raw materials are added and basic catalyst is reacted；When the Abbe refractometer of reaction solution is when between 1.460 1.470, it is cooled to 50 ~ 70 DEG C rapidly, resorcinol, metacresol and 3 is then added, the mixed phenol of 5 xylenols composition, is reacted, after vacuum dehydration, auxiliary material is added into reaction kettle, discharging is to get product after adjusting viscosity.Pultrusion prepared by the present invention has many advantages, such as that low environmental protection, solidification temperature, quick solidifying, storage period is long, solidification bubble-free, product strength is high, performance is stable, good combination property with phenolic resin.
Description
Technical field
The present invention relates to the preparation methods of thermosetting phenolic resin in chemical field, and in particular to a kind of one pack system
The preparation method of high ortho position thermosetting property pultrusion phenolic resin.
Background technology
Thermosetting phenolic resin be by phenol and formaldehyde under alkaline condition, through addition, condensation reaction, and control certain
The fluid resin of the extent of reaction obtained certain molecular mass and certain viscosity.According to the chemical constitution of raw material selected by design
With the process conditions such as monomer functionality, the molar ratio of phenol and aldehyde dosage, reaction time and temperature, to prepare the phenolic aldehyde of different purposes
Resin.The phenolic resin that at present prepared by conventional method has hardening time long, and storage cycle is short, needs sour solidification, or must be through
The defects of crossing high temperature and pressure could cure, complex forming technology seriously limits phenolic resin answering in dragging and squeezing glass fiber reinforced plastics field
With.
Invention content
The object of the present invention is to provide a kind of high ortho position thermosetting phenolics of one pack system for producing phenolic aldehyde dragging and squeezing glass fiber reinforced plastics
Resin, prepared phenolic resin have low environmental protection, solidification temperature, quick solidifying, storage period length, solidification bubble-free, product strength
The advantages that high, performance stabilization, good combination property.
To achieve the above object, the technical scheme is that：The high ortho position thermosetting property pultrusion phenolic resin of one pack system
Preparation method includes the following steps：
（1）, paraformaldehyde, water and basic catalyst be proportionally added into reaction kettle, so that paraformaldehyde is cracked completely, obtain
Formalin；
In this step, reaction temperature is 75-95 DEG C, reaction time 30-60min, and at the end of the step, paraformaldehyde is complete
Fully dissolved；
（2）, a certain amount of acetic acid is first added into reaction kettle, phenol and zinc oxide is then added, make reaction solution pH 5-7 it
Between, keep 120-180min at 80-95 DEG C；Then other aldehydes raw materials and basic catalyst is added, make reaction solution pH adjust to
Between 7-9, after keeping 20 ~ 30min, it is cooled to 80-95 DEG C according to the speed of 6 DEG C/10min, constant temperature；
（3）, when the Abbe refractometer of reaction solution is between 1.460-1.470, be cooled to 50 ~ 70 DEG C rapidly, then plus
Enter resorcinol, metacresol and 3, the mixed phenol of 5 xylenols composition keeps constant temperature to be opened when the cloud point of reaction solution reaches 15 DEG C
Beginning vacuum dehydration；
This step, in vacuum dewatering process, vacuum degree is not less than 0.09 MPa, and sets reaction temperature as 80 DEG C, vacuum
Resin actual temperature is at 55-60 DEG C in dehydration, after a certain period of time, when resin actual temperature reaches 70 DEG C in kettle, stops
Heating, cools, and stops vacuum dehydration；
（4）, after vacuum dehydration, auxiliary material is added into reaction kettle, adjustment viscosity is to 1000-3000mpa.s, then
Discharging is to get product.
Step（2）In, other aldehydes raw materials are the mixed aldehyde of acetaldehyde, butyraldehyde or both, and the basic catalyst is
Magnesia or barium hydroxide.
Step（4）In, the auxiliary material is methanol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether
（Between EL10-EL80）, it is triphenylmethyl radical, vinyl acetate, carbon tetrachloride, one or more in hydroquinone.
During entire preparation method, the molar ratio of phenols raw material used and aldehydes raw material is 1：1.1-1.6.
