CN103012831B - Method for preparing low-temperature foaming agent - Google Patents

Method for preparing low-temperature foaming agent Download PDF

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Publication number
CN103012831B
CN103012831B CN201210544705.0A CN201210544705A CN103012831B CN 103012831 B CN103012831 B CN 103012831B CN 201210544705 A CN201210544705 A CN 201210544705A CN 103012831 B CN103012831 B CN 103012831B
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acid
foaming agent
urea
temperature
low
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CN103012831A (en
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董梅
陈海贤
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HANGZHOU HI-TECH FINE CHEMICAL Co Ltd
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HANGZHOU HI-TECH FINE CHEMICAL Co Ltd
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Abstract

The invention provides a method for preparing a low-temperature foaming agent. According to the method, carbamide, acids and sodium nitrite are used as main raw materials, and the raw materials can be subjected to solid-state reaction and also can be subjected to liquid-state reaction to generate the white low-temperature foaming agent. If wet method reaction is adopted, the method comprises the following steps of: a. adding the carbamide and the acids to a certain amount of water according to a certain proportion; b. adjusting the reaction temperature to be 20-80 DEG C, and starting a stirring device for stirring; c. filtering, washing and drying filter liquor after stirring for 1-2h; and d. adding an obtained white material and the sodium nitrite to a high-speed mixer according to a certain proportion, adjusting the rotate speed, and mixing for 0.5-1h to obtain the white low-temperature foaming agent. If dry method reaction is adopted, the carbamide and the acids can be added to the high-speed mixer for pre-mixing for 0.5-1h, and then a certain amount of the sodium nitrite is added to the high-speed mixer for mixing for 0.5-1h at a high speed. The white low-temperature foaming agent prepared by the method can be suitable for a plurality of plastic and rubber foaming, subsequent processing is not needed, the use is convenient, the decomposition rate is mild, and the operational safety is high.

