阅读说明：本技术 一种亲水阻燃发泡树脂及其加工方法 (Hydrophilic flame-retardant foaming resin and processing method thereof ) 是由 焦正 刘立起 于 2021-01-30 设计创作，主要内容包括：本发明涉及一种亲水阻燃发泡树脂及其加工方法,其特征在于,其原料重量份数为：三聚氰胺为600～700份,多聚甲醛为300～400份,甲醛改性剂为12～20份,焦亚硫酸钠为30～40份,氢氧化钠为1～2份,脱盐水为380～410份,二甘醇胺为8～12份。本申请的特点在于：亲水亲油,能使发泡各组分快速乳化分散；树脂粘度65000Pa.s,有利于与乳化设备配合实现量产；引入二甘醇胺能使燃烧后烟密度降低；得到的泡沫韧性更佳,永久变形更小。(The invention relates to a hydrophilic flame-retardant foaming resin and a processing method thereof, which are characterized by comprising the following raw materials in parts by weight: 600-700 parts of melamine, 300-400 parts of paraformaldehyde, 12-20 parts of formaldehyde modifier, 30-40 parts of sodium metabisulfite, 1-2 parts of sodium hydroxide, 380-410 parts of desalted water and 8-12 parts of diglycolamine. The application is characterized in that: hydrophilic and oleophilic, and can quickly emulsify and disperse all foaming components; the viscosity of the resin is 65000Pa.s, which is beneficial to realizing mass production by matching with emulsification equipment; the introduction of diglycolamine can reduce the smoke density after combustion; the obtained foam has better toughness and smaller permanent deformation.)

1. The hydrophilic flame-retardant foaming resin is characterized by comprising the following raw materials in parts by weight:

2. the hydrophilic flame-retardant foaming resin according to claim 1, wherein the weight part of the paraformaldehyde is 320-380 parts.

3. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the weight part of the paraformaldehyde is 350 parts.

4. The hydrophilic flame-retardant foaming resin as claimed in claim 1, wherein the formaldehyde modifier is used in an amount of 14 to 18 parts by weight.

5. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the formaldehyde modifier is present in an amount of 16 parts by weight.

6. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the weight part of the sodium metabisulfite is 32 to 38 parts.

7. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the weight part of the sodium metabisulfite is 35 parts.

8. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the sodium hydroxide is present in an amount of 1.5 parts by weight.

9. The hydrophilic flame-retardant foamed resin according to claim 1, wherein the desalted water is present in an amount of 390 parts by weight.

10. The hydrophilic flame-retardant foaming resin according to claim 1, wherein the formaldehyde modifier is prepared by the following steps: 4, 4, 4-triamino triphenylamine and adipic acid are used as raw materials, N-dimethylacetamide is used as a solvent, phosphoric acid is used as a catalyst, and then the reaction is carried out at the temperature of 150-185 ℃ in a nitrogen atmosphere; and after reacting for 10-20 hours, cooling to normal temperature, adding methanol, filtering filter residues, and performing vacuum drying on the filter residues at 120 ℃ to obtain the required formaldehyde modifier.

Technical Field

The invention relates to the technical field of resin, in particular to hydrophilic flame-retardant foaming resin and a processing method thereof.

Background

In recent years, with the continuous upgrade of consumption level and the rapid development of high-performance decoration industry, the foaming resin industry has come to a high-speed development era, and various functional products have emerged endlessly. The Basotect melamine foam resin represented by BASF corporation has high elasticity, low heat conduction performance, extremely low volume density and excellent flame retardant performance, does not release mineral fibers in the processing process, has extremely wide application range, covers the fields of automobile manufacturing, aviation industry, railway shipping, heat insulation of heating, ventilation and air conditioning systems in buildings and the like, and is suitable for various railways and railway vehicles.

