CN106496471A - The preparation method of the high ortho position thermosetting pultrusion phenolic resin of one pack system - Google Patents
The preparation method of the high ortho position thermosetting pultrusion phenolic resin of one pack system Download PDFInfo
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- CN106496471A CN106496471A CN201610885947.4A CN201610885947A CN106496471A CN 106496471 A CN106496471 A CN 106496471A CN 201610885947 A CN201610885947 A CN 201610885947A CN 106496471 A CN106496471 A CN 106496471A
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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 pultrusion phenolic resin of one pack system, it is related to the preparation method of phenolic resin, first paraformaldehyde is cracked completely and obtains formalin, then a certain amount of acetic acid is initially charged, add phenol and zinc oxide makes reactant liquor pH between 57, at 80 95 DEG C, react 120 180min；It is subsequently adding other aldehydes raw materials and base catalyst is reacted；When the Abbe refractometer of reactant liquor is between 1.460 1.470,50 ~ 70 DEG C are cooled to rapidly, are subsequently adding resorcinol, metacresol and 3, the mixed phenol of 5 xylenols composition, is reacted, after vacuum dehydration, adjuvant is added in reactor, discharges, obtain final product product after adjustment viscosity.Pultrusion phenolic resin prepared by the present invention has the advantages that low environmental protection, solidification temperature, quick solidifying, storage period length, solidification bubble-free, product strength height, stable performance, good combination property.
Description
Technical field
The present invention relates in chemical field thermosetting phenolic resin preparation method, and in particular to a kind of one pack system
The preparation method of high ortho position thermosetting pultrusion phenolic resin.
Background technology
Thermosetting phenolic resin be by phenol and formaldehyde in the basic conditions, through addition, condensation reaction, and control certain
The fluid resin of certain molecular mass and certain viscosity obtained by the extent of reaction.The chemical constitution of raw material according to selected by design
With process conditions such as monomer functionality, the mol ratio of phenol and aldehyde consumption, response time and temperature, the phenolic aldehyde of different purposes is prepared
Resin.The phenolic resin that at present prepared by conventional method, long with hardening time, storage cycle is short, needs acid solidification, or must be through
Cross High Temperature High Pressure to solidify, the defect such as complex forming technology, seriously limit phenolic resin answering in dragging and squeezing glass fiber reinforced plastics field
With.
Content of the invention
It is an object of the invention to provide a kind of high ortho position thermosetting phenolic of the 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 of height, stable performance, good combination property.
For achieving the above object, the technical scheme is that：The high ortho position thermosetting pultrusion phenolic resin of one pack system
Preparation method, comprises the steps：
（1）, paraformaldehyde, water and base catalyst be proportionally added into reactor, paraformaldehyde is cracked completely, obtain formaldehyde
Solution；
In this step, reaction temperature is 75-95 DEG C, and the response time is 30-60min, and at the end of the step, paraformaldehyde is completely molten
Solution；
（2）, be initially charged a certain amount of acetic acid in reactor, be subsequently adding phenol and zinc oxide, make reactant liquor pH between 5-7,
120-180min is kept at 80-95 DEG C；Other aldehydes raw materials and base catalyst is subsequently adding, reactant liquor pH is adjusted to 7-9
Between, after keeping 20 ~ 30min, 80-95 DEG C is cooled to according to the speed of 6 DEG C/10min, constant temperature；
（3）, when the Abbe refractometer of reactant liquor is between 1.460-1.470, be cooled to rapidly 50 ~ 70 DEG C, between being subsequently adding
Benzodiazepiness, metacresol and 3, the mixed phenol of 5 xylenols composition, keep constant temperature, when the cloud point of reactant liquor reaches 15 DEG C, start true
Empty dehydration；
This step, in vacuum dewatering process, vacuum is not less than 0.09 MPa, and sets reaction temperature as 80 DEG C, vacuum dehydration
During resin actual temperature at 55-60 DEG C, after certain time, when in kettle, resin actual temperature reaches 70 DEG C, stop heating,
Cool, stop vacuum dehydration；
（4）, after vacuum dehydration terminates, in reactor, add adjuvant, adjustment viscosity then to discharge to 1000-3000mpa.s,
Obtain final product product.
