A thermoplastic polyester composite material and its preparation and application

Abstract

The present invention relates to a thermoplastic polyester composite material and its preparation and application, the components of which include: TPEE, PMAM, a modifier, and an additive. The thermoplastic polyester composite material of the present invention has good bonding effect when bonded with PC / ABS by secondary injection molding, has no abnormal appearance such as peeling and flow lines during thin-wall injection molding, has no oil separation after long-term use, and has a short molding cycle.

Description

Technical Field

[0001] The invention belongs to the field of plastic processing, and particularly relates to a thermoplastic polyester composite material and a preparation method and application thereof. Background Art

[0002] Thermoplastic polyester elastomer TPEE has excellent mechanical properties and chemical solvent resistance, and has been increasingly used in automotive parts, electronic appliances, optical fiber sheaths and other fields. It has good bonding effects with polar materials such as PC, ABS, PC / ABS alloys, etc., and can be directly bonded to the hard plastic surface through secondary injection molding and other molding processes. It has been widely used in power tool handles, automotive parts and other fields.

[0003] Due to the limitation of polymerization process, the hardness of thermoplastic polyester elastomer is generally higher than 75A, which limits its application in the application fields of low hardness and good feel. At present, in order to achieve the effect of low hardness and bonding with PC, ABS, and PC / ABS, oil-filled hydrogenated styrene elastomer is generally added to thermoplastic polyester elastomer, but there is a problem that the thickness of the rubber layer is relatively thin, especially when it is less than 0.5mm, the appearance of peeling and flow lines will appear near the gate, and the mineral oil in the material is easy to precipitate after long-term baking. Summary of the invention

[0004] In view of the defects of the prior art, the object of the present invention is to provide a thermoplastic polyester composite material and its preparation and application.

[0005] The thermoplastic polyester composite material of the present invention comprises the following components in parts by weight:

[0006] TPEE 40-60 parts;

[0007] PMAM 40-60 parts;

[0008] Modifier 2-10 parts;

[0009] Additives 0-10 parts;

[0010] The soft segment mass percentage in TPEE is 60-85%. 1 H NMR was used for testing. The specific testing method is described in Polymer Bulletin 42, 587-594 (1999);

[0011] The modifier is a mixture of wollastonite and mica powder, wherein the mass ratio of wollastonite to mica powder is (1:3) to (3:1); wherein the average particle size of wollastonite is 400-1250 meshes, and the average particle size of mica powder is 40-500 meshes, and the particle size is tested with reference to GB / T19077-2016.

[0012] TPEE: thermoplastic polyester elastomer; PMAM: linear methyl methacrylate-butyl methacrylate-methyl methacrylate triblock copolymer.

[0013] Preferably, the mass percentage of the soft segment in the TPEE is 65-80%. Within this range, good bonding effect and faster molding and high production efficiency can be achieved.

[0014] Preferably, the mass ratio of wollastonite to mica powder is (1:2) to (2:1).

[0015] Preferably, the average particle size of the wollastonite is 600-800 meshes, and the average particle size of the mica powder is 300-400 meshes. When the particle sizes of the wollastonite and mica powder are within this range, the molding cycle is short and the surface color of the product is uniform.

[0016] Preferably, the additive is one or more of a flame retardant (such as aluminum diethylphosphinate, inorganic aluminum hypophosphite, resorcinol bisdiphenyl phosphate, etc.), an antioxidant (such as 4.4'-bis(α.α-dimethylbenzyl)diphenylamine, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.), a UV resistant agent (such as 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, etc.), carbon black, a pigment (such as azo orange, iron yellow, etc.), a dye (such as ultramarine blue, azo orange, etc.), and a mineral powder (such as calcium carbonate, talc, montmorillonite, etc.).

[0017] Preferably, by weight, the components include:

[0018] TPEE 45-55 parts;

[0019] PMAM 43-55 parts;

[0020] 3-8 parts of modifier;

[0021] Additives 0-10 parts.

[0022] A method for preparing the thermoplastic polyester composite material of the present invention comprises:

[0023] The components are weighed according to weight ratio, mixed and fed into a twin-screw extruder, granulated and dried to obtain a thermoplastic polyester composite material.

[0024] Preferably, the extrusion granulation temperature is 180-250° C., the aspect ratio of the twin-screw extruder is 36-60 / 1, and the residence time of the material in the screw is 40-90 s.

[0025] The thermoplastic polyester composite material of the present invention is used in the fields of daily consumer goods, sporting goods or electric tools, such as electric tool handles, game console handles, and smart glasses frames.