Chinese patent application No. 201610835366.X discloses a foamed resin and a preparation method thereof, cardanol, a catalyst and an aldehyde compound are sequentially added into a reaction kettle at a temperature of about 60-80 ℃ for reaction, acenaphthene type tetraphenylcyclopentadienone is added, the mixture is uniformly mixed by high-speed stirring, N2 is introduced for protection, the temperature is slowly increased to 80-100 ℃ at a temperature increase speed of 1-5 ℃/min, the mixture is stirred at a constant temperature for 1.5-2.5 hours, then the mixture is cooled to room temperature, acetic acid is used for neutralizing resin liquid, and then small molecules in the system are evaporated under reduced pressure until no liquid is discharged, so that viscous liquid, namely, the acenaphthene type polyphenyl copolymerized cardanol formaldehyde foamed resin is obtained. The method is mainly used for: the acenaphthene polyphenyl copolymerized cardanol formaldehyde foaming resin is mainly used in the fields of heat insulation, sound insulation and the like. Particularly as a heat insulation material, the application of the material in the fields of buildings, aerospace aircrafts and the like is rapidly developed.

The invention discloses a preparation method of foaming resin (application number: 201811501893.2). the invention selects carboxyl methyl diphenyl phosphine to modify phenolic resin, and the reaction process is prepared by the following raw materials according to the weight ratio: 100 parts of phenolic resin; 80-95 parts of carboxymethyl diphenylphosphine; 3-5 parts of a catalyst; 4-6 parts of a surfactant; 8-10 parts of a foaming agent; 12-15 parts of a curing agent. The carboxy methyl diphenyl phosphine is synthesized by chloroacetic acid and diphenyl phosphine, and is directly added into the phenolic resin to modify the original structure of the phenolic resin. The foam prepared from the novel resin has high mechanical strength, low water absorption, greatly improved flame retardance, improved comprehensive performance, and wide development and application prospect.

A foamed resin and its preparation method of the invention patent of China (application number: 201610809654.8), add phenolic compound, catalyst, aldehyde compound into about 60-80 ℃ reaction kettle sequentially and react, add phenanthrene formula tetraphenylcyclopentadienone, stir at a high speed to make and mix evenly, introduce N2 to protect, raise the temperature to 80-100 ℃ slowly with the speed of raising the temperature of 1-5 ℃/min, stir at constant temperature for 1.5-2.5 h, cool to the room temperature; neutralizing the resin liquid with acetic acid, and then distilling off small molecules in the system under reduced pressure until no liquid is discharged to obtain viscous liquid, namely the phenanthrene polyphenyl condensed ring copolymerization cardanol formaldehyde foaming resin. According to the method, a cardanol side group and a phenanthrene condensed ring structure are introduced into the structure of the prepared novel foaming resin, so that the defect of brittleness of the phenolic resin in the prior art is overcome, and the high temperature resistance of the phenolic resin is improved.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides hydrophilic flame-retardant foaming resin and a processing method thereof.

The purpose of the invention is realized by the following technical scheme:

the hydrophilic flame-retardant foaming resin comprises the following raw materials in parts by weight:

the weight portion of the paraformaldehyde is 320-380 portions.

The weight portion of the paraformaldehyde is 350 portions.

The formaldehyde modifier accounts for 14-18 parts by weight.

The weight portion of the formaldehyde modifier is 16 portions.

The weight portion of the sodium metabisulfite is 32-38.

The weight portion of the sodium metabisulfite is 35 portions.

The weight portion of the sodium hydroxide is 1.5 portions.

The weight portion of the desalted water is 390 portions.

The preparation method of the formaldehyde modifier comprises the following steps: 4, 4, 4-triamino triphenylamine and adipic acid are used as raw materials, N-dimethylacetamide is used as a solvent, phosphoric acid is used as a catalyst, and then the reaction is carried out at the temperature of 150-185 ℃ in a nitrogen atmosphere; and after reacting for 10-20 hours, cooling to normal temperature, adding methanol, filtering filter residues, and performing vacuum drying on the filter residues at 120 ℃ to obtain the required formaldehyde modifier.