Step（2）In, other aldehydes raw materials described are the mixed aldehyde of acetaldehyde, butyraldehyde or both, and the base catalyst is
Magnesium oxide or barium hydroxide.
Step（4）In, the adjuvant is methanol, ethanol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether
（Between EL10-EL80）, triphenylmethyl radical, vinyl acetate, carbon tetrachloride, one or more in hydroquinone.
During whole preparation method, phenols raw material used is 1 with the molar ratio of aldehydes raw material：1.1-1.6.
The molecular structure schematically as follows formula of the first stage thermosetting phenolic resin prepared using conventional fabrication process（1）Institute
Show, because the methylene content of para-position is more, molecule steric effect so that n values are 2 or so.And this kind of resin is by molecular structure
Steric effect determine that its liquid viscosity is larger, activity relatively low, can meet phenolic foam material etc. acid solidifying requirements should
With field, the effect of single-component thermosetting but can not be stably realized.
n：0 ~ 2 formula（1）
The molecular structure of first stage in preparation method of the present invention prepared by first two steps high ortho position thermosetting phenolic resin is illustrated such as
Following formula（2）Shown, because the methylene content of para-position is few, the linear shape of molecule so that n values can reach 5 or so.And same point
The thermosetting phenolic resin of son amount distribution is compared with high ortho position thermosetting phenolic resin, the viscosity of high ortho position thermosetting phenolic resin
Will be low many.
n:0 ~ 5 formula（2）
Final prepared pultrusion of the invention is tied containing multiple different molecules with the high ortho position thermosetting phenolic resin of one pack system
Structure, such as following formula（3）Shown, wherein, metacresol is active higher 2.88 times than phenol, and 3,5 xylenols are higher 7.55 times than phenol activity,
And retain the resorcinol of three active sites on phenyl ring than 3, the active taller many of 5 xylenols.If only using isophthalic two
Phenol does active modification, is difficult to control to can building-up process, easy implode, so that reaction short stay is in resol
Afterwards, solidification cross-linking stage is rapidly entered, the insoluble resite not melted of solid is formed.Therefore, be given with the present invention
The phenols raw material of several different activities had both improve the activity of overall phenolic resin, had made conjunction again to use after certain proportion mixing
Operability, repeatability is had more into reaction controlling, and phenolic resin is solidified in the curing process uniformly.Resorcinol,
Cresol, 3,5 xylenols and the phenols raw material that phenol is whole synthetic reaction, in whole synthetic reaction, three kinds in addition to phenol are mixed
Close the shared mass content in total phenols raw material of phenol and be less than 20%.
n:0 ~ 5 formula（3）
Beneficial effect：
1st, pultrusion prepared by the present invention uses one pack system high adjacent position phenolic resin, low cost, good stability, preparation method simply to have
Effect, its molecular weight is 400-900, and (25 DEG C) of viscosity is 1000-3000 mPa.S, and 150 DEG C of polymerization speeds are 90-150s, calorific value
For 22-28 MJ/kg.
2nd, preparation technology of the present invention accomplishes phenolic resin synthesis on the premise of high-quality and repeatable stability is ensured
Zero-emission, no pollution, to environmental conservation, comprehensive utilization of resources, promote industry development etc. to have larger impetus.For the first time
Synthetic reaction vacuum dehydration gained waste liquid is transferred in the ponderable quantity tank of closing, during second novolak resin, can be replaced
Water is applied in the cleavage step of paraformaldehyde, reaches the purpose of non-wastewater discharge.
