CN108359066A - A kind of preparation method of high ortho position high hydroxyl content electronic-grade phenolic resin - Google Patents
A kind of preparation method of high ortho position high hydroxyl content electronic-grade phenolic resin Download PDFInfo
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- CN108359066A CN108359066A CN201810182856.3A CN201810182856A CN108359066A CN 108359066 A CN108359066 A CN 108359066A CN 201810182856 A CN201810182856 A CN 201810182856A CN 108359066 A CN108359066 A CN 108359066A
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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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Abstract
The present invention relates to a kind of preparation methods of high ortho position high hydroxyl content special type phenolic resin, it is catalyzed with zinc salt, and replace phenol with alkyl phenol moieties, aldehyde phenol reacts molar ratio and is more than 1, the foreign ion in resin, fugitive constituent and free phenol content are effectively reduced by the washing of distinctive deionization and steam purging technique after reaction.The resin that the present invention is prepared has the characteristics that high electrical insulating properties, high-adhesion, high thermal stability, high-mechanical property, low viscosity, low solidification temperature, low-k, low thermal coefficient of expansion, agent of low hygroscopicity, low stress, can be widely applied to the high-technology fields such as electronics, casting and aerospace.
Description
Technical field
The invention belongs to technical field of organic chemistry, and in particular to a kind of high ortho position high hydroxyl content electronic-grade phenolic resin
Preparation method.
Background technology
Electron level special type phenolic resin belongs to linear phenol formaldehyde (PF) series, is mainly used in epoxy-plastic packaging material and copper cladding plate neck
Domain, wherein the special type phenolic resin for epoxy-plastic packaging material production does not require nothing more than foreign ion and free phenol content is extremely low, simultaneously
Also take into account excellent electrical insulating property and material processability etc..At present mainly by external import, the country only has a small number of enterprise's productions,
But there are still larger gaps compared with external import for quality.
Domestic conventional production process is：Formaldehyde is added after being measured by certain molar ratio (being generally less than 1) with phenol to react
Kettle, the then polycondensation under acid heating condition, after reaction remove resin upper water, then under conditions of vacuumizing into
Row dehydration and hot-working.The phenolic resin impurity and free phenol content of this method production are higher, electrical insulating property, caking property and machine
Tool poor performance, it is clear that can not be as the curing agent of the epoxy molding plastic for electronic package material.To solve the above problems, this hair
It is bright to come therefrom.
Our company is formed based on the cold-box phenolic resin product of development ＆ production for many years in conjunction with the domestic and international prior art
Work(has developed the special type phenolic resin for meeting electronic package material of new generation.
Invention content
Insufficient existing for electron level special type phenolic resin and preparation method thereof in the prior art in order to overcome, the present invention provides
A kind of preparation method of abundant, excellent product performance, stable quality the linear phenol formaldehyde (PF) series electronic resins of raw material sources.
In order to solve the above technical problems, the present invention provides a kind of preparation of high ortho position high hydroxyl content electronic-grade phenolic resin
Method and technology scheme, its main feature is that：
(1) aldehydes matter and zinc salt catalyst are proportionally added into reaction kettle, stir and are warming up to 70~100 DEG C, phenols
The weight ratio of substance and zinc salt catalyst is：100: 1~2.5；
(2) quickly continuous to drip formalin, last insulation reaction, aldehydes matter and first when temperature is 70~100 DEG C
The weight ratio of aldehyde aqueous solution is：100: 115~150；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through
Reaction kettle bottom, in 0.10~0.80Mpa, reacting kettle inner pressure is controlled in -0.00~-0.09Mpa, instead for the pressure control of vapor
It answers material temperature in kettle control at 50~100 DEG C, and slowly heats up, when temperature reaches 120~140 DEG C, stopping is dehydrated；
(4) deionized water of 85~95 DEG C of temperature is added after being dehydrated into reaction kettle immediately, stirs 30~60 minutes
It is static afterwards, static 30~upper water is detached after sixty minutes, terminate after being washed 3~5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150~180 DEG C, vacuum degree reaches -0.1Mpa
When dehydration terminate；
(6) after being dehydrated, it is granulated packaging.
