A high-crystallinity PET flame-retardant reinforced material with high ball pressure temperature resistance without mold temperature addition and its preparation method

Abstract

The present invention discloses a high-crystallinity PET flame-retardant reinforced material resistant to high ball pressure temperature without adding mold temperature and a preparation method thereof. The high-crystallinity PET flame-retardant reinforced material is made of raw materials comprising the following weight percentages: 35-55% of polyethylene terephthalate, 1-3% of toughening agent, 8-15% of flame retardant, 2-5% of flame retardant synergist, 1-5% of crystallization promoter, 0.5-2% of nucleation promoter, 1-5% of molecular chain flexibility agent, 30-40% of filling and reinforcing agent, 0.2-0.5% of antioxidant, 0.5-2% of lubricating and dispersing agent, and 0.01-2% of other additives. The compound system of specific flame retardant and flame retardant synergist of the present invention can effectively improve the ball pressure temperature resistance of the product and ensure the flame retardant performance with less addition amount.

Description

Technical Field

[0001] The present invention belongs to the field of flame-retardant reinforced PET materials, and particularly relates to a high-crystallinity PET flame-retardant reinforced material with high ball pressure temperature resistance without adding mold temperature and a preparation method thereof. Background Art

[0002] Polyethylene terephthalate (PET) is one of the most important synthetic materials at present, having good heat resistance, chemical resistance, mechanical properties and electrical properties. In particular, it has good transparency, excellent insulation, and relatively low production cost and high performance-price ratio.

[0003] However, at present, PET is mainly widely used in films and fibers. As an engineering plastic, the application of pure PET modified materials is relatively less. This is mainly due to the slow crystallization rate and long molding cycle of PET. In addition, the glass transition temperature of PET is very high, and it cannot crystallize continuously at room temperature. Therefore, its injection mold temperature needs to reach 100-140°C to ensure high-crystallinity PET, which makes its production cycle too long to meet the production capacity requirements of most enterprises. Now some enterprises produce modified PET materials by reducing the mold temperature or even not adding mold temperature, which also leads to insufficient high-temperature resistance, and the ball pressure temperature cannot even reach 120°C. Summary of the Invention

[0004] The purpose of the present invention is to solve the above problems existing in the prior art, and provide a high-strength high-crystallinity PET flame-retardant reinforced material for oven with high ball pressure temperature resistance and a preparation method thereof.

[0005] To achieve the above purpose, the technical scheme adopted by the present invention is as follows:

[0006] The present invention provides a high-crystallinity PET flame-retardant reinforced material with high ball pressure temperature resistance without adding mold temperature, which is made of raw materials comprising the following weight percentages:

[0007]

[0008]

[0009] Among them, the flame retardant is any one or a mixture selected from brominated polystyrene, polybrominated styrene, and decabromodiphenylethane;

[0010] Preferably, the TGA5% thermal weight loss temperature of the flame retardant ≥ 300°C;

[0011] The flame retardant synergist is a mixture of one or more selected from antimony pentoxide, sodium antimonate, and wollastonite;

[0012] Preferably, the purity of the flame retardant synergist ≥ 99%;

[0013] The crystallization promoter is diallyl anhydride - acetyl acetate copolymer. It can react with the end groups of PET molecules, react with the polar groups at the ends of PET molecular chains to form homogeneous nucleation sites of PET, and easily and rapidly form thermodynamically stable crystal nuclei of a certain size at a relatively high temperature, enabling the subsequent crystal nucleus growth to proceed rapidly, and greatly shortening the crystallization induction period;

[0014] The nucleation promoter is a long-chain linear saturated carboxylate sodium with a carbon chain length of 16 - 32; the preferred carbon chain length is 28 - 32;

[0015] The molecular chain softener is a mixture of one or more selected from diethylene glycol, triethylene glycol, and polyether ester.

[0016] According to one embodiment of the present invention, the intrinsic viscosity range of the polyethylene terephthalate is 0.6 - 0.9 dl / g.

[0017] According to one embodiment of the present invention, the toughening agent is ethylene - butyl acrylate - glycidyl methacrylate copolymer (EBA - GMA), ethylene - methyl acrylate copolymer (EMA), or a mixture thereof.

