Polyamide composite material, method for producing same, and use thereof

Abstract

The application discloses a kind of polyamide composite and its preparation method and application.The polyamide composite of the application includes polyamide composition A and polyamide composition B, the polyamide composition A includes the following components by weight fraction: polyamide resin 35-85 parts, filler 7-32 parts, white pigment 7-32 parts, modification auxiliary 0.2-2 parts, phosphate and its derivative 0.2-2 parts;The modification auxiliary is nylon chain extender;The melting point of the polyamide resin is 270-330 DEG C, and the thermal weight loss is less than 15% at 370 DEG C, the polyamide composition B is industrial post-recycled polyamide composition A, and the mass ratio of polyamide composition B in the polyamide composite is ≤85%.The polyamide composite prepared by the application has good reflectivity and strength, and is especially suitable for LED reflection support.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular compound compositions, and more particularly to a polyamide composite material and a preparation method and application thereof. BACKGROUND

[0002] Many countries and regions have set their own emission reduction targets, and the plastic product industry is currently exploring renewable materials, which are divided into three categories: post-consumer materials (PCR-Post Consumer Resin), post-industrial materials (PIR-Post Industrial Resin), and bio-based materials (Bio-based material); among them, PCR is a material that is recycled after being pre-processed (disassembled, sorted, cleaned), crushed, melted, and regranulated; PIR is a material that is directly recycled and regranulated from the water gap, vice card, and defective products produced during factory injection molding. In particular, the super-high mold cavity number injection molding process in the LED industry produces more post-industrial recycled materials; in the prior art, post-industrial recycled materials are generally mixed and used with new materials, but in actual application, it is found that the polyamide composite material used for LEDs with post-industrial recycled materials will result in poor strength and reflectivity of the LED support, making it difficult to meet application requirements. SUMMARY

[0003] The purpose of the present application is to overcome the defects and deficiencies of the prior art polyamide composite material containing post-industrial recycled materials, and to provide a polyamide composite material.

[0004] Another purpose of the present application is to provide a preparation method of a polyamide composite material.

[0005] Still another purpose of the present application is to provide a polyamide composite material for use in LED reflector supports.

[0006] The above purposes of the present application are achieved by the following technical solutions:

[0007] The present application protects a polyamide composite material, which comprises a polyamide composition A and a polyamide composition B, wherein the polyamide composition A comprises the following components by weight fraction:

[0008] 35-85 parts of polyamide resin, 7-32 parts of filler, 7-32 parts of white pigment, 0.2-2 parts of modification aid, and 0.2-2 parts of phosphate and its derivatives; the modification aid is a nylon chain extender; the melting point of the polyamide resin is 270-330℃, and the thermal weight loss at 370℃ is less than 15%;

[0009] The polyamide composition B is a post-industrial recycled polyamide composition A;

[0010] The mass ratio of the polyamide composition B in the polyamide composite is ≤ 85%.

[0011] The polyamide composite provided in the present application contains an industrial post-recycled material and a polyamide composition A, and the addition ratio of a polyamide composition B is adjusted, the thermal stability of the polyamide resin is adjusted, and a nylon chain extender is combined as a modification aid to allow the broken molecular chains to re-polymerize. However, the rearrangement of the nylon chain extender and the molecular chains is a mutually competitive reaction, and we surprisingly found that the use of a phosphate-based aid can effectively inhibit the rearrangement of the molecular chains without affecting the reaction between the molecular chains, so the strength and reflectivity of the polyamide composite can be effectively improved.

[0012] It should be noted that the industrial post-recycled polyamide composition A is a water gate material produced by injection molding of the polyamide composition A described in the present application.

[0013] Specifically, the polyamide resin is a semi-aromatic polyamide resin.

[0014] The semi-aromatic polyamide resin is composed of units formed by aliphatic diamines of 3-36 carbon atoms and aromatic diacids; preferably aliphatic diamines of 6-10 carbon atoms, more preferably aliphatic diamines of 9 or 10 carbon atoms; and the aromatic diacid is preferably one or more of terephthalic acid and isophthalic acid.

[0015] Specifically, the semi-aromatic polyamide includes at least one of PA6T, PA4T, PA6I, PA9T, PA10T, and PA12T.

[0016] In some specific embodiments, the polyamide composition B is obtained by injection molding of the polyamide composition A described in the present application, and the injection molding temperature is 350℃-340℃-330℃-330℃-320℃, and the injection molding speed is 320-380 mm / s.

[0017] In some specific embodiments, the polyamide composition B has an L value > 70, an a value of -5-5, and a b value of -15-15.

[0018] The polyamide resin has an L value > 80, an a value of -5-0, and a b value of -5-5.

[0019] Specifically, the Lab value of the polyamide resin is measured using a Color Eye 7000A color difference meter, and the polyamide resin is injection molded into a sample size of 60mm x 60mm x 0.8mm.

