CN102816410A - Polyetheramine toughened phenol formaldehyde foam and preparation method thereof - Google Patents

Abstract

The invention discloses a polyetheramine toughened phenolic foam and a preparation method thereof. The polyetheramine toughened phenolic foam consists of 100 parts of polyetheramine modified phenolic resin, 3 to 10 parts of surface It consists of active agent, 5-15 parts of foaming agent and 5-20 parts of curing agent. Its preparation method is to add curing agent, surfactant and foaming agent in sequence to polyetheramine modified phenolic resin, stir and mix at high speed, pour into the mold, heat and foam to form, and obtain the polyether resin with less slag dropping and high toughness. Etheramine toughened phenolic foam is an excellent thermal insulation material.

Description

A kind of polyetheramine toughened phenolic foam and preparation method thereof

technical field

The present invention relates to a phenolic foam, in particular to a polyetheramine toughened phenolic foam and a preparation method thereof.

Background technique

Foam plastics are used more and more in the field of heat insulation and heat preservation due to their low thermal conductivity, light weight, and convenient construction. The disadvantages of combustion, large amount of smoke, high toxicity, and low heat-resistant temperature have greatly restricted its application in practical applications, especially in ships and buildings.

Phenolic Foam (PF for short) is a material with excellent performance in fire prevention, heat insulation, sound insulation, light weight and energy saving. , polyurethane (PU), polyethylene (PE), etc., which are more than twice as high as traditional thermal insulation materials such as mineral wool, light cork, perlite, glass wool, etc. flammability. Phenolic foam has the advantages of low price, good fire resistance, non-combustibility, low smoke generation, good flame penetration resistance, etc. Therefore, it is very active in research and development in foreign developed countries, and has been widely used in ships, construction and other fields. Phenolic foam is currently a rapidly developing variety of foreign synthetic foams. In recent years, the consumption has grown rapidly and the scope of application has continued to expand. World consumption was less than 100 tons before 1968, reached 32,000 tons in 1976, reached 40,000 tons in 1986, reached 85,000 tons in the 1990s, and now exceeds 200,000 tons. Phenolic foam has become a "new candidate for thermal insulation materials" and has received more and more attention. For example, phenolic foam in the former Soviet Union has accounted for 25% of the total synthetic foam, with an annual growth rate of 38%. The United States produced 5,000 tons of phenolic foam in 1980 and 50,000 tons in 1985, 10 times that of five years ago. At the same time, the United States was the first to apply phenolic foam to high-tech fields such as submarines, ships, and aerospace industries. Phenolic foam accounts for 46% of the sound insulation materials used in the construction industry. The Ministry of Construction of Japan promulgated the decree of "Phenolic foam as a standard building fire-resistant material", and the market scale has reached tens of thousands of tons per year. In France, phenolic foam is used as a material for sealing and controlling fire, and many large apartments in cities such as Marseille and Lyon have installed phenolic foam panels on the walls. At the same time, since high-rise buildings, transportation, shipbuilding industry, aviation industry, space technology, etc. have put forward strict requirements on the thermal stability and flame retardancy of synthetic foam plastics in recent years, phenolic foam plastics have been widely valued by people. .

Phenolic foam insulation material has the following significant advantages:

1. Non-combustibility The oxygen index of phenolic foam insulation material is greater than 40, which is the best flame retardancy among all organic insulation materials.

2. Low thermal conductivity The thermal conductivity of phenolic foam insulation material is the lowest among all thermal insulation materials.

3. Low smoke density and toxicity Phenolic foam insulation materials have the lowest smoke density and toxicity among all organic insulation materials. The smoke density and toxicity of polystyrene, rubber and plastic, polyethylene, and polyurethane foam are all high.

4. Strong resistance to flame penetration When the phenolic foam is exposed to an open flame, carbonization is formed on the surface, without dripping, curling, or melting. After being fired, a graphite layer of structural carbon is formed on the surface, which effectively protects the inner structure of the foam. The flame resistance can reach more than 1 hour without being penetrated 100 mm, which is the best among all organic insulation materials.