The molar ratio of the 4, 4, 4-triamino triphenylamine to the adipic acid is 1: 0.47;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the N, N-dimethylacetamide solvent is 15%;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the phosphoric acid is 0.3 percent;

the volume ratio of the N, N-dimethylacetamide to the methanol is 1: 0.13;

a processing method of hydrophilic flame-retardant foaming resin comprises the following specific steps:

opening an electric appliance system of a microwave reaction kettle, setting the temperature to be 101 ℃, the power to be 0.58kw, the time to be 17 minutes (within 17 minutes), immediately entering a heat preservation stage after the resin is thoroughly transparent, setting the temperature to be 97 ℃, the time to be 60 minutes and the power to be 0.1kw in the heat preservation stage, starting a cooling water circulation device after the setting is completed, opening a stirrer of the reaction kettle to 230 revolutions per minute, firstly adding desalted water, then sequentially adding sodium hydroxide, diglycolamine, melamine, sodium metabisulfite, a formaldehyde modifier and paraformaldehyde into the reaction kettle, locking a feeding port, closing a shielding door, starting the reaction kettle after the uniform stirring, and completing the reaction process; after the heat preservation is finished and the reaction kettle automatically stops heating, closing the microwave cooling water system and the condensed water of the reaction kettle condenser, and simultaneously starting the resin cooling system to rapidly cool to 40 ℃ for later use; obtaining the hydrophilic flame-retardant foaming resin.

Compared with the prior art, the invention has the following positive effects:

1. hydrophilic and oleophilic, and can quickly emulsify and disperse all foaming components.

2. The viscosity of the resin is 65000Pa.s, which is beneficial to realizing mass production by matching with emulsification equipment.

3. Introduction of diglycolamine can reduce smoke density after combustion.

4. The obtained foam has better toughness and smaller permanent deformation.

Drawings

FIG. 1 reaction equation for preparation of Formaldehyde modifier

FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of formaldehyde modifier.

Detailed Description

The following provides a specific embodiment of a hydrophilic flame-retardant foamed resin and a method for processing the same according to the present invention.

Example 1

The hydrophilic flame-retardant foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde modifier comprises the following steps: 4, 4, 4-triamino triphenylamine and adipic acid are used as raw materials, N-dimethylacetamide is used as a solvent, phosphoric acid is used as a catalyst, and then the reaction is carried out at the temperature of 150-185 ℃ in a nitrogen atmosphere; and after reacting for 10-20 hours, cooling to normal temperature, adding methanol, filtering filter residues, and performing vacuum drying on the filter residues at 120 ℃ to obtain the required formaldehyde modifier.

The molar ratio of the 4, 4, 4-triamino triphenylamine to the adipic acid is 1: 0.47;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the N, N-dimethylacetamide solvent is 15%;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the phosphoric acid is 0.3 percent;

the volume ratio of the N, N-dimethylacetamide to the methanol is 1: 0.13;

in the hydrogen nuclear magnetic resonance spectrum of the formaldehyde modifier, 1 corresponds to an amido bond characteristic absorption peak formed after the reaction of adipic acid and 4, 4, 4-triamino triphenylamine, the corresponding chemical shift is 8.01ppm, 2 and 3 correspond to 4, 4, 4-triamino triphenylamine and adipic acid to form a benzene ring structure, the benzene ring structure is influenced by the amide functional group, the splitting condition of the characteristic absorption peak exists, the chemical shifts of 2(7.35ppm) and 3(6.46ppm) on the benzene ring are split, 4 corresponds to a benzene ring characteristic absorption peak which is not reacted on the benzene ring, the chemical shift is 6.21ppm, and the sum of the characteristic peak area of the corresponding 4 chemical shifts and the characteristic peak areas of 2 and 3 is 2: 1, so that the reaction of one amino group on the 4, 4, 4-triamino triphenylamine is also demonstrated, the adipic acid is a bifunctional group structure, so that 4 is demonstrated, 4, 4-triamino triphenylamine and adipic acid react according to the molar ratio of 2: 1 to form a small molecular structure; in the atlas, 5 is an unreacted amino characteristic absorption peak, and the ratio of the chemical shift of 5 to the chemical shift of 1 is 2: 1, so that the reaction of 4, 4, 4-triamino triphenylamine and adipic acid according to the molar ratio of 2: 1 is also proved; 6 and 7 correspond to characteristic absorption peaks on the adipic acid structure.

