阅读说明：本技术 一种耐热阻燃聚氯乙烯皮革材料 (Heat-resistant flame-retardant polyvinyl chloride leather material ) 是由 徐毓敏 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氯乙烯皮革材料,该耐热阻燃聚氯乙烯皮革材料包含一种新型的阻燃剂,该阻燃剂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[(6-氧代-6H-二苯并[C,E][1,2]氧磷杂己环-6-基)甲基]丁二醇发生酯化反应得到羟基封端的含磷氯化石蜡,最后再与异氰尿酸酯三酰氯反应得到新型阻燃剂,该阻燃剂用于制备耐热阻燃聚氯乙烯皮革材料可以保证材料除具有良好的力学性能、加工性能外及良好的耐高温性能外,还具有非常好的高难燃性能,而且成本低廉。(The invention discloses a heat-resistant flame-retardant polyvinyl chloride leather material, which comprises a novel flame retardant, and the preparation method of the flame retardant 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 [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol to obtain phosphorus-containing chlorinated paraffin of hydroxyl end capping, and finally reacting with isocyanurate triacyl chloride to obtain the novel flame retardant, wherein the flame retardant is used for preparing the heat-resistant flame-retardant polyvinyl chloride leather material and can ensure that the material has good mechanical property, processing property, high temperature resistance and high flame-retardant property, and the cost is low.)

1. A heat-resistant flame-retardant polyvinyl chloride leather material is characterized in that the heat-resistant flame-retardant polyvinyl chloride leather material is prepared by processing polyvinyl chloride resin, ammonium polyphosphate, aluminum hydroxide, antimony trioxide, calcium stearate and a flame retardant; the flame retardant has a structure represented by formula (I):

in the formula (I), R₁、R₂、R₃Is a chlorinated paraffin chain segment.

2. The preparation method of the flame retardant 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

Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive thionyl chloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxy-terminated phosphorus-containing chlorinated Paraffins

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and acid-binding agent triethylamine for esterification reaction to obtain hydroxyl-terminated chlorinated paraffin containing phosphorus;

and (4): preparation of Isocyanuric chloride

Acylating tris (2-carboxyethyl) isocyanurate by thionyl chloride to obtain isocyanurate triacyl chloride;

and (5): preparation of flame retardant

Slowly dripping the isocyanurate triacyl chloride prepared in the step (4) into a mixed system of the hydroxyl-terminated phosphorus-containing chlorinated paraffin prepared in the step (3) and triethylamine serving as an acid-binding agent for esterification reaction, and reacting to obtain the product.

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) reacts with excess thionyl chloride under reflux conditions for 4-6 h to obtain chlorinated paraffin containing acyl chloride.

5. The method according to claim 2, wherein the acid chloride-containing chlorinated paraffin is reacted with [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol at a molar ratio of 1 to 1.1:1 in the step (3).

6. The preparation method of claim 2, wherein the esterification reaction in step (3) is carried out under the conditions that chlorinated paraffin containing acyl chloride is slowly added dropwise into a mixed solution of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] phospho-cyclohex-6-yl) methyl ] butanediol and an 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 2-4H.

7. The method according to claim 2, wherein in the step (4), the tris (2-carboxyethyl) isocyanurate reacts with excess thionyl chloride under reflux conditions for 4-6 hours to obtain isocyanurate trichloride.

8. The method according to claim 2, wherein the molar ratio of the isocyanurate trichloride reacted with the hydroxyl-terminated chlorinated phosphorus-containing paraffin in step (5) is 1-1.2: 3.

9. The preparation method of claim 2, wherein the esterification reaction in the step (5) is carried out under the reaction conditions that firstly, the isocyanurate triacyl chloride is slowly dripped into the mixed solution of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the acid-binding agent in the ice-water bath for reaction, and after the dripping is finished, the reaction is continued in the ice-water bath for 3-5 hours.

Technical Field

The invention relates to a heat-resistant flame-retardant polyvinyl chloride leather material, and belongs to the technical field of heat-resistant flame-retardant high polymer materials.

Background

The artificial leather is made up by using various PVC and PU with different formulas and making them pass through the processes of foaming or film-covering treatment on the basis of textile fabric base or non-woven fabric base, and can be made up according to the requirements of different strength, wear-resisting degree, cold-resisting degree, colour, gloss and pattern, etc. and has the characteristics of extensive design and colour variety, good water-proofing property, regular side width, high utilization rate and low cost. It is a very popular class of materials from the early days to the present, and is commonly used to make various leather products, or parts of leather materials. The surface of the product is very fine and smooth, has no flaws and is durable, so the product is widely applied to automobiles, furniture and home furnishing.

