CN108276539A - A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde - Google Patents
A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde Download PDFInfo
- Publication number
- CN108276539A CN108276539A CN201711441309.4A CN201711441309A CN108276539A CN 108276539 A CN108276539 A CN 108276539A CN 201711441309 A CN201711441309 A CN 201711441309A CN 108276539 A CN108276539 A CN 108276539A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- butanol
- preparation
- phenolic aldehyde
- etherification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to the preparation field of resin more particularly to a kind of preparation methods of bisphenol-f type butanol etherification phenolic aldehyde；Include the following steps：1. Bisphenol F and formaldehyde in molar ratio 1:3~6 feed intake, and stirring is warming up to 60~90 DEG C, until being completely dissolved to material, then it is cooled to 40~50 DEG C and 2. puts into basic catalyst at 50 DEG C or less, control temperature carries out hydroxymethylation at 50~70 DEG C, 2~7h is reacted, until content of formaldehyde is down to 6.0~11%；3. carrying out vacuum dehydration, control vacuum degree is in 50Torr hereinafter, dehydration is to 60 DEG C；4. putting into butanol, it is 4.0~6.0 to be adjusted with acid pH, and butanol etherification reaction is carried out at 90~110 DEG C；5. being washed after the completion of etherification reaction, 50~65 DEG C are heated to, stratification；6. carrying out vacuum dehydration to oil phase, moisture and free formaldehyde are removed, then physical property is adjusted with butanol；The preparation method of the bisphenol-f type butanol etherification phenolic aldehyde of the present invention can prepare one kind and be harmful to human health, and to resin that the adhesive property of inside coating, chemical resistance all greatly improve.
Description
Technical field
The present invention relates to process for preparing resins technical field, especially a kind of bisphenol-f type butanol in food coating
It is etherified the preparation method of phenolic aldehyde.
Background technology
With the raising of Consciousness of food security, food service industry wants bisphenol-A in filling coating and formaldehyde monomers residual quantity
Ask more stringent, according to existing synthesis technology, it is difficult to the residual quantity of bisphenol-A and formaldehyde monomers be reduced simultaneously, generally for drop
Low content of bisphenol A, needs the dosage for increasing formaldehyde, remaining a large amount of formaldehyde in body is expected after hydroxymethylation, using ammonium hydroxide
The mode of absorption is difficult to detach totally, and the formaldehyde remained in material body has very high reactivity with ammonium hydroxide condensation polymer, right
The etherification reaction of next step causes very big interference, and resin gel may be caused when serious, if reducing formaldehyde dosage, in resin
Content of bisphenol A will increase, and be unable to reach the code requirement of food service industry.
Currently used is bisphenol A-type butylated phenolic resin, is disclosed to resin in patent CN102276776A
Formula and technique, synthesis technology be divided into two steps：It is anti-to be first that bisphenol-A carries out under base catalyst methylolation with formaldehyde
Answer, then neutralized, stratification, upper water separation etc.；Second step is that butanol is added to carry out etherification reaction in acid condition,
Then it is evaporated under reduced pressure to obtain resin.In order to reduce content of free aldehyde in resin, in and when suitable ammonium hydroxide is added to first
Aldehyde is absorbed, these aldehyde ammonia conjugates are dissolved in water phase, are discharged when water detaches；However butanol made from the Patent design
The higher problem of free formaldehyde content present in etherified resin, is easy to cause in resin etherification procedure and the risk of gel occurs.
In view of the above shortcomings, the designer, is actively subject to research and innovation, it is a kind of safe and harmless to found, and
There is the preparation side of the bisphenol-f type butanol etherification phenolic aldehyde greatly improved to adhesive property, the chemical resistance of inside coating
Method makes it with more the utility value in industry.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide one kind to be not only harmful to human health, but also internally
Adhesive property, the chemical resistance of wall coating have the preparation method of the bisphenol-f type butanol etherification phenolic aldehyde greatly improved.
