A kind of impact-resistant foamed polyester material and preparation method thereof

Abstract

The invention discloses an impact-resistant foamed polyester material and a preparation method thereof, and relates to the technical field of polyester materials. The impact-resistant foamed polyester material comprises the following steps: firstly, polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer are mixed and reacted to obtain high-strength polyurethane; then, hexakis(4-aminophenoxy)cyclotriphosphazene, terephthalic acid and ethylene glycol are mixed and reacted to obtain flame-retardant PET; then, TPEE, high-strength polyurethane and flame-retardant PET are mixed and reacted to perform foaming to obtain the impact-resistant foamed polyester material. The impact-resistant foamed polyester material prepared by the invention has good impact resistance, flame retardancy and UV aging resistance and high strength.

Description

Technical Field

[0001] The invention relates to the technical field of polyester materials, in particular to an impact-resistant foamed polyester material and a preparation method thereof. Background Art

[0002] In the plastics industry, especially in the fields of packaging, automotive interiors, and electronic appliances, the requirements for the comprehensive performance of materials are becoming increasingly higher. Among them, foamed polyester materials are favored for their light weight, heat preservation, and sound insulation. However, traditional foamed polyester materials, such as polyethylene terephthalate (PET), despite having good mechanical properties and chemical resistance, are relatively weak in flame retardancy and impact resistance, limiting their application in a wider range of fields.

[0003] In order to improve the impact resistance of PET materials, researchers usually use polyurethane (PU) to toughen them. Polyurethane is a polymer material with good elasticity and flexibility, which can significantly improve the toughness of the base material. However, although this method can effectively improve the impact resistance of PET, it is also accompanied by a decrease in material strength, which is a challenge for some applications that require both high strength and high toughness.

[0004] Therefore, the applicant prepared an impact-resistant foamed polyester material to solve the above problems. Summary of the invention

[0005] In order to solve the existing technical problems, the present invention provides an impact-resistant foamed polyester material, wherein the impact-resistant foamed polyester material is obtained by mixing TPEE, high-strength polyurethane and flame-retardant PET and then foaming; the flame-retardant PET is obtained by mixing hexa(4-aminophenoxy)cyclotriphosphazene, terephthalic acid and ethylene glycol.

[0006] Furthermore, the high-strength polyurethane is obtained by mixing and reacting polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer.

[0007] Furthermore, the isocyanate trimer includes any one or more of hexamethylene diisocyanate trimer, 2,4-toluene diisocyanate trimer, and isophorone diisocyanate trimer.

[0008] The present invention also provides a method for preparing an impact-resistant foamed polyester material, which is characterized by comprising the following preparation steps:

[0009] Flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate are mixed, then ultrasonicated at 50°C for 2-4 hours, and then added to a two-stage twin-screw extrusion foaming unit for foaming, and the feeding rate is 200kg / h, and the injection rate of carbon dioxide is 3.5kg / h. At the same time, the temperature of the entire unit is controlled as follows: 230°C, 275°C, 275°C, 275°C, 275°C for the upper stage machine; 220°C, 190°C, 170°C, 170°C, 170°C; 160°C for the lower stage machine.

[0010] Furthermore, the mass ratio of the flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate is 1:0.2~0.4:0.1:1.2~1.6.

[0011] Furthermore, the preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum-dehydrated polyether polyol and 3-hydroxycyclopentanone are mixed, stirred at a speed of 500-700 r / min for 20-40 min, then heated to 70°C, 0.8-1 times the amount of isocyanate trimer of the polyether polyol is added dropwise, the temperature is continued to be raised to 80°C and stirred for 2 hours, then dissolved in dichloromethane 4-6 times the mass of the polyether polyol, and mercuric chloride and iodine are added in sequence, and stirred at room temperature for 40-70 min. At this time, the ortho-position of the carbonyl group of cyclopentanone is chlorinated to obtain a high-strength polyurethane.

[0012] Furthermore, the molar ratio of the vacuum dehydrated polyether polyol, 3-hydroxycyclopentanone, mercuric chloride and iodine is 1:0.4~0.6:0.2~0.3:0.4~0.6.

[0013] Furthermore, the polyether polyol adopts polyether N220.

