PBT / PET / PC flame-retardant alloy material as well as preparation method and application thereof

Abstract

The invention discloses a PBT / PET / PC flame-retardant alloy material as well as a preparation method and application thereof, and relates to the technical field of engineering plastics. The invention provides a PBT / PET / PC flame-retardant alloy material. The PBT / PET / PC flame-retardant alloy material is prepared from the following components in parts by weight: 9 to 61 parts of PBT resin, 5 to 20 parts of PET resin, 7 to 36 parts of PC resin, 5 to 20 parts of flame retardant, 1 to 4 parts of alkyl methacrylate-organic silicon / alkyl acrylate grafted copolymer and 10 to 50 parts of glass fiber. According to the PBT / PET / PC flame-retardant alloy material provided by the invention, under the adjustment of the alkyl methacrylate-organosilicone / alkyl acrylate graft copolymer with a core-shell rubber structure, the PBT / PET / PC flame-retardant alloy material can effectively isolate heat from being transferred to the inside when being heated, and meanwhile, the core has excellent heat resistance, so that the flame-retardant alloy material has a good flame-retardant effect. The PBT resin, the PET resin and the PC resin in specific parts by weight are combined, so that the PBT / PET / PC flame-retardant alloy material with good mechanical property and good heat resistance is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and in particular to a PBT / PET / PC flame-retardant alloy material, its preparation method and application. Background Art

[0002] Currently, polybutylene terephthalate (PBT) resin is widely used in the fields of electronic appliances, automotive parts, etc. due to its excellent mechanical properties, chemical corrosion resistance and processing fluidity. However, as a typical highly crystalline polymer, PBT often causes deformation and warping of products due to the anisotropy of crystallization shrinkage during the injection molding process, which seriously restricts its application in precision structural parts.

[0003] To improve the warping problem of PBT, the prior art usually adopts a polymer blending and modification strategy, such as melting and blending PBT with amorphous or low-crystalline resins such as polyethylene terephthalate (PET) and polycarbonate (PC) to form an alloy system. By increasing the proportion of the amorphous phase, such an alloy system can effectively reduce the overall crystallinity of the material, thereby alleviating the warping deformation caused by uneven shrinkage. However, this technical solution has significant defects: PBT and polymers containing ester groups or carbonate groups such as PET and PC are prone to transesterification side reactions during high-temperature processing, resulting in the destruction of the regularity of the molecular chain structure.

[0004] Therefore, a PBT / PET / PC flame-retardant alloy material with good mechanical properties and heat resistance has broad application prospects. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art and provide a PBT / PET / PC flame-retardant alloy material with good mechanical properties and heat resistance, its preparation method and application.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: a PBT / PET / PC flame-retardant alloy material, comprising the following components in parts by weight: 9-61 parts of PBT resin, 5-20 parts of PET resin, 7-36 parts of PC resin, 5-20 parts of flame retardant, 1-4 parts of methacrylic acid alkyl ester-organosilicon / acrylic acid alkyl ester graft copolymer, and 10-50 parts of glass fiber.

[0007] Preferably, the weight percentage content of the PBT resin in the PBT / PET / PC flame-retardant alloy material is not less than 10%; the weight percentage content of the PET resin in the PBT / PET / PC flame-retardant alloy material is not less than 2%; the weight percentage content of the PC resin in the PBT / PET / PC flame-retardant alloy material is not less than 5%.

[0008] Preferably, the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer has a core-shell rubber structure, with a grafting rate of 5-90% and a glass transition temperature of -150 to -20 °C.

[0009] Preferably, in the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer, the alkyl methacrylate includes at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, and butyl methacrylate; the silicone / acrylic alkyl ester refers to a polymer obtained by polymerizing a mixture of silicone monomers and acrylic alkyl ester monomers.

[0010] Preferably, the silicone monomer includes at least one of dimethyl siloxane, hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, trimethyltriphenyl cyclotetrasiloxane, tetramethyltetraphenyl cyclotetrasiloxane, and octaphenyl cyclotetrasiloxane.

[0011] The present invention provides a PBT / PET / PC flame-retardant alloy material. Under the regulation of the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer with a core-shell rubber structure, when the PBT / PET / PC flame-retardant alloy material is heated, on the one hand, it can isolate heat and reduce the heat transfer to the interior. On the other hand, the core of the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer with a core-shell rubber structure itself has excellent heat resistance. Combined with specific weight parts of PBT resin, PET resin, and PC resin, a PBT / PET / PC flame-retardant alloy material with a relatively high crystallization temperature is prepared. When the PBT / PET / PC flame-retardant alloy material has a relatively high crystallization temperature, the degree of transesterification is lower, and the heat resistance and mechanical properties are better.