5. High corrosion resistance and aging resistance   The phenolic foam insulation material has been cured and formed, and it has no obvious aging phenomenon after being exposed to sunlight for a long time. The service life is significantly longer than other materials. It is almost resistant to the corrosion of all inorganic acids, organic acids and salts.

6. High thermal stability The service temperature of phenolic foam insulation material is -190～+150℃, which is the widest among all organic thermal insulation materials and has the best thermal stability.

But at the same time, the compressive strength of ordinary phenolic foam is ≤180KPa, the impact strength is ≤110J/m ² , and the slag dropping rate is ≥10%. Promote apps.

Contents of the invention

One of the objectives of the present invention is to provide a polyetheramine toughened phenolic foam and a preparation method thereof in order to solve the problems of existing phenolic foams such as brittleness, low strength and easy slag drop.

Technical scheme of the present invention

A polyetheramine toughened phenolic foam, calculated by parts by weight, its composition and content are as follows:

Polyetheramine modified phenolic resin 100 parts

Surfactant 3～10 parts

Foaming agent 5-15 parts

Curing agent 5-20 parts

The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps:

(1) Control the molar ratio of phenol and formaldehyde between 1:1.5~2, mix phenol and formaldehyde and add sodium hydroxide solution to control the pH of the reaction system to be 7.5~10, stir and heat up to 60~80 ℃ heat preservation reaction for 30 ~ 60min to obtain the reaction solution A;

(2) Add polyetheramine of 3% to 20% of the weight of phenol to the reaction solution A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction solution B;

(3) Add phosphoric acid dropwise to the reaction solution B obtained in step (2), and control the pH value to 6.5-7.5 to obtain a polyetheramine-modified phenolic resin;

Described surfactant is Tween-80;

Described whipping agent is pentane;

Described curing agent, calculated by mass percentage, its composition and content are as follows:

Phosphoric acid 5% ~ 60%

p-toluenesulfonic acid 20%～45%

Boric acid 5% ~ 15%

Water 15%～40%

The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent.

The preparation method of above-mentioned a kind of polyetheramine toughened phenolic foam, concrete steps are as follows:

That is, in the polyetheramine modified phenolic resin, add curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir and mix at high speed, pour into the mold, heat and foam to form, and prepare polyetheramine toughened Phenolic foam.

Beneficial effects of the present invention

A polyetheramine toughened phenolic foam of the present invention uses polyetheramine as a toughening agent to synthesize a polyetheramine modified phenolic resin, and then foams to obtain a polyetheramine toughened phenolic foam, which maintains the thermal conductivity of the phenolic foam It has the traditional advantages of low coefficient, low smoke, and flame resistance, and at the same time overcomes the shortcomings of phenolic foam such as easy slag drop, brittle texture, low strength, and poor toughness. The compressive strength of the final polyetheramine toughened phenolic foam can refer to GB8813 -1988 standard, ≥210KPa, impact strength is measured according to GB/T1043-1993 standard, ≥230J/m ² , slag drop rate is measured according to GB/T12812-1991 standard, ≤5%.

In addition, the preparation method of a polyetheramine toughened phenolic foam of the present invention has a simple and controllable production process and conditions, and various chemical raw materials used are all industrial grades, so it is suitable for industrial scale production.

Detailed ways

The present invention is further illustrated below by specific examples, but the present invention is not limited.

Various chemical raw materials used in each embodiment of the present invention are industrial-grade products provided by Shanghai Sinopharm.

The instrument used to measure the compressive strength is the Sun 500 universal material testing machine produced by Italy-GALDABLNI;

The instrument used to measure the impact strength is the JC-3002 Charpy impact testing machine produced by Jiangdu Jingcheng Testing Instrument Factory;

The slag dropping rate is measured according to the GB/T12812-1991 standard, which is obtained by manual grinding and calculation.