And the synthesis of traditional phenolic resin is with liquid formaldehyde as raw material, after manufacture the phase draw water through vacuum, gained is given up in a large number
Liquid, two indexs of the phenol content of the waste liquid and COD already exceed 6.5 ten thousand times and 2.3 ten thousand times that country allows discharge standard, pollution
Degree is self-evident；By improving using paraformaldehyde and phenol, catalyst direct reaction, by being not required to dehydration, phenolic aldehyde is produced
Resin, under this process conditions, although produce without sewage waste liquor, but：（1）, the cracking of this technique paraformaldehyde not exclusively, make most
The non-constant width of whole phenolic resin molecular weight distribution, 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 jointly reaction temperature control, if do without water conducted
Body, reaction liberated heat are difficult to disperse away rapidly, and cause reaction localized heat release too high, cause solidification caking, or even have
Quick-fried kettle is dangerous, and causes the temperature control of extraneous supply heat to be difficult to grasp as the temperature of reactant is unbalanced；（3）、
As paraformaldehyde is not cracked completely, phenol and (CH2O)nAfter reaction, n values between 10-30, n middle CH2O structures are not
Stable, slowly crack after phenolic cure, not only destroy the molecular structure of phenolic aldehyde, and form free formaldehyde and slowly release
It is placed in air ambient, also results in long-term air pollution；（4）, proportionally feed intake, carry out phenolic resin synthesis, but portion
Point formaldehyde fails to participate in chemical reaction, certainly will cause same ratio phenol final also exist with free state, phenol has corrosion
Property, therefore, this technological reaction not exclusively, makes final phenolic aldehyde product also be provided with certain corrosivity.（5）, the technique the first stage
There are in a large number free aldehyde and free phenols in phenolic resin, and in the case of having catalyst, even refrigerated storage, still slowly can enter
The synthesis of row phenolic resin and cross-linking reaction, so that resol viscosity B coefficent is fast, resin storage time is short to wait crowd
Many drawbacks.
3rd, pultrusion one pack system high adjacent position phenolic resin prepared by the present invention, has than conventional thermosetting phenolic resin following
Advantage：（Ⅰ）Curing rate is fast；（Ⅱ）Residual carbon is high；（Ⅲ）Rigidity of the product in the case where being heated is good；Than traditional high ortho position thermosetting
Phenolic resin has advantages below：（Ⅰ）This phenolic resin can be used as the raw material for preparing glass/phenolic composite；（Ⅱ）Solidification
Speed is fast, and does not need acid curing agent；（Ⅲ）After solidification, closely knit bubble-free.
4th, relevant auxiliary materials are with the addition of in resin synthesis process, and described several adjuvants can be played and adjust resin viscosity
Purpose, reduces resin viscosity, is more convenient for using.Additionally, in rear operation, pultrusion production forming process, inorganic matters can be filled out
Material, alkali-free rove, tape edge felt etc. are infiltrated in phenol resin solution, and the good infiltration compatibility, to phenolic fiberglass reinforced plastics finished product
Quality plays a decisive role；And DOP, DNP, the OP-10 or castor oil polyoxyethylene ether in the present invention（Between EL10-EL80）Can
With improve resin with interpolation filler the compatibility, be allowed to be difficult to precipitate.Triphenylmethyl radical, vinyl acetate, four chlorinations
Carbon or hydroquinone can play a part of inhibition to resin, improve the storage time of resin, and the resin can preserve 4 at low temperature
More than individual month.
5th, the present invention no longer controls the reaction end in per stage in phenolic resin building-up process with timing node（By
Affect in each side such as operation, equipment, raw material and environment, if every batch of resins synthesis control reaction section with the equivalent responses time
Point certainly will be very big to the performance impact of final products, and therefore the phenolic resin of each producer's actual production is unstable at present, viscosity
Suddenly big or suddenly small, active higher or low and needs can not be met）, but the present invention is in the beginning or end of each stage of reaction
There are corresponding detection meanss（Such as：Cloud point, thinner ratio, Abbe refractometer, viscosity etc.）, reach and fast and accurately detect online
As a result, so as to flexibly controlling reaction process.Final resin can be made to reach expected design performance, and repeatable high, surely
Qualitative good.
6th, the characteristics of present invention has preparation process is simple, low cost, excellent performance, the pultrusion of preparation are high adjacent with 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 applicable to the quick shaping process such as pultrusion
To prepare composite, the resin application of other techniques such as handss paste, spraying, winding is can be also widely applied to.
