阅读说明：本技术 一种耐热阻燃聚氨酯泡沫材料及其制备方法 (Heat-resistant flame-retardant polyurethane foam material and preparation method thereof ) 是由 邱元栏 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种耐热阻燃聚氨酯泡沫材料,该聚氨酯泡沫材料由具有阻燃功能的聚酯多元醇发泡固化而成,该多元醇的制备方法是先由氯化石蜡和对羟基苯甲酸反应制备含羧基氯化石蜡,再由含羧基氯化石蜡经酰化得含酰氯氯化石蜡,然后再与三(2-羟乙基)异氰尿酸酯通过酯化反应得到异氰尿酸酯改性的含羟基氯化石蜡,然后再与四溴苯酐发生酯化反应制备得到具有阻燃功能的多元醇,该制备方法操作简单、原料来源广,反应条件温和,满足工业化生产,制备的聚氨酯泡沫材料具有优异的阻燃耐热性能。(The invention discloses a heat-resistant flame-retardant polyurethane foam material, which is prepared by foaming and curing polyester polyol with a flame-retardant function, wherein the preparation method of the polyol comprises the steps of firstly preparing chlorinated paraffin containing carboxyl by reacting the chlorinated paraffin with p-hydroxybenzoic acid, then acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then carrying out esterification reaction with tris (2-hydroxyethyl) isocyanurate to obtain hydroxyl-containing chlorinated paraffin modified by isocyanurate, and then carrying out esterification reaction with tetrabromophthalic anhydride to prepare the polyol with the flame-retardant function.)

1. The heat-resistant flame-retardant polyurethane foam material is characterized by being prepared by solidifying polyester polyol, water, a foaming agent, a foam stabilizer and isocyanate; the polyester polyol is prepared by reacting dihydric alcohol shown in a formula (I) with tetrabromophthalic anhydride:

in the formula (I), R is a chlorinated paraffin chain segment.

2. A preparation method of polyester polyol with a flame retardant function is characterized by comprising the following steps:

step (1): preparation of chlorinated paraffins containing carboxyl groups

Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;

step (2): preparation of chlorinated paraffins containing acid chlorides

Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxyl-containing isocyanurate modified chlorinated Paraffin

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction to obtain chlorinated paraffin containing hydroxyl;

and (4): preparation of polyester polyol

And (4) reacting the chlorinated paraffin diol prepared in the step (3) with tetrabromophthalic anhydride to prepare the polyester polyol with the flame retardant function.

3. The method according to claim 2, wherein the chlorinated paraffin containing a carboxyl group is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at a temperature of 55-80 ℃ for 10-30 hours.

4. The preparation method according to claim 2, wherein the chlorinated paraffin containing carboxyl groups in the step (2) is reacted with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.

5. The method according to claim 2, wherein the mole ratio of the chlorinated paraffin containing acid chloride to tris (2-hydroxyethyl) isocyanurate in the step (3) is 1 to 1.1: 1.

6. The preparation method of claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction conditions that chlorinated paraffin containing acyl chloride is slowly added dropwise into the mixed solution of tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dropwise addition is completed, the reaction is continued in the ice-water bath for 2-4 hours.

7. The preparation method of claim 2, wherein in the step (4), the chlorinated paraffin diol, tetrabromophthalic anhydride and a proper amount of water-carrying agent toluene or cyclohexane are heated to 120-190 ℃ under stirring and reacted for 3-6 hours under the catalysis of p-benzenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants, so as to obtain the flame-retardant polyester polyol.

Technical Field

The invention relates to a heat-resistant flame-retardant polyurethane foam material and a preparation method thereof, belonging to the field of flame-retardant foam materials.

Background

Polyurethane foam is an insulating and heat-insulating material with the best performance in the world at present, and is also a good sound-insulating material, and the polyurethane foam is widely applied to refrigerators, roofs, ceilings, walls, cold storages, floors and the like as a heat-insulating material at present with more and more importance on energy conservation and environmental protection requirements. However, polyurethane foam has a relatively low density, has a plurality of cellular structures, is more easily burnt than non-foam materials, and emits a large amount of heat and toxic smoke during combustion, thereby affecting the health and life safety of people. Therefore, the heat resistance and flame retardancy of rigid polyurethane foams have become important technical indicators of polyurethane foams. A large number of regulations are provided in various countries and regions, and the flame retardant property of the polyurethane foam material is required to reach a certain standard before production, so that the development of the polyurethane flame retardant technology is greatly promoted by the emergence of various regulations.

The chlorinated paraffin is a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good barrier property, low price and the like, can be used as additives such as a plasticizer, a flame retardant and the like, but the addition type flame retardant is large in addition amount and general in flame retardance, and the addition type flame retardant is easy to migrate out of a polymer network along with the time migration, so that the flame retardance durability is reduced.

Disclosure of Invention

Aiming at the defects existing in the application of chlorinated paraffin and polyurethane foam materials in the prior art, the invention aims to provide a polyurethane flame-retardant foam material prepared from isocyanurate modified polyester polyol of which the molecular side chain contains chlorinated paraffin molecules.

The invention also aims to provide a method for preparing the polyol with the flame retardant function, which has the advantages of wide raw material source, simple operation and mild reaction conditions.

The invention provides a heat-resistant flame-retardant polyurethane foam material which is characterized in that the polyurethane foam material is obtained by solidifying polyester polyol, water, a foaming agent, a foam stabilizer and isocyanate; the polyester polyol is prepared by reacting dihydric alcohol shown in a formula (I) with tetrabromophthalic anhydride:

in the formula (I), R is a chlorinated paraffin chain segment.

