PREPARATION OF FUNCTIONALIZED ORGANIC MAGNESIUM SALT AND USE THEREOF IN PREPARATION OF POLYESTER COMPOSITE MATERIAL

Abstract

The present invention discloses a method for preparing a functionalized organic magnesium salt. The method includes completely dissolving organic acid in distilled water to form an organic acid aqueous solution, adding an inorganic magnesium salt into the organic acid aqueous solution, magnetically stirring for 1-5 h at 70-100 C., removing distilled water, and performing vacuum drying to obtain a white powdery solid which is a functionalized organic magnesium salt. An intrinsic flame-retardant PET composite material prepared by using the functionalized organic magnesium salt as a flame retardant not only achieves the compatibility between inorganic particles and a matrix, but also solves the problem of poor flame retardant performance of PET plastics in the existing production process.

Claims

1. A method for preparing a functionalized organic magnesium salt, comprising completely dissolving organic acid in distilled water to form an organic acid aqueous solution, adding an inorganic magnesium salt into the organic acid aqueous solution, magnetically stirring for 1-5 h at 70-100 C., removing distilled water, and performing vacuum drying to obtain a white powdery solid which is a functionalized organic magnesium salt.

2. The method for preparing a functionalized organic magnesium salt according to claim 1, wherein the organic acid is at least one of phosphorous acid, succinic acid, p-aminobenzoic acid and pimelic acid.

3. The method for preparing a functionalized organic magnesium salt according to claim 1, wherein the inorganic magnesium salt is magnesium hydroxide, magnesium carbonate, magnesium borate and magnesium oxide.

4. The method for preparing a functionalized organic magnesium salt according to claim 3, wherein the particle size of the inorganic magnesium salt is 400-600 nm.

5. The method for preparing a functionalized organic magnesium salt according to claim 1, wherein a molar ratio of the organic acid to inorganic particles is (0.5:1)-(3:1).

6. (canceled)

7. (canceled)

8. (canceled)

9. The method for preparing a functionalized organic magnesium salt according to claim 2, wherein a molar ratio of the organic acid to inorganic particles is (0.5:1)-(3:1).

10. The method for preparing a functionalized organic magnesium salt according to claim 3, wherein a molar ratio of the organic acid to inorganic particles is (0.5:1)-(3:1).

11. The method for preparing a functionalized organic magnesium salt according to claim 4, wherein a molar ratio of the organic acid to inorganic particles is (0.5:1)-(3:1).

12. Use of a functionalized organic magnesium salt prepared by the method according to claim 1 in preparation of a polyester composite material.

13. Use of the functionalized organic magnesium salt according to claim 1 in preparation of a polyester composite material, wherein terephthalic acid, ethylene glycol, antimony trioxide and the functionalized organic magnesium salt are added into a reaction kettle, and esterification reaction is carried out at 210-240 C. and 0.2-0.35 MPa under nitrogen atmosphere; after the esterification is finished, the system enters a vacuum polycondensation stage: the temperature is first controlled at 260-280 C. for low vacuum polycondensation for 0.5-1.5 h, and then the temperature is raised to 270-280 C. for high vacuum polycondensation; when the stirring power no longer continues to increase, the reaction is finished, a material is discharged and subjected to grain-sized dicing, and the master batch is dried at 120-160 C. for 12-24 h to remove moisture, so that a polyester composite material is obtained.

14. Use of the functionalized organic magnesium salt according to claim 1 in preparation of a flame-retardant polyester composite material, wherein a molar ratio of the terephthalic acid to the ethylene glycol is (1:1.2)-(1:1.5).

15. Use of the functionalized organic magnesium salt according to claim 1 in preparation of a flame-retardant polyester composite material, wherein the consumption of the functionalized organic magnesium salt is 1%-10% of the total mass of the polyester.