Using the molecular structure schematically as follows formula of first stage thermosetting phenolic resin prepared by conventional fabrication process（1）Institute
Show, because the methylene content of contraposition is more, molecule steric effect so that n values are 2 or so.And this kind of resin is by molecular structure
Three-dimensional effect determine that its liquid viscosity is larger, activity is relatively low, can meet answering for the sour solidifying requirements such as phenolic foam material
With field, it cannot but stablize the effect for realizing single-component thermosetting.
n：0 ~ 2 formula（1）
The molecular structure of first stage high ortho position thermosetting phenolic resin in preparation method of the present invention prepared by first two steps shows
Meaning such as following formula（2）It is shown, because the methylene content of contraposition is few, the linear shape of molecule so that n values can reach 5 or so.And it is same
The thermosetting phenolic resin of sample molecular weight distribution is compared with high ortho position thermosetting phenolic resin, high ortho position thermosetting phenolic resin
Viscosity wants much lower.
n:0 ~ 5 formula（2）
Containing there are many different points in the final prepared high ortho position thermosetting phenolic resin of pultrusion one pack system of the present invention
Minor structure, such as following formula（3）It is shown, wherein metacresol is 2.88 times higher than the activity of phenol, and 3,5 xylenols are higher than phenol activity
7.55 times, and the resorcinol of three active sites of reservation is than 3 on phenyl ring, the taller many of activity of 5 xylenols.If only used
Resorcinol does active modification, and building-up process can be made to be difficult to control, and implode is easy, to make reaction short stay in first stage phenol
After urea formaldehyde, solidification cross-linking stage is rapidly entered, forms the insoluble resite not melted of solid.Therefore, with the present invention
The phenols raw material of several different activities provided uses after being mixed with certain proportion, has both improved the activity of whole phenolic resin,
Make synthetic reaction control with more operability, repeatability again, and phenolic resin is made to cure in the curing process uniformly.Isophthalic two
Phenol, metacresol, 3,5 xylenols and phenol are the phenols raw material of entire synthetic reaction, in entire synthetic reaction, three in addition to phenol
Kind mixed phenol mass content shared in total phenols raw material is no more than 20%.
n:0 ~ 5 formula（3）
Advantageous effect：
1, pultrusion one pack system high adjacent position phenolic resin prepared by the present invention, at low cost, stability is good, and preparation method is simple
Effectively, molecular weight 400-900, (25 DEG C) of viscosity are 1000-3000 mPa.S, and 150 DEG C of polymerization speeds are 90-150s, heat
Value is 22-28 MJ/kg.
2, preparation process of the present invention accomplishes phenolic resin synthesis under the premise of ensureing high quality and repeatable stability
Zero-emission, no pollution, to environmental protection, comprehensive utilization of resources promotes industry development etc. to have larger impetus.For the first time
Waste liquid is transferred in closed ponderable quantity sink obtained by synthetic reaction vacuum dehydration, when second of novolak resin, can be replaced
Water application achievees the purpose that non-wastewater discharge in the cleavage step of paraformaldehyde.
And the synthesis of traditional phenolic resin is using liquid formaldehyde as raw material, after manufacture the phase draw water through vacuum, gained largely gives up
Liquid, two indexs of phenol content and COD of the waste liquid, which already exceed country, allows 6.5 ten thousand times and 2.3 ten thousand times of discharge standard, pollution
Degree is self-evident；It is directly reacted with phenol, catalyst using paraformaldehyde by improving, phenolic aldehyde can be produced by being not required to dehydration
Resin, under this process conditions, although being generated without sewage waste liquor,：（1）, the cracking of this technique paraformaldehyde it is incomplete, make most
Whole phenolic resin molecular weight distribution is very wide, and viscosity is especially big, poor mechanical property after phenolic resin curing；（2）, phenolic aldehyde tree
Fat building-up process has external heat supply and autoreactivity heat release to build reaction temperature control jointly, is conducted if no water is done
Body, the heat for reacting releasing are difficult to disperse away rapidly, and cause reaction localized heat release excessively high, cause solidification to lump, or even have
Quick-fried kettle is dangerous, and causes the temperature control of extraneous supply heat to be difficult to grasp since the temperature of reactant is unbalanced；（3）、
Since paraformaldehyde does not crack completely, phenol and (CH2O)nAfter reaction, n values are between 10-30, n intermediate CH2O structures are not
Stablize, slowly cracked after phenolic cure, not only destroy the molecular structure of phenolic aldehyde, and forms free formaldehyde and slowly release
It is placed in air environment, also causes long-term air pollution；（4）, proportionally feed intake, carry out phenolic resin synthesis, but portion
Formaldehyde is divided to fail to participate in chemical reaction, the phenol for being bound to cause same ratio finally also exists with free state, and phenol has corrosion
Property, therefore, this technological reaction is incomplete, and final phenolic aldehyde product is made also to be provided with certain corrosivity.（5）, the technique the first stage
There are largely free aldehyde and free phenols in phenolic resin, and in the case of having catalyst, even refrigerated storage, still can slowly into
The synthesis of row phenolic resin and cross-linking reaction, to keep resol viscosity change fast, the short equal crowds of resin storage time
More drawbacks.