Specific embodiment
Embodiment 1
Paraformaldehyde 350g, water 400g and sodium hydroxide 4.5g are successively added in reactor, after mix homogeneously according to 6 DEG C/
The speed of 10min is warming up to 80 DEG C, is kept stirring for 60min, after paraformaldehyde is completely dissolved, adds 6g or so acetic acid.Stirring
A moment sequentially adds 1000g phenol and 25g or so zinc oxide in reactor and makes reactant liquor PH between 5-7, according to 6 DEG C/
The speed of 10min rises high-temperature to 95 DEG C, keeps 120min.35g acetaldehyde and 6g or so magnesium oxide is added, adjusts reaction environment PH
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 rate is penetrated between 1.460-1.470, be cooled to rapidly 65 DEG C, add the mixed phenol of resorcinol, 3,5 xylenols and metacresol
（Three's mass ratio is 3:1:1）Common 100g, keeps constant temperature, when the cloud point of reaction solution reaches 15 DEG C or so, starts vacuum and takes off
Water, sets the temperature of vacuum dehydration as 80 DEG C, and now material actual temperature after certain time, works as reactor between 55-60 DEG C
When interior actual temperature reaches 70 DEG C, stop heating, stop vacuum dehydration.According to the viscosity of feed liquid in now kettle, adjuvant first is added
Alcohol, ethanol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), vinyl acetate, tetrachloro
Change one or more in carbon, hydroquinone, when the viscosity of resin reaches 2000mpa.s-3000mpa.s, temperature is down to 40 DEG C
Hereinafter, triphenylmethyl radical 0.2g is added, stir discharging, obtains pultrusion one pack system high adjacent position phenolic resin, 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 mix homogeneously according to 6 DEG C/
The speed of 10min is warming up to 85 DEG C, is kept stirring for 50min, after paraformaldehyde is completely dissolved, adds 12g or so acetic acid.Stirring
A moment sequentially adds 1000g phenol and 30g or so zinc oxide in reactor and makes reactant liquor PH between 5-7, according to 6 DEG C/
The speed of 10min rises high-temperature to 80 DEG C, keeps 180min.45.2g acetaldehyde and 10g or so magnesium oxide is added, reaction environment is made
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 Ah
When shellfish refractive index is between 1.460-1.470,50 DEG C are cooled to rapidly, add the mixed of resorcinol, 3,5 xylenols and metacresol
Close phenol（Three's mass ratio is 2:1:1）Common 250g, keeps constant temperature, when the cloud point of reaction solution reaches 15 DEG C or so, starts true
Empty dehydration, sets the temperature of vacuum dehydration as 80 DEG C, now material actual temperature between 55-60 DEG C, after certain time, when anti-
When answering actual temperature in device to reach 70 DEG C, stop heating, stop vacuum dehydration.According to the viscosity of feed liquid in now kettle, add auxiliary
Material methanol, ethanol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), trityl freedom
One or more in base, vinyl acetate, carbon tetrachloride, hydroquinone, when the viscosity of resin reaches 2000mpa.s-
3000mpa.s, stir 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 mix homogeneously according to 6 DEG C/
The speed of 10min is warming up to 95 DEG C, is kept stirring for 30min, after paraformaldehyde is completely dissolved, adds 10g or so acetic acid.Stirring
A moment sequentially adds 1000g phenol and 30g or so zinc oxide in reactor and makes reactant liquor PH between 5-7, according to 6 DEG C/
The speed of 10min rises high-temperature to 90 DEG C, keeps 140min.32.39g butyraldehyde and 40g or so barium hydroxide is added, reaction ring is made
Border PH is adjusted between 7-9, after keeping 30min, is cooled to 95 DEG C according to the speed of 6 DEG C/10min, constant temperature；When reaction solution
When Abbe refractometer is between 1.460-1.470,70 DEG C are cooled to rapidly, add resorcinol, 3,5 xylenols and metacresol
Mixed phenol（Three's mass ratio is 3:1:2）Common 180g, 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, now material actual temperature between 55-60 DEG C, after certain time, when
When actual temperature reaches 70 DEG C in reactor, stop heating, stop vacuum dehydration.According to the viscosity of feed liquid in now kettle, add
Adjuvant methanol, ethanol, 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 1000mpa.s-
3000mpa.s, stir 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-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 mix homogeneously according to 6 DEG C/