[0014] Furthermore, the preparation steps of the flame-retardant PET are as follows: under nitrogen protection, terephthalic acid and hexa(4-aminophenoxy)cyclotriphosphazene are dissolved in DMF with a mass 4 to 5 times that of terephthalic acid in sequence, the temperature is raised to 180 to 190° C., and the mixture is stirred for reaction for 2 hours. Then, ethylene glycol and tetrabutyl titanate are added in sequence, the temperature is raised to 250 to 260° C., the mixture is stirred for reaction for 2 to 4 hours, the temperature is raised to 270° C., and the mixture is vacuumed for pre-condensation within 20 minutes. After 2 hours, the condensation is completed to obtain flame-retardant PET.

[0015] Furthermore, the molar ratio of terephthalic acid, hexakis(4-aminophenoxy)cyclotriphosphazene, ethylene glycol, and tetrabutyl titanate is 11-13:1:5-7:0.01-0.03.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The impact-resistant foamed polyester material of the invention comprises the following steps: firstly, polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer are mixed and reacted to obtain high-strength polyurethane; then, hexakis(4-aminophenoxy)cyclotriphosphazene, terephthalic acid and ethylene glycol are mixed and reacted to obtain flame-retardant PET; then, TPEE, high-strength polyurethane and flame-retardant PET are mixed and reacted and foamed to obtain the impact-resistant foamed polyester material. The impact-resistant foamed polyester material prepared by the invention has good impact resistance and flame retardancy and high strength.

[0018] Firstly, hexa(4-aminophenoxy)cyclotriphosphazene, terephthalic acid and ethylene glycol are mixed to prepare flame-retardant PET. Hexa(4-aminophenoxy)cyclotriphosphazene can not only improve the flame retardancy of flame-retardant PET, but also form a hyperbranched structure of PET, thereby enhancing the mechanical properties of flame-retardant PET.

[0019] Secondly, polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer are mixed and reacted to obtain high-strength polyurethane, wherein mercuric chloride and iodine are introduced after polymerization to chlorinate the ortho position of the carbonyl group in cyclopentanone and introduce a five-membered ring into the polyurethane, thereby enhancing the strength of the polyurethane.

[0020] Finally, high-strength polyurethane and flame-retardant PET are mixed and reacted and then foamed to obtain an impact-resistant foamed polyester material. The polyurethane penetrates into the cavity of the flame-retardant PET, and the ortho-chlorinated cyclopentanone of the carbonyl group on the molecular chain branch reacts with the unreacted benzoic acid on the flame-retardant PET to generate (2-oxocyclopentyl) benzoate. At the same time, the high-strength polyurethane and flame-retardant PET form an interpenetrating network structure, which enhances the UV aging resistance and impact resistance of the impact-resistant foamed polyester material. DETAILED DESCRIPTION

[0021] The present invention is further described in detail below in conjunction with examples, but the following examples should not be construed as limiting the present invention.

[0022] The TPEE used in the examples and comparative examples of the present invention is TPEE resin-H63DMG.

[0023] The isocyanate trimer used in the examples and comparative examples of the present invention is isocyanate trimer Wannate® HTBL-175S.

[0024] The following table shows the properties of the TPEE resin:

[0025] Example 1

[0026] A method for preparing an impact-resistant foamed polyester material, the preparation steps are as follows:

[0027] Flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate are mixed, then ultrasonicated at 50°C for 2h, and then added to a two-stage twin-screw extrusion foaming unit for foaming, and the feeding rate is 200kg / h, and the injection rate of carbon dioxide is 3.5kg / h. At the same time, the temperature of the entire unit is controlled as follows: 230°C, 275°C, 275°C, 275°C, 275°C for the upper stage machine; 220°C, 190°C, 170°C, 170°C, 170°C for the lower stage machine; and the head temperature is 160°C.