3, pultrusion one pack system high adjacent position phenolic resin prepared by the present invention has following than conventional thermosetting phenolic resin
Advantage：（Ⅰ）Curing rate is fast；（Ⅱ）Residual carbon is high；（Ⅲ）Rigidity of the product under heated is good；Than traditional high ortho position thermosetting property
Phenolic resin has the following advantages：（Ⅰ）This phenolic resin can be used as preparing the raw material of glass/phenolic composite；（Ⅱ）Solidification
Speed is fast, and does not need acid curing agent；（Ⅲ）After solidification, closely knit bubble-free.
4, relevant auxiliary materials are added in resin synthesis process, several auxiliary materials, which can play, adjusts resin viscosity
Purpose makes resin viscosity reduce, and is more convenient for using.In addition, in rear process, during pultrusion production molding, inorganic matter can be filled out
Material, alkali-free rove, tape edge felt etc. infiltrate in phenol resin solution, good infiltration compatibility, to phenolic fiberglass reinforced plastics finished product
Quality plays a decisive role；And DOP, DNP, OP-10 in the present invention or castor oil polyoxyethylene ether（Between EL10-EL80）It can
To improve the compatibility of resin and added filler, it is allowed to be not easy to precipitate.Triphenylmethyl radical, vinyl acetate, four chlorinations
Carbon or hydroquinone can play the role of inhibition to resin, improve the storage time of resin, which can save 4 at low temperature
A month or more.
5, the present invention no longer controls the reaction end in per stage in phenolic resin building-up process with timing node（By
It is influenced in various aspects such as operation, equipment, raw material and environment, if every batch of resins synthesis is saved with the equivalent responses time to control reaction
Point certainly will be very big on the influence of the performance of final products, therefore the phenolic resin of each producer's actual production at present is unstable, viscosity
It is suddenly big or suddenly small, it is active higher or relatively low and cannot meet the needs）, but the present invention is in the beginning or end of each stage of reaction
There is corresponding detection means（Such as：Cloud point, thinner ratio, Abbe refractometer, viscosity etc.）, reach and fast and accurately detect online
As a result, to flexibly control reaction process.Final resin can be made to reach expected design performance, and repeatability is high, surely
It is qualitative good.
6, the present invention have the characteristics that preparation process it is simple, it is at low cost, have excellent performance, the pultrusion of preparation is with the high neighbour of one pack system
Position phenolic resin can meet the stringent process conditions of production phenolic aldehyde dragging and squeezing glass fiber reinforced plastics, can be applied to the quick shaping process such as pultrusion
Composite material is prepared, the resin application field of other techniques such as hand paste, spraying, winding is can be also widely applied to.
Specific implementation mode
Embodiment 1
Paraformaldehyde 350g, water 400g and sodium hydroxide 4.5g are successively added in reactor, after mixing according to 6
DEG C/speed of 10min is warming up to 80 DEG C, it is kept stirring 60min, after paraformaldehyde is completely dissolved, 6g or so acetic acid is added.It stirs
Mixing a moment sequentially adds 1000g phenol and 25g or so zinc oxide into reactor and makes reaction solution PH between 5-7, according to 6 DEG C/
The speed of 10min increases temperature to 95 DEG C, keeps 120min.35g acetaldehyde and 6g or so magnesia is added, makes reaction environment PH tune
It is whole between 7-9, after keeping 20min, be cooled to 85 DEG C according to the speed of 6 DEG C/10min, constant temperature；When the Abbe of reaction solution is rolled over
When penetrating rate between 1.460-1.470, it is cooled to 65 DEG C rapidly, resorcinol, the mixed phenol of 3,5 xylenols and metacresol is added
（Three's mass ratio is 3:1:1）Total 100g keeps constant temperature, and when the cloud point of reaction solution reaches 15 DEG C or so, it is de- to start vacuum
Water sets the temperature of vacuum dehydration as 80 DEG C, and material actual temperature is between 55-60 DEG C at this time, after a certain period of time, works as reactor
When interior actual temperature reaches 70 DEG C, stop heating, stops vacuum dehydration.According to the viscosity of feed liquid in kettle at this time, auxiliary material first is added
Alcohol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), vinyl acetate, tetrachloro
One or more in change carbon, hydroquinone, when the viscosity of resin reaches 2000mpa.s-3000mpa.s, temperature is down to 40 DEG C
Hereinafter, adding triphenylmethyl radical 0.2g, discharging is stirred evenly, obtains pultrusion one pack system high adjacent position phenolic resin, is set
Lipid can be as follows：
| Free phenol | Solid content | Gel time | Calorific value | Viscosity | Ortho para position ratio | |
| GY-03 | 11.55% | 82.65% | 104s | 24 MJ/kg | 2775 mPa.S | 1.89 |
Embodiment 2
Paraformaldehyde 400g, water 500g and sodium hydroxide 4.5g are successively added in reactor, after mixing according to 6
DEG C/speed of 10min is warming up to 85 DEG C, it is kept stirring 50min, after paraformaldehyde is completely dissolved, 12g or so acetic acid is added.
