CN102276776A - Production method of butylated bisphenol A formaldehyde resin - Google Patents
Production method of butylated bisphenol A formaldehyde resin Download PDFInfo
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- CN102276776A CN102276776A CN 201110179468 CN201110179468A CN102276776A CN 102276776 A CN102276776 A CN 102276776A CN 201110179468 CN201110179468 CN 201110179468 CN 201110179468 A CN201110179468 A CN 201110179468A CN 102276776 A CN102276776 A CN 102276776A
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- formaldehyde
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- dihydroxyphenyl propane
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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 that is used for can lining enamel---the production method of butanol etherification dihydroxyphenyl propane formaldehyde resin.
Background technology
Food cans inwall major part needs coating protection; the purpose of coating is to make the direct and jar metal layer contacting of Foods or drinks; prevent Foods or drinks and metal generation galvanic corrosion; 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 cans such as meat, vegetables, fruit and nectar.The main principles of chemistry of this class coating synthetic 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 carry out etherificate in advance.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 to slough 1 molecular water mutually 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 the high bake drying.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 the etherification of phenolic resin existence now 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 butanol etherification dihydroxyphenyl propane formaldehyde resin, free aldehyde＜0.1% in institute's synthetic resin, 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 butanol etherification 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, 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 take place to step; Underpressure distillation gets butanol etherification dihydroxyphenyl propane formaldehyde resin.
Preferably, 1. the reaction times is 1h～4h to step.
Preferably, the 1. middle mol ratio of step is 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, the 2. middle formaldehyde-trapping agent of step is an ammoniacal liquor.
Preferably, the 1. middle formaldehyde of step is Paraformaldehyde 96, phenyl aldehyde or crotonic aldehyde.
Preferably, the 3. middle alkanol of step is selected from butanols, Pentyl alcohol, methyl alcohol or ethanol.
Preferably, the compound adding alkanol after the 3. middle underpressure distillation of step is regulated its solid content.
Preferably, the 3. middle adjusting pH of step value is oxalic acid, phosphoric acid, formic acid, acetic acid or sulfuric acid.
Compared with prior art, the production method of butanol etherification 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.Adopt chemical process then, remove unreacted free aldehyde in the system, make content of free aldehyde＜0.1% (using the oxammonium hydrochloride method to detect), the content of free dihydroxyphenyl propane is 0 (using vapor-phase chromatography to detect), thereby reduces the harm to 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, the formalin 303g (mol ratio of dihydroxyphenyl propane and formaldehyde is 1: 2.5) that adds 38% concentration, stir the sodium hydroxide solution 24.5g that adds 25% concentration down, temperature rises to 40 ℃, and constant temperature 4h rises to 65 ℃ of temperature then, 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 phosphoric acid that adds 85% concentration down, adjust PH5.5, rise to 100 ℃ of constant temperature 15h.Underpressure distillation then 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 the oxammonium hydrochloride method is 0.05%.NMR detects 80% methylol by butanol etherification.
Embodiment 2
In the 2000ml four-hole bottle, add the 350g dihydroxyphenyl propane, the formalin 460.5g (mol ratio of dihydroxyphenyl propane and formaldehyde is 1: 3.8) that adds 38% concentration, stir the sodium hydroxide solution 24.5g that adds 25% concentration down, temperature rises to 40 ℃, and constant temperature 3h rises to 65 ℃ of temperature then, 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 phosphoric acid that adds 85% concentration down, adjusting PH is 6, rises to 100 ℃ of constant temperature 16h.Underpressure distillation then 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 the oxammonium hydrochloride method is 0.03%.NMR detects 88% methylol by butanol etherification.
Embodiment 3
In the 2000ml four-hole bottle, add the 350g dihydroxyphenyl propane, the formalin 703.5g (mol ratio of dihydroxyphenyl propane and formaldehyde is 1: 5.8) that adds 38% concentration, stir the sodium hydroxide solution 26.5g that adds 25% concentration down, temperature rises to 40 ℃, constant temperature 6h rises to 75 ℃ of temperature, constant temperature 3h then, 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 acetic acid that adds 85% concentration down, adjusting pH is 4.5, rises to 90 ℃ of constant temperature 24h.Underpressure distillation then 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 the oxammonium hydrochloride method 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 (10)
1. the production method of a butanol etherification 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, 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 take place to step; Underpressure distillation gets butanol etherification dihydroxyphenyl propane formaldehyde resin.
2. production method as claimed in claim 1 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: the 1. middle mol ratio of step is 1: 2～4.
4. production method as claimed in claim 1 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. 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: the 2. middle formaldehyde-trapping agent of step is an ammoniacal liquor.
7. production method as claimed in claim 1 is characterized in that: the 1. middle formaldehyde of step is Paraformaldehyde 96, phenyl aldehyde or crotonic aldehyde.
8. as claim 1 or 7 described production methods, it is characterized in that: the 3. middle alkanol of step is selected from butanols, Pentyl alcohol, methyl alcohol or ethanol.
9. production method as claimed in claim 1 is characterized in that: the compound after the 3. middle underpressure distillation of step adds alkanol and regulates its solid content.
10. 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.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110179468 CN102276776B (en) | 2011-06-29 | 2011-06-29 | Production method of butylated bisphenol A formaldehyde resin |
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| CN 201110179468 CN102276776B (en) | 2011-06-29 | 2011-06-29 | Production method of butylated bisphenol A formaldehyde resin |
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| CN102276776A true CN102276776A (en) | 2011-12-14 |
| CN102276776B CN102276776B (en) | 2013-01-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012704A (en) * | 2011-12-31 | 2013-04-03 | 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07185731A (en) * | 1993-11-19 | 1995-07-25 | Kao Corp | Binder composition for casting mold and production of casting mold |
| 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 |
-
2011
- 2011-06-29 CN CN 201110179468 patent/CN102276776B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07185731A (en) * | 1993-11-19 | 1995-07-25 | Kao Corp | Binder composition for casting mold and production of casting mold |
| 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 (2)
| Title |
|---|
| 《材料保护》 20051231 郑易安等 环氧改性新型双酚A酚醛树脂的研制 第51-53页 1-10 第38卷, 第12期 * |
| 《环氧树脂与环氧涂料》 20030331 李桂林 "食品罐用涂料" 第502－504页 1－10 , * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012704A (en) * | 2011-12-31 | 2013-04-03 | 柯美达（北京）科技有限公司 | Preparation method of toughening thermoset phenolic resin |
| 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 |
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| CN102276776B (en) | 2013-01-16 |
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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. |
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