Example 1

A polyetheramine toughened phenolic foam, its composition and content are as follows:

Polyetheramine modified phenolic resin 50g

Surfactant 3g

Foaming agent 3g

Curing agent 4g

The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps:

(1) Add 90g of phenol and 56g of paraformaldehyde into a three-necked flask, add 9g of 10% sodium hydroxide solution, heat up to 60-80°C under stirring conditions, and keep warm for 30-60 minutes to obtain reaction solution A;

(2) Add 10 g of polyetheramine T-2000 to the reaction solution A obtained in step (1) and heat it up to 85-95°C, keep it warm for 60-90 minutes, stop the reaction, and cool to room temperature to obtain reaction solution B;

(3), adding phosphoric acid dropwise to the reaction solution B obtained in step (2) to control the pH value to 6.5 to 7.5, to obtain 163 g of polyetheramine modified phenolic resin;

Described surfactant is Tween-80;

Described whipping agent is pentane;

Described curing agent, its composition and content are as follows:

Phosphoric acid 29g (58%)

p-toluenesulfonic acid 11g (22%)

Boric acid 2.5g (5%)

Water 7.5g (15%)

The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent.

The preparation method of above-mentioned a kind of polyetheramine toughened phenolic foam, concrete steps are as follows:

That is, in the polyetheramine modified phenolic resin, after adding curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir at high speed for 30 seconds, quickly pour it into a mold with a certain volume, close the mold, and set the temperature at 70 Foaming and solidification at ℃ for 1 hour, cooling, and demoulding to obtain polyetheramine toughened phenolic foam with a density of about 70kg/ ^m3 .

The polyetheramine toughened phenolic foam obtained above has a compressive strength of 229KPa measured with reference to the GB8813-1988 standard, an impact strength of 283J/m ² measured with reference to the GB/T1043-1993 standard, and a slag dropping rate of 283J/m2 with reference to GB/T12812-1991 The standard was determined to be 3.1%.

Example 2

A polyetheramine toughened phenolic foam, its composition and content are as follows:

Polyetheramine modified phenolic resin 50g

Surfactant 5g

Foaming agent 7g

Curing agent 9g

The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps:

(1) Add 80g of phenol and 66g of paraformaldehyde into a three-necked flask, and add 7g of 10% sodium hydroxide solution, heat up to 60-80°C under stirring conditions, and keep warm for 30-60 minutes to obtain reaction solution A;

(2) Add 15g of polyetheramine T-5000 to the reaction liquid A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction liquid B;

(3), adding phosphoric acid dropwise to the reaction solution B obtained in step (2) to control the pH value to 6.5 to 7.5, to obtain 164 g of polyetheramine modified phenolic resin;

Described surfactant is Tween-80;

Described whipping agent is pentane;

Described curing agent, its composition and content are as follows:

Phosphoric acid 3g (6%)

p-toluenesulfonic acid 22g (44%)

Boric acid 6g (12%)

Water 19g (38%)

The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent.

The preparation method of above-mentioned a kind of polyetheramine toughened phenolic foam, concrete steps are as follows:

That is, in the polyetheramine modified phenolic resin, after adding curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir at high speed for 30 seconds, quickly pour it into a mold with a certain volume, close the mold, and set the temperature at 70 Foaming and solidification at ℃ for 1 hour, cooling, and demoulding to obtain polyetheramine toughened phenolic foam with a density of about 40kg/ ^m3 .

The polyetheramine toughened phenolic foam obtained above has a compressive strength of 221KPa measured with reference to the GB8813-1988 standard, an impact strength of 248J/m ² measured with reference to the GB/T1043-1993 standard, and a slag dropping rate of 248J/m2 with reference to GB/T12812-1991 The standard was determined to be 4.2%.

