CN102276776B - Production method of butylated bisphenol A formaldehyde resin - Google Patents
Production method of butylated bisphenol A formaldehyde resin Download PDFInfo
- Publication number
- CN102276776B CN102276776B CN 201110179468 CN201110179468A CN102276776B CN 102276776 B CN102276776 B CN 102276776B CN 201110179468 CN201110179468 CN 201110179468 CN 201110179468 A CN201110179468 A CN 201110179468A CN 102276776 B CN102276776 B CN 102276776B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- production method
- dihydroxyphenyl propane
- alkanol
- bisphenol
- 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.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a production method of butylated bisphenol A formaldehyde resin. The method comprises the following steps: (1) performing a methylolation reaction between bisphenol A and formaldehyde in the molar ratio of 1:(1.5-6) for 1 to 8 hours at the temperature of between 40 and 55 DEG C in the presence of a base catalyst; (2) heating the material after the reaction in the step (1) to the temperature of between 60 and 80 DEG C, maintaining the temperature for 1 to 8 hours until the weight-average molecular weight is between 300 and 1100, regulating the pH value to be neutral, and adding formaldehyde scavenger to remove free formaldehyde; and (3) adding alkanol into the mixed material in the step (2) to perform an etherification reaction for 4 to 26 hours at the temperature of between 80 and 110 DEG C when the pH value is between 4 and 6.5, wherein the dosage of the alkanol is 1 to 5 times the weight of bisphenol A; and reducing pressure and distilling to obtain the butylated bisphenol A formaldehyde resin. The free aldehyde content of the butylated bisphenol A formaldehyde resin prepared by the method is less than 0.1 percent, and the content of free bisphenol A is 0, so that harm to a human body is reduced, and the resin can be used as a paint for the inner wall of a can.
Description
Technical field
The present invention relates to the process for preparing resins technical field, especially a kind of synthetic resins for can lining enamel---the production method of alkanol etherificate dihydroxyphenyl propane formaldehyde resin.
Background technology
Food cans inwall major part needs coating protection; the purpose of coating is to make Foods or drinks not directly and the tank metal layer contacting; prevent Foods or drinks and metal electrochemical corrosion; such as the acid etching of acidic food or the sulphur corrosion of sulfur-bearing food etc., with quality index such as the health that guarantees Foods or drinks, quality, color and luster, local flavor, quality guaranteed perioves.
China succeeded in developing epoxy novolac type inner-wall paint first from 1969, filming of it (is golden yellow through high bake after 200～210 ℃/10～12min), have excellent resist chemical performance and machining property, be applicable to the cans such as meat, vegetables, fruit and nectar.The synthetic main principles of chemistry of this class coating are macromolecule epoxy resin and heat-reactive phenolic resin copolycondensation crosslinking reaction, usually addition-condensation under base catalysis makes heat-reactive phenolic resin by phenol and formaldehyde, contain methylol and butoxy and hydroxyl on the resol phenyl ring, when the hydroxyl on methylol and butoxy and the Resins, epoxy carried out the copolycondensation crosslinking reaction, phenolic hydroxyl group played katalysis.
In order to make the tendency of good intermiscibility, solubleness and reduction resol self polycondensation of thermosetting resin acquisition and Resins, epoxy, just need to carry out in advance etherificate.Can carry out in the material of crosslinking curing with Resins, epoxy at all, Resins, epoxy with best through the formed film performance of resol crosslinking curing of butanol etherification, corrosion resistance is the strongest.
Using the butanol etherification resol resin, mainly is in order to improve the solvability of resin in solvent.Etherificate mechanism is mutually to slough 1 molecular water between the methylol in butanols and the resol, forms butylated phenolic resin.Butylated phenolic resin dissolves in the aromatic solvent, paint film acidproof, water tolerance is better, needs high bake dry.General and oily or other synthetic resins share, the lacquer good corrosion resistance that makes like this, and paint film is pliable and tough.
But the problem of producing now the etherification of phenolic resin existence is: have free aldehyde and free dihydroxyphenyl propane in the resin.Free aldehyde damages healthy, and contaminate environment.Free dihydroxyphenyl propane can cause endocrine disturbance, threatens fetus and children's growth.