Preferably, in the step (2), formalin is continuously dripped in 1~2 hour, adds rear insulation reaction 1
~10 hours.
Preferably, the aldehydes matter is selected from the mixture of phenol and alkyl phenol.
Preferably, the alkyl phenol is selected from o-cresol, paracresol, octyl phenol, nonyl phenol, anacardol and in butylphenol
One or more combinations, more preferably, the weight ratio of the mixture of the phenol and alkyl phenol is：60~85: 15
~40.
Preferably, the zinc salt catalyst is one or more in zinc acetate, zinc sulfate, zinc chloride, zinc nitrate.
Preferably, the formalin is the formaldehyde saturated aqueous solution that mass percent concentration is 36.5~37.5%.
Preferably, the preparation method technical solution of a kind of electronic-grade phenolic resin, its main feature is that：
(1) aldehydes matter and zinc salt catalyst are proportionally added into reaction kettle, stir and are warming up to 70~100 DEG C；
(2) start timing when temperature reaches 70~100 DEG C, continuously drip formalin in 1~2 hour, add
Insulation reaction 1~10 hour after complete；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through
Reaction kettle bottom, in 0.10~0.80Mpa, reacting kettle inner pressure is controlled in -0.00~-0.09Mpa, instead for the pressure control of vapor
It answers material temperature in kettle control at 50~100 DEG C, and slowly heats up, when temperature reaches 120~140 DEG C, stopping is dehydrated；
(4) deionized water of 85~95 DEG C of temperature is added after being dehydrated into reaction kettle immediately, stirs 30~60 minutes
It is static afterwards, static 30~upper water is detached after sixty minutes, terminate after being washed 3~5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150~180 DEG C, vacuum degree reaches -0.1Mpa
When dehydration terminate；
(6) after being dehydrated, it is granulated packaging.
Compared with prior art, the present invention having the following advantages that：
(1) zinc salt catalyst catalysis is selected to be conducive to the phenolic resin that high ortho position is prepared, viscosity is low, weight average molecular weight
Between 500~1500, the mobility of resin, while high adjacent position phenolic resin and epoxy resin reaction activity are effectively improved
Low, curing rate is fast, and curing degree is high, and properties of product are stablized,
(2) by the way that one or more induced by alkyl hydroxybenzene substance modifications is added, the heat-resistant stability of resin, mechanicalness are improved
Energy and processing performance etc.,
(3) aldehyde phenol reaction molar ratio is more than 1, is conducive to increase the methylol group content in phenolic resin, increases reaction and hands over
Join point, improve solidification rate,
(4) formaldehyde is effectively controlled reaction rate, prevents the generation of a large amount of isomers by the way of being added dropwise,
(5) on synthesis technology, a set of electron level deionized water equipment is established, resin is fully washed, is removed
Foreign ion in resin, and it is based on the distinctive vapor generation system of electron level deionized water and steam purging technique,
The free-phenol in resin is taken out of by vapor at high temperature, effectively reduces the free phenol content in resin.
The phenolic resin impurity content that the method for the present invention is prepared is few, and free phenol content is low, and fugitive constituent is low, electrical property and
Good mechanical property, can be as the curing agent of " epoxy molding plastic of encapsulation semiconductor devices and integrated circuit ".And it is prepared
Phenolic resin has high electrical insulating properties, high-adhesion, high thermal stability, high-mechanical property, low viscosity, low solidification temperature, low Jie
The features such as electric constant, low thermal coefficient of expansion, agent of low hygroscopicity, low stress, it is contour to can be widely applied to electronics, casting and aerospace
New technical field.
Specific implementation mode
Said program is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
(1) 85 kilograms of phenol, 15 kilograms of o-cresol are added in reaction kettle, 1.6 kilograms of zinc acetate stirs and is warming up to 90
℃；
(2) start timing when temperature reaches 90 DEG C, 37% 120 public affairs of formalin are continuously dripped in 2 hours
Jin, adds rear insulation reaction 2 hours；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through
Reaction kettle bottom, in 0.80Mpa, reacting kettle inner pressure is controlled in -0.09Mpa, material in reactor temperature for the pressure control of vapor
Degree control slowly heats up at 50~100 DEG C, and when temperature reaches 120 DEG C, stopping is dehydrated；
(4) deionized water of 95 DEG C of temperature is added after being dehydrated into reaction kettle immediately, stirring is static after sixty minutes, quiet
Upper water is only detached after sixty minutes, is terminated after being washed 5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150 DEG C, vacuum degree is dehydrated when reaching -0.1Mpa
Terminate；
(6) after being dehydrated, it is granulated packaging.