The present invention provides a kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde, including：
1. Bisphenol F and formaldehyde in molar ratio 1:3~6 feed intake, and stirring is warming up to 60~90 DEG C of dissolvings, maintains 0.5~2h extremely
Material is completely dissolved, and is then cooled to 40~50 DEG C；
2. putting into basic catalyst at 50 DEG C or less, control temperature carries out 2~7h of hydroxymethylation at 50~70 DEG C, until
Content of formaldehyde is down to 6.0~11%；
3. carrying out vacuum dehydration, control vacuum degree is in 50Torr hereinafter, dehydration is to 60 DEG C；
4. putting into butanol into the material of step 3., butanol dosage is 1~3 times of Bisphenol F dosage, with inorganic acid for adjusting pH
It is 4.0~6.0, being flowed back by azeotropic at 90~110 DEG C carries out butanol etherification reaction, and the etherification reaction time is 6~20h；
5. water is added after the completion of etherification reaction to be washed, be heated to 55~65 DEG C, stratification, separation lower layer's water phase and
Lower layer's oil phase；
6. to step 5. in oil phase carry out vacuum dehydration, remove moisture and free formaldehyde, then physical property is adjusted with butanol.
Further, 1. middle Bisphenol F and the molar ratio of formaldehyde are 1 to the step:3.5~5.5.
Further, the step 2. in basic catalyst be selected from sodium hydroxide, potassium hydroxide or sodium carbonate.
Further, the step 2. in basic catalyst and Bisphenol F weight ratio be 0.02~0.06:1.
Further, 2. middle hydroxymethylation temperature is 50~65 DEG C to the step, and the reaction time is 3~6h.
Further, the step 2. in after the completion of hydroxymethylation, free formaldehyde content is controlled 6.0~9.0%
Between.
Further, the step 3. in vacuum dehydration vacuum degree be 30~80Torr.
Further, the step 4. in pH adjustings inorganic acid be one kind in sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid or
Person is a variety of.
Further, 4. the middle butanol etherification reaction time is 8~15h to the step.
Further, the step 6. in the vacuum degree of vacuum dehydration be 30~80Torr, temperature is 60~70 DEG C..
According to the above aspect of the present invention, the present invention has at least the following advantages：1) compared with prior art, bisphenol-f type fourth of the present invention
Etherified phenolic resin and preparation method thereof replaces bisphenol-A using Bisphenol F, is avoided from source bisphenol-A raw material introducing painting
Layer, is fully achieved quality requirements of the food service industry to inside coating；2) free formaldehyde present in butoxy resin is contained
Higher problem is measured, by the technique washed after etherification reaction, free formaldehyde in resin, Er Qieke can not only be removed
To remove the salinity in resin, play the role of cleansed resin, the butoxy resin prepared using the present invention is not only strong to human body
Health is harmless, has to adhesive property, the chemical resistance of inside coating and greatly improves.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after coordinating attached drawing to be described in detail such as.
Description of the drawings
Fig. 1 is the GPC spectrograms of resin in the embodiment of the present invention one；
Fig. 2 be the present invention comparative example one in resin GPC spectrograms；
Fig. 3 is the GPC spectrograms of resin in the embodiment of the present invention two；
Fig. 4 be the present invention comparative example two in resin GPC spectrograms.
Specific implementation mode
With reference to the accompanying drawings and examples, the specific implementation mode of the present invention is described in further detail.Implement below
Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment one
Referring to Fig. 1,500g Bisphenol Fs are added in 3000mL four-hole boiling flasks, the formaldehyde 766.9g of 44% content is heated to 80
DEG C, 40 DEG C are cooled to after being completely dissolved hereinafter, 50% sodium hydroxide 20g of input, is warming up to 60 DEG C, starts to sample after constant temperature 4hr
Free formaldehyde content is detected, is cooled when reaching 7.0~9.0%, vacuum dehydration is carried out at 50 DEG C or less, in 40~60Torr
Dehydrated under vacuum is added 700g butanol, stirs evenly to 55~60 DEG C, is 4.5~5.5 with 25% sulphur acid for adjusting pH, heats up, protects
Material is held in normal pressure azeotropic reflux state, butanol etherification reaction is carried out, maintains back flow reaction 10hr, 500g water is added and carries out water
It washes, adjusts temperature at 55~60 DEG C, stratification removes the water phase of lower layer, and the resin solution on upper layer is evaporated in vacuo,
It is warming up to 60~65 DEG C under 40~60Torr vacuum, stops vacuum, the solid content that resin is adjusted with butanol is 65%, is prepared
The GPC spectrograms of resin sample are Fig. 1.