The invention also provides a preparation method of the polyester polyol, which comprises the following steps:

step (1): preparation of chlorinated paraffins containing carboxyl groups

Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;

step (2): preparation of chlorinated paraffins containing acid chlorides

Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxyl-containing isocyanurate modified chlorinated Paraffin

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction to obtain chlorinated paraffin containing hydroxyl;

and (4): preparation of polyester polyol

And (4) reacting the chlorinated paraffin diol prepared in the step (3) with tetrabromophthalic anhydride to prepare the polyester polyol with the flame retardant function.

The preparation method of the polyester polyol with the flame retardant function further comprises the following preferred scheme:

preferably, the chlorinated paraffin containing carboxyl is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at the temperature of 55-80 ℃ for 10-30 h.

Preferably, the chlorinated paraffin containing carboxyl in the step (2) reacts with phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to obtain chlorinated paraffin containing acyl chloride.

More preferably, the reaction molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate in the step (3) is 1-1.1: 1.

Preferably, the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly dripped into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dripping is finished, the reaction is continuously carried out in the ice-water bath for 2-4 hours.

Preferably, in the step (4), the chlorinated paraffin diol, tetrabromophthalic anhydride and a proper amount of water-carrying agent toluene or cyclohexane are heated to 120-190 ℃ under stirring and are reacted for 3-6 hours under the catalysis of p-benzenesulfonic acid with the mass fraction of 1-5% of the total mass of the reactants, so as to obtain the flame-retardant polyester polyol.

The invention has the beneficial effects that: according to the invention, the traditional chlorinated paraffin molecule is introduced into an isocyanurate molecular chain through a chemical bond for the first time to form a novel polyol, and then the novel polyol is polymerized with tetrabromobenzene anhydride to form the polyester polyol with a flame retardant function. The whole preparation process has the advantages of easily available raw materials, low cost, simple operation, high purity of the obtained product and high yield, and meets the requirements of industrial production.

Drawings

FIG. 1 is an infrared chart of the polyester polyol obtained in example 3.

Detailed Description

The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.

Example 1

1) Preparation of chlorinated paraffin 42 containing carboxyl group: dissolving 20g of chlorinated paraffin 42 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.

2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.

3) Preparation of isocyanurate modified chlorinated paraffin 42 diol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 101mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 42 dihydric alcohol.

4) Preparation of polyester polyol: 100mol of chlorinated paraffin 42 glycol, 80mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 3 hours at 190 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z1.

Example 2

1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.

2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.

3) Preparation of isocyanurate modified chlorinated paraffin 52 dihydric alcohol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 102mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 52 dihydric alcohol.

4) Preparation of polyester polyol: 100mol of chlorinated paraffin 52 glycol, 70mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 120 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z2.

Example 3

1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.

2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 7 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.

3) Preparation of isocyanurate modified chlorinated paraffin 70 dihydric alcohol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 305mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain chlorinated paraffin 70 dihydric alcohol.

4) Preparation of polyester polyol: 100mol of chlorinated paraffin 70 glycol, 75mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 120 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z3.

Example 4

1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 210mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 25g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.

2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of chlorinated paraffin 52 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 65 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 containing acyl chloride.

3) Preparation of isocyanurate modified chlorinated paraffin 52 dihydric alcohol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 103mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 52 dihydric alcohol.

4) Preparation of polyester polyol: 100mol of chlorinated paraffin 52 glycol, 85mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are introduced into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 5 hours at 130 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. Vacuum distilling to obtain Z4.

Comparative example 1

(1) Preparation of isocyanurate diol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 103mol of acetyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate diol.

(2) Preparation of polyester polyol: 100mol of isocyanuric acid ester dihydric alcohol, 85mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 5 hours at 130 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. The product D1 is obtained after reduced pressure distillation.

Comparative example 2

(1) Preparation of isocyanurate diol: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 103mol of acetyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the isocyanurate diol.

(2) Preparation of polyester polyol: 100mol of isocyanuric acid ester dihydric alcohol, 75mol of tetrabromophthalic anhydride and a proper amount of p-benzenesulfonic acid are added into a reaction kettle, nitrogen is introduced into the reaction kettle, the reaction is carried out for 6 hours at 120 ℃ until no water is generated, and the reaction is stopped. Cooling, filtering and rotary steaming to obtain a crude product. The product D2 is obtained after reduced pressure distillation.

Preparation and testing of polyurethane foams

The prepared flame-retardant polyester polyol, phthalic anhydride polyester polyol, catalyst triethylenediamine, foam stabilizer B8460 (German Texas company), water, foaming agent (cyclopentane), chlorinated paraffin were added into a stirring kettle according to the proportion in Table 1, mixed uniformly, a certain amount of combined polyol was taken out from a beaker, a certain amount of isocyanate MR200(BASF company) was added according to the isocyanate group and hydroxyl group ratio of 1.2:1, stirred uniformly rapidly, and then poured into a mold, heated, foamed and cured, and the polyurethane foam was taken out for testing, and the test results are shown in Table 2.

TABLE 1 Combined polyol formulation (parts by mass)

TABLE 2 polyurethane foam Properties (test methods refer to national standards)

In conclusion, the chlorinated paraffin is introduced into the isocyanurate molecular ring through a chemical bond to form a dihydric alcohol, and then the dihydric alcohol reacts with tetrabromophthalic anhydride to prepare the polyester polyol with the flame retardant function, so that the polyurethane flame retardant foam has good mechanical property and flame retardant property.