CN102838727A - Preparation method for high softening point o-cresol formaldehyde epoxy resin - Google Patents
Preparation method for high softening point o-cresol formaldehyde epoxy resin Download PDFInfo
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- CN102838727A CN102838727A CN2011101720909A CN201110172090A CN102838727A CN 102838727 A CN102838727 A CN 102838727A CN 2011101720909 A CN2011101720909 A CN 2011101720909A CN 201110172090 A CN201110172090 A CN 201110172090A CN 102838727 A CN102838727 A CN 102838727A
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Abstract
The present invention provides a preparation method for a high softening point o-cresol formaldehyde epoxy resin. The preparation method comprises the following steps: adopting o-cresol and paraformaldehyde as raw materials, carrying out a reaction for 3-5 hours under a catalysis effect of a catalyst, and carrying out a post-treatment to obtain a high softening point o-cresol formaldehyde resin; mixing the synthesized linear high softening point o-cresol formaldehyde resin and epichlorohydrin according to a mass ratio of 1:3-1:10; adding an auxiliary agent; carrying out an etherification reaction at a temperature of 30-100 DEG C; adding an alkali to catalyze a ring closing reaction under a vacuum degree of 0.01-0.1 MPa; recovering the epichlorohydrin; and carrying out a refinement reaction and a post-treatment. The o-cresol formaldehyde epoxy resin prepared by adopting the preparation method of the present invention has the following characteristics that: high softening point of 80-95 DEG C can be achieved; epoxy equivalent is low; hydrolyzable chlorine content is low; and a high yield can be achieved. In addition, the o-cresol formaldehyde epoxy resin of the present invention is a special function type epoxy resin focused for green electronics encapsulation, IC packaging and circuit board (green oil), wherein the o-cresol formaldehyde epoxy resin has characteristics of high heat resistance, low moisture absorption, and low thermal expansion coefficient.
Description
Technical field
The present invention relates to a kind of preparation method of high softening-point o-cresol formaldehyde epoxy resin.
Background technology
The high softening-point o-cresol formaldehyde epoxy resin is that a kind of emphasis is applied to that environment-friendly electronic is sealed, high heat-resisting, the features type epoxy resin that hangs down moisture absorption, low thermal coefficient of expansion of IC encapsulation, circuit card (green oil) usefulness.It is different from the LV o-cresol formaldehyde epoxy resin, and because of its molecular weight is bigger, long-chain is prone to curl, and the increase of the space steric effect of ortho position methyl, makes epoxy group(ing) be grafted to phenolic hydroxyl group and produces difficulty, and epoxy equivalent (weight) rises thereupon.When being devoted to improve the EOCN softening temperature, the present invention keeps lower epoxy equivalent (weight) and hydrolyzable chlorine.
In the prior art; Japanese Patent JP6153317 provides a kind of linear o-cresol formaldehyde resin and epoxy chloropropane in the presence of solvent and PTC catalyzer, to add the alkaline solution etherificate; Prepare the method for o-cresol formaldehyde epoxy resin; But in reaction process, system is very easily emulsification under the effect of PTC, and PTC valency height causes production cost high.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high softening-point o-cresol formaldehyde epoxy resin.
The objective of the invention is to realize like this: concrete technical scheme is: a kind of preparation method of high softening-point o-cresol formaldehyde epoxy resin is characterized in that: comprise following two steps:
1. the preparation of the linear o-cresol formaldehyde resin of high softening-point:
Under normal pressure, be raw material with ortho-cresol and Paraformaldehyde 96, proportioning raw materials is 1.01～1.5 (molar content ratios), is 80～120 ℃ in temperature, reaction 3～10h under the katalysis of catalyzer obtains the linear o-cresol formaldehyde resin of high softening-point through aftertreatment;
2. the preparation of high softening-point o-cresol formaldehyde epoxy resin:
Is that 1:3～1:10 mixes back adding auxiliary agent with linear o-cresol formaldehyde resin of the 1. described high softening-point of step and epoxy chloropropane by mass ratio; Under the protection of high pure nitrogen; Add basic catalyst in the time of 30～100 ℃ and carry out etherification reaction 1～5h, under vacuum tightness 0.01～0.1MPa, add basic catalyst then and carry out catalysis ring-closure reaction 2～7h, reacted back intensification dehydration at 35～80 ℃; Reclaim epoxy chloropropane; The dissolution with solvents that adds 1～6 times of o-cresol formaldehyde resin quality then, when 60～90 ℃ of temperature, refining reaction 2～7h.Desolventizing gets product after washing to neutrality.
