阅读说明：本技术 ***化阻燃密胺树脂的生产 (The production of the fire-retardant melamine resin of etherization ) 是由 李平 王文武 唐琼 张志轩 于 2018-05-23 设计创作，主要内容包括：乙醚化阻燃密胺树脂的生产,包括：乙醚化三羟甲基三聚氰胺；酸性条件下直接吸附反应脱除甲醛；以及添加增效阻燃剂。根据本发明的阻燃密胺树脂无论在甲醛含量还是阻燃性能等方面均十分优异,适合用于多种常规涂料,水溶性好且成本低。(The production of the fire-retardant melamine resin of etherization, comprising: ether trimethylol melamine；Direct adsorption reaction removes formaldehyde under acid condition；And addition synergistic flame retardants.Fire-retardant melamine resin according to the present invention no matter content of formaldehyde or in terms of it is very excellent, suitable for a variety of conventional coating, good water solubility and at low cost.)

1. a kind of production method of flame-retarded resin, comprising:

1) ethyl alcohol and trimethylol melamine is added in etherifying reactor, so that mole of trimethylol melamine and ethyl alcohol Than for 1:(4~6)；

It 2) is 50 DEG C~70 DEG C by the control of reaction solution temperature, pH value is adjusted to 3~5, reacts 0.5~1 hour；

3) by the reaction solution after etherification reaction by filter, wherein filter is equipped with diatomite, and diatomite is coated with 2,4- Dinitrobenzene；

4) reaction solution pH after filtering is adjusted to 8~9；

5) fire retardant is added in reaction solution, wherein the mass ratio of fire retardant and the trimethylol melamine of above-mentioned addition is 1%~5%；

6) 100 DEG C or so are warming up to, or so half an hour is stirred to react；And

7) to above-mentioned reaction solution dealcoholysis 0.5~3h of dehydration at 75~95 DEG C of temperature and vacuum condition, to be hindered Fire resin.

2. production method according to claim 1, wherein fire retardant group becomes (mass percent): silica: 60~65%； Aluminium hydroxide: 10~15%；Antimony oxide: 20~25%.

3. production method according to claim 1, wherein the granularity of diatomite is 60~80 mesh, bulk density is 0.45~ 0.5g/ml, specific surface area are 4~5m²/g。

4. production method according to claim 3, wherein every kilogram of diatomite coats 10~15mg2,4- dinitrobenzene.

5. a kind of flame-retarded resin is produced according to the method for one of the claims 1-4.

Technical field

The present invention relates to the environmental protection productions of flame-retarded resin.

Background technique

Etherified amino resins are synthesized using melamine such as hexamethylolmelamine or trimethylol melamine etc. It is known technology in this field, may refer to the patent or patent application CN 103739563B, CN before applicant 103739803B, CN103709111B, CN 105968283A, CN105968281A, CN105968282A and

CN106008870A, herein also to introduce entire contents in a manner of.But these prior arts are generally existing The problems such as content of formaldehyde is higher, anti-flammability is insufficient.

Summary of the invention

The object of the present invention is to provide a kind of production methods of flame-retarded resin, can at least overcome the above-mentioned prior art to mention And certain defect.

The production method of flame-retarded resin according to the present invention, comprising:

1) ethyl alcohol and trimethylol melamine is added in etherifying reactor, so that trimethylol melamine and ethyl alcohol Molar ratio is 1:(4~6)；

It 2) is 50 DEG C~70 DEG C by the control of reaction solution temperature, pH value is adjusted to 3~5, reacts 0.5~1 hour；

3) by the reaction solution after etherification reaction by filter, wherein filter is equipped with diatomite, and diatomite is coated with 2,4- dinitrobenzene；

4) reaction solution pH after filtering is adjusted to 8~9；

5) fire retardant is added in reaction solution, wherein the quality of fire retardant and the trimethylol melamine of above-mentioned addition Than being 1%~5%；

6) 100 DEG C or so are warming up to, or so half an hour is stirred to react；And

7) to above-mentioned reaction solution dealcoholysis 0.5~3h of dehydration at 75~95 DEG C of temperature and vacuum condition, thus To flame-retarded resin.

According to the present invention, fire retardant group becomes (mass percent): silica: 60~65%；Aluminium hydroxide: 10~ 15%；Antimony oxide: 20~25%.It can be silica that fire retardant, which preferably constitutes: 65%；Aluminium hydroxide: 15%；Three oxygen Change two antimony: 20%.

Fire retardant of the invention, silica especially contained therein can be with the melamine of remaining a small amount of in raw material Amine generates synergistic effect, to reach highly effective flame-retardant purpose.In addition, this fire retardant also is compliant with more due to being halogen-free flame retardants The environmental requirement of kind application.