[0026] When thermoplastic polyester composites are bonded to PC / ABS by secondary injection molding, the main bonding component is TPEE. After TPEE and PMAM are blended and compounded, PMAM has a certain polarity and a certain compatibility with TPEE. TPEE can be evenly distributed in the composite and can be evenly bonded to the surface of PC / ABS. There will be no appearance abnormalities such as peeling and flow lines at the gate, and it is not easy to precipitate. After adding the modifier, it can help the dispersion of TPEE and improve the bonding effect; in the cooling process after injection molding, the modifier can play a nucleation role, accelerate the hardening of the composite, and shorten the molding cycle.

[0027] Beneficial Effects

[0028] The thermoplastic polyester composite material of the present invention has good bonding effect when bonded with PC / ABS by secondary injection molding, has no abnormal appearance phenomena such as peeling and flow lines during thin-wall injection molding, has no oil separation during long-term use, and has a short molding cycle. DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0030] 1. Source of raw materials

[0031] TPEE with different soft segment contents is prepared with reference to the synthesis method disclosed in British patent GB1323727. The preparation steps are as follows: put the measured dimethyl terephthalate, 1,4-butanediol, and polytetrahydrofuran ether into a reactor, heat to 200-230°C, add a catalyst for esterification reaction, and after the esterification reaction is completed, heat to 240-260°C, gradually reduce the pressure of the system to below 0.5 mmHg, and continue the reaction for 2-3 hours. After the reaction is completed, high-purity nitrogen is filled into the reactor, and the melt is pressed out of the reactor die. After pelletizing, the desired thermoplastic polyester elastomer TPEE is obtained. By changing the amount of polytetrahydrofuran ether fed, the following 5 TPEE with different soft segment contents are obtained:

[0032] TPEE-1, soft segment mass percentage is 80%;

[0033] TPEE-2, soft segment mass percentage is 65%;

[0034] TPEE-3, the soft segment mass percentage is 60%;

[0035] TPEE-4, soft segment mass percentage is 90%;

[0036] TPEE-5, the soft segment mass percentage is 50%;

[0037] PMAM: KURARITY LA2330, produced by Kuraray;

[0038] SEBS filled with mineral oil, SEBS G1654 / 150N = 1 / 1.5 (mass ratio), wherein SEBS G1654 is produced by Kraton, and 150N is produced by CNOOC;

[0039] Wollastonite-1 600 mesh, wollastonite-106, produced by Shanghai Tianhan Mineral Powder Technology Co., Ltd.;

[0040] Wollastonite-2 800 mesh, HQ-800, produced by Dalian Global Minerals Co., Ltd.;

[0041] Wollastonite-3 1200 mesh, HQ-1250, produced by Dalian Global Minerals Co., Ltd.

[0042] Wollastonite-4 1800 mesh, HK-2000F, produced by Dalian Global Minerals Co., Ltd.

[0043] Mica powder-1 400 mesh, AY-04N mesh, purchased from Guangzhou Dachao Chemical Co., Ltd.;

[0044] Mica powder-2 300 mesh, 300HC, produced by Lingshou County Huajing Mica Co., Ltd.;

[0045] Mica powder-3 50 mesh, AY-03N; produced by Jiangmen Jingda Mica Materials Co., Ltd.;

[0046] Mica powder-4 600 mesh, W-600, produced by Lingshou County Huajing Mica Co., Ltd.;

[0047] Modifier-1: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 1:1;

[0048] Modifier-2: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 2:1;

[0049] Modifier-3: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 1:3;

[0050] Modifier-4: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 3:1;

[0051] Modifier-5: wollastonite 800 mesh and mica powder 300 mesh, mass ratio is 1:1;

[0052] Modifier-6: wollastonite 1200 mesh and mica powder 50 mesh, mass ratio is 1:1;

[0053] Modifier-7: wollastonite 600 mesh and mica powder 600 mesh, mass ratio is 1:1;

[0054] Modifier-8: wollastonite 1800 mesh and mica powder 400 mesh, mass ratio is 1:1;

[0055] Modifier-9: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 1:6;

[0056] Modifier-10: wollastonite 600 mesh and mica powder 400 mesh, mass ratio is 5:1;

[0057] Modifier-11: wollastonite 600 mesh;

[0058] Modifier 12: Mica powder 400 mesh.

[0059] Additives: antioxidant tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester in a mass ratio of 2:3:5, ultraviolet light absorber 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, and carbon black.

[0060] The additives used in the parallel examples and comparative examples are the same commercially available products.

[0061] 2. Preparation methods of embodiments and comparative examples

[0062] The components are weighed according to the weight ratio, mixed and fed into a twin-screw extruder, granulated and dried to obtain a thermoplastic polyester composite material; the extrusion granulation temperature is 180-250°C, the aspect ratio of the twin-screw extruder is 36-60 / 1, and the material stays in the screw for 40-90s.