Comparative example one
Referring to Fig. 2,500g bisphenol-As are added in 3000mL four-hole boiling flasks, the formaldehyde 672.7g of 44% content is heated to 80
DEG C, 40 DEG C are cooled to after being completely dissolved hereinafter, 50% sodium hydroxide 20g of input, is warming up to 60 DEG C, starts to sample after constant temperature 4hr
Free formaldehyde content is detected, is cooled when reaching 7.0~9.0%, vacuum dehydration is carried out at 50 DEG C or less, in 40~60Torr
Dehydrated under vacuum is added 700g butanol, stirs evenly to 55~60 DEG C, is 4.5~5.5 with 25% sulphur acid for adjusting pH, heats up, protects
Material is held in normal pressure azeotropic reflux state, butanol etherification reaction is carried out, maintains back flow reaction 10hr, 500g water is added and carries out water
It washes, adjusts temperature at 55~60 DEG C, stratification removes the water phase of lower layer, and the resin solution on upper layer is evaporated in vacuo,
It is warming up to 60~65 DEG C under 40~60Torr vacuum, stops vacuum, the solid content that resin is adjusted with butanol is 65%, is prepared
The GPC spectrograms of resin sample are Fig. 2.
Embodiment two
Referring to Fig. 3,500g Bisphenol Fs are added in 3000mL four-hole boiling flasks, the formaldehyde 596.5g of 44% content is heated to 80
DEG C, 40 DEG C are cooled to after being completely dissolved hereinafter, 50% sodium hydroxide 25g of input, is warming up to 60 DEG C, starts to sample after constant temperature 4hr
Free formaldehyde content is detected, is cooled when reaching 6.0~8.0%, vacuum dehydration is carried out at 50 DEG C or less, in 40~60Torr
Dehydrated under vacuum is added 700g butanol, stirs evenly to 55~60 DEG C, is 4.5~5.5 with 85% phosphorus acid for adjusting pH, heats up, protects
Material is held in normal pressure azeotropic reflux state, butanol etherification reaction is carried out, maintains back flow reaction 10hr, 500g water is added and carries out water
It washes, adjusts temperature at 55~60 DEG C, stratification removes the water phase of lower layer, and the resin solution on upper layer is evaporated in vacuo,
It is warming up to 60~65 DEG C under 40~60Torr vacuum, stops vacuum, the solid content that resin is adjusted with butanol is 65%, is prepared
Resin sample GPC spectrograms be Fig. 3.
Comparing embodiment two
Referring to Fig. 4,500g bisphenol-As are added in 3000mL four-hole boiling flasks, the formaldehyde 523.2g of 44% content is heated to 80
DEG C, 40 DEG C are cooled to after being completely dissolved hereinafter, 50% sodium hydroxide 25g of input, is warming up to 60 DEG C, starts to sample after constant temperature 4hr
Free formaldehyde content is detected, is cooled when reaching 6.0~8.0%, vacuum dehydration is carried out at 50 DEG C or less, in 40~60Torr
Dehydrated under vacuum is added 700g butanol, stirs evenly to 55~60 DEG C, is 4.5~5.5 with 85% phosphorus acid for adjusting pH, heats up, protects
Material is held in normal pressure azeotropic reflux state, butanol etherification reaction is carried out, maintains back flow reaction 10hr, 500g water is added and carries out water
It washes, adjusts temperature at 55~60 DEG C, stratification removes the water phase of lower layer, and the resin solution on upper layer is evaporated in vacuo,
It is warming up to 60~65 DEG C under 40~60Torr vacuum, stops vacuum, the solid content that resin is adjusted with butanol is 65%, is prepared
Resin sample GPC spectrograms be Fig. 4.
It should be noted that the formaldehyde in above-described embodiment is the formalin that content is 35~50%, when washing
Water be 1~3 times of Bisphenol F or bisphenol-A, in this manner it is ensured that while the dosage of formaldehyde, avoid causing resin gel
Glue, and free formaldehyde is removed using washing process, the bisphenol-f type butanol etherification for the code requirement for meeting food service industry is prepared
Phenolic aldehyde.