According to the invention, it is further possible to include: to be added after fire retardant in step 5), continue to add a small amount of melamine Acid, the mass ratio with the trimethylol melamine of above-mentioned addition are 0.1%~0.5%.By the cyanuric acid being added Also can react generation melamine cyanurate with melamine a small amount of existing in above-mentioned reaction solution, thus can be added Fire retardant be formed together synergy halogen-free flame retardants so that the flame retardant effect of resin of the invention significantly increase it is (such as reachable UL94V-0 grades horizontal).

According to a particular embodiment of the invention, the granularity of diatomite is 60~80 mesh, and bulk density is 0.45~0.5g/ Ml, specific surface area are 4~5m²/g。

Preferred embodiment in accordance with the present invention, every kilogram of diatomite can coat 10~15mg2,4- dinitrobenzene.It can be with Diatomite is coated using the methylene chloride saturated solution of 2,4- dinitrobenzene.

The present invention by completing after being etherified directly by reaction solution by being filled with above-mentioned diatomite in acid condition Filter, so as to convert extra formaldehyde to stable formaldehyde hydrazone, to essentially eliminate the free formaldehyde in product.

The present invention also by be added in reaction solution fire retardant and/or cyanuric acid with a small amount of trimerization for wherein containing Cyanamide generates synergistic effect, to significantly enhance its flame retardant effect.

The present invention, by suitable raw material proportioning and reaction condition, is obtained using trimethylol melamine and ethyl alcohol as raw material Obtained ether melamine resin (or " amino resins ").This ethyl alcohol etherified amino resins can be used for a variety of conventional coating, water Dissolubility is good and at low cost.

Specific embodiment

The present invention is further illustrated combined with specific embodiments below, it will be understood by those skilled in the art that being described below Embodiment be intended merely to more fully understand and implement the present invention, not be used to any restrictions are made to the present invention.

Etherificate

Ethyl alcohol and trimethylol melamine is added in etherifying reactor, so that trimethylol melamine and ethyl alcohol rub You are than being 1:(4~6) left and right.The trimethylol melamine being wherein added be using melamine and equivalent of formaldehyde (such as The molar ratio of melamine and formaldehyde is 1:3 or so) it is prepared under weak basic condition；Its preparation process also can be found in application Above-mentioned patent or patent application before people, are not described in detail herein.

It is 50 DEG C~70 DEG C by the control of reaction solution temperature, preferably 60 DEG C or so, pH value adjusts (such as using hydrochloric acid) It is 3~5, preferably 4 or so, reacts 30~60 minutes, preferably 50 minutes or so.

Formaldehyde removal

Etherification reaction solution is directly passed through into (tubular type) filter.Wherein diatom of the filling Jing Guo coating processing in filter Soil.

The granularity of diatomite is 60~80 mesh, and bulk density is 0.45~0.5g/ml, and specific surface area is 4~5m²/g。

The dissolution of 2,4- dinitrobenzene is constituted into saturated solution in methylene chloride, is then coated with diatomite, coated weight is every Kilogram diatomite coats 10~15mg 2,4- dinitrobenzene.

It is adjusted by means of the acidity of etherification reaction solution, free formaldehyde contained therein is in the silicon by containing above-mentioned processing Stable formaldehyde hydrazone can be converted to when the filter of diatomaceous earth, to realize efficient, the economic removal of formaldehyde.

Flame retardant treatment

Reaction solution pH (such as using sodium hydroxide) after filtering is adjusted to 8~9；Resistance is added in reaction solution again Agent is fired, wherein the mass ratio of fire retardant and the trimethylol melamine of above-mentioned addition is 1%~5%；It is warming up to 100 DEG C of left sides The right side is stirred to react or so half an hour.

Wherein fire retardant composition is preferably (mass percent): silica: 65%；Aluminium hydroxide: 15%；Three oxidations two Antimony: 20%.

Furthermore it is also possible to it is optionally added cyanuric acid again, the mass ratio with the trimethylol melamine of above-mentioned addition It is 0.1%~0.5%.

Post-processing

To above-mentioned reaction solution dealcoholysis dehydration 0.5 under 75~95 DEG C of temperature (preferably 80 DEG C or so) and vacuum condition ~3h (preferably 2h or so), to obtain flame-retarded resin.

Flame-retarded resin produced according to the present invention, no matter content of formaldehyde (sample detection content be less than 2mg/100g), Flame retardant property (sample detection reaches UL94V-0 grades of levels) etc. is very excellent；It is water-soluble suitable for a variety of conventional coating Property it is good and at low cost.