阅读说明：本技术 一种羟乙基腰果酚封端三聚氰胺甲醛树脂的制备方法 (A kind of preparation method of ethoxy anacardol sealing end melamine resin ) 是由 顾奇 斯鑫磊 褚昭宁 于 2019-08-20 设计创作，主要内容包括：本发明公开了一种羟乙基腰果酚封端三聚氰胺甲醛树脂的制备方法,它将1-6份羟乙基腰果酚、0.5-5份多聚甲醛和0.8-1.3份的三聚氰胺混合并于60-100℃温度、pH值为9-14下搅拌0.5-3小时,随后加入0-4份羟乙基腰果酚于70-80℃温度搅拌0-3小时后,再加入1-4份羟乙基腰果酚,加酸调节pH=3-7、搅拌降温至40-80℃且搅拌0.5-3小时后,加碱调节pH=7-10,再减压蒸馏除去反应产生的甲醛和水轻组分,所得蒸馏后料液中加入1-7份羟乙基腰果酚,加酸调节pH=1-5,于40-70℃保温搅拌0.3-1小时,再加碱调节pH=7-11,减压蒸馏除去反应产生的甲醛和水轻组分,蒸馏后的产品搅拌保温至70~90℃并加入0-4份的溶剂后,出料。本发明的羟乙基腰果酚作为反应物参与反应并作为反应液相溶剂,反应后余留的羟乙基腰果酚无需分离,有效减少VOC排放。(The invention discloses a kind of preparation methods of ethoxy anacardol sealing end melamine resin, it is by 1-6 parts of ethoxy anacardols, 0.5-5 parts of paraformaldehydes and 0.8-1.3 parts of melamine, which mix, is incorporated in 60-100 DEG C of temperature, pH value is to stir 0.5-3 hours under 9-14, 0-4 parts of ethoxy anacardols are then added after 70-80 DEG C of temperature stirs 0-3 hours, add 1-4 parts of ethoxy anacardols, add acid for adjusting pH=3-7, after stirring is cooled to 40-80 DEG C and stirring 0.5-3 hours, alkali is added to adjust pH=7-10, it is evaporated under reduced pressure the formaldehyde generated except dereaction and water light component again, 1-7 parts of ethoxy anacardols are added in feed liquid after gained distillation, add acid for adjusting pH=1-5, in 40-70 DEG C of insulated and stirred 0 .3-1 hour, then plus alkali adjust pH=7-11, vacuum distillation except dereaction generate formaldehyde and water light component, after distillation product stirring heat preservation to 70 ~ 90 DEG C and after 0-4 part of solvent is added, discharge.For ethoxy anacardol of the invention as reactant participation reaction and as reaction liquid phase solvent, the ethoxy anacardol remained after reaction effectively reduces VOC emission without separating.)

1. a kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that by weight, packet Include following steps:

1) 1-6 parts of ethoxy anacardols, 0.5-5 parts of paraformaldehydes and 0.8-1.3 parts of melamine are put into the reactor, are stirred It mixes after being warming up to 60-100 DEG C plus alkali adjusts pH value to 9-14, insulated and stirred 0.5-3 hours；

2) 0-4 parts of ethoxy anacardols are then added, at a temperature of 70-80 DEG C after insulated and stirred 0-3 hours, add 1-4 parts Ethoxy anacardol adds acid for adjusting pH value to 3-7, is stirred for being cooled to 40-80 DEG C, and insulated and stirred 0.5-3 hours；

3) after step 2 insulated and stirred, alkali is added to adjust pH value to 7-10, then be evaporated under reduced pressure the first for removing and being stirred to react generation Aldehyde and water light component, feed liquid after being distilled；

4) 1-7 parts of ethoxy anacardols are added in feed liquid after distillation obtained by step 3), add acid for adjusting pH value to 1-5, in 40-70 DEG C Lower insulated and stirred 0.3-1 hours, then plus alkali adjusts pH value to 7-11, then be evaporated under reduced pressure remove the formaldehyde for being stirred to react generation and Water light component, the product stirring heat preservation after distillation is to 70 ~ 90 DEG C and after being added 0-4 parts of solvent, discharging.

