阅读说明：本技术 一种具有阻燃功能的聚氨酯泡沫及其制备方法 (Polyurethane foam with flame retardant function and preparation method thereof ) 是由 徐松波 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种具有阻燃功能的聚氨酯泡沫,该聚氨酯泡沫材料由具有阻燃功能的聚酯多元醇固化而成,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,然后再与四溴苯酐反应得到二元酸,该二元酸与溴代多元醇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,可用于制备阻燃聚氨酯泡沫材料。(The invention discloses polyurethane foam with a flame-retardant function, which is prepared by curing polyester polyol with the 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, then carrying out reaction with tetrabromophthalic anhydride to obtain dibasic acid, and carrying out esterification reaction on the dibasic acid and brominated polyol to prepare the polyol with the flame-retardant function.)

1. The polyurethane foam with the flame retardant function 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 dibasic acid shown in a formula (I) with bromine-containing polyol:

wherein in the formula (I), R is a chlorinated paraffin chain segment; the bromine-containing polyol is 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol or dibromo neopentyl glycol or a mixture of the two.

2. The preparation method of the flame-retardant polyester polyol is characterized by comprising the following steps of:

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 chlorinated paraffin modified by isocyanuric ester containing dihydroxy

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 brominated isocyanurate-modified chlorinated Paraffin dibasic acid

Reacting the chlorinated paraffin containing the dibasic hydroxyl group obtained in the step (3) with tetrabromophthalic anhydride to obtain brominated isocyanurate modified chlorinated paraffin dibasic acid;

and (5): preparation of polyols

And (3) reacting the brominated isocyanurate modified chlorinated paraffin dibasic acid obtained in the step (4) with bromine-containing polyol to obtain the flame-retardant polyol, wherein the bromine-containing polyol is 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol or dibromo neopentyl glycol or a mixture of the two.

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

5. The method according to claim 2, wherein the mole ratio of the chlorinated paraffin containing the acid chloride to the tris (2-hydroxyethyl) isocyanurate in the step (3) is 1 to 1.2: 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 method of claim 2, wherein the reaction molar ratio of the chlorinated paraffin containing a dibasic hydroxyl group to tetrabromophthalic anhydride in the step (4) is 1: 2.

8. The preparation method according to claim 2, wherein the reaction conditions in the step (4) are reaction at a temperature of 60-80 ℃ for 3-7 h.

9. The preparation method of claim 2, wherein the reaction condition in the step (5) is brominated isocyanurate-modified chlorinated paraffin dibasic acid, and the bromine-containing polyol and a proper amount of water-carrying agent toluene or cyclohexane are heated to 120-190 ℃ under stirring and are reacted for 3-6 h under the catalysis of p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants, so as to obtain the flame-retardant polyol product.

Technical Field

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

Background

The polyurethane foam plastic is a low-density microporous urethane high polymer material generated by the reaction of polyester or polyether polyol and isocyanate, has the properties of light weight, low water absorption, good heat insulation and preservation properties, strong weather resistance, low heat conductivity coefficient, better mechanical properties, chemical corrosion resistance and the like, has stronger bonding strength with various materials, and is widely used as heat insulation and preservation materials of petrochemical pipelines, refrigeration equipment, transportation equipment, buildings and the like. However, polyurethane foams that have not been flame-retarded are susceptible to burning and are hazardous to human life and property safety due to the presence of hydrocarbon, ether, ester, and like groups in the structure. Therefore, the heat resistance and flame retardancy of polyurethane foams have become important technical indicators of polyurethane foam materials. 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 of chlorinated paraffin flame retardant in the prior art, the invention aims to provide a bromine-containing isocyanurate modified flame-retardant polyol with a molecular side chain containing 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 polyurethane foam with a flame retardant function, which is characterized in that the polyurethane foam material is prepared by solidifying polyester polyol, water, a foaming agent, a foam stabilizer and isocyanate; the polyester polyol is prepared by reacting dibasic acid shown in a formula (I) with bromine-containing polyol:

wherein in the formula (I), R is a chlorinated paraffin chain segment; the bromine-containing polyol is 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol or dibromo neopentyl glycol or a mixture of the two.

The invention also provides a preparation method of the polyol with the flame retardant function, 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 chlorinated paraffin modified by isocyanuric ester containing dihydroxy

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 brominated isocyanurate-modified chlorinated Paraffin dibasic acid

Reacting the chlorinated paraffin containing the dibasic hydroxyl group obtained in the step (3) with tetrabromophthalic anhydride to obtain brominated isocyanurate modified chlorinated paraffin dibasic acid;

and (5): preparation of polyols

And (3) reacting the brominated isocyanurate modified chlorinated paraffin dibasic acid obtained in the step (4) with bromine-containing polyol to obtain the flame-retardant polyol, wherein the bromine-containing polyol is 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol or dibromo neopentyl glycol or a mixture of the two.

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

in the preferable scheme, the chlorinated paraffin and the p-hydroxybenzoic acid in the step (1) react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.

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

In a preferable scheme, the reaction molar ratio of the chlorinated paraffin containing acyl chloride and the tris (2-hydroxyethyl) isocyanurate in the step (3) is 1-1.2: 1.

In a preferable scheme, 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 the reaction is continued in the ice-water bath for 2-4 hours after the dripping is finished.

In a preferred scheme, the reaction molar ratio of the chlorinated paraffin containing the dibasic hydroxyl and the tetrabromophthalic anhydride in the step (4) is 1: 2.

In the preferable scheme, the reaction condition in the step (4) is that the reaction is carried out for 3-7 hours at the temperature of 60-80 ℃.

In the preferable scheme, in the step (5), the reaction condition is brominated isocyanurate modified chlorinated paraffin dibasic acid, bromine-containing polyol and a proper amount of water-carrying agent toluene or cyclohexane are heated to 120-190 ℃ under the catalysis of p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants, and the reaction is carried out for 3-6 hours under stirring, so as to obtain the flame-retardant polyol product.

The invention has the beneficial effects that: according to the invention, the traditional chlorinated paraffin and tetrabromophthalic anhydride molecules are introduced into an isocyanurate molecular chain through chemical bonds for the first time to form a novel dibasic acid, and then the dibasic acid and bromine-containing polyol are polymerized into the 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 image of the polyol prepared in example 2.

FIG. 1: 3500cm^-1Is a stretching vibration absorption peak of hydroxyl in the polyhydric alcohol, and is 2920cm^-1And 2860cm^-1Is the absorption peak of stretching vibration of methyl and methylene, 1470cm^-1And 1370cm^-1The bending vibration absorption peak of methyl group. 1745cm^-1Is the stretching vibration of C ═ O in the ester groupAbsorption peak, 1690cm^-1And 1420cm^-1Is the expansion vibration absorption peak of C ═ O in isocyanurate, 1150cm^-1At the stretching vibration peak of the C-N single bond, 1230cm^-1And 1050cm^-1Is a characteristic absorption peak of the C-O-C ether bond of 710cm^-1Is the stretching vibration peak of C-Cl bond, 550cm^-1And (b) is a stretching vibration peak of the C-Br bond.

Detailed Description

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