[0012] Preferably, the PBT / PET / PC flame-retardant alloy material comprises the following components in parts by weight: 20-40 parts of PBT resin, 10-15 parts of PET resin, 15-25 parts of PC resin, 10-15 parts of flame retardant, 2-3 parts of alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer, and 30-40 parts of glass fiber.

[0013] Optionally, the weight parts of the PBT resin are one of 9 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 55 parts, 60 parts, 61 parts or the range value of any two of them; the weight parts of the PET resin are one of 5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or the range value of any two of them; the weight parts of the PC resin are one of 7 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 36 parts or the range value of any two of them; the flame retardant is one of 5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or the range value of any two of them; the weight parts of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer are one of 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or the range value of any two of them; the weight parts of the glass fiber are one of 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts or the range value of any two of them.

[0014] Optionally, the PC includes bisphenol A polycarbonate.

[0015] Preferably, the average particle size of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer is 200-700 nm. Further preferably, the average particle size of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer is 200-400 nm.

[0016] Optionally, the average particle size of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer is one of 200 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 600 nm, 700 nm or the range value of any two of them.

[0017] Optionally, the average particle size of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer is measured by a transmission electron microscope.

[0018] Preferably, the flame retardant is at least one of bromine-based flame retardants and antimony-based flame retardants. Optionally, the bromine-based flame retardant is at least one of brominated triazine, brominated epoxy resin, and tetrabromobisphenol A, and the antimony-based flame retardant is at least one of antimony oxides and antimonates; such as antimony trioxide, sodium antimonate, etc.

[0019] Preferably, the flame retardant is a mixture of brominated epoxy resin and antimony trioxide, and the weight ratio of brominated epoxy resin to antimony trioxide is (3 - 4):1.

[0020] Preferably, the glass fiber is at least one of flat glass fiber and round glass fiber.

[0021] Preferably, the glass fiber is flat glass fiber, the flatness ratio of the glass fiber is 3 - 4, and the average length is 2.5 - 3.5 mm. Optionally, the flatness ratio and average length of the glass fiber are measured by an optical microscope.

[0022] When the flat glass fiber is used, the warpage degree of the prepared PBT / PET / PC flame retardant alloy material is lower, and the warpage height < 6 mm.

[0023] Specifically, the test method for the warpage degree is as follows: injection mold a 100*100*2 mm square plate, place the square plate on a marble flat plate, fix one corner tightly against the marble plane, measure the distance between the diagonal position of the square plate and the marble plane, and measure its maximum warpage height.

[0024] Preferably, the melt index of the PBT resin at 250 °C / 1.2 kg according to ISO 1133-1:2011 is 10 - 60 g / 10 min; and / or, the melt index of the PET at 270 °C / 1.2 kg according to ISO 1133-1:2011 is 30 - 100 g / 10 min; and / or, the melt index of the PC at 300 °C / 1.2 kg according to ISO 1133-1:2011 is 5 - 40 g / 10 min.

[0025] Optionally, the PBT resin has a melt index of 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 45 g / 10 min, 48 g / 10 min, 50 g / 10 min, 60 g / 10 min according to ISO 1133-1:2011 at 250 °C / 1.2 kg, or a range value of any two of them; and / or, the PET has a melt index of 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 45 g / 10 min, 48 g / 10 min, 50 g / 10 min, 60 g / 10 min, 65 g / 10 min, 70 g / 10 min, 75 g / 10 min, 80 g / 10 min, 90 g / 10 min, 100 g / 10 min according to ISO 1133-1:2011 at 270 °C / 1.2 kg, or a range value of any two of them; and / or, the PC has a melt index of 5 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min according to ISO 1133-1:2011 at 300 °C / 1.2 kg, or a range value of any two of them;

[0026] Preferably, the PBT / PET / PC flame-retardant alloy material further comprises 0.1 - 6 parts of a processing aid, and the aid is at least one of an antioxidant, a lubricant, and an ester exchange inhibitor.

[0027] Optionally, the antioxidant is 0.1 - 1.5 parts by weight, and the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant, such as antioxidant 168 (tris[2,4-di-tert-butylphenyl] phosphite), antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), etc.

[0028] Optionally, the lubricant is 0.1 - 1.5 parts by weight, and the lubricant is at least one of a silicone masterbatch, a stearate, a stearate ester, and an ethylene bisstearamide, such as pentaerythritol stearate, zinc stearate, etc.

[0029] Optionally, the ester exchange inhibitor is 0.1 - 3 parts, and the ester exchange inhibitor is at least one of sodium dihydrogen phosphate, zinc dihydrogen phosphate, and disodium dihydrogen pyrophosphate.