[0020] The polyamide resin in the present application has a melting point of 270-330℃, for example, but not limited to, a melting point of 270℃, 275℃, 280℃, 285℃, 290℃, 295℃, 300℃, 305℃, 310℃, 315℃, 320℃, 325℃ or 330℃, etc. can achieve the present application.

[0021] The polyamide resin in the present application has a thermal weight loss of less than 15% at 370℃, for example, but not limited to, less than 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6% or 5%, etc. can achieve the present application.

[0022] The mass ratio of the polyamide composition B in the polyamide resin composite material in the present application is ≤85%, for example, but not limited to, ≤85%, 80%, 75%, 70%, 65%, 60%, 55% or 50%, etc. can achieve the present application.

[0023] The mass ratio of the polyamide resin in the polyamide composition A is preferably not less than 30%.

[0024] Preferably, the phosphate salt is one or more of potassium phosphate, sodium phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphate ester, phosphite ester, and disodium hydrogen pyrophosphate.

[0025] In a specific embodiment, the phosphite ester includes one or more of (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 1,3-phenylene phosphonic acid (2,6-tolyl) tetraester, or hydroquinone bis(diphenyl phosphate).

[0026] Preferably, the mass ratio of the polyamide composition B in the polyamide composite material is 60%-80%.

[0027] Preferably, the polyamide composition A includes the following components by weight fraction: polyamide resin 50-70 parts, filler 14-25 parts, white pigment 14-25 parts, modification aid 0.6-1.6 parts, and phosphate salt and its derivative 0.5-1 part.

[0028] Specifically, the melting point of the polyamide resin can be tested according to the ASTM D3418-2003 standard test, specifically, a Perkin Elmer Diamond DSC analyzer can be used, under a nitrogen atmosphere, a flow rate of 40mL / min, first heated to 340℃ at a rate of 10℃ / min, held at 340℃ for 2min, then cooled to 50℃ at a rate of 10℃ / min, and then heated to 340℃ at a rate of 10℃ / min.

[0029] Specifically, the thermal gravimetric performance of the polyamide resin is determined according to the standard GB / T 27761-2011.

[0030] Specifically, the Netzsch TG209 analyzer is used, the nitrogen atmosphere is 40mL / min, the temperature is raised to 120℃ at a rate of 20℃ / min, the temperature is kept at 120℃ for 30min, then the temperature is raised to 370℃ at a rate of 20℃ / min, and then the temperature is kept at 370℃ for 60min; the weight loss from the initial temperature to 370℃ to the end of the constant temperature for 60min can be calculated to obtain the weight loss at 370℃ constant temperature.

[0031] Further preferably, the SMT retention rate of the polyamide resin is not less than 80%.

[0032] Specifically, the SMT retention rate is determined by measuring the bending strength of the polyamide resin according to the standard ISO 178-2019, and recording the initial bending strength; then the sample is kept after SMT, and the bending strength is measured according to the same method, and recorded as the bending strength after SMT; the SMT retention rate = the bending strength after SMT / the initial bending strength*100%.

[0033] Optionally, the relative viscosity of the polyamide resin is 1.8-2.4.

[0034] Specifically, the relative viscosity of the polyamide resin can be tested according to the standard GB 12006.1-1989.

[0035] Specifically, the relative viscosity of the polyamide with a concentration of 0.25g / dl is measured in 98% concentrated sulfuric acid at 25±0.01℃.

[0036] Further, the relative viscosity of the polyamide resin is 2.0-2.4.

[0037] Specifically, the white pigment is at least one of titanium dioxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide, silicon dioxide, aluminum oxide, barium carbonate, aluminum nitride, boron nitride, potassium titanate, calcium silicate, aluminum borate, calcium sulfate, and barium sulfate; preferably titanium dioxide.

[0038] Specifically, the filler is at least one of glass fiber, wollastonite, potassium titanate whisker, kaolin or mica.

[0039] The nylon chain extender in the application can be selected according to the prior art, for example but not limited to one or more of anhydride chain extender, epoxy chain extender, oxazoline chain extender, carbonate chain extender, isocyanate chain extender, polyamine chain extender and polyol chain extender.

[0040] Specifically, the oxazoline chain extender is 4-acetyl-2,2-dimethyl oxazoline-3-carboxylic acid tert-butyl ester.

[0041] Specifically, the anhydride chain extender is maleic anhydride grafted ethylene copolymer.

[0042] Specifically, the isocyanate chain extender is m-xylylene diisocyanate.

[0043] Specifically, the diamine chain extender is one or more of diethylenetriamine, diaminodiphenyl methane, hexamethylenediamine, ethylenediamine, butanediamine or isophorone diamin.