[0018] According to one embodiment of the present invention, the filling and reinforcing agent is a mixture of one or more selected from ultrafine talc powder, mica powder, and E - glass fiber.

[0019] According to one embodiment of the present invention, the antioxidant is any two selected from antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 626, and antioxidant 627A.

[0020] According to one embodiment of the present invention, the lubricating and dispersing agent is a mixture of one or more selected from ethylene bisstearamide EBS, silicone, modified ethylene bisstearamide TAF, and pentaerythritol stearate PETS lubricant.

[0021] According to one embodiment of the present invention, the other additives include one or more selected from coupling agents, masterbatch, and weathering agents.

[0022] According to another aspect of the present invention, it provides a preparation method of the above - mentioned high - crystallization PET flame - retardant and reinforcing material with high ball - pressure temperature without mold temperature addition, comprising the following steps:

[0023] (1) Mix the toughening agent, flame - retardant synergist, crystallization promoter, nucleation promoter, molecular chain softener, flame retardant, antioxidant, lubricating and dispersing agent, and other additives in a mixer at 600 - 1200 revolutions per minute for 2 - 5 minutes, then add polyethylene terephthalate in proportion and mix at 600 - 1200 revolutions per minute for 2 - 5 minutes.

[0024] (2) Add the mixture to the main feed on a twin-screw extruder with a length-diameter ratio of 36:1 - 44:1, add the filler and reinforcing agent to the side feed, and then perform extrusion, strand drawing, drying, and pelletizing to obtain a highly crystalline PET flame-retardant and reinforced material.

[0025] Preferably, in step (2), the extrusion speed is 250 - 450 revolutions per minute, and the extrusion temperature is 160 - 270 °C.

[0026] The present invention has the following advantages compared with the prior art:

[0027] 1. The compounding system of specific flame retardants and flame retardant synergists in the present invention can effectively improve the heat deflection temperature of the product and ensure the flame retardant performance with fewer addition amounts. The present invention uses a ternary compounding system of a crystallization promoter - nucleating promoter - molecular chain softening agent. Among them, the crystallization promoter reduces the TG, thereby reducing the cold crystallization temperature and increasing the crystallization rate. The nucleating promoter provides more crystallization sites, supplements and improves the defects between crystal regions. The molecular chain softening agent improves the mobility of the amorphous phase, further increases the crystallization rate, and at the same time reduces the melting temperature. It not only reduces the processing temperature but also increases the crystallization rate and crystallinity of the material. It realizes the production of PET without mold temperature, and ensures that the ball pressure diameter ≤ 2 mm under the conditions of a heat deflection temperature of 210 °C and 1 h.

[0028] 2. The thermal decomposition temperature of the flame retardant used in the present invention exceeds 360 °C, which greatly improves the heat resistance; when compounded with the flame retardant synergist, the decomposition caused by the high-temperature modification and injection molding of PET is greatly reduced, enabling it to have more stable glow wire performance and flame retardant effect with less addition amount.

[0029] 3. The present invention further modifies and improves the material through an enhancing, toughening, and compatibilizing system. Finally, a high-strength and high heat deflection temperature oven-use highly crystalline PET flame-retardant and reinforced material that does not require mold temperature production is obtained. Detailed Embodiments

[0030] The following further clarifies the present invention with specific embodiments. These embodiments are only illustrative and not restrictive.

[0031] Materials used in the examples and comparative examples:

[0032] Polyethylene terephthalate: BG80, Yizheng, Sinopec, intrinsic viscosity 0.8 dl / g

[0033] Toughening agent: PTW, DuPont, USA, melt index (190 °C / 2.16 kg) measured according to ASTM D1238 ISO 1133 is 12 g / 10 min

[0034] Flame retardant: SAYTEX 621, Albemarle, USA, TGA 5% thermal weight loss temperature 379°C;

[0035] CXB - 2000H, Woo Jin, Korea

[0036] Flame retardant synergist: Sodium antimonate, Hubei Chengfeng Chemical Industry, industrial grade