Description

A kind of preparation method of production of low-temperature foaming agent
Technical field
The present invention relates to whipping agent field, be specifically related to a kind of preparation method of production of low-temperature foaming agent.
Background technology
As everyone knows, in rubber item, add whipping agent, can in the rubber item course of processing, produce tiny abscess, whipping agent, under specified temp, forms the foamy structure of porous in the expandability materials such as resin, the most frequently used whipping agent has Cellmic C 121,4,4 '-OBSH, benzol sulfohydrazide, p-toluene sulfonyl hydrazide, dinitrosopentamethlyene tetramine and sodium bicarbonate etc.
4,4 '-OBSH, benzol sulfohydrazide, p-toluene sulfonyl hydrazide, dinitrosopentamethlyene tetramine because of its price higher, gas forming amount is less, use range has been subject to certain limitation.And Cellmic C 121 is as the higher whipping agent of a kind of gas forming amount, reasonable price, the parent who is always subject to every field producer looks at, and becomes purposes whipping agent the most widely.But ADC foaming agent decomposition temperature is 205 DEG C of left and right, decomposition temperature is higher, and rubber-plastic foamed temperature is many between 140-180 DEG C, directly cannot reach foaming effect with ADC whipping agent, therefore the method adopting is at present to add zinc salt in ADC whipping agent, and zinc salt can be used as the activator of ADC whipping agent, and the decomposition of ADC whipping agent is played to promoter action, can make ADC whipping agent decompose at a lower temperature, meet various rubber-plastic foamed requirements with this.But the whipping agent price after modification is higher, its fancy price cannot be born by the producer that some industrial scales are less, and therefore, the lower whipping agent of a kind of low cost, decomposition temperature is in the urgent need to filling up this deficiency.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, and a kind of preparation method of production of low-temperature foaming agent is provided.The method is taking urea, acid and Sodium Nitrite as main raw material, can liquid reaction also can solid state reaction, generate a kind of white production of low-temperature foaming agent.The white production of low-temperature foaming agent that the method makes requires 180 DEG C and the foaming of following product of rubber and plastic, asphalt foaming agent and the field such as cement foamed applicable to blowing temperature, without carrying out subsequent disposal, easy to use, and decomposition rate gentleness, and processing safety is high.
The object of the invention is to complete by following technical solution.The preparation method of this production of low-temperature foaming agent, the method is taking urea, acidic substance and Sodium Nitrite as raw material, adopts dry method or wet method to react and obtains white production of low-temperature foaming agent;
Wet Method Reaction comprises following step:
A. first weigh urea and the acidic substance of certain mass, the mol ratio of urea and acidic substance is that 1mol urea reacts with the ratio of 2mol hydrogen ion or proton, acidic substance be for can discharge hydrogen ion at the aqueous solution, or the proton of emitting under heating and melting state compound;
B. load weighted acidic substance are added to the water, the massfraction that makes acidic substance is 30-70%, and control temperature of reaction is 20-80 DEG C;
C. open stirrer, in the situation that stirring, urea is added with solid form in the aqueous solution that directly adds acidic substance, stir 1-2h;
D. react complete, filtrate is filtered, washed, dry at the temperature that is less than 70 DEG C, obtain white powder solid;
E. white powder solid is added in high-speed mixer and mixes 0.5-1h with Sodium Nitrite mass ratio 100:5-100:40, obtain white production of low-temperature foaming agent;
Dry process reaction step is as follows: first can react with 2mol hydrogen ion or proton according to 1mol urea, weighing the urea of certain mass and acid adds and in high-speed mixer, is pre-mixed 0.5-1h, then according to the Sodium Nitrite of 5%-40% that adds urea and acid solid masses total amount, high-speed mixing 0.5-1h, obtains white production of low-temperature foaming agent.
As preferably, described acidic substance are in the aqueous solution, to emit hydrogen ion or be heated to molten state the material that discharges proton, the mineral acid material adopting be inorganic salts as highly acid ammonium salt, or to adopt organic solid-state acid be oxalic acid, citric acid, stearic one or more combination.
Urea can adopt Wet Method Reaction also can adopt dry process reaction with reacting of acidic substance, but in Wet Method Reaction, urea is to add with solid form, and object is the output capacity that increases product, and saves unnecessary water resource waste.Adopt the synthetic production of low-temperature foaming agent of urea, acidic substance and nitrous acid, be intended to utilize the oxidisability of nitrous acid by the nitrogen oxidation in urea, reach thereby emit nitrogen the effect that goods is produced to tolerance.
Urea reacts the white solid obtaining and need be dried at low temperatures with acidic substance, drying temperature should not exceed 70 DEG C, and excess Temperature easily makes material decompose.
Adopt dry process reaction, should first urea and acid be pre-mixed, and then add Sodium Nitrite to mix, to ensure the abundant mixing of material.
Employing liquid phase process reaction is, after urea and acidic substance are reacted in the aqueous solution, to obtain dry white mass, and then carry out solid-state mixing with Sodium Nitrite.Sodium Nitrite can not directly add in the aqueous solution, prevents that material from just decomposing in the aqueous solution.
This white production of low-temperature foaming agent can be used for 180 DEG C of blowing temperature requirements and the foaming of following product of rubber and plastic, asphalt foaming agent and the field such as cement foamed, without carrying out special processing, easy to use.
Beneficial effect of the present invention is: production of low-temperature foaming agent preparation method provided by the present invention, simple to operate, make up the deficiency of high-temperature foaming agent, raw material is easy to get, and cost is lower, and product price is cheap, whipping agent directly uses, without carrying out subsequent disposal, be applicable to foaming less demandingly, the less producer of industrial scale needs.
Embodiment
Below by embodiment, the present invention is further elaborated, and the present invention is understood better in help by embodiment, but the present invention is not limited only to following embodiment.
Embodiment 1
First weigh 50kg ammonium chloride in 50kg water, open reactor and stir, temperature of reaction is controlled at 20 DEG C, adds load weighted 15kg urea solid in advance, continues to stir 1h, after completion of the reaction, filters, washs, is dried.Obtain white solid powder.These white solid powder are added in high-speed mixer, add 3.5kg Sodium Nitrite, carry out high-speed mixing 1h, obtain white production of low-temperature foaming agent, after tested, the decomposition temperature of whipping agent is 120-150 DEG C, gas forming amount 110mL/g.
Embodiment 2
First weigh 50kg oxalic acid in 20kg water, open reactor and stir, temperature of reaction is controlled at 50 DEG C, adds load weighted 48kg urea solid in advance, continues to stir 1.5h, after completion of the reaction, filters, washs, is dried.Obtain white solid powder.These white solid powder are added in high-speed mixer, add 25kg Sodium Nitrite, carry out high-speed mixing 1.5h, obtain white production of low-temperature foaming agent, after tested, the decomposition temperature of whipping agent is 120-150 DEG C, gas forming amount 120mL/g.
Embodiment 3
First weigh 50kg citric acid in 20kg water, open reactor and stir, temperature of reaction is controlled at 80 DEG C, adds load weighted 23kg urea solid in advance, continues to stir 2h, after completion of the reaction, filters, washs, is dried.Obtain white solid powder.These white solid powder are added in high-speed mixer, add 29kg Sodium Nitrite, carry out high-speed mixing 2h, obtain white production of low-temperature foaming agent, after tested, the decomposition temperature of whipping agent is 120-150 DEG C, gas forming amount 125mL/g.
Embodiment 4
In the high-speed mixer of 50L, add 20kg urea and 10kg stearic acid, first mix 0.5h, after add 5kg Sodium Nitrite, carry out high-speed mixing 2h.Material obtains white production of low-temperature foaming agent after going out still, and after tested, the decomposition temperature of whipping agent is 120-150 DEG C, gas forming amount 110mL/g.