The fingers such as viscosity, free formaldehyde content, bisphenol A monomer content are detected respectively to the sample in aforementioned four embodiment
Mark, and by GPC spectrum analysis, molecular resin numerical quantity is obtained, the comparative analysis of the above detection data has been listed in Table 1 below.
The measurement data of resin sample in 1 four embodiments of table
| Embodiment one | Comparing embodiment one | Embodiment two | Comparing embodiment two | |
| Solid content, % | 65.2 | 65.1 | 65.4 | 65.3 |
| Viscosity, cps | 189 | 245 | 213 | 279 |
| Free formaldehyde content, % | 0.41 | 0.48 | 0.22 | 0.27 |
| Bisphenol A monomer content, % | 0 | 0.37 | 0 | 1.38 |
| Number-average molecular weight | 1027 | 1115 | 791 | 686 |
| Weight average molecular weight | 2723 | 2623 | 1180 | 1062 |
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde, which is characterized in that include the following steps：
1. Bisphenol F and formaldehyde in molar ratio 1:3~6 feed intake, and stirring is warming up to 60~90 DEG C of dissolvings, maintains 0.5~2h to material
It is completely dissolved, is then cooled to 40~50 DEG C；
2. putting into basic catalyst at 50 DEG C or less, control temperature carries out 2~7h of hydroxymethylation at 50~70 DEG C, until formaldehyde
Content is down to 6.0~11%；
3. carrying out vacuum dehydration, control vacuum degree is in 50Torr hereinafter, dehydration is to 60 DEG C；
4. putting into butanol into the material of step 3., butanol dosage is 1~3 times of Bisphenol F dosage, is with inorganic acid for adjusting pH
4.0~6.0, it is flowed back by azeotropic at 90~110 DEG C and carries out butanol etherification reaction, the etherification reaction time is 6~20h；
5. water is added after the completion of etherification reaction to be washed, 55~65 DEG C are heated to, stratification detaches lower layer's water phase and lower layer
Oil phase；
6. to step 5. in oil phase carry out vacuum dehydration, remove moisture and free formaldehyde, then physical property is adjusted with butanol.
2. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 1.
Middle Bisphenol F and the molar ratio of formaldehyde are 1:3.5~5.5.
3. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 2.
In basic catalyst be selected from sodium hydroxide, potassium hydroxide or sodium carbonate.
4. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 2.
In basic catalyst and Bisphenol F weight ratio be 0.02~0.06:1.
5. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 2.
Middle hydroxymethylation temperature is 50~65 DEG C, and the reaction time is 3~6h.
6. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 2.
After the completion of middle hydroxymethylation, free formaldehyde content controls between 6.0~9.0%.
7. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 3.
The vacuum degree of middle vacuum dehydration is 30~80Torr.
8. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 4.
The inorganic acid of middle pH adjustings is one or more of sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid.
9. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 4.
The middle butanol etherification reaction time is 8~15h.
10. the preparation method of bisphenol-f type butanol etherification phenolic aldehyde according to claim 1, it is characterised in that：The step is 6.