[0063] 3. Test standards and methods

[0064] Adhesion evaluation method:

[0065] The test was carried out in accordance with the German Engineers Association standard VDI 2019:2016. A PC / ABS plastic strip with a size of 150*40*2mm was placed in the mold cavity. The thermoplastic polyester composite material was injected at a temperature of 210-230°C. A secondary injection molding was performed on the surface of the PC / ABS hard rubber strip, and the 90-degree peel force was tested with a tensile testing machine.

[0066] Adhesion rating by failure mode:

[0067] Grade A: The interface between the thermoplastic polyester composite and PC / ABS is destroyed, and there is no thermoplastic polyester composite residue on the PC / ABS surface;

[0068] Grade B: The interface between the thermoplastic polyester composite and PC / ABS is damaged, and the residual area of ​​the thermoplastic polyester composite on the PC / ABS surface is less than 50% of the PC / ABS area;

[0069] Grade C: The interface between the thermoplastic polyester composite and PC / ABS is damaged, and the residual area of ​​the thermoplastic polyester composite on the PC / ABS surface is greater than 50% of the PC / ABS area;

[0070] Grade D: The thermoplastic polyester composite material is fractured, and there is no damage to the PC / ABS interface;

[0071] Evaluation by bonding effect: D grade > C grade > B grade > A grade

[0072] Peeling on the surface of the workpiece:

[0073] The thermoplastic polyester composite material was injected into a mold cavity with a size of 200*25*0.5mm, and the appearance near the gate was observed to see if there were any defects such as peeling.

[0074] Oil separation:

[0075] The thermoplastic polyester composite material was injection molded into a 100*100*1 mm square plate, which was placed in an oven at 85° C. and baked for 2000 h. Whether oily substances were precipitated on the surface of the square plate was observed.

[0076] Forming speed evaluation method:

[0077] The thermoplastic polyester composite material was injection molded into a disc-shaped product with a diameter of 50 mm and a thickness of 10 mm. Under the same injection molding process conditions, the cooling time was changed. The shortest cooling time when the product could be demoulded normally without deformation was recorded as t, and the molding speed was judged by comparing the t value.

[0078] Table 1 Proportions of the embodiments (parts by weight)

[0079]

[0080] Table 2 Comparative Example Proportions (parts by weight)

[0081]

[0082]

[0083] Table 3 Performance data of the embodiment

[0084]

[0085] Table 4 Performance effect data of comparative examples

[0086]

[0087] It can be seen from Examples 1-12 of the present invention that when the thermoplastic polyester composite prepared by using TPEE, PMAM, wollastonite and mica powder is bonded to PC / ABS by secondary injection molding, the bonding effect can reach the highest level D, the cooling time is less than 346s, the surface has no abnormal appearance such as peeling and flow lines, and there is no oil separation problem after long-term baking.

Claims

1. A thermoplastic polyester composite material, characterized in that: By weight, the components include: TPEE 40-60 parts; PMAM 40-60 parts; Modifier 2-10 parts; Additives 0-10 parts; The mass percentage of soft segments in TPEE is 60-85%; The modifier is a mixture of wollastonite and mica powder, wherein the mass ratio of wollastonite to mica powder is (1:3) to (3:1); wherein the average particle size of wollastonite is 400-1250 meshes, and the average particle size of mica powder is 40-500 meshes; Wherein PMAM is a linear methyl methacrylate-butyl methacrylate-methyl methacrylate triblock copolymer; The TPEE is prepared from dimethyl terephthalate, 1,4-butanediol and polytetramethylene glycol.

2. The thermoplastic polyester composite material according to claim 1, characterized in that: The mass percentage of the soft segment in the TPEE is 65-80%.

3. The thermoplastic polyester composite material according to claim 1, characterized in that: The mass ratio of the wollastonite to the mica powder is (1:2) to (2:1).

4. The thermoplastic polyester composite material according to claim 1, characterized in that: The average particle size of the wollastonite is 600-800 meshes, and the average particle size of the mica powder is 300-400 meshes.

5. The thermoplastic polyester composite material according to claim 1, characterized in that: The additive is one or more of flame retardants, antioxidants, UV resistant agents, carbon black, pigments, dyes, and mineral powders.

6. The thermoplastic polyester composite material according to claim 1, characterized in that: By weight, the components include: TPEE 45-55 parts; PMAM 43-55 parts; 3-8 parts of modifier; Additives 0-10 parts.

7. A method for preparing the thermoplastic polyester composite material according to claim 1, comprising: The components are weighed according to weight ratio, mixed and fed into an extruder, granulated and dried to obtain a thermoplastic polyester composite material.

8. Use of the thermoplastic polyester composite material according to claim 1 in the field of daily consumer goods, sporting goods or electric tools.

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