[0044] Specifically, the polyol chain extender is one or more of 1,4-butanediol, trimethylolpropane or 1,2-propanediol.

[0045] Specifically, it can be BRUGGOLEN M1251 / M1253, BASF chain extender ADR 4368C or CHEMCORD CM 3020 nylon special chain extender.

[0046] In addition, one or more of the following can also be included in the polyamide composition A: antioxidants, light stabilizers, impact modifiers, flame retardants, optical brighteners, lubricants, plasticizers, thickening agents, antistatic agents, release agents or colorants.

[0047] The present application also protects a method for preparing the above-mentioned polyamide composite material, comprising the following steps: mixing the components, melt extruding, and obtaining the polyamide composite material; specifically, a twin-screw extruder can be used for melt extrusion, and the temperature for melt extrusion is 230-330 DEG C.

[0048] The application of the above-mentioned polyamide composite material in an LED reflection bracket is also within the protection scope of the present application.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] The present application provides a polyamide composite material containing not more than 85% of industrial post-recycled materials and a polyamide composition A, the polyamide composition A adding a nylon chain extender as a modification aid and cooperating with a phosphate aid, and cooperating with a polyamide resin with a specific melting point and a specific thermal weight loss performance range, which can effectively improve the reflectivity and strength of the polyamide composite material. DETAILED DESCRIPTION

[0051] The present application will be further described below in combination with the specific embodiments, but the embodiments do not limit the present application in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present application are conventionally purchased raw materials and reagents.

[0052] 1. Raw material reagent

[0053] Polyamide resin 1: Vicnyl 700NC003, melting point 316℃, thermal weight loss at 370℃ 6.3%, relative viscosity 2.15, manufacturer Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0054] Polyamide resin 2: Vicnyl 6100NC003, melting point 290℃, thermal weight loss at 370℃ 8.2%, relative viscosity 2.12, manufacturer Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0055] Polyamide resin 3: Vicnyl 702NC003, melting point 316℃, thermal weight loss at 370℃ 7.6%, relative viscosity 1.85, manufacturer Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0056] Polyamide resin 4: Vicnyl 3100NC003, melting point 343℃, thermal weight loss at 370℃ 9.7%, relative viscosity 2.09, manufacturer Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0057] Polyamide resin 5: Vicnyl 400NC003, melting point 305℃, thermal weight loss at 370℃ 26%, relative viscosity 2.18, manufacturer Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0058] Phosphate and its derivatives 1: (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, purchased from KOPULUS;

[0059] Phosphate and its derivatives 2: dihydrogen sodium pyrophosphate, purchased from Anhui Zhong Xu Biological Technology Co., Ltd.;

[0060] The filler is glass fiber, the model number is E7CS10-03-568H, and the manufacturer is China Jushi Co., Ltd.;

[0061] The white pigment is titanium dioxide, the model number is BLR-895, and the manufacturer is Longbaiguituan Co., Ltd.;

[0062] Modified auxiliary 1: carbonate chain extender, BRUGGOLEN M1251, Bruegmann;

[0063] Modified auxiliary 2: polyamine chain extender, diethylene triamine, commercially available;

[0064] 2. The polyamide composite material of each embodiment and the comparative example of the application is prepared by the following preparation method:

[0065] After the components are weighed according to the formula and uniformly mixed, they are added to a twin-screw extruder for melt blending, extrusion and granulation, thereby obtaining the polyamide composite material.

[0066] The melt-extruding conditions of the twin-screw extruder are as follows: the temperature of the first zone is 165°C, the temperature of the second zone is 230°C, the temperature of the third zone is 310°C, the temperature of the fourth zone is 320°C, the temperature of the fifth zone is 320°C, the temperature of the sixth zone is 320°C, the temperature of the seventh zone is 310°C, the temperature of the eighth zone is 310°C, the temperature of the ninth zone is 310°C, the temperature of the tenth zone is 310°C, and the rotation speed of the main machine is 450 r / min.

[0067] 3. Performance test

[0068] The injection-molded samples (2.8 mm*3.5 mm*0.15 mm) after three times of infrared reflow soldering are randomly divided into two groups A and B. Group A is subjected to light reflectivity test after reflow soldering, and group B is subjected to push force test. The infrared reflow soldering device is SMT infrared reflow soldering device, and the setting conditions are as follows:

[0069] a. Preheating stage: the temperature is raised from room temperature to 150°C within 120 seconds;

[0070] b. Heating stage: the temperature is raised from 150°C to 190°C within 90 seconds;

[0071] c. Reflow stage: the temperature is raised to 217°C at a rate of 2.5°C per second, and then the temperature is raised from 217°C to 260°C and then lowered to 217°C within 80 seconds;

[0072] d. Cooling stage: the temperature is lowered to room temperature at a rate of more than 2°C per second.