The vacuum degree of middle vacuum dehydration is 30~80Torr, and temperature is 60~70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711441309.4A CN108276539A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711441309.4A CN108276539A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108276539A true CN108276539A (en) | 2018-07-13 |
Family
ID=62802269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711441309.4A Pending CN108276539A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108276539A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4157324A (en) * | 1977-01-31 | 1979-06-05 | Monsanto Company | High ortho etherified resole resins admixed with coreactive resins |
| US4310653A (en) * | 1980-10-08 | 1982-01-12 | Desoto, Inc. | Production of monomeric etherified bisphenol-formaldehyde condensates |
| JPH02228314A (en) * | 1989-03-02 | 1990-09-11 | Kansai Paint Co Ltd | Preparation of phenol resin |
| CN1075723A (en) * | 1992-02-27 | 1993-09-01 | 三井东压化学株式会社 | The method for preparing Bisphenol F and novolak phenol resins simultaneously |
| CN101096403A (en) * | 2006-06-29 | 2008-01-02 | 西北工业大学 | Linetype bisphenol F phenolic resin and preparation method thereof |
| CN102276776A (en) * | 2011-06-29 | 2011-12-14 | 山东圣泉化工股份有限公司 | Production method of butylated bisphenol A formaldehyde resin |
| KR20120110540A (en) * | 2011-03-29 | 2012-10-10 | 현대제철 주식회사 | Phenol-formaldehyde resin and method of manufacturing phenol-formaldehyde resin |
-
2017
- 2017-12-27 CN CN201711441309.4A patent/CN108276539A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4157324A (en) * | 1977-01-31 | 1979-06-05 | Monsanto Company | High ortho etherified resole resins admixed with coreactive resins |
| US4310653A (en) * | 1980-10-08 | 1982-01-12 | Desoto, Inc. | Production of monomeric etherified bisphenol-formaldehyde condensates |
| JPH02228314A (en) * | 1989-03-02 | 1990-09-11 | Kansai Paint Co Ltd | Preparation of phenol resin |
| CN1075723A (en) * | 1992-02-27 | 1993-09-01 | 三井东压化学株式会社 | The method for preparing Bisphenol F and novolak phenol resins simultaneously |
| CN101096403A (en) * | 2006-06-29 | 2008-01-02 | 西北工业大学 | Linetype bisphenol F phenolic resin and preparation method thereof |
| KR20120110540A (en) * | 2011-03-29 | 2012-10-10 | 현대제철 주식회사 | Phenol-formaldehyde resin and method of manufacturing phenol-formaldehyde resin |
| CN102276776A (en) * | 2011-06-29 | 2011-12-14 | 山东圣泉化工股份有限公司 | Production method of butylated bisphenol A formaldehyde resin |
Non-Patent Citations (1)
| Title |
|---|
| 河北省环境科学学会编: "《环境与健康：河北省环境科学学会与健康论坛暨 2008年学术年会论文集》", 31 March 2009, 河北科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384936B (en) | A kind of preparation method of multi-vinyl silicone oil | |
| CN104231197B (en) | A kind of amino modified phenolic resin and preparation method thereof | |
| CN103626999A (en) | Industrial synthesis method of polyarylether sulfone resin | |
| CN108276539A (en) | A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde | |
| CN107522830A (en) | A kind of preparation method of dipping modified melamine-formaldehyde resin | |
| CN103087280B (en) | Method for synthesizing phenolic resins by using paraformaldehyde | |
| CN104774298B (en) | A kind of production technology of super Amino Group Resin Containing Low Free Formaldehyde | |
| CN103897125A (en) | Method for preparing thermosetting phenol resin | |
| CN111072462A (en) | Bio-based bisphenol monomer, bio-based epoxy resin, composite material of bio-based bisphenol monomer and bio-based epoxy resin and preparation method of composite material | |
| CN105330799B (en) | The preparation method of melamine, Cardanol Modified PF Resin | |
| CN102276776B (en) | Production method of butylated bisphenol A formaldehyde resin | |
| CN103183798A (en) | Method for producing phenolic resin, resin material, and method for producing resin molded material | |
| CN106366318A (en) | Production method of hydroxyl silicone oil | |
| CN102643400B (en) | Meta-xylene formaldehyde resin and producing method thereof | |
| CN209468358U (en) | A kind of de- low molecule device of methyl vinyl silicone rubber | |
| CN107151299B (en) | A kind of delicate fragrance type phenol-formaldehyde resin modified and preparation method thereof for sand casting | |
| CN111978499B (en) | Synthesis process of phenolic resin | |
| CN104130353A (en) | Method for synthesizing ternary-copolymerized super-absorbent resin | |
| CN116355162A (en) | Modified bisphenol A type butanol etherified phenolic resin and preparation method and application thereof | |
| CN101544714B (en) | Polymerization method of polyvinyl acetate with low polymerization degree | |
| CN101338028B (en) | Resorcinol resins and method for preparing resorcinol resins | |
| CN106186243B (en) | A kind of formaldehydeless cationic coagulant and its preparation method and application | |
| CN110894273A (en) | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof | |
| CN102516481B (en) | Method for preparing sand-coated phenolic resin | |
| CN110194825A (en) | A kind of modified low nitrogen furan resin and production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180713 |
|
| RJ01 | Rejection of invention patent application after publication |