The catalyzer of step of the present invention described in 1. is one or more of phosphoric acid, oxalic acid, acetate, hydrochloric acid, sulfuric acid, tosic acid, and the solids content of said catalyzer is 0.1～10% of a said ortho-cresol weight.
The postprocessing working procedures of step of the present invention described in 1. is the solubilizing agent dissolving, and washing is to neutral, and desolventizing gets product then.The desolventizing mode adopts wet distillation.
Solvent for use of the present invention is one or more in toluene, YLENE, pimelinketone, the MIBK.
Step according to the invention auxiliary agent 2. is a kind of of ethers or alcohols, and amount of auxiliary is 0.05～1% of an o-cresol formaldehyde resin.
The basic catalyst of step according to the invention in 2. is one or more of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate of concentration 30～50%.
The solids content of the basic catalyst that etherification reaction according to the invention is used be step 2. described in the o-cresol formaldehyde resin content 0.01～1%.
The solids content that adds the used alkali of base catalysis ring-closure reaction of the present invention be step 2. described in the o-cresol formaldehyde resin content 35～60%.
Step according to the invention has reclaimed behind the epoxy chloropropane dissolution with solvents of 1～6 times of adding o-cresol formaldehyde resin quality in the crude resin in 2., 60～90 ℃ of refining reaction temperature, and the reaction times is 2～7h.
The invention has the advantages that: the product softening temperature that this method is made is high; It is 80～95 ℃; Epoxy equivalent (weight) is low, and below 200g/eq, hydrolyzable chlorine is low; Below 50ppm, even if the PCB that adopts the resistance solder paste China ink of this production of resins to apply also can keep its good electrical insulation properties in the environment of high temperature, humidity.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1:
Under the normal pressure, in the four-hole bottle that has stirring, TM, prolong, add ortho-cresol 128g, Paraformaldehyde 96 30g; Be warmed up to 98 ℃, add phosphatase 11 0g, temperature of reaction is controlled at 98 ℃; Behind the reaction 6h; Add toluene 200mL dissolving, add the pure water washing, take the mode desolventizing of wet distillation to obtain high softening-point o-cresol formaldehyde rosin products to neutral; Then 60g high softening-point o-cresol formaldehyde resin and 370g epoxy chloropropane are joined in the 1L four-hole boiling flask that has stirring, TM, prolong; Add glycol dimethyl ether 0.1g; Under the protection of high pure nitrogen, add the 1g30% sodium hydrogen carbonate solution in the time of 40 ℃ and carry out etherification reaction, under vacuum tightness 0.03MPa, add 30g50% sodium hydroxide solution catalysis ring-closure reaction behind the 2h; Reclaim epoxy chloropropane behind the reaction 6h; Add the dissolving of 200g toluene then,, add the refining 3h of 4g20% sodium hydroxide solution 65 ℃ of temperature.Refining reaction finishes the back and adds the pure water washing to neutral, and desolventizing gets product 75.5g.
Product index is following: softening temperature: 82 ℃, and epoxy equivalent (weight): 198.4g/ep, organochlorine: 44ppm, inorganic chlorine: 4ppm, viscosity (150 ℃): 1273cp, fugitive constituent: 0.05%.