[0028] The mass ratio of the flame-retardant PET, high-strength polyurethane, TPEE, and sodium carbonate is 1:0.2:0.1:1.2. The preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum dehydrated polyether N220 and 3-hydroxycyclopentanone are mixed, stirred at a speed of 500r / min for 20min, then heated to 70°C, 0.8 times the amount of isocyanate trimer of polyether N220 is added dropwise, the temperature is continued to be raised to 80°C and stirred for 2h, then dissolved in dichloromethane 4 times the mass of polyether N220, and mercuric chloride and iodine are added in sequence, stirred at room temperature for 40min, at this time, the ortho-position of the carbonyl group of cyclopentanone is chlorinated to obtain high-strength polyurethane; the molar ratio of the vacuum dehydrated polyether N220, 3-hydroxycyclopentanone, mercuric chloride, and iodine is 1:0.4:0.2:0.4.

[0029] The preparation steps of the flame-retardant PET are as follows: under nitrogen protection, terephthalic acid and hexa(4-aminophenoxy)cyclotriphosphazene are sequentially dissolved in DMF with a mass 4 times that of terephthalic acid, the temperature is raised to 180°C, and the mixture is stirred for reaction for 2 hours, and then ethylene glycol and tetrabutyl titanate are sequentially added, the temperature is raised to 250°C, the mixture is stirred for reaction for 2 hours, the temperature is raised to 270°C, and vacuumization is performed within 20 minutes for pre-condensation, and the condensation is completed after 2 hours to obtain the flame-retardant PET; the molar ratio of terephthalic acid, hexa(4-aminophenoxy)cyclotriphosphazene, ethylene glycol, and tetrabutyl titanate is 11:1:5:0.01. Example 2

[0030] A method for preparing an impact-resistant foamed polyester material, the preparation steps are as follows:

[0031] Flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate are mixed, then ultrasonicated at 50°C for 3 hours, and then added to a two-stage twin-screw extrusion foaming unit for foaming, and the feeding rate is 200kg / h, and the injection rate of carbon dioxide is 3.5kg / h. At the same time, the temperature of the entire unit is controlled as follows: 230°C, 275°C, 275°C, 275°C, 275°C for the upper stage machine; 220°C, 190°C, 170°C, 170°C, 170°C; 160°C for the head machine.

[0032] The mass ratio of the flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate is 1:0.3:0.1:1.4.

[0033] The preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum-dehydrated polyether N220 and 3-hydroxycyclopentanone are mixed, stirred at a speed of 600 r / min for 30 minutes, then heated to 70°C, 0.9 times the amount of isocyanate trimer of the polyether N220 substance is added dropwise, the temperature is continued to be raised to 80°C and stirred for 2 hours, then dissolved in dichloromethane 5 times the mass of the polyether N220, and mercuric chloride and iodine are added in sequence, and stirred at room temperature for 60 minutes, at which time, the ortho-position of the cyclopentanone carbonyl group is chlorinated to obtain a high-strength polyurethane; the molar ratio of the vacuum-dehydrated polyether N220, 3-hydroxycyclopentanone, mercuric chloride, and iodine is 1:0.5:0.25:0.5.

[0034] The preparation steps of the flame-retardant PET are as follows: under nitrogen protection, terephthalic acid and hexa(4-aminophenoxy)cyclotriphosphazene are dissolved in DMF with a mass 4.5 times that of terephthalic acid in sequence, the temperature is raised to 170°C, and the mixture is stirred for reaction for 2 hours, and then ethylene glycol and tetrabutyl titanate are added in sequence, the temperature is raised to 255°C, the mixture is stirred for reaction for 3 hours, the temperature is raised to 270°C, and vacuumization is performed within 20 minutes for pre-condensation, and the condensation is completed after 2 hours to obtain the flame-retardant PET; the molar ratio of terephthalic acid, hexa(4-aminophenoxy)cyclotriphosphazene, ethylene glycol, and tetrabutyl titanate is 12:1:6:0.02. Example 3

[0035] A method for preparing an impact-resistant foamed polyester material, the preparation steps are as follows:

[0036] Flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate are mixed, then ultrasonicated at 50°C for 4 hours, and then added to a two-stage twin-screw extrusion foaming unit for foaming, and the feeding rate is 200kg / h, and the injection rate of carbon dioxide is 3.5kg / h. At the same time, the temperature of the entire unit is controlled as follows: 230°C, 275°C, 275°C, 275°C, 275°C for the upper stage machine; 220°C, 190°C, 170°C, 170°C, 170°C for the lower stage machine; and the head temperature is 160°C.