Because the materials are mostly inflammable, the material becomes a generating source of smoke gas poison and heat energy in the fire scene. Therefore, the fire hazard brought to the safe life quality and property of people is greatly limited, and the application in special fields with higher fire-proof grade requirements (such as furniture materials in intensive places of people, such as public places, commercial places, entertainment places, educational places and the like) is also greatly limited.

Disclosure of Invention

Aiming at the defects of the polyvinyl chloride leather in the prior art, the invention aims to provide the chlorinated paraffin flame retardant modified by the phosphorus-containing isocyanurate, which has high flame retardant efficiency and is applied to the polyvinyl chloride leather material. The physical and chemical properties are stable, the heat resistance is good, the compatibility with high polymer materials is good, the functions of plasticization and carbon formation and dripping prevention are achieved, and the defects in the prior art can be overcome.

The invention also aims to provide a method for preparing the phosphorus-containing isocyanurate modified chlorinated paraffin flame retardant, which is applied to polyvinyl chloride leather materials and has the advantages of wide raw material source, simple operation and mild reaction conditions.

The invention discloses a heat-resistant flame-retardant polyvinyl chloride leather material which is characterized by being prepared by processing polyvinyl chloride resin, ammonium polyphosphate, aluminum hydroxide, antimony trioxide, calcium stearate and a flame retardant; the flame retardant has a structure represented by formula (I):

in the formula (I), R₁、R₂、R₃Is a chlorinated paraffin chain segment.

The invention also provides a preparation method of the flame retardant, 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

Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive thionyl chloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxy-terminated phosphorus-containing chlorinated Paraffins

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and acid-binding agent triethylamine for esterification reaction to obtain hydroxyl-terminated chlorinated paraffin containing phosphorus;

and (4): preparation of Isocyanuric chloride

Acylating tris (2-carboxyethyl) isocyanurate by thionyl chloride to obtain isocyanurate triacyl chloride;

and (5): preparation of flame retardant

Slowly dripping the isocyanurate triacyl chloride prepared in the step (4) into a mixed system of the hydroxyl-terminated phosphorus-containing chlorinated paraffin prepared in the step (3) and triethylamine serving as an acid-binding agent for esterification reaction, and reacting to obtain the product.

The preparation method of the flame retardant 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 excessive thionyl chloride under the reflux condition for 4-6 h to prepare chlorinated paraffin containing acyl chloride.

Preferably, the mole ratio of the chlorinated paraffin containing acyl chloride in the step (3) to the [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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.

Preferably, in the step (4), the tris (2-carboxyethyl) isocyanurate reacts with excessive thionyl chloride under the reflux condition for 4-6 h to prepare isocyanurate triacyl chloride.

Preferably, the reaction molar ratio of the isocyanurate triacyl chloride to the hydroxyl-terminated phosphorus-containing chlorinated paraffin in the step (5) is 1-1.2: 3.

Preferably, the esterification reaction in the step (5) is carried out under the reaction condition that firstly, the isocyanurate triacyl chloride is slowly dripped into the mixed solution of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the acid-binding agent in the ice-water bath for reaction, and after the dripping is finished, the reaction is continuously carried out for 3-5 hours in the ice-water bath.

The invention has the beneficial effects that: according to the invention, the isocyanurate is used as a bridge chain to connect the traditional chlorinated paraffin and the phosphorus-containing flame retardant to synthesize the novel flame retardant for the first time, three excellent flame-retardant elements of nitrogen, phosphorus and chlorine are simultaneously embedded into branched molecules, and the three elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, so that higher flame-retardant efficiency can be shown.

Drawings

FIG. 1 is an infrared image of a flame retardant prepared in example 2.

FIG. 1: 2920cm^-1And 2860cm^-1Is the absorption peak of stretching vibration of methyl and methylene, 1470cm^-1And 1370cm^-1Bending vibration absorption peak of methyl group, 1745cm^-1Is the absorption peak of stretching vibration of C ═ O in the ester group, 1690cm^-1And 1420cm^-1Is the expansion vibration absorption peak of C ═ O in isocyanurate, 1600cm^-1Is P-C₆H₅1230cm of deformation vibration absorption peak^-1And 1050cm^-1Is a characteristic absorption peak of a C-O-C ether bond of 1200cm^-1Where is P ═ O absorption peak of stretching vibration, 1150cm^-1Has a stretching vibration peak of 980cm of C-N single bond^-1The point is the vibration characteristic absorption peak of P-C, 755cm^-1In the form of a benzene ringDisubstituted C-H out-of-plane flexural vibration peak, 710cm^-1Here is the stretching vibration peak of the C-Cl 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.