Stirring a moment, which sequentially adds 1000g phenol and 30g or so zinc oxide into reactor, makes reaction solution PH between 5-7, according to 6
DEG C/speed of 10min increases temperature to 80 DEG C, keep 180min.45.2g acetaldehyde and 10g or so magnesia is added, makes reaction ring
Border PH is adjusted between 7-9, after keeping 25min, is cooled to 80 DEG C according to the speed of 6 DEG C/10min, constant temperature；When reaction solution
When Abbe refractometer is between 1.460-1.470, it is cooled to 50 DEG C rapidly, is added resorcinol, 3,5 xylenols and metacresol
Mixed phenol（Three's mass ratio is 2:1:1）Total 250g keeps constant temperature, when the cloud point of reaction solution reaches 15 DEG C or so, starts
Vacuum dehydration sets the temperature of vacuum dehydration as 80 DEG C, and material actual temperature is between 55-60 DEG C at this time, after a certain period of time, when
When actual temperature reaches 70 DEG C in reactor, stop heating, stops vacuum dehydration.According to the viscosity of feed liquid in kettle at this time, it is added
Auxiliary material methanol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), trityl are certainly
By one or more in base, vinyl acetate, carbon tetrachloride, hydroquinone, when the viscosity of resin reaches 2000mpa.s-
3000mpa.s stirs evenly discharging, obtains pultrusion one pack system high adjacent position phenolic resin, and resin property is as follows：
| Free phenol | Solid content | Gel time | Calorific value | Viscosity | Ortho para position ratio | |
| GY-07 | 12.14% | 76.56% | 74s | 26 MJ/kg | 2435 mPa.S | 1.80 |
Embodiment 3
Paraformaldehyde 370g, water 450g and sodium hydroxide 4.5g are successively added in reactor, after mixing according to 6
DEG C/speed of 10min is warming up to 95 DEG C, it is kept stirring 30min, after paraformaldehyde is completely dissolved, 10g or so acetic acid is added.
Stirring a moment, which sequentially adds 1000g phenol and 30g or so zinc oxide into reactor, makes reaction solution PH between 5-7, according to 6
DEG C/speed of 10min increases temperature to 90 DEG C, keep 140min.32.39g butyraldehyde and 40g or so barium hydroxide is added, makes anti-
It answers environmental PH to adjust between 7-9, after keeping 30min, is cooled to 95 DEG C according to the speed of 6 DEG C/10min, constant temperature；It is molten when reacting
When the Abbe refractometer of liquid is between 1.460-1.470, it is cooled to 70 DEG C rapidly, resorcinol, 3,5 xylenols and first is added
The mixed phenol of phenol（Three's mass ratio is 3:1:2）Total 180g keeps constant temperature, when the cloud point of reaction solution reaches 15 DEG C or so,
Start vacuum dehydration, sets the temperature of vacuum dehydration as 80 DEG C, material actual temperature is between 55-60 DEG C at this time, certain time
Afterwards, when actual temperature reaches 70 DEG C in reactor, stop heating, stop vacuum dehydration.According to the viscosity of feed liquid in kettle at this time,
Auxiliary material methanol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), triphen first is added
It is one or more in base free radical, vinyl acetate, carbon tetrachloride, hydroquinone, when the viscosity of resin reaches
1000mpa.s-3000mpa.s stirring evenly discharging, pultrusion one pack system high adjacent position phenolic resin is obtained, resin property is as follows：
| Free phenol | Solid content | Gel time | Calorific value | Viscosity | Ortho para position ratio | |
| GY-06 | 11.97% | 78.25% | 85s | 26 MJ/kg | 2034 mPa.S | 1.84 |
Embodiment 4
Paraformaldehyde 382g, water 400g and sodium hydroxide 4.25g are successively added in reaction vessel, after mixing according to
The speed of 6 DEG C/10min is warming up to 80 DEG C, is kept stirring 60min, and after paraformaldehyde is completely dissolved, 6g or so acetic acid is added.