Embodiment 2:
Under the normal pressure, in the four-hole bottle that has stirring, TM, prolong, add ortho-cresol 118g, Paraformaldehyde 96 30g; Be warmed up to 100 ℃, add acetate 15g, temperature of reaction is controlled at 100 ℃; Behind the reaction 10h; Add YLENE 200mL dissolving, add the pure water washing, take the mode desolventizing of wet distillation to obtain high softening-point o-cresol formaldehyde rosin products to neutral; Then 60g high softening-point o-cresol formaldehyde resin and 280g epoxy chloropropane are joined in the 1L four-hole boiling flask that has stirring, TM, prolong; Add Virahol 0.2g; Under the protection of high pure nitrogen, add the 2g30% sodium hydrogen carbonate solution in the time of 80 ℃ and carry out etherification reaction, under vacuum tightness 0.03MPa, add 40g45% sodium hydroxide solution catalysis ring-closure reaction behind the 2h; Reclaim epoxy chloropropane behind the reaction 4h; Add the 200g xylene soluble then,, add the refining 4.5h of 2g20% potassium hydroxide solution 78 ℃ of temperature.Refining reaction finishes the back and adds the pure water washing to neutral, and desolventizing gets product 82g.
Product index is following: softening temperature: 85.1 ℃, and epoxy equivalent (weight): 197g/ep, organochlorine: 50ppm, inorganic chlorine: do not have viscosity (150 ℃): 1892cp, fugitive constituent: 0.02%.
Embodiment 3:
Under the normal pressure, in the four-hole bottle that has stirring, TM, prolong, add ortho-cresol 122g, Paraformaldehyde 96 30g; Be warmed up to 110 ℃, add hydrochloric acid 5g, temperature of reaction is controlled at 110 ℃; Behind the reaction 4h; Add YLENE 200mL dissolving, add the pure water washing, take the mode desolventizing of wet distillation to obtain high softening-point o-cresol formaldehyde rosin products to neutral; Then 60g high softening-point o-cresol formaldehyde resin and 300g epoxy chloropropane are joined in the 1L four-hole boiling flask that has stirring, TM, prolong; Add 1,4-dioxane 0.05g is under the protection of high pure nitrogen; Add the 1g30% sodium hydrogen carbonate solution in the time of 55 ℃ and carry out etherification reaction; Under vacuum tightness 0.03MPa, add 50g30% potassium hydroxide solution catalysis ring-closure reaction behind the 2h, reclaim epoxy chloropropane behind the reaction 5h, add the dissolving of 200g pimelinketone then; 82 ℃ of temperature, add the refining 4h of 11g10% sodium carbonate solution.Refining reaction finishes the back and adds the pure water washing to neutral, and desolventizing gets product 78.2g.
Product index is following: softening temperature: 87 ℃, and epoxy equivalent (weight): 198g/ep, organochlorine: 33ppm, inorganic chlorine: 2ppm, viscosity (150 ℃): 2325cp, fugitive constituent: 0.04%.
Embodiment 4:
Under the normal pressure, in the four-hole bottle that has stirring, TM, prolong, add ortho-cresol 114g, Paraformaldehyde 96 30g; Be warmed up to 95 ℃, add oxalic acid 15g, temperature of reaction is controlled at 95 ℃; Behind the reaction 5h; Add pimelinketone 200mL dissolving, add the pure water washing, take the mode desolventizing of wet distillation to obtain high softening-point o-cresol formaldehyde rosin products to neutral; Then 60g high softening-point o-cresol formaldehyde resin and 460g epoxy chloropropane are joined in the 1L four-hole boiling flask that has stirring, TM, prolong; Add polyoxyethylene glycol 0.4g; Under the protection of high pure nitrogen, add the 1g30% sodium hydrogen carbonate solution in the time of 72 ℃ and carry out etherification reaction, under vacuum tightness 0.03MPa, add 38g60% sodium carbonate solution catalysis ring-closure reaction behind the 2h; Reclaim epoxy chloropropane behind the reaction 7h; Add the dissolving of 200g pimelinketone then,, add the refining 6h of 22g25% sodium hydrogen carbonate solution 92 ℃ of temperature.Refining reaction finishes the back and adds the pure water washing to neutral, and desolventizing gets product 85.5g.