Embodiment 2
(1) 1.8 kilograms of 75 kilograms of phenol, 20 kilograms of metacresol, 5 kilograms of anacardol and zinc acetate are added in reaction kettle,
It stirs and is warming up to 85 DEG C；
(2) start timing when temperature reaches 90 DEG C, 37% formalin 140 is continuously dripped in 2.5 hours
Kilogram, add rear insulation reaction 3 hours；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through
Reaction kettle bottom, in 0.60Mpa, reacting kettle inner pressure is controlled in -0.07Mpa, material in reactor temperature for the pressure control of vapor
Degree control slowly heats up at 50~100 DEG C, and when temperature reaches 130 DEG C, stopping is dehydrated；
(4) deionized water of 90 DEG C of temperature is added after being dehydrated into reaction kettle immediately, it is static after stirring 30 minutes, it is quiet
Upper water is only detached after forty minutes, is terminated after being washed 5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150 DEG C, vacuum degree is dehydrated when reaching -0.1Mpa
Terminate；
(6) after being dehydrated, it is granulated packaging.
Embodiment 3
(1) 2.3 kilograms of 60 kilograms of phenol, 25 kilograms of nonyl phenol, 15 kilograms of anacardol and zinc acetate are added in reaction kettle,
It stirs and is warming up to 95 DEG C；
(2) start timing when temperature reaches 95 DEG C, 37% formalin 125 is continuously dripped in 1.5 hours
Kilogram, add rear insulation reaction 4 hours；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through
Reaction kettle bottom, in 0.60Mpa, reacting kettle inner pressure is controlled in -0.08Mpa, material in reactor temperature for the pressure control of vapor
Degree control slowly heats up at 50~100 DEG C, and when temperature reaches 120 DEG C, stopping is dehydrated；
(4) deionized water of 90 DEG C of temperature is added after being dehydrated into reaction kettle immediately, stirring is static after forty minutes, quiet
Upper water is only detached after sixty minutes, is terminated after being washed 5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150 DEG C, vacuum degree is dehydrated when reaching -0.1Mpa
Terminate；
(6) after being dehydrated, it is granulated packaging.
Table 1 lists the physical and chemical index for the high ortho position high hydroxyl content electronic-grade phenolic resin that embodiment 1,2,3 is obtained.
Table 1
The present invention replaces part phenol, aldehyde phenol to react molar ratio and be more than 1 by adding alkyl phenol, the side for being used in combination zinc salt to be catalyzed
The high ortho position that method is prepared, the phenolic resin of high methylol group content, compared with prior art, mobility is preferable, curing rate
Soon, solidification is uniform, improves the mechanical performance and thermal stability of product.In addition, distinctive steam purging technique, greatly drops
Ion in low resin, free-phenol and volatile content.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention.It is all according to spirit of that invention
The equivalent transformation or modification that essence is done, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of high ortho position high hydroxyl content electronic-grade phenolic resin, which is characterized in that it includes the following steps：
(1) aldehydes matter and zinc salt catalyst are proportionally added into reaction kettle, stir and are warming up to 70~100 DEG C, aldehydes matter
Weight ratio with zinc salt catalyst is：100: 1~2.5；
(2) quickly continuous to drip formalin, last insulation reaction, aldehydes matter and formalin when temperature is 70~100 DEG C
The weight ratio of solution is：100: 115~150；
(3) heat preservation finishes, and carries out vacuum dehydration, opens simultaneously electron level deionized system, vapor is passed through reaction
Bottom, in 0.10~0.80Mpa, reacting kettle inner pressure is controlled in -0.00~-0.09Mpa, reaction kettle for the pressure control of vapor
Interior temperature of charge control slowly heats up at 50~100 DEG C, and when temperature reaches 120~140 DEG C, stopping is dehydrated；
(4) deionized water of 85~95 DEG C of temperature, stirring 30~quiet after sixty minutes is added after being dehydrated into reaction kettle immediately
Only, static 30~and upper water is detached after sixty minutes, terminate after being washed 3~5 times with same method；
(5) heating carries out vacuum dehydration after washing, and when temperature reaches 150~180 DEG C, vacuum degree reaches de- when -0.1Mpa
Water terminates；
(6) after being dehydrated, it is granulated packaging.