[0073] (1) Light reflectivity test after reflow soldering: the light reflectivity of the injection-molded samples at 460 nm is tested using Color Eye 7000A color difference meter after three times of infrared reflow soldering.

[0074] (2) Push force test: the samples after reflow soldering are placed under the push force testing machine to test the push force of the LED support.

[0075] Examples 1-11 and Comparative Examples 1-6

[0076] The weight fractions of the components of the polyamide composite materials in Examples 1-11 and Comparative Examples 1-6 and the performance test results are shown in Tables 1 and 2.

[0077] Table 1 Weight fractions of the components of the polyamide composite materials in Examples 1-11

[0078]

[0079] It should be noted that the polyamide composition B in each of the examples and comparative examples is obtained by injection molding using the corresponding polyamide composition A, the polyamide composition B in examples 1-11 is obtained by injection molding using the polyamide composition A in examples 1-11, the polyamide composition B in comparative examples 1-6 is obtained by injection molding using the polyamide composition A in comparative examples 1-6, and the total amount of the polyamide composition A and the polyamide composition B is 100%.

[0080] Table 2: weight parts of each component of the polyamide composite in comparative examples 1-6

[0081]

[0082] As can be seen from Table 1 and Table 2, the polyamide composite prepared in the present application has good reflectivity and strength, the R460 reflectivity is not less than 80%, and the bracket push force is not less than 650g.

[0083] In comparative example 1, no modifying aid is added, and the reflectivity and strength of the polyamide composite prepared by adding the phosphate and its derivatives are significantly decreased. This is because the molecular chains are broken after the high temperature and high shear in the injection molding process, the molecular chains gradually become smaller, and thus the mechanical properties are severely decreased. In addition, the terminal active groups generated by the chain breaking increase, which also causes the material to yellow and reduces the reflectivity of the material.

[0084] In comparative example 2, when the proportion of the polyamide composition B is too high, the reflectivity and strength of the polyamide composite prepared are significantly decreased. This is because when the amount of the polyamide composition B is too high, the breaking rate is much higher than the repairing speed of the modifying aid, thereby leading to the performance decrease.

[0085] In comparative example 3, when the melting point of the polyamide resin is too high, the reflectivity of the polyamide composite prepared is significantly decreased.

[0086] In comparative example 4, when the thermal weight loss of the polyamide resin is high, the reflectivity and strength of the polyamide composite prepared are significantly decreased.

[0087] In comparative example 5, if only the modifying aid is added without adding the phosphate and its derivatives, the strength of the polyamide composite prepared is significantly decreased.

[0088] The above examples of the present application are only examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A polyamide composite, characterized in that, The polyamide composition A comprises the following components in parts by weight: The polyamide resin is 35-85 parts, the filler is 7-32 parts, the white pigment is 7-32 parts, the modification aid is 0.2-2 parts, and the phosphate and its derivative is 0.2-2 parts; the modification aid is a nylon chain extender; the melting point of the polyamide resin is 270-330℃, and the thermal weight loss at 370℃ is less than 15%; The polyamide composition B is an industrial post-recycled polyamide composition A; The mass percentage of the polyamide composition B in the polyamide composite material is ≤85%; The phosphate and its derivative includes phosphite and / or dihydrogen disodium pyrophosphate.

2. The polyamide composite of claim 1, wherein, The polyamide composition A comprises the following components in parts by weight: polyamide resin 50-70 parts, filler 14-25 parts, white pigment 14-25 parts, modification aid 0.6-1.6 parts, and phosphate and its derivative 0.5-1 part.

3. The polyamide composite of claim 1, wherein, The mass percentage of the polyamide composition B in the polyamide composite material is 60%-80%.

4. The polyamide composite of claim 1, wherein, The relative viscosity of the polyamide resin is 1.8-2.

4.

5. The polyamide composite of claim 1, wherein, The white pigment is at least one of titanium dioxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate, and aluminum oxide; the filler is at least one of glass fiber, wollastonite, potassium titanate whisker, kaolin, or mica.

6. The polyamide composite of claim 1, wherein, The nylon chain extender is at least one of anhydride chain extender, epoxy chain extender, oxazoline chain extender, carbonate chain extender, isocyanate chain extender, polyamine chain extender, and polyol chain extender.

7. The polyamide composite of claim 1, wherein, The polyamide composition A can also include one or more of antioxidants, light stabilizers, impact modifiers, flame retardants, fluorescent brighteners, lubricants, plasticizers, thickeners, antistatic agents, release agents, or colorants.

8. A process for the production of the polyamide composite according to any one of claims 1 to 7, characterized in that The polyamide composite material is obtained by mixing and melt extruding the components.

9. The polyamide composite material of any one of claims 1-7 for use in an LED reflector support.

10. An LED reflector holder, characterized by, The polyamide composite material is prepared by using any one of claims 1-7.

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