Summary of the invention
The present invention is directed to deficiency, propose a kind of production method of alkanol etherificate dihydroxyphenyl propane formaldehyde resin, the resin Free Aldehyde content that is synthesized＜0.1%, the content of free dihydroxyphenyl propane is 0, has reduced the harm to the person.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of production method of alkanol etherificate dihydroxyphenyl propane formaldehyde resin may further comprise the steps:
1., in the presence of basic catalyst, dihydroxyphenyl propane and formaldehyde 1: 1.5 in molar ratio～6 carries out hydroxymethylation 1h～8h under 40 ℃～55 ℃;
2., the 1. reacted material to 60 of heating step ℃～80 ℃, keep 1h～8h, to weight-average molecular weight be 300～1100; Adjust pH adds formaldehyde-trapping agent and removes free formaldehyde to neutral;
3., 2. add alkanol in the compound to step, the alkanol consumption is 1～5 times of dihydroxyphenyl propane weight, is 4～6.5,80 ℃～110 ℃ in the pH value etherification reaction 4h～26h occur; Underpressure distillation gets alkanol etherificate dihydroxyphenyl propane formaldehyde resin;
Described step 3. middle alkanol is selected from butanols, Pentyl alcohol, methyl alcohol or ethanol.
Preferably, 1. the reaction times is 1h～4h to step.
Preferably, step 1. in mol ratio be 1: 2～4.
Preferably, step 1. the neutral and alkali catalyzer be selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium basic carbonate, triethylamine, Trimethylamine 99, trolamine, diethanolamine.
Preferably, step 1. the mol ratio of neutral and alkali catalyzer and dihydroxyphenyl propane be 0.01～0.5: 1.
Preferably, step 2. in formaldehyde-trapping agent be ammoniacal liquor.
What preferably, step was regulated the pH value in 3. is oxalic acid, phosphoric acid, formic acid, acetic acid or sulfuric acid.
Compared with prior art, the production method of alkanol etherificate dihydroxyphenyl propane formaldehyde resin of the present invention, the proportioning of adjustment dihydroxyphenyl propane and formaldehyde makes the formaldehyde amount of substance excessive, thereby makes the dihydroxyphenyl propane complete reaction.Then adopt chemical process, remove unreacted free aldehyde in the system, content of free aldehyde＜0.1%(use hydroxyamine hydrochloride is detected), the content of free dihydroxyphenyl propane is that 0(uses vapor-phase chromatography to detect), thereby minimizing is to the harm of the person.
Embodiment
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
In the 2000ml four-hole bottle, add the 350g dihydroxyphenyl propane, adding the formalin 303g(dihydroxyphenyl propane of 38% concentration and the mol ratio of formaldehyde is 1:2.5), stir the lower sodium hydroxide solution 24.5g that adds 25% concentration, temperature rises to 40 ℃, and then constant temperature 4h rises to 65 ℃ of temperature, constant temperature 4h, add 50% sulfuric acid 15g, in and sodium hydroxide, stir 15min.The ammoniacal liquor 80g that adds 20% concentration removes unreacted free aldehyde, stirs for some time, and static layering is removed upper water.Add the 1050g propyl carbinol, stir the lower phosphoric acid that adds 85% concentration, adjust PH5.5, rise to 100 ℃ of constant temperature 15h.Then underpressure distillation is 60% etherificate dihydroxyphenyl propane formaldehyde resin admittedly contain.Detect by GPC, weight-average molecular weight 2150, the free dihydroxyphenyl propane of gas chromatographic detection is 0, detecting free aldehyde by hydroxyamine hydrochloride is 0.05%.NMR detects 80% methylol by butanol etherification.
Embodiment 2
In the 2000ml four-hole bottle, add the 350g dihydroxyphenyl propane, adding the formalin 460.5g(dihydroxyphenyl propane of 38% concentration and the mol ratio of formaldehyde is 1:3.8), stir the lower sodium hydroxide solution 24.5g that adds 25% concentration, temperature rises to 40 ℃, and then constant temperature 3h rises to 65 ℃ of temperature, constant temperature 6h, add 50% sulfuric acid 15g, in and sodium hydroxide, stir 15min.The ammoniacal liquor 100g that adds 20% concentration removes unreacted free aldehyde, stirs for some time, and static layering is removed upper water.Add the 1400g propyl carbinol, stir the lower phosphoric acid that adds 85% concentration, adjusting PH is 6, rises to 100 ℃ of constant temperature 16h.Then underpressure distillation is 65% etherificate dihydroxyphenyl propane formaldehyde resin admittedly contain.Detect by GPC, weight-average molecular weight 1700, the free dihydroxyphenyl propane of gas chromatographic detection is 0, detecting free aldehyde by hydroxyamine hydrochloride is 0.03%.NMR detects 88% methylol by butanol etherification.