2. preparation method according to claim 1, which is characterized in that in the step (2), continuously dripped in 1~2 hour
Formalin is added, adds rear insulation reaction 1~10 hour.
3. preparation method according to claim 1, which is characterized in that the aldehydes matter is selected from the mixed of phenol and alkyl phenol
Close object.
4. preparation method according to claim 3, which is characterized in that the alkyl phenol is selected from o-cresol, paracresol, octyl
Phenol, nonyl phenol, anacardol and to one or more combinations in butylphenol.
5. preparation method according to claim 3, which is characterized in that the parts by weight of the mixture of the phenol and alkyl phenol
Ratio is：60~85: 15~40.
6. preparation method according to claim 1, which is characterized in that the zinc salt catalyst be selected from zinc acetate, zinc sulfate,
It is one or more in zinc chloride, zinc nitrate.
7. preparation method according to claim 1, which is characterized in that the formalin is that mass percent concentration is
36.5~37.5% formaldehyde saturated aqueous solution.
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| CN201810182856.3A CN108359066A (en) | 2018-03-06 | 2018-03-06 | A kind of preparation method of high ortho position high hydroxyl content electronic-grade phenolic resin |
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| CN201810182856.3A CN108359066A (en) | 2018-03-06 | 2018-03-06 | A kind of preparation method of high ortho position high hydroxyl content electronic-grade phenolic resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014570A (en) * | 2019-12-31 | 2020-04-17 | 苏州兴业材料科技股份有限公司 | Phenol urethane cold core box binder and preparation method thereof |
| CN112300349A (en) * | 2020-10-20 | 2021-02-02 | 江苏麒祥高新材料有限公司 | Preparation and application of high-ortho phenolic adhesive resin |
| CN115636913A (en) * | 2022-09-27 | 2023-01-24 | 山东阳谷华泰化工股份有限公司 | Preparation method of low-free-phenol phenolic resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154542A (en) * | 2003-11-25 | 2005-06-16 | Hitachi Chem Co Ltd | Metal-modified phenolic resin and method for producing the same |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN102181026A (en) * | 2011-04-06 | 2011-09-14 | 连云港市中和科技有限公司 | Production method for electronic-grade phenolic resin |
| CN106046283A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | High-ortho benzyl ether phenolic resin and preparation method thereof, and method for applying high-ortho benzyl ether phenolic resin to cold box binder |
-
2018
- 2018-03-06 CN CN201810182856.3A patent/CN108359066A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154542A (en) * | 2003-11-25 | 2005-06-16 | Hitachi Chem Co Ltd | Metal-modified phenolic resin and method for producing the same |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN102181026A (en) * | 2011-04-06 | 2011-09-14 | 连云港市中和科技有限公司 | Production method for electronic-grade phenolic resin |
| CN106046283A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | High-ortho benzyl ether phenolic resin and preparation method thereof, and method for applying high-ortho benzyl ether phenolic resin to cold box binder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014570A (en) * | 2019-12-31 | 2020-04-17 | 苏州兴业材料科技股份有限公司 | Phenol urethane cold core box binder and preparation method thereof |
| CN112300349A (en) * | 2020-10-20 | 2021-02-02 | 江苏麒祥高新材料有限公司 | Preparation and application of high-ortho phenolic adhesive resin |
| CN115636913A (en) * | 2022-09-27 | 2023-01-24 | 山东阳谷华泰化工股份有限公司 | Preparation method of low-free-phenol phenolic resin |
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Application publication date: 20180803 |