The speed of 10min is warming up to 80 DEG C, is kept stirring for 60min, after paraformaldehyde is completely dissolved, adds 6g or so acetic acid.Stirring
A moment sequentially adds 1000g phenol and 25g zinc oxide etc. in reactor, rises high-temperature to 95 according to the speed of 6 DEG C/10min
DEG C, keep 120min.40g acetaldehyde and 8g or so magnesium oxide is added, reaction environment PH is adjusted between 7-9, is kept 30min
Afterwards, the speed according to 6 DEG C/10min is cooled to 85 DEG C, keeps constant temperature；When the cloud point of reaction solution reaches 25 DEG C or so, start
Vacuum dehydration, and reaction temperature is set as 80 DEG C（Actual temperature is because the boiling point of water reduces under negative pressure, it is impossible to more than 65 DEG C）,
When real reaction temperature is 70 DEG C, stop vacuum dehydration, add the mixture and other adjuvants of 100g ethanol and resorcinol
（DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), triphenylmethyl radical, vinyl acetate, tetrachloro
Change one or more in carbon, hydroquinone）, slow cooling discharge, obtain another kind of high ortho position thermosetting phenolic resin, resin
Performance is 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 is added in reaction vessel.Start reactor stirring, in adjustment kettle
Temperature is 90-95 DEG C, and constant temperature about 30min treats that paraformaldehyde is completely dissolved, is cooled to 70 DEG C, sequentially adds in reactor
1000g phenol, acetic acid 5g, after about 5min, plus 20g or so magnesium oxide makes reaction PH between 6-8, according to the speed of 3 DEG C/2min
High-temperature is risen to 95 DEG C, 150min is kept.Speed according to 3 DEG C/2min is cooled to 85 DEG C, keeps constant temperature, when reaction solution
Water thinner ratio reaches 10:20（Or cloud point reaches 20 DEG C）When, resorcinol, 3,5 xylenols and a first is added in reaction vessel
The common 100g of the mixed phenol of phenol, after 5min, starts vacuum dehydration, when pump-out reaches 350g, stops vacuum dehydration, adds adjuvant
Methanol, ethanol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether (between EL10-EL80), trityl freedom
One or more in base, vinyl acetate, carbon tetrachloride, hydroquinone, makes the viscosity of resin reach 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 pultrusion phenolic resin of one pack system, it is characterised in that：Comprise the steps：
（1）, paraformaldehyde, water and base catalyst be proportionally added into reactor, paraformaldehyde is cracked completely, obtain formaldehyde
Solution；
（2）, be initially charged a certain amount of acetic acid in reactor, be subsequently adding phenol and zinc oxide, make reactant liquor pH between 5-7,
120-180min is kept at 80-95 DEG C；Other aldehydes raw materials and base catalyst is subsequently adding, reactant liquor pH is adjusted to 7-9
Between, after keeping 20 ~ 30min, 80-95 DEG C is cooled to according to the speed of 6 DEG C/10min, constant temperature；
（3）, when the Abbe refractometer of reactant liquor is between 1.460-1.470, be cooled to rapidly 50 ~ 70 DEG C, between being subsequently adding
Benzodiazepiness, metacresol and 3, the mixed phenol of 5 xylenols composition, keep constant temperature, when the cloud point of reactant liquor reaches 15 DEG C, start true
Empty dehydration；
（4）, after vacuum dehydration terminates, in reactor, add adjuvant, adjustment viscosity then to discharge to 1000-3000mpa.s,
Obtain final product product.
2. the preparation method of the high ortho position thermosetting pultrusion phenolic resin of one pack system as claimed in claim 1, it is characterised in that：
Step（2）In, other aldehydes raw materials described are the mixed aldehyde of acetaldehyde, butyraldehyde or both, the base catalyst be magnesium oxide or
Barium hydroxide.
3. the preparation method of the high ortho position thermosetting pultrusion phenolic resin of one pack system as claimed in claim 1, it is characterised in that：
Step（4）In, the adjuvant is methanol, ethanol, ethylene glycol, DOP, DNP, OP-10, castor oil polyoxyethylene ether, trityl
One or more in free radical, vinyl acetate, carbon tetrachloride, hydroquinone.
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| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
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| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
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