Example 3

A polyetheramine toughened phenolic foam, its composition and content are as follows:

Polyetheramine modified phenolic resin 50g

Surfactant 2g

Foaming agent 5g

Curing agent 7g

The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps:

(1) Add 90g of phenol and 50g of paraformaldehyde into a three-necked flask, and add 12g of 10% sodium hydroxide solution, heat up to 60-80°C under stirring conditions, and keep warm for 30-60 minutes to obtain reaction solution A;

(2) Add 4g of polyetheramine D-2000 to the reaction liquid A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction liquid B;

(3), adding phosphoric acid dropwise to the reaction solution B obtained in step (2) to control the pH value to 6.5-7.5, to obtain 152 g of polyetheramine modified phenolic resin;

Described surfactant is Tween-80;

Described whipping agent is pentane;

Described curing agent, its composition and content are as follows:

Phosphoric acid 15g (30%)

p-toluenesulfonic acid 18g (36%)

Boric acid 5g (10%)

Water 12g (24%)

The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent.

The preparation method of above-mentioned a kind of polyetheramine toughened phenolic foam, concrete steps are as follows:

That is, in the polyetheramine modified phenolic resin, after adding curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir at high speed for 30 seconds, quickly pour it into a mold with a certain volume, close the mold, and set the temperature at 70 It was foamed and solidified at ℃ for 1 hour, cooled, demoulded, and a polyetheramine toughened phenolic foam with a density of about 50kg/ ^m3 was obtained.

The polyetheramine toughened phenolic foam obtained above has a compressive strength of 212KPa measured with reference to the GB8813-1988 standard, an impact strength of 233J/m ² measured with reference to the GB/T1043-1993 standard, and a slag dropping rate of 233J/m2 with reference to GB/T12812-1991 The standard was determined to be 4.8%.

Example 4

A polyetheramine toughened phenolic foam, its composition and content are as follows:

Polyetheramine modified phenolic resin 50g

Surfactant 3g

Foaming agent 5g

Curing agent 5g

The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps:

(1) Add 90g of phenol and 60g of paraformaldehyde into a three-necked flask, and add 10g of 10% sodium hydroxide solution, heat up to 60-80°C under stirring conditions, and keep warm for 30-60 minutes to obtain reaction solution A;

(2) Add 15g of polyetheramine D-400 to the reaction liquid A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction liquid B;

(3), adding phosphoric acid dropwise to the reaction solution B obtained in step (2) to control the pH value to 6.5-7.5, to obtain 170 g of polyetheramine modified phenolic resin;

Described surfactant is Tween-80;

Described whipping agent is pentane;

Described curing agent, its composition and content are as follows:

Phosphoric acid 15g (30%)

p-toluenesulfonic acid 18g (36%)

Boric acid 5g (10%)

Water 12g (24%)

The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent.

The preparation method of above-mentioned a kind of polyetheramine toughened phenolic foam, concrete steps are as follows:

That is, in the polyetheramine modified phenolic resin, after adding curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir at high speed for 30 seconds, quickly pour it into a mold with a certain volume, close the mold, and set the temperature at 70 It was foamed and solidified at ℃ for 1 hour, cooled, demoulded, and a polyetheramine toughened phenolic foam with a density of about 60kg/ ^m3 was obtained.

The polyetheramine toughened phenolic foam obtained above has a compressive strength of 223KPa measured with reference to the GB8813-1988 standard, an impact strength of 266J/m ² measured with reference to the GB/T1043-1993 standard, and a slag dropping rate with reference to GB/T12812-1991 The standard was determined to be 3.9%.

The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall fall within the scope of protection of the present invention.

Claims (10)