[0030] In addition, the present invention provides the above-mentioned PBT / PET / PC flame-retardant alloy material, which includes the following steps: mixing each component in proportion to obtain a mixture A; adding the mixture A to the main feeding port of a screw extruder, adding glass fiber to the side feeding port of the screw extruder, and performing melt extrusion and pelletizing to obtain the PBT / PET / PC flame-retardant alloy material.

[0031] Preferably, the rotation speed of the twin-screw extruder is 250 - 350 r / min, and the temperature is 220 - 260 °C.

[0032] Furthermore, the present invention provides an automotive component including the above-mentioned PBT / PET / PC flame-retardant alloy material, and also provides the application of the above-mentioned PBT / PET / PC flame-retardant alloy material in the automotive field.

[0033] Specifically, the present invention provides the application of the above-mentioned PBT / PET / PC flame-retardant alloy material in the field of domain controllers.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a PBT / PET / PC flame-retardant alloy material. Under the regulation of the core-shell rubber structure of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer, when the PBT / PET / PC flame-retardant alloy material is heated, on the one hand, it can isolate heat and reduce the heat transfer to the inside. On the other hand, the core of the core-shell rubber structure of the alkyl methacrylate-silicone / alkyl acrylate graft copolymer itself has excellent heat resistance. Combined with specific parts by weight of PBT resin, PET resin, and PC resin, a PBT / PET / PC flame-retardant alloy material with a relatively high crystallization temperature is prepared. When the PBT / PET / PC flame-retardant alloy material has a relatively high crystallization temperature, the degree of transesterification is lower, and the heat resistance and mechanical properties are better. Detailed Embodiments

[0035] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. The purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. The experimental reagents and instruments involved in the embodiments and comparative examples of the present invention are all common ordinary reagents and instruments unless otherwise specified, and can be obtained from commercial channels. In the embodiments and comparative examples, the experimental methods used are all conventional methods unless otherwise specified; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch of raw materials.

[0036] The raw materials used in the present invention are further described, but are not limited to the following raw materials:

[0037] PBT Resin - 1: PBT GX121, manufactured by Yizheng, melt index is 15 g / 10 min (250 °C / 1.2 kg);

[0038] PBT Resin - 2: PBT GX111, manufactured by Yizheng, melt index is 60 g / 10 min (250 °C / 1.2 kg);

[0039] PBT Resin - 3: PBT - GX112M, manufactured by Yizheng, melt index is 27 g / 10 min (250 °C / 1.2 kg);

[0040] PET Resin - 1: PET FG600, manufactured by Yizheng, melt index is 30 g / 10 min (270 °C / 1.2 kg);

[0041] PET Resin - 2: PET CR - 7702, manufactured by Zhuhai Huaren Chemical Materials Technology Co., Ltd., melt index is 82 g / 10 min (270 °C / 1.2 kg);

[0042] PC Resin - 1: PC 2220, manufactured by Wanhua, melt index is 20 g / 10 min (300 °C / 1.2 kg);

[0043] PC Resin - 2: PC 2100, manufactured by Wanhua, melt index is 9 g / 10 min (300 °C / 1.2 kg);

[0044] PC Resin - 3: PC H - 3000F, manufactured by Mitsubishi, melt index is 35 g / 10 min (300 °C / 1.2 kg);

[0045] Flame Retardant: Brominated epoxy resin and antimony trioxide are used in combination, weight ratio is 3:1, commercially available.

[0046] Alkyl Methacrylate - Silicone / Alkyl Acrylate Graft Copolymer - 1: S - 2501, average particle size 200 nm, Mitsubishi Rayon Co., Ltd., Japan;

[0047] Alkyl Methacrylate - Silicone / Alkyl Acrylate Graft Copolymer - 2: S - 2100, average particle size 700 nm, Mitsubishi Rayon Co., Ltd., Japan;

[0048] Glass Fiber 1: Flat glass fiber, ECS3F - 03 - 534A, aspect ratio is 3, average length 2.5 - 3.5 mm, Jushi Glass Fiber;

[0049] Glass Fiber 2: Round glass fiber, grade ECS11 - 4.5 - 534A, average length 4.5 mm, average diameter 11 microns, manufacturer Jushi;

[0050] The antioxidant is a composite of commercially available hindered phenol antioxidant 1010 and commercially available phosphite antioxidant 168 in a mass ratio of 1:1;

[0051] The lubricant is a silicone masterbatch, MB50 - 002, commercially available;

[0052] Transesterification inhibitor: Sodium dihydrogen phosphate, commercially available.

[0053] Ethylene - butyl acrylate - glycidyl methacrylate: ELVALOY RESINS PTW, DuPont.