[0037] Sb 2 O 3 99.8%, Flash Star Antimony Industry

[0038] Sb 2 O 5 ≥99.8%, Flash Star Antimony Industry

[0039] Crystallization promoter: PX520, Dongguan Tailong New Materials, pH value 6.0 - 7.0

[0040] Nucleation promoter: NAV101, Clariant, melting point 174 - 180

[0041] Molecular chain softener: Diethylene glycol (DEG), CNOOC and Shell Petrochemical Company Limited, melting point - 8.0°C

[0042] Filler and reinforcing agent: EDR13 - 2000 - 988A, Jushi, fiber diameter 13μm, linear density tex2000 Antioxidants: 1010, 168, BASF

[0043] Lubricating and dispersing agent: EBS, Kayser Sung Kong, melting point 144 - 146°C

[0044] Silane coupling agent: KH560, Hubei Chengfeng Chemical Industry, industrial grade

[0045] Masterbatch: PE2718, Cabot, carbon black content 50%

[0046] The following table shows the contents of each component used in the examples, and the unit is weight percentage.

[0047] Table 1. Raw material composition in each example and comparative example

[0048]

[0049]

[0050] Example 1

[0051] In Example 1, the flame retardant used was brominated polystyrene SAYTEX 621, the flame retardant synergist was sodium antimonate, the crystallization promoter was diallyl maleic anhydride-acetyl acetate copolymer PX520, the nucleation promoter was long-chain linear saturated carboxylate sodium NAV101, the molecular chain softener was diethylene glycol DEG, the filler and reinforcing agent was EDR13-2000-988A, the antioxidant was a compound of antioxidant 1010 and 168 in a ratio of 1:1, the dispersing lubricant was EBS, and other additives included 0.3% of silane coupling agent KH560 and 1.0% of color masterbatch PE2718.

[0052] The preparation method of a high-crystallinity PET flame retardant and reinforcing material with high ball pressure temperature resistance without mold temperature addition is as follows:

[0053] Mix the toughening agent, flame retardant synergist, crystallization promoter, nucleation promoter, molecular chain softener, flame retardant, antioxidant, lubricating and dispersing agent, and other additives in a mixer at 1000 rpm for 3 min, and then add polyethylene terephthalate in proportion and mix at 1000 rpm for 3 min.

[0054] The mixed material is extruded in a twin-screw extruder with a ratio of 40:1. The filler and reinforcing agent is added through side feeding, the screw speed is 410 r / min, and the extrusion temperature is set at 160 °C / 270 °C / 260 °C / 240 °C / 200 °C / 200 °C / 200 °C / 200 °C / 220 °C / 240 °C. Extrude, draw into strands, dry, pelletize, and after mixing evenly, make samples for testing to obtain the high-crystallinity PET flame retardant and reinforcing material.

[0055] Example 2

[0056] Except for the components and contents in Table 1 above, that is, the dosage of the nucleation promoter long-chain linear saturated carboxylate sodium NAV101 is 1%, which is 1% less than that in Example 1, the dosage of the molecular chain softener diethylene glycol DEG is 1%, which is 2% less than that in Example 1, and the content of PET is increased by 3%, the high-crystallinity PET flame retardant and reinforcing material is prepared in the same method as in Example 1.

[0057] Example 3

[0058] Except for the components and contents in Table 1 above, that is, the dosage of the flame retardant is 15%, which is 5% more than that in Example 1, the dosage of sodium antimonate is 3%, which is 1% more than that in Example 1, and the content of PET is reduced by 6%, the high-crystallinity PET flame retardant and reinforcing material is prepared in the same method as in Example 1.

[0059] Comparative Example 1

[0060] Except for the components and contents in Table 1 above, that is, the flame retardant used is brominated epoxy CXB-2000H and the flame retardant synergist is antimony trioxide, a highly crystalline PET flame retardant reinforced material is prepared in the same manner as in Example 1.

[0061] Comparative Example 2

[0062] Except for the components and contents in Table 1 above, that is, the nucleation promoter long-chain linear saturated carboxylate sodium NAV101 and the molecular chain softener diethylene glycol DEG are not added, and the content of PET is increased by 5%, a highly crystalline PET flame retardant reinforced material is prepared in the same manner as in Example 1.