Embodiment 3
In the 2000ml four-hole bottle, add the 350g dihydroxyphenyl propane, adding the formalin 703.5g(dihydroxyphenyl propane of 38% concentration and the mol ratio of formaldehyde is 1:5.8), stir the lower sodium hydroxide solution 26.5g that adds 25% concentration, temperature rises to 40 ℃, then constant temperature 6h rises to 75 ℃ of temperature, constant temperature 3h, add in 50% the sulfuric acid and sodium hydroxide, stir 15min.The ammoniacal liquor 100g that adds 20% concentration removes unreacted free aldehyde, stirs for some time, and static layering is removed upper water.Add the 1800g propyl carbinol, stir the lower acetic acid that adds 85% concentration, adjusting pH is 4.5, rises to 90 ℃ of constant temperature 24h.Then underpressure distillation is 65% etherificate dihydroxyphenyl propane formaldehyde resin admittedly contain.
Detect by GPC, the weight-average molecular weight of this etherificate dihydroxyphenyl propane formaldehyde resin is 1700, and the free dihydroxyphenyl propane of gas chromatographic detection is 0, and detecting free aldehyde by hydroxyamine hydrochloride is 0.02%.NMR detects 90% methylol by butanol etherification.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. the production method of an alkanol etherificate dihydroxyphenyl propane formaldehyde resin may further comprise the steps:
1., in the presence of basic catalyst, dihydroxyphenyl propane and formaldehyde 1: 1.5 in molar ratio～6 carries out hydroxymethylation 1h～8h under 40 ℃～55 ℃;
2., the 1. reacted material to 60 of heating step ℃～80 ℃, keep 1h～8h, to weight-average molecular weight be 300～1100; Adjust pH adds formaldehyde-trapping agent and removes free formaldehyde to neutral;
3., 2. add alkanol in the compound to step, the alkanol consumption is 1～5 times of dihydroxyphenyl propane weight, is 4～6.5,80 ℃～110 ℃ in the pH value etherification reaction 4h～26h occur; Underpressure distillation gets alkanol etherificate dihydroxyphenyl propane formaldehyde resin;
Described step 3. middle alkanol is selected from butanols, Pentyl alcohol, methyl alcohol or ethanol.
2. production method as claimed in claim 1, it is characterized in that: 1. the reaction times is 1h～4h to step.
3. production method as claimed in claim 1 is characterized in that: step 1. in mol ratio be 1: 2～4.
4. production method as claimed in claim 1, it is characterized in that: step 1. neutral and alkali catalyzer is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium basic carbonate, triethylamine, Trimethylamine 99, trolamine, diethanolamine.
5. such as claim 1 or 4 described production methods, it is characterized in that: the step 1. mol ratio of neutral and alkali catalyzer and dihydroxyphenyl propane is 0.01～0.5: 1.
6. production method as claimed in claim 1 is characterized in that: step 2. in formaldehyde-trapping agent be ammoniacal liquor.