[0054] Examples 1 - 8 and Comparative Examples 1 - 4

[0055] The PBT / PET / PC flame - retardant alloy material described in the present invention, the composition of the PBT / PET / PC flame - retardant alloy material is shown in Table 1 - Table 2. The preparation method of the PBT / PET / PC flame - retardant alloy material includes the following steps: Mix each component evenly in proportion to obtain mixture A; Add mixture A to the main feeding port of a screw extruder, add glass fiber to the side feeding port of the screw extruder, and after melting and extrusion and pelletizing, obtain the PBT / PET / PC flame - retardant alloy material. The rotation speed of the twin - screw extruder is 300 r / min, and the temperature is 220 - 260 °C.

[0056] Performance testing

[0057] Tensile properties: Tested in accordance with the ISO 527 - 2:2012 standard.

[0058] Crystallization temperature: Tested in accordance with the ISO 11357 - 3 - 2011 standard; Plastics - Differential scanning calorimetry (DSC) - Part 3: Determination of enthalpy and temperature of melting and crystallization; Heating rate 20 k / min, nitrogen atmosphere.

[0059] Thermogravimetric residue mass: ISO 11358 - 1:2014 Plastics - Thermogravimetry (TG) of polymers.

[0060] Table 1

[0061]

[0062]

[0063] Table 2

[0064]

[0065]

[0066] As can be seen from the above table, the tensile strength of the PBT / PET / PC flame-retardant alloy material prepared in the embodiment of the present invention is ≥108 N, the crystallization temperature is ≥160 °C, and the residual mass after thermal weight loss is ≥96%.

[0067] As can be seen from the comparison between Example 1 and Example 4, the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer with a core-shell rubber structure can well improve the mechanical properties and heat resistance of the PBT / PET / PC flame-retardant alloy material. When the average particle size of the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer is 200-400 nm, the mechanical properties and heat resistance are better.

[0068] As can be seen from the comparison between Example 1 and Examples 5-7, when there are 20-40 parts of PBT resin, 10-15 parts of PET resin, 15-25 parts of PC resin, 10-15 parts of flame retardant, 2-3 parts of alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer, and 30-40 parts of glass fiber, the mechanical properties and heat resistance are better.

[0069] As can be seen from the comparison between Example 1 and Comparative Examples 1-3, the dosage of the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer in the PBT / PET / PC flame-retardant alloy material system has a certain range. Too little will not play a role in thermal stability. In Comparative Example 2, ethylene-butyl acrylate-glycidyl methacrylate was used to replace the alkyl methacrylate-silicone / acrylic alkyl ester graft copolymer, and it was found that it had no effect on improving the thermal stability.

[0070] As can be seen from the comparison between Example 1 and Comparative Example 4, the PET / PC alloy requires a higher processing temperature compared to this system, and the higher processing temperature will cause the transesterification process of the two polymers to intensify, and its thermal stability is worse.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PBT / PET / PC flame retardant alloy material, characterized in that: The invention comprises the following components in parts by weight: 9-61 parts of PBT resin, 5-20 parts of PET resin, 7-36 parts of PC resin, 5-20 parts of flame retardant, 1-4 parts of methacrylate-organic silicon / alkyl acrylate graft copolymer and 10-50 parts of glass fiber.

2. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 20-40 parts of PBT resin, 10-15 parts of PET resin, 15-25 parts of PC resin, 10-15 parts of flame retardant, 2-3 parts of methacrylate-organic silicon / alkyl acrylate graft copolymer and 30-40 parts of glass fiber.

3. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The average particle size of the alkyl methacrylate-organic silicon / alkyl acrylate graft copolymer is 200-700 nm.

4. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The flame retardant is at least one of a brominated flame retardant and an antimony flame retardant.

5. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The glass fiber has an aspect ratio of 3-4 and an average length of 2.5-3.5 mm.

6. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The PBT resin has a melt index of 10-60 g / 10 min at 250° C. / 1.2 kg according to ISO1133-1:2011; and / or, the PET has a melt index of 30-100 g / 10 min at 270° C. / 1.2 kg according to ISO 1133-1:2011; And / or, the PC has a melt index of 5-40 g / 10 min at 300° C. / 1.2 kg according to ISO 1133-1:2011.

7. The PBT / PET / PC flame retardant alloy material according to claim 1, characterized in that: The invention also comprises 0.1-6 parts of a processing aid, wherein the processing aid is at least one of an antioxidant, a lubricant and an ester exchange inhibitor.

8. A PBT / PET / PC flame retardant alloy material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: uniformly mixing the components in proportion to obtain a mixture A; adding the mixture A to a main feeding port of a screw extruder, adding glass fiber to a side feeding port of the screw extruder, and performing melt extrusion and granulation to obtain a PBT / PET / PC flame retardant alloy material.

9. An automobile component, comprising the PBT / PET / PC flame retardant alloy material according to any one of claims 1 to 7.

10. Use of the PBT / PET / PC flame retardant alloy material according to any one of claims 1 to 7 in the automotive field.

Images