阅读说明：本技术 一种发泡树脂及其制备方法 (Foaming resin and preparation method thereof ) 是由 焦正 刘立起 于 2021-01-30 设计创作，主要内容包括：本发明涉及一种发泡树脂及其制备方法,其特征在于,其原料重量份数为：二甘醇胺为300份,三聚氰胺为80～90份,甲醛吸收剂为1～3份,磷酸为2～4份,次磷酸为4～10份。本申请有效节约原材料,减轻产品质量；发泡剂成本低廉,环保；工艺简单,易于推广。(The invention relates to a foaming resin and a preparation method thereof, which is characterized in that the foaming resin comprises the following raw materials in parts by weight: 300 parts of diglycolamine, 80-90 parts of melamine, 1-3 parts of formaldehyde absorbent, 2-4 parts of phosphoric acid and 4-10 parts of hypophosphorous acid. The application effectively saves raw materials and lightens the product quality; the foaming agent has low cost and is environment-friendly; the process is simple and easy to popularize.)

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

2. the foamed resin according to claim 1, wherein the melamine is present in an amount of 82 to 88 parts by weight.

3. The foamable resin of claim 1, wherein the melamine is present in an amount of 85 parts by weight.

4. The foamable resin of claim 1, wherein the formaldehyde absorbent is present in an amount of 2 parts by weight.

5. The foamable resin according to claim 1, wherein the phosphoric acid is present in an amount of 3 parts by weight.

6. The foaming resin of claim 1, wherein the hypophosphorous acid is present in an amount of 6 to 8 parts by weight.

7. The foamable resin according to claim 1, wherein the hypophosphorous acid is present in an amount of 7 parts by weight.

8. The foamable resin of claim 1, wherein the formaldehyde absorbent: 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 160-180 ℃ in a nitrogen atmosphere; and after the reaction is carried out for 12-18 h, cooling to normal temperature, then adding methanol, filtering the filter residue, and carrying out vacuum drying on the filter residue at 120 ℃ to obtain the required formaldehyde absorbent.

Technical Field

The invention relates to the technical field of resin, in particular to foaming resin and a preparation method thereof.

Background

The foaming resin has the characteristics of heat insulation, flame retardancy, light weight and chemical corrosion resistance, is flame-retardant when meeting open fire, has only carbon deposit on the surface of the resin under the forced combustion condition, and hardly generates smoke or emits harmful gas, so the foaming resin is widely applied in many fields along with the improvement of the requirements of fire resistance and flame retardancy of buildings, decorations and decorative materials.

The Chinese invention patent (application number: 201810444360.9) provides a foaming resin with low-temperature foaming function, a preparation method and application thereof, wherein the foaming resin is prepared from the following materials in parts by mass: 10-12 parts of low-temperature foaming powder, 45-55 parts of acrylic resin, 35-45 parts of water, 2-3 parts of an organic silicon flatting agent, 1-3 parts of polyurethane emulsion, 0.5-2 parts of emulsified silicone oil, 5-6 parts of silicon wax polymer emulsion, 1 part of an aqueous thickening agent and 1-2 parts of glycerol; during preparation, all the components except the water-based acrylic resin are uniformly mixed in water, then the mixture is added into the water-based acrylic resin, and the mixture is stirred at the rotating speed of 800 revolutions per minute for half an hour to prepare the foamed resin. Uniformly spraying the prepared foaming resin on the surface of the treated leather by using a spray gun, and then drying in a drying oven at 105 ℃ for 3-5 seconds; according to the invention, the low-temperature foaming powder is added to the acrylic resin main body, the foaming temperature is lower than that of common foaming resin, the low-temperature foaming powder has an excellent residue covering function, the leather grade is obviously improved, and the damage to leather in the leather processing process can be obviously reduced.