16. Use of the functionalized organic magnesium salt according to claim 1 in preparation of a flame-retardant polyester composite material, wherein the consumption of the catalyst antimony trioxide is 1/10000-2/10000 of the molar weight of the terephthalic acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is an infrared absorption spectrum of a functionalized organic magnesium salt prepared according to the present invention;

[0022] FIG. 2 illustrates thermal stability analysis of the functionalized organic magnesium salt prepared according to the present invention;

[0023] FIG. 3 is an XRD curve of the functionalized organic magnesium salt prepared according to the present invention;

[0024] FIG. 4 shows infrared absorption spectrum curves of a flame-retardant polyester composite material and a pure polyester prepared according to the present invention;

[0025] FIG. 5 shows peak heat release rate curves of the flame-retardant polyester composite material and the pure polyester prepared according to the present invention; and

[0026] FIG. 6 shows total heat release amount curves of the flame-retardant polyester composite material and the pure polyester prepared according to the present invention.

DETAILED DESCRIPTION

[0027] A method for preparing a PET composite material containing a functionalized organic magnesium salt is further described below through specific embodiments.

Embodiment 1

[0028] (1) Organic functionalization of magnesium hydroxide: 16.28 g of succinic acid was taken and dissolved in 300 mL of distilled water, 4 g of magnesium hydroxide was added after the succinic acid was completely dissolved, magnetic stirring was carried out for 2 h at 90 C., distilled water was removed, and vacuum drying was performed to obtain a white powdery solid which was a functionalized organic magnesium salt SMH.

[0029] (2) Preparation of a flame-retardant PET composite material: 830.65 g of terephthalic acid, 403.44 g of ethylene glycol, 0.29 g of antimony trioxide and 24.6 g of SMH were taken, mixed and added into a 1.5 L reaction kettle. The air tightness of the instrument was checked, nitrogen was slowly introduced to eliminate air in the kettle, and the temperature was controlled at 200 C. for esterification reaction; when the column top temperature was less than 100 C., the esterification reaction was finished, and water was drained. Then the system entered the polycondensation stage. After half vacuum polycondensation for 0.5 h, the temperature was slowly raised to 260 C. for high vacuum polymerization. When the stirring power no longer increased, the reaction was finished, a material was discharged and subjected to grain-sized dicing, and the master batch was dried at 130 C. for 13 h to remove moisture, so that a flame-retardant PET composite material was obtained.

[0030] (3) Properties of the flame-retardant PET composite material: flame retardancy: an oxygen index of 25% and a peak heat release rate of 600 kW/m.sup.2. Mechanical properties: bending strength of 70 MPa and bending modulus of 1600 MPa.

Embodiment 2

[0031] (1) Organic functionalization of magnesium oxide: 34 g of p-aminobenzoic acid was dissolved in 500 mL of distilled water; 5 g of magnesium oxide was added after the p-aminobenzoic acid was completely dissolved, magnetic stirring was carried out for 3 h at 80 C., distilled water was removed, and vacuum drying was performed to obtain a white powdery solid which was a functionalized organic magnesium salt PMO.

[0032] (2) Preparation of a flame-retardant PET composite material: 830.65 g of terephthalic acid, 403.44 g of ethylene glycol, 0.29 g of antimony trioxide and 50 g of PMO were taken, mixed and added into a 1.5 L reaction kettle. The air tightness of the instrument was checked, nitrogen was slowly introduced to eliminate air in the kettle, and the temperature was controlled at 220 C. for esterification reaction; when the column top temperature was less than 100 C., the esterification reaction was finished, and water was drained. Then the system entered the polycondensation stage. After half vacuum polycondensation for 0.5 h, the temperature was slowly raised to 275 C. for high vacuum polymerization. When the stirring power no longer increased, the reaction was finished, and a material was discharged and subjected to grain-sized dicing. The master batch was dried at 140 C. for 14 h to remove moisture, so that a flame-retardant PET composite material was obtained.

[0033] (3) Properties of the flame-retardant PET composite material: flame retardancy: an oxygen index of 27% and a peak heat release rate of 500 kW/m.sup.2. Mechanical properties: bending strength of 75 MPa and bending modulus of 1700 MPa.