[0063] Comparative Example 3

[0064] Except for the components and contents in Table 1 above, that is, the nucleation promoter long-chain linear saturated carboxylate sodium NAV101 is not added, and the content of PET is increased by 2%, a highly crystalline PET flame retardant reinforced material is prepared in the same manner as in Example 1.

[0065] Experimental Example

[0066] In the above Examples and Comparative Examples,

[0067] The specific gravity is tested in accordance with GB / T 1033.1-2008,

[0068] The glow wire is tested in accordance with GB / T 5169.12 / .13,

[0069] The flame retardant 2.5V0 and flame retardant 1.6V0 are tested in accordance with UL94-2018,

[0070] The test method for the ball pressure temperature test is carried out in accordance with GB / T 5169.21-2017,

[0071] The test results are as follows:

[0072]

[0073] As can be seen from the above table, compared with Comparative Example 1, the flame retardant compound system of brominated polystyrene and sodium antimonate can effectively improve the ball pressure temperature resistance of the product, and ensure the flame retardant performance with fewer addition amounts, while the combination of Comparative Example 1 has poor results in the flame retardant 1.6V0 test. Compared with Comparative Example 2 and Comparative Example 3, the ternary compound system of crystal growth promoter - nucleation promoter - molecular chain softener shows better performance in the ball pressure temperature test, and can obtain PET products with good flame retardant effect and higher ball pressure temperature resistance without adding mold temperature.

[0074] The above specific embodiments are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. For those of ordinary skill in the art, without departing from the principle of the present invention, several changes and improvements can still be made, and these changes and improvements should also be regarded as the protection scope of the present invention.

Claims

1. A high-crystalline PET flame-retardant reinforced material that is resistant to high ball pressure temperature and does not require mold temperature, and is made of raw materials containing the following weight percentages: in, The flame retardant is any one selected from brominated polystyrene, polybrominated styrene, decabromodiphenylethane, or a mixture thereof. The flame retardant synergist is a mixture of one or more selected from antimony pentoxide, sodium antimonate, and wollastonite. The crystallization accelerator is a diallyl anhydride-acetyl acetate copolymer, The nucleation promoter is a long-chain linear saturated sodium carboxylate with a carbon chain length of 16-32. The molecular chain softener is a mixture of one or more selected from diethylene glycol, triethylene glycol, and polyether ester. The other auxiliary agents include one or more selected from coupling agents, masterbatches, and weathering agents.

2. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein: The intrinsic viscosity of the polyethylene terephthalate is in the range of 0.6-0.9 dl / g.

3. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein: The toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate copolymer, or a mixture thereof.

4. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein: The nucleation promoter is a long-chain linear saturated sodium carboxylate with a carbon chain length of 28-32.

5. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein the filler reinforcing agent is a mixture of one or more selected from ultrafine talc powder, mica powder, and alkali-free glass fiber.

6. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein the antioxidant is any two selected from antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 626, and antioxidant 627A.

7. The highly crystalline PET flame retardant reinforced material according to claim 1, wherein the lubricating dispersant is a mixture of one or more lubricants selected from ethylene bis stearic acid amide EBS, silicone, modified ethylene bis stearic acid amide TAF, and pentaerythritol stearate PETS.

8. The method for preparing a high-crystalline PET flame-retardant reinforced material that does not require mold temperature and is resistant to high ball pressure temperature according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) Toughening agent, flame retardant synergist, crystallization accelerator, nucleation accelerator, molecular chain softener, flame retardant, antioxidant, lubricating dispersant and other additives are mixed in proportion in a mixer at 600-1200 revolutions per minute for 2-5 minutes, and then polyethylene terephthalate is added in proportion and mixed at 600-1200 revolutions per minute for 2-5 minutes. (2) The mixed material is added to the main feed of a twin-screw extruder with a length-to-diameter ratio of 36:1-44:1, and the filler reinforcing agent is added to the side feed, and the mixture is extruded, stretched, blown and pelletized to obtain a high-crystalline PET flame retardant reinforced material.

9. The preparation method according to claim 8, wherein: The extrusion speed in step (2) is 250-450 revolutions per minute, and the extrusion temperature is 160-270°C.

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