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 55 ℃ for 30h 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: and adding 70mol of chlorinated paraffin 42 containing carboxyl into the reaction kettle, dropwise adding 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 6 hours to obtain chlorinated paraffin 42 containing acyl chloride.

(3) Preparation of the hydroxyl-terminated phosphorus-containing chlorinated paraffin 42: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 reactant at 0 ℃ for 2H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated chlorinated paraffin 42 containing phosphorus.

(4) Preparation of isocyanurate triacyl chloride: adding 60mol of tris (2-carboxyethyl) isocyanurate into a reaction kettle, dropwise adding 200mol of thionyl chloride, stirring and heating until reflux, and reacting for 4 hours to obtain isocyanurate triacyl chloride.

(5) Preparation of the flame retardant: adding 300mol of the hydroxyl-terminated phosphorus-containing chlorinated paraffin 42 prepared in the step (3) 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 102mol of isocyanurate triacyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 5h, 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 flame retardant F1.

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 80 ℃ for 10 hours 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 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 4 hours to obtain chlorinated paraffin 52 containing acyl chloride.

(3) Preparation of hydroxyl-terminated phosphorus-containing chlorinated paraffin 52: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 102mol of chloride-containing chlorinated paraffin 52 at 0 ℃, reacting the reactants at 0 ℃ for 4H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated phosphorus-containing chlorinated paraffin 52.

(4) Preparation of isocyanurate triacyl chloride: adding 60mol of tris (2-carboxyethyl) isocyanurate into a reaction kettle, dropwise adding 200mol of thionyl chloride, stirring and heating until reflux, and reacting for 6 hours to obtain isocyanurate triacyl chloride.

(5) Preparation of the flame retardant: adding 300mol of the hydroxyl-terminated phosphorus-containing chlorinated paraffin 52 prepared in the step (3) 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 isocyanurate triacyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 4h, 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 flame retardant F2.

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 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 5 hours to obtain the chlorinated paraffin 70 containing acyl chloride.

(3) Preparation of hydroxyl-terminated phosphorus-containing chlorinated paraffin 70: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 102mol of chloride-containing chlorinated paraffin 70 at 0 ℃, reacting the reactant at 0 ℃ for 3H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated phosphorus-containing chlorinated paraffin 70.

(4) Preparation of isocyanurate triacyl chloride: adding 60mol of tris (2-carboxyethyl) isocyanurate into a reaction kettle, dropwise adding 200mol of thionyl chloride, stirring and heating until reflux, and reacting for 5 hours to obtain isocyanurate triacyl chloride.

(5) Preparation of the flame retardant: adding 300mol of the hydroxyl-terminated phosphorus-containing chlorinated paraffin 70 prepared in the step (3) 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 isocyanurate triacyl 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 flame retardant F3.

Preparing a polyvinyl chloride leather material: 100 parts of PVC resin, 2 parts of ammonium polyphosphate, 8 parts of aluminum hydroxide, 5 parts of antimony trioxide, 2.5 parts of calcium stearate and 40 parts of prepared flame retardant or chlorinated paraffin are put into a mixer, mixed and stirred uniformly at 90 ℃ to obtain a mixture, and then the mixture is extruded by a shaping grinding tool of a conical double-screw extruder to form a sheet.

Comparative example 1

40 parts by mass of chlorinated paraffin 42, 30 parts by mass of tris (2-hydroxyethyl) isocyanurate and 30 parts by mass of DOPO were uniformly mixed to obtain flame retardant D1.

Comparative example 2

40 parts by mass of chlorinated paraffin 52, 30 parts by mass of tris (2-hydroxyethyl) isocyanurate and 30 parts by mass of DOPO were uniformly mixed to obtain flame retardant D2.

Comparative example 3

40 parts by mass of chlorinated paraffin 70, 30 parts by mass of tris (2-hydroxyethyl) isocyanurate and 30 parts by mass of DOPO were uniformly mixed to obtain flame retardant D3.

The polyvinyl chloride leather materials were tested for their properties according to the experimental methods specified in standards QB-T3812.5-1999, QB-T381.6-1999 and QB-T2712-2005, and the results are shown in Table 1.

Table 1 performance data for polyvinyl chloride leather materials prepared in examples 1-3:

in conclusion, the branched flame retardant has three excellent flame retardant elements, namely nitrogen, phosphorus and chlorine, embedded in the branched flame retardant molecule, and the three elements generate synergistic interaction from different flame retardant mechanisms, so that higher flame retardant efficiency can be shown.