Product index is following: softening temperature: 91.2 ℃, and epoxy equivalent (weight): 199g/ep, organochlorine: 48ppm, inorganic chlorine: 5ppm, viscosity (150 ℃): 3743cp, fugitive constituent: 0.02%.
Embodiment 5:
Under the normal pressure, in the four-hole bottle that has stirring, TM, prolong, add ortho-cresol 110g, Paraformaldehyde 96 30g; Be warmed up to 105 ℃, add tosic acid 1g, temperature of reaction is controlled at 105 ℃; Behind the reaction 2h; Add MIBK 200mL dissolving, add the pure water washing, take the mode desolventizing of wet distillation to obtain high softening-point o-cresol formaldehyde rosin products to neutral; Then 60g high softening-point o-cresol formaldehyde resin and 450g epoxy chloropropane are joined in the 1L four-hole boiling flask that has stirring, TM, prolong; Add propylene glycol monomethyl ether 0.6g; Under the protection of high pure nitrogen, add the 1g30% sodium hydrogen carbonate solution in the time of 45 ℃ and carry out etherification reaction, under vacuum tightness 0.03MPa, add 42g55% potassium hydroxide solution catalysis ring-closure reaction behind the 2h; Reclaim epoxy chloropropane behind the reaction 2h; Add the dissolving of 200g MIBK then,, add the refining 5h of 25g5% sodium hydroxide solution 87 ℃ of temperature.Refining reaction finishes the back and adds the pure water washing to neutral, and desolventizing gets product 79.3g.
Product index is following: softening temperature: 94.4 ℃, and epoxy equivalent (weight): 199g/ep, organochlorine: 49ppm, inorganic chlorine: 4ppm, viscosity (150 ℃): 4296cp, fugitive constituent: 0.05%.
Claims (8)
1. the preparation method of a high softening-point o-cresol formaldehyde epoxy resin is characterized in that: comprise following two steps:
The preparation of the linear o-cresol formaldehyde resin of
high softening-point:
Under normal pressure, be raw material with ortho-cresol and Paraformaldehyde 96, proportioning raw materials is 1.01～1.5 (molar content ratios), is 80～120 ℃ in temperature, reaction 3～10h under the katalysis of catalyzer obtains the linear o-cresol formaldehyde resin of high softening-point through aftertreatment;
The preparation of
high softening-point o-cresol formaldehyde epoxy resin:
Is that 1:3～1:10 mixes back adding auxiliary agent with linear o-cresol formaldehyde resin of the described high softening-point of step
and epoxy chloropropane by mass ratio; Under the protection of high pure nitrogen; Add basic catalyst in the time of 30～100 ℃ and carry out etherification reaction 1～5h; Under vacuum tightness 0.01～0.1MPa, add basic catalyst then and carry out catalysis ring-closure reaction 2～7h at 35～80 ℃; Reacted back intensification dehydration; Reclaim epoxy chloropropane, add the dissolution with solvents of 1～6 times of o-cresol formaldehyde resin quality then, when 60～90 ℃ of temperature; Refining reaction 2～7h, desolventizing gets product after washing to neutrality.
2. method according to claim 1; It is characterized in that: the catalyzer described in the step
is one or more of phosphoric acid, oxalic acid, acetate, hydrochloric acid, sulfuric acid, tosic acid, and the solids content of said catalyzer is 0.1～10% of a said ortho-cresol weight.
3. method according to claim 1; It is characterized in that: the postprocessing working procedures described in the step
is the solubilizing agent dissolving; Washing is to neutral, and desolventizing gets product then; The desolventizing mode adopts wet distillation.
4. method according to claim 1 is characterized in that: solvent for use is one or more in toluene, YLENE, pimelinketone, the MIBK.
5. method according to claim 1; It is characterized in that: the auxiliary agent described in the step
is a kind of of ethers or alcohols, and amount of auxiliary is 0.05～1% of an o-cresol formaldehyde resin.
6. method according to claim 1 is characterized in that: described in the step
basic catalyst be one or more of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate of concentration 30～50%.