The Chinese invention patent (application number: 201410776860.4) discloses a water-based PU foaming resin, which is prepared from the following raw materials in parts by weight: 52-60 parts of waterborne polyurethane resin, 20-38 parts of water, 5-12 parts of polystyrene foaming agent, 3-10 parts of sodium dodecyl sulfate, 1-2 parts of organic silicon flatting agent, 1-3 parts of palm oil, 1-3 parts of polyacrylic emulsion, 1-5 parts of recycled paper pulp waste liquid and 0.5-2 parts of emulsified silicone oil. The aqueous PU foaming resin disclosed by the invention is simple in formula, adopts aqueous raw materials, is high in environmental friendliness, and can play a role in assisting in foaming by adding the treated paper pulp waste liquid. The aqueous PU foaming resin also has the characteristics of good stability and high cost performance.

The Chinese invention patent (application number: 201610835374.4) discloses a pimaric acid modified phenolic foam resin, relating to a foam resin, which is prepared from the following raw materials in parts by weight: 100 parts of phenolic resin; 80-95 parts of pimaric acid; 3-5 parts of a catalyst; 2-6 parts of a surfactant; 8-10 parts of a foaming agent; 12-15 parts of a curing agent. The pimaric acid is selected to modify the phenolic resin, and the pimaric acid is a nontoxic substance directly extracted from plants and directly added into the phenolic resin, so that the proportion of harmful substances in the resin is reduced, and the product is more environment-friendly. The novel resin has high mechanical strength, low water absorption, improved carbon residue rate, improved comprehensive performance, and wide development and application prospect.

The foaming resin represented by the Pasteur Basotecet series foaming resin has excellent sound absorption performance, ultralow heat conductivity coefficient, extremely low volume density, fireproof characteristic and the like, is widely applied to high-added-value fields such as high-grade building decoration, automobiles, rail vehicles, aerospace and the like, and is rapidly developed. Therefore, the development of the foaming resin product with domestic independent intellectual property rights can wholly achieve or partially exceed the performances of the same type of products abroad, thereby meeting the vigorous demands of the market and being one of the key development directions which are urgently needed to be broken through at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a foaming resin and a preparation method thereof.

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

the foaming resin comprises the following raw materials in parts by weight:

the melamine is 82-88 parts by weight.

The melamine accounts for 85 parts by weight.

The formaldehyde absorbent accounts for 2 parts by weight.

The weight portion of the phosphoric acid is 3 portions.

The weight portion of the hypophosphorous acid is 6-8.

The weight portion of the hypophosphorous acid is 7 portions.

The preparation method of the formaldehyde absorbent 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 160-180 ℃ in a nitrogen atmosphere; and after the reaction is carried out for 12-18 h, cooling to normal temperature, then adding methanol, filtering the filter residue, and carrying out vacuum drying on the filter residue at 120 ℃ to obtain the required formaldehyde absorbent.

The molar ratio of the 4, 4, 4-triamino triphenylamine to the adipic acid is 1: 0.45;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the N, N-dimethylacetamide solvent is 10 percent;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the phosphoric acid is 0.1 percent;

the volume ratio of the N, N-dimethylacetamide to the methanol is 1: 0.1;

a preparation method of foaming resin comprises the following specific steps:

adding diglycolamine into a reaction kettle, opening a nitrogen valve (introducing a nitrogen conduit below the liquid level), slowly adjusting a buffer valve, observing the flow rate until one bubble is blown out every 2 seconds, and replacing the air in the reaction kettle; starting stirring, adding melamine and formaldehyde absorbent, dropwise adding phosphoric acid and hypophosphorous acid by using a funnel, uniformly stirring, opening a condensation reflux device, starting a heating device (a heat-conducting oil furnace) to start heating, controlling the heating speed, and heating to 210 ℃ (the set temperature of the heat-conducting oil furnace is 5-10 ℃ higher than the temperature of the solution in the kettle); after about 3 hours, the reaction solution was transparent, and after the reaction solution was transparent, the temperature was maintained for 13 hours; closing a cooling water valve of the reaction condenser, opening a cooling water valve of the reaction kettle, and cooling to 150 ℃; closing a cooling water valve of the reaction kettle, opening a vacuum control valve, opening a cooling water valve of the distillation condenser, and starting a vacuum system; adjusting the nitrogen flow (the nitrogen flow rate under negative pressure can be accelerated to be adjusted to be small); after the vacuum is stable, the heating control switch is turned on to heat and raise the temperature. Controlling the distillation temperature at 195 ℃, and turning off the heating control switch; when no fraction flows out, the distillation is finished, and a cooling water valve of a distillation condenser is closed; opening a cooling water valve of the reaction kettle to cool, opening an exhaust valve of the vacuum buffer tank when the temperature is reduced to 150 ℃, and stopping the vacuum system after the temperature is stabilized; closing the nitrogen valve; when the temperature is reduced to 80 ℃, closing a cooling water valve, adding quantitative distilled water, uniformly stirring, and discharging; obtaining the foaming resin.