The melamine is easy to generate self-degradation reaction under acidic and neutral conditions, and formaldehyde is generated and released, so that the problem that the formaldehyde content in the existing melamine resin is higher is caused; the formaldehyde and the amino can be subjected to polycondensation reaction under acidic and alkaline conditions, so that the amino functional group with an alkaline structure is introduced in the design process, and the amino in the formaldehyde modifier and the formaldehyde are subjected to polycondensation reaction by utilizing the alkaline structure of the tertiary amino in the formaldehyde modifier in humid air, so that the formaldehyde molecules released from the material can be fixed and absorbed. Meanwhile, in order to avoid the problems that a small molecular structure is easy to migrate and the reaction activity of 4, 4, 4-triamino triphenylamine is low in a molecular structure, the high hydrophilic structure amide group is introduced into the 4, 4, 4-triamino triphenylamine structure, so that the affinity effect of the formaldehyde modifier and water molecules is improved, and the problems that low-molecular polyamine and moisture hygroscopicity are poor and tertiary amine functional groups are difficult to convert into basic structure quaternary ammonium functional groups are solved.

A processing method of hydrophilic flame-retardant foaming resin comprises the following specific steps:

opening an electric appliance system of a microwave reaction kettle, setting the temperature to be 101 ℃, the power to be 0.58kw, the time to be 17 minutes (within 17 minutes), immediately entering a heat preservation stage after the resin is thoroughly transparent, setting the temperature to be 97 ℃, the time to be 60 minutes and the power to be 0.1kw in the heat preservation stage, starting a cooling water circulation device after the setting is completed, opening a stirrer of the reaction kettle to 230 revolutions per minute, firstly adding desalted water, then sequentially adding sodium hydroxide, diglycolamine, melamine, a formaldehyde modifier, sodium metabisulfite and paraformaldehyde into the reaction kettle, locking a feeding port, closing a shielding door, starting the reaction kettle after the uniform stirring, and completing the reaction process; after the heat preservation is finished and the reaction kettle automatically stops heating, closing the microwave cooling water system and the condensed water of the reaction kettle condenser, and simultaneously starting the resin cooling system to rapidly cool to 40 ℃ for later use; obtaining the hydrophilic flame-retardant foaming resin.

Example 2

The hydrophilic flame-retardant foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde modifier comprises the following steps: the same as in example 1.

A processing method of hydrophilic flame-retardant foaming resin comprises the following specific steps:

opening an electric appliance system of a microwave reaction kettle, setting the temperature to be 101 ℃, the power to be 0.58kw, the time to be 17 minutes (within 17 minutes), immediately entering a heat preservation stage after the resin is thoroughly transparent, setting the temperature to be 97 ℃, the time to be 60 minutes and the power to be 0.1kw in the heat preservation stage, starting a cooling water circulation device after the setting is completed, opening a stirrer of the reaction kettle to 230 revolutions per minute, firstly adding desalted water, then sequentially adding sodium hydroxide, diglycolamine, melamine, sodium metabisulfite, a formaldehyde modifier and paraformaldehyde into the reaction kettle, locking a feeding port, closing a shielding door, starting the reaction kettle after the uniform stirring, and completing the reaction process; after the heat preservation is finished and the reaction kettle automatically stops heating, closing the microwave cooling water system and the condensed water of the reaction kettle condenser, and simultaneously starting the resin cooling system to rapidly cool to 40 ℃ for later use; obtaining the hydrophilic flame-retardant foaming resin.

Example 3

The hydrophilic flame-retardant foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde modifier comprises the following steps: the same as in example 1.

A processing method of hydrophilic flame-retardant foaming resin comprises the following specific steps:

opening an electric appliance system of a microwave reaction kettle, setting the temperature to be 101 ℃, the power to be 0.58kw, the time to be 17 minutes (within 17 minutes), immediately entering a heat preservation stage after the resin is thoroughly transparent, setting the temperature to be 97 ℃, the time to be 60 minutes and the power to be 0.1kw in the heat preservation stage, starting a cooling water circulation device after the setting is completed, opening a stirrer of the reaction kettle to 230 revolutions per minute, firstly adding desalted water, then sequentially adding sodium hydroxide, diglycolamine, melamine, sodium metabisulfite, a formaldehyde modifier and paraformaldehyde into the reaction kettle, locking a feeding port, closing a shielding door, starting the reaction kettle after the uniform stirring, and completing the reaction process; after the heat preservation is finished and the reaction kettle automatically stops heating, closing the microwave cooling water system and the condensed water of the reaction kettle condenser, and simultaneously starting the resin cooling system to rapidly cool to 40 ℃ for later use; obtaining the hydrophilic flame-retardant foaming resin.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.