Claims (1)

1. a preparation method for production of low-temperature foaming agent, is characterized in that: the method is taking urea, acid and Sodium Nitrite as raw material, adopts dry method or wet method to react and obtains white production of low-temperature foaming agent;
Wet Method Reaction comprises following step:
A. first weigh urea and the acid of certain mass, the mol ratio of urea and acid is that 1mol urea reacts with the ratio of 2mol hydrogen ion or proton, acid be for can discharge hydrogen ion at the aqueous solution, or the proton of emitting under heating and melting state compound;
B. load weighted acid is added to the water, the massfraction that makes acid is 30-70%, and control temperature of reaction is 20-80 DEG C;
C. open stirrer, in the situation that stirring, urea is directly added with solid form in the aqueous solution of acid, stir 1-2h;
D. react complete, filtrate is filtered, washed, dry at the temperature that is less than 70 DEG C, obtain white powder solid;
E. white powder solid is added in high-speed mixer and mixes 0.5-1h with Sodium Nitrite mass ratio 100:5-100:40, obtain white production of low-temperature foaming agent;
Dry process reaction step is as follows: first react according to 1mol urea and 2mol hydrogen ion or proton, weighing the urea of certain mass and acid adds and in high-speed mixer, is pre-mixed 0.5-1h, then add the Sodium Nitrite of the 5%-40% of urea and acid solid masses total amount, high-speed mixing 0.5-1h, obtains white production of low-temperature foaming agent;
Described acid is in the aqueous solution, to emit hydrogen ion or be heated to molten state the material that discharges proton, adopts highly acid ammonium salt, or adopts oxalic acid, citric acid, stearic one or more combination.
CN201210544705.0A 2012-12-14 2012-12-14 Method for preparing low-temperature foaming agent Active CN103012831B (en)

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CN105481288A (en) * 2015-11-24 2016-04-13 武汉武达博硕园科技有限公司 Preparation method of efficient and stable special foaming agent for gypsum
CN109577017A (en) * 2017-09-28 2019-04-05 上海译科实业有限公司 A kind of foaming agent and preparation method thereof for synthetic leather
CN107877769A (en) * 2017-10-17 2018-04-06 安徽天安新材料有限公司 The preparation method of synthetic leather

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