7. method according to claim 1 is characterized in that: the solids content of the basic catalyst that said etherification reaction is used is 0.01～1% of an o-cresol formaldehyde resin content described in the step
.
8. method according to claim 1 is characterized in that: the said solids content that adds the used alkali of base catalysis ring-closure reaction is 35～60% of an o-cresol formaldehyde resin content described in the step
.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788341A (en) * | 2014-01-26 | 2014-05-14 | 江西省飓风化工有限公司 | Preparation method of o-cresol formaldehyde epoxy resin |
| CN106478905A (en) * | 2016-11-23 | 2017-03-08 | 西安元创化工科技股份有限公司 | A kind of preparation method of the o-cresol-formaldehyde resin of without sewage discharge |
| CN108102075A (en) * | 2018-01-24 | 2018-06-01 | 山东莱芜润达新材料有限公司 | A kind of preparation method of low chlorophenol formaldehyde epoxy resin |
| CN108250408A (en) * | 2017-01-15 | 2018-07-06 | 杨记 | A kind of synthesis for hydrogenating phenol aldehyde type epoxy resin preparation method and applications resin |
| CN108948301A (en) * | 2017-05-25 | 2018-12-07 | 宁夏共享化工有限公司 | A kind of modification triethylamine cold box resin that moisture resistance is good and its production method |
| CN112979922A (en) * | 2021-03-09 | 2021-06-18 | 福建准信新材料有限公司 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121772A (en) * | 2006-08-09 | 2008-02-13 | 中国石油化工集团公司 | Method for preparing line-type o-cresol novolac resin |
| CN101121775A (en) * | 2006-08-09 | 2008-02-13 | 中国石油化工集团公司 | Method for preparing line-type o-cresol novolac epoxy resin |
-
2011
- 2011-06-24 CN CN2011101720909A patent/CN102838727A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121772A (en) * | 2006-08-09 | 2008-02-13 | 中国石油化工集团公司 | Method for preparing line-type o-cresol novolac resin |
| CN101121775A (en) * | 2006-08-09 | 2008-02-13 | 中国石油化工集团公司 | Method for preparing line-type o-cresol novolac epoxy resin |
Non-Patent Citations (2)
| Title |
|---|
| 《合成树脂及塑料》 19950815 史子瑾等 "OCN树脂的分子量与ECN树脂性能的关系" 第43-45，34页 1-8 第12卷, 第3期 * |
| 史子瑾等: ""OCN树脂的分子量与ECN树脂性能的关系"", 《合成树脂及塑料》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788341A (en) * | 2014-01-26 | 2014-05-14 | 江西省飓风化工有限公司 | Preparation method of o-cresol formaldehyde epoxy resin |
| CN103788341B (en) * | 2014-01-26 | 2015-08-12 | 江西省飓风化工有限公司 | The preparation method of o-cresol formaldehyde epoxy resin |
| CN106478905A (en) * | 2016-11-23 | 2017-03-08 | 西安元创化工科技股份有限公司 | A kind of preparation method of the o-cresol-formaldehyde resin of without sewage discharge |
| CN108250408A (en) * | 2017-01-15 | 2018-07-06 | 杨记 | A kind of synthesis for hydrogenating phenol aldehyde type epoxy resin preparation method and applications resin |
| CN108948301A (en) * | 2017-05-25 | 2018-12-07 | 宁夏共享化工有限公司 | A kind of modification triethylamine cold box resin that moisture resistance is good and its production method |
| CN108948301B (en) * | 2017-05-25 | 2022-02-18 | 宁夏共享化工有限公司 | Modified triethylamine cold core box resin with good moisture resistance and production method thereof |
| CN108102075A (en) * | 2018-01-24 | 2018-06-01 | 山东莱芜润达新材料有限公司 | A kind of preparation method of low chlorophenol formaldehyde epoxy resin |
| CN112979922A (en) * | 2021-03-09 | 2021-06-18 | 福建准信新材料有限公司 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
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Application publication date: 20121226 |