1. A polyetheramine toughened phenolic foam is characterized in that, calculated in parts by weight, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 3～10 parts Foaming agent 5-15 parts Curing agent 5-20 parts The polyetheramine modified phenolic resin described therein is prepared by the method comprising the following steps: (1) Control the molar ratio of phenol and formaldehyde between 1:1.5~2, mix phenol and formaldehyde and add sodium hydroxide solution to control the pH value at 7.5~10, heat up to 60~80°C under stirring conditions, Heat preservation reaction for 30-60 minutes to obtain reaction solution A; (2) Add polyetheramine of 3% to 20% of the weight of phenol to the reaction solution A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction solution B; (3) Add phosphoric acid dropwise to the reaction solution B obtained in step (2), and control the pH value to 6.5-7.5 to obtain a polyetheramine-modified phenolic resin; Described surfactant is Tween-80; Described whipping agent is pentane; Described curing agent, calculated by mass percentage, its composition and content are as follows: Phosphoric acid 5%～60% p-toluenesulfonic acid 20%～45% Boric acid 5%～15% Water 15%～40%; The preparation method of the above-mentioned curing agent is to mix and dissolve phosphoric acid, p-toluenesulfonic acid, boric acid and water to obtain the curing agent. 2. A kind of polyetheramine toughened phenolic foam as claimed in claim 1, is characterized in that by weight parts, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 4～10 parts Foaming agent 6-14 parts Curing agent 8 to 18 parts. 3. a kind of polyetheramine toughened phenolic foam as claimed in claim 2, is characterized in that by weight parts, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 6 parts Foaming agent 6 parts Curing agent 8 parts The curing agent described therein is calculated by mass percentage, and its composition and content are as follows: Phosphoric acid 58% p-toluenesulfonic acid 22% Boric acid 5% Water 15%. 4. a kind of polyetheramine toughened phenolic foam as claimed in claim 2, is characterized in that by weight parts, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 10 parts Foaming agent 14 parts Curing agent 18 parts Described curing agent, calculated by mass percentage, its composition and content are as follows: Phosphoric acid 6% p-toluenesulfonic acid 44% Boric acid 12% Water 38%. 5. A kind of polyetheramine toughened phenolic foam as claimed in claim 2, is characterized in that by weight parts, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 4 parts Foaming agent 10 parts Curing agent 14 parts Described curing agent, calculated by mass percentage, its composition and content are as follows: Phosphoric acid 30% p-toluenesulfonic acid 36% Boric acid 10% Water 24%. 6. A kind of polyetheramine toughened phenolic foam as claimed in claim 2, is characterized in that calculated by weight, its composition and content are as follows: Polyetheramine modified phenolic resin 100 parts Surfactant 6 parts Foaming agent 10 parts Curing agent 10 parts Described curing agent, calculated by mass percentage, its composition and content are as follows: Phosphoric acid 30% p-toluenesulfonic acid 36% Boric acid 10% Water 24%. 7. A polyetheramine toughened phenolic foam as claimed in claim 1, 2, 3, 4, 5 or 6, characterized in that in the step (1) of the preparation process of the polyetheramine modified phenolic resin Described sodium hydroxide solution concentration is 10%. 8. A polyetheramine toughened phenolic foam as claimed in claim 7, characterized in that the polyetheramine described in step (3) of the preparation process of the polyetheramine modified phenolic resin is D-230 , D-400, D-2000, T-2000, T-3000 or T-5000. 9. the preparation method of a kind of polyetheramine toughened phenolic foam as claimed in claim 1, 2, 3, 4, 5 or 6, is characterized in that the steps are as follows: That is, in the polyetheramine modified phenolic resin, add curing agent, surfactant Tween-80, and foaming agent pentane in sequence, stir and mix at high speed, pour into the mold, heat and foam to form, and obtain polyetheramine toughened Phenolic foam. 10. the polyetheramine modified phenolic resin described in a kind of polyetheramine toughening phenolic foam as claimed in claim 8 is characterized in that preparing by the method comprising the following steps: (1) Control the molar ratio of phenol and formaldehyde between 1:1.5~2, mix phenol and formaldehyde and add sodium hydroxide solution to control the pH value at 7.5~10, heat up to 60~80°C under stirring conditions, Heat preservation reaction for 30-60 minutes to obtain reaction solution A; (2) Add polyetheramine of 3% to 20% of the weight of phenol to the reaction solution A obtained in step (1) and raise the temperature to 85-95°C, keep the temperature for 60-90 minutes, stop the reaction, and cool to room temperature to obtain the reaction solution B; (3) Add phosphoric acid dropwise to the reaction solution B obtained in step (2) to control the pH value to 6.5-7.5 to obtain polyetheramine modified phenolic resin.