2. a kind of preparation method of ethoxy anacardol sealing end melamine resin as described in claim 1, feature It is in step 4), the solvent is n-butanol, isobutanol, isopropanol, methanol or dimethylbenzene.

3. a kind of preparation method of ethoxy anacardol sealing end melamine resin as described in claim 1, feature Being that step 1), step 3) or step 4) adjust the alkali that pH value is added is inorganic alkali solution, and the inorganic alkali solution is hydrogen-oxygen Change the aqueous solution of sodium or sodium carbonate.

4. a kind of preparation method of ethoxy anacardol sealing end melamine resin as claimed in claim 3, feature It is that the inorganic alkali solution is sodium hydrate aqueous solution, the mass concentration of the sodium hydrate aqueous solution is 40 ~ 55%, preferably It is 48%.

5. a kind of preparation method of ethoxy anacardol sealing end melamine resin as described in claim 1, feature Being that step 2 or step 4) adjust the acid that pH value is added is inorganic acid solution, and the inorganic acid solution is the concentrated sulfuric acid or dense salt Acid, the mass concentration of the concentrated sulfuric acid are 95% ~ 98%, the concentration 36% ~ 38% of the concentrated hydrochloric acid.

6. a kind of preparation method of ethoxy anacardol sealing end melamine resin as described in claim 1, feature It is in step 3), the temperature of vacuum distillation is 70 ~ 130 DEG C, and the pressure of vacuum distillation is 90 mmHg or less.

7. a kind of preparation method of ethoxy anacardol sealing end melamine resin as described in claim 1, feature It is in step 4), the temperature of vacuum distillation is 80 ~ 150 DEG C, and the pressure of vacuum distillation is 70 mmHg or less.

Technical field

The present invention relates to a kind of preparation methods of ethoxy anacardol sealing end melamine resin.

Background technique

Existing melamine resin carries out sealing end etherification method, principal monomer structure using substances such as methanol Are as follows:

Existing melamine resin high polymer design feature and sealing end methyl-etherified are as follows:

Existing methyl-etherified melamine resin, capping reagent such as methanol used in technique, can generate a large amount of first The recovered liquid of alcohol, formaldehyde, recovered liquid are difficult to directly use, and need to purify by rectifying column, and production and recovered liquid purify generation Methanol steam is inflammable and explosive, pollute environment, recovered liquid can still be generated after repeatedly purifying it is liquid and waste slag produced etc., secondly, in resin system The organic solvent used, in resin film forming drying process, volatile quantity is big, easily endangers environment, and organic gas is inflammable and explosive, There is some potential safety problems.

Summary of the invention

For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of ethoxy anacardol envelopes Hold the preparation method of melamine resin.

The preparation method of a kind of ethoxy anacardol sealing end melamine resin, it is characterised in that by weight Part meter, comprising the following steps:

1) 1-6 parts of ethoxy anacardols, 0.5-5 parts of paraformaldehydes and 0.8-1.3 parts of melamine are put into the reactor, are stirred It mixes after being warming up to 60-100 DEG C plus alkali adjusts pH value to 9-14, insulated and stirred 0.5-3 hours；

2) 0-4 parts of ethoxy anacardols are then added, at a temperature of 70-80 DEG C after insulated and stirred 0-3 hours, add 1-4 parts Ethoxy anacardol adds acid for adjusting pH value to 3-7, is stirred for being cooled to 40-80 DEG C, and insulated and stirred 0.5-3 hours；

3) after step 2 insulated and stirred, alkali is added to adjust pH value to 7-10, then be evaporated under reduced pressure the first for removing and being stirred to react generation Aldehyde and water light component, feed liquid after being distilled；