7. production method as claimed in claim 1 is characterized in that: what step was regulated pH value in 3. is oxalic acid, phosphoric acid, formic acid, acetic acid or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110179468 CN102276776B (en) | 2011-06-29 | 2011-06-29 | Production method of butylated bisphenol A formaldehyde resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110179468 CN102276776B (en) | 2011-06-29 | 2011-06-29 | Production method of butylated bisphenol A formaldehyde resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276776A CN102276776A (en) | 2011-12-14 |
| CN102276776B true CN102276776B (en) | 2013-01-16 |
Family
ID=45102549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110179468 Active CN102276776B (en) | 2011-06-29 | 2011-06-29 | Production method of butylated bisphenol A formaldehyde resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276776B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012704B (en) * | 2011-12-31 | 2014-08-13 | 柯美达（北京）科技有限公司 | Preparation method of toughening thermoset phenolic resin |
| CN108276539A (en) * | 2017-12-27 | 2018-07-13 | 可隆化工（苏州）有限公司 | A kind of preparation method of bisphenol-f type butanol etherification phenolic aldehyde |
| CN111299497A (en) * | 2020-04-01 | 2020-06-19 | 山东莱芜润达新材料有限公司 | Curing agent of precoated sand binder and preparation method thereof |
| 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 |
|---|---|---|---|---|
| CN1175969A (en) * | 1995-01-25 | 1998-03-11 | 佐治亚-太平洋树脂公司 | Aqueous phenolic resin dispersions |
| CN101611107A (en) * | 2007-02-22 | 2009-12-23 | 氰特特种表面技术奥地利有限公司 | Be used for the coating composition that contains resol that can applies |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3301236B2 (en) * | 1993-11-19 | 2002-07-15 | 花王株式会社 | Binder composition for mold and method for producing mold |
-
2011
- 2011-06-29 CN CN 201110179468 patent/CN102276776B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175969A (en) * | 1995-01-25 | 1998-03-11 | 佐治亚-太平洋树脂公司 | Aqueous phenolic resin dispersions |
| CN101611107A (en) * | 2007-02-22 | 2009-12-23 | 氰特特种表面技术奥地利有限公司 | Be used for the coating composition that contains resol that can applies |
Non-Patent Citations (3)
| Title |
|---|
| 李桂林."食品罐用涂料".《环氧树脂与环氧涂料》.2003,第502－504页. |
| 李桂林."食品罐用涂料".《环氧树脂与环氧涂料》.2003,第502-504页. * |
| 郑易安等.环氧改性新型双酚A酚醛树脂的研制.《材料保护》.2005,第38卷(第12期),第51-53页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276776A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102276776B (en) | Production method of butylated bisphenol A formaldehyde resin | |
| CN102137880B (en) | Novolac and epoxy resin composition | |
| CN102153717A (en) | Fluorine-containing novolac resin and preparation method and application of fluorine-containing novolac resin | |
| JP5513747B2 (en) | NOVOLAC RESIN AND PROCESS FOR PRODUCING THE SAME | |
| JP5417981B2 (en) | Coating composition and coated can using the same | |
| CN103897125A (en) | Method for preparing thermosetting phenol resin | |
| Fan et al. | On the structure and cure acceleration of phenol–urea–formaldehyde resins with different catalysts | |
| US4368299A (en) | Epoxy resin compositions | |
| CN104788634A (en) | Preparation method of high-temperature-resistant modified sulfonated phenol formaldehyde resin for drilling fluids | |
| JPWO2011118147A1 (en) | Solid resol type phenolic resin and process for producing the same | |
| CN105001386B (en) | High-activity phenolic compound modified expandable phenolic resin and preparation method thereof | |
| JP5581046B2 (en) | Method for producing novolac resin and novolac resin | |
| JP2007031527A (en) | Naphthol resin and its manufacturing process | |
| CN106750067A (en) | A kind of preparation method of lignin Cardanol Modified PF Resin | |
| CN102161740A (en) | Preparation method phenolic resin | |
| CN116355162A (en) | Modified bisphenol A type butanol etherified phenolic resin and preparation method and application thereof | |
| CN106916059A (en) | A kind of method that multi-sulfonic catalysis of functional ionic liquid prepares raspberry ketone | |
| CN110194825A (en) | A kind of modified low nitrogen furan resin and production technology | |
| CN106750066A (en) | A kind of preparation method of the phenolic resin of modified by cardanol | |
| JP4362891B2 (en) | Metacresol resin composition for paint | |
| JP5532675B2 (en) | Resol-type phenolic resin and method for producing the same | |
| JP2005097429A (en) | Method for producing phenol novolac resin | |
| JP3926034B2 (en) | Resin synthesis method | |
| JP2005162963A (en) | Alkali-resolized novolac-type phenol resin and manufacturing method thereof | |
| CN104119500A (en) | Epoxy-resin curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 250204 chemical industry park, Diao Town, Ji'nan, Shandong, Zhangqiu Patentee after: SHANDONG SHENGQUAN NEW MATERIAL CO., LTD. Address before: 250204 chemical industry park, Diao Town, Ji'nan, Shandong, Zhangqiu Patentee before: Shandong Shengquan Chemical Industry Co., Ltd. |