Stirring a moment sequentially adds 1000g phenol and 25g zinc oxide etc. into reactor, and temperature is increased according to the speed of 6 DEG C/10min
To 95 DEG C, 120min is kept.40g acetaldehyde and 8g or so magnesia is added, so that reaction environment PH is adjusted between 7-9, keeps
After 30min, 85 DEG C are cooled to according to the speed of 6 DEG C/10min, keeps constant temperature；When the cloud point of reaction solution reaches 25 DEG C or so
When, start vacuum dehydration, and set reaction temperature as 80 DEG C（Actual temperature is because the boiling point of water reduces under negative pressure, it is impossible to super
Cross 65 DEG C）, when real reaction temperature is 70 DEG C, stop vacuum dehydration, be added 100g ethyl alcohol and resorcinol mixture and
Other auxiliary materials（DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), triphenylmethyl radical, acetic acid second
It is one or more in enester, carbon tetrachloride, hydroquinone）, slow cooling discharging obtains another high ortho position thermosetting phenolic
Resin, resin property are as follows：
| Free phenol | Solid content | Gel time | Calorific value | Viscosity | Ortho para position ratio | |
| GY-02 | 8.35% | 78.52% | 140s | 29 MJ/kg | 3036 mPa.S | 1.76 |
Embodiment 5
Paraformaldehyde 399g, water 400g and sodium hydroxide 4.5g are added into reaction vessel.Start reaction kettle stirring, adjustment
Temperature in the kettle is 90-95 DEG C, and constant temperature about 30min waits for that paraformaldehyde is completely dissolved, is cooled to 70 DEG C, is added successively into reactor
Enter 1000g phenol, acetic acid 5g, after about 5min, adds 20g or so magnesia to make reaction PH between 6-8, according to the speed of 3 DEG C/2min
Degree increases temperature to 95 DEG C, keeps 150min.85 DEG C are cooled to according to the speed of 3 DEG C/2min, constant temperature is kept, works as reaction solution
Water thinner ratio reach 10:20（Or cloud point reaches 20 DEG C）When, be added resorcinol into reaction vessel, 3,5 xylenols and
After the mixed phenol total 100g, 5min of cresols, start vacuum dehydration, when pump-out reaches 350g, stops vacuum dehydration, be added auxiliary
Expect that methanol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), trityl are free
It is one or more in base, vinyl acetate, carbon tetrachloride, hydroquinone, so that the viscosity of resin is reached 3000mpa.s or so,
Cooling discharge, obtains high activity thermosetting phenolic resin, and resin property is as follows：
| Free phenol | Solid content | Gel time | Calorific value | Viscosity | Ortho para position ratio | |
| GY-05 | 11.88% | 76.6% | 137s | 30 MJ/kg | 3560 mPa.S | 1.65 |
Claims (3)
1. the preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system, it is characterised in that：Include the following steps：
（1）, paraformaldehyde, water and basic catalyst be proportionally added into reaction kettle, so that paraformaldehyde is cracked completely, obtain formaldehyde
Solution；
（2）, a certain amount of acetic acid is first added into reaction kettle, phenol and zinc oxide is then added, makes reaction solution pH between 5-7,
120-180min is kept at 80-95 DEG C；Then other aldehydes raw materials and basic catalyst is added, reaction solution pH is made to adjust to 7-9
Between, after keeping 20 ~ 30min, it is cooled to 80-95 DEG C according to the speed of 6 DEG C/10min, constant temperature；
（3）, when the Abbe refractometer of reaction solution is between 1.460-1.470, be cooled to 50 ~ 70 DEG C rapidly, then be added between
Benzenediol, metacresol and 3, the mixed phenol of 5 xylenols composition, keep constant temperature, when the cloud point of reaction solution reaches 15 DEG C, start true
Sky dehydration；
（4）, after vacuum dehydration, auxiliary material is added into reaction kettle, then adjustment viscosity goes out to 1000-3000mPas
Material is to get product.
2. the preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system as described in claim 1, it is characterised in that：
Step（2）In, other aldehydes raw materials are the mixed aldehyde of acetaldehyde, butyraldehyde or both, the basic catalyst be magnesia or
Barium hydroxide.
3. the preparation method of the high ortho position thermosetting property pultrusion phenolic resin of one pack system as described in claim 1, it is characterised in that：
Step（4）In, the auxiliary material is methanol, ethyl alcohol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether, trityl
It is one or more in free radical, vinyl acetate, carbon tetrachloride, hydroquinone.
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