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

the application effectively saves raw materials and lightens the product quality; the foaming agent has low cost and is environment-friendly; the process is simple and easy to popularize.

Drawings

FIG. 1 is a reaction equation for preparing a formaldehyde absorbent;

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

Detailed Description

The following provides a specific embodiment of an amino acoustic foam of the present invention.

Example 1

The foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde absorbent 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 160-180 ℃ in a nitrogen atmosphere; and after the reaction is carried out for 12-18 h, cooling to normal temperature, then adding methanol, filtering the filter residue, and carrying out vacuum drying on the filter residue at 120 ℃ to obtain the required formaldehyde absorbent.

The molar ratio of the 4, 4, 4-triamino triphenylamine to the adipic acid is 1: 0.45;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the N, N-dimethylacetamide solvent is 10 percent;

the mass fraction of the 4, 4, 4-triamino triphenylamine in the phosphoric acid is 0.1 percent;

the volume ratio of the N, N-dimethylacetamide to the methanol is 1: 0.1;

in the hydrogen nuclear magnetic resonance spectrum of the formaldehyde absorbent, 1 corresponds to an amido bond characteristic absorption peak formed after 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 amide functional groups, 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 absorbent and the formaldehyde are subjected to polycondensation reaction by utilizing the alkaline structure of the tertiary amino in the formaldehyde absorbent in humid air, so that the formaldehyde molecules released from the material are 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 absorbent 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 preparation method of foaming resin comprises the following specific steps:

adding diglycolamine into a reaction kettle, opening a nitrogen valve (introducing a nitrogen conduit below the liquid level), slowly adjusting a buffer valve, observing the flow rate until one bubble is blown out every 2 seconds, and replacing the air in the reaction kettle; starting stirring, adding melamine and formaldehyde absorbent, dropwise adding phosphoric acid and hypophosphorous acid by using a funnel, uniformly stirring, opening a condensation reflux device, starting a heating device (a heat-conducting oil furnace) to start heating, controlling the heating speed, and heating to 210 ℃ (the set temperature of the heat-conducting oil furnace is 5-10 ℃ higher than the temperature of the solution in the kettle); after about 3 hours, the reaction solution was transparent, and after the reaction solution was transparent, the temperature was maintained for 13 hours; closing a cooling water valve of the reaction condenser, opening a cooling water valve of the reaction kettle, and cooling to 150 ℃; closing a cooling water valve of the reaction kettle, opening a vacuum control valve, opening a cooling water valve of the distillation condenser, and starting a vacuum system; adjusting the nitrogen flow (the nitrogen flow rate under negative pressure can be accelerated to be adjusted to be small); after the vacuum is stable, the heating control switch is turned on to heat and raise the temperature. Controlling the distillation temperature at 195 ℃, and turning off the heating control switch; when no fraction flows out, the distillation is finished, and a cooling water valve of a distillation condenser is closed; opening a cooling water valve of the reaction kettle to cool, opening an exhaust valve of the vacuum buffer tank when the temperature is reduced to 150 ℃, and stopping the vacuum system after the temperature is stabilized; closing the nitrogen valve; when the temperature is reduced to 80 ℃, closing a cooling water valve, adding quantitative distilled water, uniformly stirring, and discharging; obtaining the foaming resin.