[0037] The mass ratio of the flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate is 1:0.4:0.1:1.6.

[0038] The preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum-dehydrated polyether N220 and 3-hydroxycyclopentanone are mixed, stirred at a speed of 700 r / min for 40 minutes, then heated to 70°C, and an isocyanate trimer with an amount 1 times that of the polyether N220 is added dropwise, and the temperature is continued to be raised to 80°C and stirred for 2 hours, and then dissolved in dichloromethane with a mass 6 times that of the polyether N220, and mercuric chloride and iodine are added in sequence, and stirred at room temperature for 70 minutes, at which time, the ortho-position of the cyclopentanone carbonyl group is chlorinated to obtain a high-strength polyurethane; the molar ratio of the vacuum-dehydrated polyether N220, 3-hydroxycyclopentanone, mercuric chloride, and iodine is 1:0.6:0.3:0.6.

[0039] The preparation steps of the flame-retardant PET are as follows: under nitrogen protection, terephthalic acid and hexa(4-aminophenoxy)cyclotriphosphazene are dissolved in DMF with a mass 5 times that of terephthalic acid in sequence, the temperature is raised to 190° C., and the mixture is stirred for reaction for 2 hours, and then ethylene glycol and tetrabutyl titanate are added in sequence, the temperature is raised to 260° C., the mixture is stirred for reaction for 4 hours, the temperature is raised to 270° C., and vacuumization is performed within 20 minutes for pre-condensation, and the condensation is completed after 2 hours to obtain the flame-retardant PET; the molar ratio of terephthalic acid, hexa(4-aminophenoxy)cyclotriphosphazene, ethylene glycol, and tetrabutyl titanate is 13:1:7:0.03.

[0040] Comparative Example 1

[0041] The difference between Comparative Example 1 and Example 2 is that only flame-retardant PET is foamed to prepare impact-resistant foamed polyester material, wherein the feeding rate of flame-retardant PET is 200 kg / h; the injection rate of carbon dioxide is 3.5 kg / h; and the remaining steps and components are the same as those in Example 2.

[0042] Comparative Example 2

[0043] The difference between Comparative Example 2 and Example 2 is that the polyether polyol and isocyanate trimer are mixed and reacted to prepare the high-strength polyurethane; the remaining steps and components are the same as those in Example 2.

[0044] Comparative Example 3

[0045] The difference between Comparative Example 3 and Example 2 is that the high-strength polyurethane is prepared by mixing polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer without introducing mercuric chloride and iodine; the remaining steps and components are the same as those in Example 2.

[0046] Comparative Example 4

[0047] The difference between Comparative Example 4 and Example 2 is that an equal amount of ammonium polyphosphate is used instead of hexa(4-aminophenoxy)cyclotriphosphazene, and mixed with terephthalic acid and ethylene glycol to prepare flame-retardant PET; the remaining steps and components are the same as those in Example 2.

[0048] Effect example

[0049] PCT: The test samples of the embodiment and the comparative example were placed in an ultraviolet lamp aging test box (model: UVZN-320), and the test samples were subjected to ultraviolet accelerated aging test (PCT) according to the method described in ISO4892.3 "Plastics Laboratory Light Source Exposure Method Part 3 Fluorescent Ultraviolet Lamp". The test conditions are as follows: light source, UVA-340; radiation energy, 0.83W / (m 2 nm); test temperature, 70°C; 4 hours of illumination, 1 hour of light-off interval, 50 hours of cycle test, and test the tensile strength after UV aging.

[0050] Table 1 below shows the test results of various properties of the impact-resistant foamed polyester materials prepared by using Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0051] Table 1

[0052]

[0053] From Table 1, it can be found that the impact-resistant foamed polyester material prepared in the embodiment has good impact resistance, flame retardancy, and resistance to ultraviolet aging, and has high strength; Example 2 is compared with Comparative Examples 1 to 3 to find that the impact-resistant foamed polyester material is prepared by mixing polyether polyol, 3-hydroxycyclopentanone, and isocyanate trimer and introducing mercuric chloride and iodine to obtain a high-strength polyurethane, and the impact-resistant foamed polyester material prepared has good impact resistance and resistance to ultraviolet aging, and has high strength; Example 2 is compared with Comparative Example 4 to find that the impact-resistant foamed polyester material is prepared by mixing hexa(4-aminophenoxy)cyclotriphosphazene, terephthalic acid, and ethylene glycol to prepare a flame-retardant PET, and the impact-resistant foamed polyester material prepared has good impact resistance and flame retardancy, and has high strength.