4) 1-7 parts of ethoxy anacardols are added in feed liquid after distillation obtained by step 3), add acid for adjusting pH value to 1-5, in 40-70 DEG C Lower insulated and stirred 0.3-1 hours, then plus alkali adjusts pH value to 7-11, then be evaporated under reduced pressure remove the formaldehyde for being stirred to react generation and Water light component, the product stirring heat preservation after distillation is to 70 ~ 90 DEG C and after being added 0-4 parts of solvent, discharging.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that step 4) In, the solvent is n-butanol, isobutanol, isopropanol, methanol or dimethylbenzene.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that step 1) it is inorganic alkali solution that, step 3) or step 4), which adjust the alkali that pH value is added, and the inorganic alkali solution is sodium hydroxide or carbon The aqueous solution of sour sodium.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that the nothing Machine aqueous slkali is sodium hydrate aqueous solution, and the mass concentration of the sodium hydrate aqueous solution is 40 ~ 55%, preferably 48%.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that step 2 Or step 4) adjust pH value be added acid be inorganic acid solution, the inorganic acid solution be the concentrated sulfuric acid or concentrated hydrochloric acid, it is described dense The mass concentration of sulfuric acid is 95% ~ 98%, the concentration 36% ~ 38% of the concentrated hydrochloric acid.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that step 3) In, the temperature of vacuum distillation is 70 ~ 130 DEG C, and the pressure of vacuum distillation is 90 mmHg or less.

A kind of preparation method of ethoxy anacardol sealing end melamine resin, it is characterised in that step 4) In, the temperature of vacuum distillation is 80 ~ 150 DEG C, and the pressure of vacuum distillation is 70 mmHg or less.

Compared with prior art, the beneficial effect that the present invention obtains is:

1) the etherified sealed end object used in the present invention is ethoxy anacardol, is a kind of new structure.The present invention uses ethoxy waist Fruit phenol introduces anacardol design feature as sealing end, and ethoxy anacardol is produced via anacardol phenolic group modified Object, anacardol are a kind of pale yellow oily liquids made of being refined in natural cashew nut shell oil, and anacardol is with its special change It learns structure and also has the following characteristics that containing benzene ring structure, there is high temperature resistance；Polar hydroxyl can provide system to contact surface Wetting and activity；Carbon 15 straight chain of the meta position containing unsaturated double-bond, can provide system good toughness, excellent hydrophobicity and hypotonic Permeability and from stemness, ethoxy anacardol structure are as follows:

2) by the present invention in that use ethoxy anacardol simultaneously as reaction system liquid phase and end-capping reagent, can directly avoid using Organic solvent bring risk, environmental hazard and recycling and reusing cost, i.e. ethoxy anacardol can replace or part replaces now There is the organic solvent that technology uses, and ethoxy anacardol itself is used as non-activated thinner, toughener, can effectively reduce into Consumption of organic solvent in product resin, improves resin property, and ethoxy anacardol etherified sealed end of the present invention is multisection type.

3) ethoxy anacardol is the liquid phase for being used as reaction system, and participates in reacting as reactant, remaining after reaction The ethoxy anacardol stayed can be used as non-activated thinner and replace or partially replace organic solvent, effectively reduce VOC without separation Discharge.

4) present invention is prepared for the melamine resin of ethoxy anacardol etherified sealed end, by the spy of cashew nut phenolic group Point, and its etherificate structure, while there is the performance of hydrophilic and oleophilic, and the modification of cashew nut phenolic group can effectively improve the soft of resin paint film Toughness, impact resistance, and solidification temperature is reduced to a certain extent, reduce energy consumption, chemical-resistance is improved, in industrial paint, vapour Vehicle paint has a unique use in field.Ethoxy anacardol oneself viscosity is low simultaneously, has certain dilution effect, solvent-free Product compared with traditional melamine resin, have the characteristics that extremely low VOC.

5) in the preparation process of ethoxy anacardol sealing end melamine resin of the present invention, being evaporated under reduced pressure twice is In order to remove the water of formaldehyde and reaction generation, carry out reaction towards positive direction.Ethoxy anacardol is added several times to trimerization Cyanamide formaldehyde resin carries out substep etherified sealed end, this is because the reaction carries out more difficulty, therefore need to be reacted step by step.Subtract Pressure distillation process adjusts pH and autohemagglutination occurs to prevent product in the vacuum distillation process of higher temperature to alkalinity.

Specific embodiment

The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.

In following embodiment, paraformaldehyde is selected from 92% paraformaldehyde, is purchased from Changchun chemical industry (Taiwan) company.