Example 2

The foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde absorbent is the same as that of the example 1.

A preparation method of foaming resin comprises the following specific steps:

adding diglycolamine into a reaction kettle, opening a nitrogen valve (introducing a nitrogen conduit below the liquid level), slowly adjusting a buffer valve, observing the flow rate until one bubble is blown out every 2 seconds, and replacing the air in the reaction kettle; starting stirring, adding melamine and formaldehyde absorbent, dropwise adding phosphoric acid and hypophosphorous acid by using a funnel, uniformly stirring, opening a condensation reflux device, starting a heating device (a heat-conducting oil furnace) to start heating, controlling the heating speed, and heating to 210 ℃ (the set temperature of the heat-conducting oil furnace is 5-10 ℃ higher than the temperature of the solution in the kettle); after about 3 hours, the reaction solution was transparent, and after the reaction solution was transparent, the temperature was maintained for 13 hours; closing a cooling water valve of the reaction condenser, opening a cooling water valve of the reaction kettle, and cooling to 150 ℃; closing a cooling water valve of the reaction kettle, opening a vacuum control valve, opening a cooling water valve of the distillation condenser, and starting a vacuum system; adjusting the nitrogen flow (the nitrogen flow rate under negative pressure can be accelerated to be adjusted to be small); after the vacuum is stable, the heating control switch is turned on to heat and raise the temperature. Controlling the distillation temperature at 195 ℃, and turning off the heating control switch; when no fraction flows out, the distillation is finished, and a cooling water valve of a distillation condenser is closed; opening a cooling water valve of the reaction kettle to cool, opening an exhaust valve of the vacuum buffer tank when the temperature is reduced to 150 ℃, and stopping the vacuum system after the temperature is stabilized; closing the nitrogen valve; when the temperature is reduced to 80 ℃, closing a cooling water valve, adding quantitative distilled water, uniformly stirring, and discharging; obtaining the foaming resin.

Example 3

The foaming resin comprises the following raw materials in parts by weight:

the preparation method of the formaldehyde absorbent is the same as that of the example 1.

A preparation method of foaming resin comprises the following specific steps:

adding diglycolamine into a reaction kettle, opening a nitrogen valve (introducing a nitrogen conduit below the liquid level), slowly adjusting a buffer valve, observing the flow rate until one bubble is blown out every 2 seconds, and replacing the air in the reaction kettle; starting stirring, adding melamine and formaldehyde absorbent, dropwise adding phosphoric acid and hypophosphorous acid by using a funnel, uniformly stirring, opening a condensation reflux device, starting a heating device (a heat-conducting oil furnace) to start heating, controlling the heating speed, and heating to 210 ℃ (the set temperature of the heat-conducting oil furnace is 5-10 ℃ higher than the temperature of the solution in the kettle); after about 3 hours, the reaction solution was transparent, and after the reaction solution was transparent, the temperature was maintained for 13 hours; closing a cooling water valve of the reaction condenser, opening a cooling water valve of the reaction kettle, and cooling to 150 ℃; closing a cooling water valve of the reaction kettle, opening a vacuum control valve, opening a cooling water valve of the distillation condenser, and starting a vacuum system; adjusting the nitrogen flow (the nitrogen flow rate under negative pressure can be accelerated to be adjusted to be small); after the vacuum is stable, the heating control switch is turned on to heat and raise the temperature. Controlling the distillation temperature at 195 ℃, and turning off the heating control switch; when no fraction flows out, the distillation is finished, and a cooling water valve of a distillation condenser is closed; opening a cooling water valve of the reaction kettle to cool, opening an exhaust valve of the vacuum buffer tank when the temperature is reduced to 150 ℃, and stopping the vacuum system after the temperature is stabilized; closing the nitrogen valve; when the temperature is reduced to 80 ℃, closing a cooling water valve, adding quantitative distilled water, uniformly stirring, and discharging; obtaining the 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.