Embodiment 3

[0034] (1) Organic functionalization of magnesium carbonate: 11.25 g of pimelic acid was taken and dissolved in 500 mL of distilled water, 3 g of magnesium carbonate was added after the pimelic acid was completely dissolved, magnetic stirring was carried out for 5 h at 90 C., distilled water was removed, and vacuum drying was performed to obtain a white powdery solid which was an organic magnesium salt PMC.

[0035] (2) Preparation of a flame-retardant PET composite material: 830.65 g of terephthalic acid, 403.44 g of ethylene glycol, 0.29 g of antimony trioxide and 74 g of PMC were taken, mixed and added into a 1.5 L reaction kettle. The air tightness of the instrument was checked, nitrogen was slowly introduced to eliminate air in the kettle, and the temperature was controlled at 240 C. for esterification reaction; when the column top temperature was less than 100 C., the esterification reaction was finished, and water was drained. Then the system entered the polycondensation stage. After half vacuum polycondensation for 1.0 h, the temperature was slowly raised to 280 C. for high vacuum polymerization. When the stirring power no longer increased, the reaction was finished, and a material was discharged and subjected to grain-sized dicing. The master batch was dried at 160 C. for 15 h to remove moisture, so that a flame-retardant PET composite material was obtained.

[0036] (3) Properties of the flame-retardant PET composite material: flame retardancy: an oxygen index of 28% and a peak heat release rate of 450 kW/m.sup.2. Mechanical properties: bending strength of 75 MPa and bending modulus of 1760 MPa.

Embodiment 4

[0037] (1) Organic functionalization of magnesium borate: 6.5 g of phosphorous acid was taken and dissolved in 200 mL of distilled water, 6 g of magnesium borate was added after the phosphorous acid was completely dissolved, magnetic stirring was carried out for 4 h at 90 C., distilled water was removed, and vacuum drying was performed to obtain a white powdery solid which was an organic magnesium salt PMB.

[0038] (2) Preparation of a flame-retardant PET composite material: 830.65 g of terephthalic acid, 403.44 g of ethylene glycol, 0.29 g of antimony trioxide and 98 g of PMB were taken, mixed and added into a 1.5 L reaction kettle. The air tightness of the instrument was checked, nitrogen was slowly introduced to eliminate air in the kettle, and the temperature was raised to be controlled at 240 C. for esterification reaction; when the column top temperature was less than 100 C., the esterification reaction was finished, and water was drained. Then the system entered the polycondensation stage. After half vacuum polycondensation for 1.0 h, the temperature was slowly raised to 275 C. for high vacuum polymerization. When the stirring power no longer increased, the reaction was finished, and a material was discharged and subjected to grain-sized dicing. The master batch was dried at 160 C. for 16 h to remove moisture, so that a flame-retardant PET composite material was obtained.

[0039] (3) Properties of the flame-retardant PET composite material: flame retardancy: an oxygen index of 27% and a peak heat release rate of 400 kW/m.sup.2. Mechanical properties: bending strength of 60 MPa and bending modulus of 1500 MPa.

COMPARATIVE EXAMPLE

Preparation of a PET Composite Material

[0040] (1) 830.65 g of terephthalic acid, 403.44 g of ethylene glycol and 0.29 g of antimony trioxide were mixed and added into a 1.5 L reaction kettle. The air tightness of the instrument was checked, nitrogen was slowly introduced to eliminate air in the kettle, and the temperature was controlled at 230 C. for esterification reaction; when the column top temperature was less than 100 C., the esterification reaction was finished, and water was drained. Then the system entered the polycondensation stage. After half vacuum polycondensation for 0.5 h, the temperature was slowly raised and controlled at 275 C. for high vacuum polymerization. When the stirring power no longer increased, the reaction was finished, and a material was discharged and subjected to grain-sized dicing. The master batch was dried at 120 C. for 12 h to remove moisture.

[0041] (2) Properties of the flame-retardant PET composite material: flame retardancy: an oxygen index of 24% and a peak heat release rate of 650 kW/m.sup.2. Mechanical properties: bending strength of 65 MPa and bending modulus of 1560 MPa.