[0054] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. An impact-resistant foamed polyester material, characterized in that: The impact-resistant foamed polyester material is obtained by mixing TPEE, high-strength polyurethane and flame-retardant PET and then foaming; the flame-retardant PET is obtained by mixing hexa(4-aminophenoxy)cyclotriphosphazene, terephthalic acid and ethylene glycol; the high-strength polyurethane is obtained by mixing polyether polyol, 3-hydroxycyclopentanone and isocyanate trimer; The preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum-dehydrated polyether polyol and 3-hydroxycyclopentanone are mixed, stirred at a speed of 500-700 r / min for 20-40 minutes, then heated to 70° C., 0.8-1 times the amount of isocyanate trimer of the polyether polyol substance is added dropwise, the temperature is continued to be raised to 80° C. and stirred for 2 hours, then dissolved in dichloromethane 4-6 times the mass of the polyether polyol, and mercuric chloride and iodine are added in sequence, and stirred at room temperature for 40-70 minutes to obtain high-strength polyurethane; The molar ratio of the vacuum dehydrated polyether polyol, 3-hydroxycyclopentanone, mercuric chloride and iodine is 1:0.4-0.6:0.2-0.3:0.4-0.6; The polyether polyol is polyether N220; The mass ratio of the flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate is 1:0.2-0.4:0.1:1.2-1.6; The preparation steps of the flame-retardant PET are as follows: under nitrogen protection, terephthalic acid and hexa(4-aminophenoxy)cyclotriphosphazene are sequentially dissolved in DMF with a mass of 4 to 5 times that of terephthalic acid, the temperature is raised to 180 to 190° C., stirred for reaction for 2 hours, and then ethylene glycol and tetrabutyl titanate are sequentially added, the temperature is raised to 250 to 260° C., stirred for reaction for 2 to 4 hours, the temperature is raised to 270° C., and vacuum is drawn within 20 minutes for pre-condensation, and the condensation is completed after 2 hours to obtain the flame-retardant PET; The molar ratio of terephthalic acid, hexakis (4-aminophenoxy) cyclotriphosphazene, ethylene glycol and tetrabutyl titanate is 11-13:1:5-7:0.01-0.

03.

2. The impact-resistant foamed polyester material according to claim 1, characterized in that: The isocyanate trimer includes any one or more of hexamethylene diisocyanate trimer, 2,4-toluene diisocyanate trimer, and isophorone diisocyanate trimer.

3. A method for preparing an impact-resistant foamed polyester material as claimed in any one of claims 1 to 2, characterized in that: The method comprises the following preparation steps: Flame-retardant PET, high-strength polyurethane, TPEE and sodium carbonate are mixed, then ultrasonicated at 50°C for 2-4 hours, and then added to a two-stage twin-screw extrusion foaming unit for foaming, and the feeding rate is 200kg / h, and the injection rate of carbon dioxide is 3.5kg / h. At the same time, the temperature of the entire unit is controlled as follows: 230°C, 275°C, 275°C, 275°C, 275°C for the upper stage machine; 220°C, 190°C, 170°C, 170°C, 170°C; 160°C for the lower stage machine.

4. The method for preparing the impact-resistant foamed polyester material according to claim 3, characterized in that: The preparation method of the high-strength polyurethane is as follows: under nitrogen conditions, vacuum-dehydrated polyether polyol and 3-hydroxycyclopentanone are mixed, stirred at a speed of 500-700 r / min for 20-40 minutes, then heated to 70° C., 0.8-1 times the amount of isocyanate trimer of the polyether polyol substance is added dropwise, the temperature is continued to be raised to 80° C. and stirred for 2 hours, then dissolved in dichloromethane 4-6 times the mass of the polyether polyol, and mercuric chloride and iodine are added in sequence, and stirred at room temperature for 40-70 minutes to obtain high-strength polyurethane.

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