CN107513262B

CN107513262B - Polyketone compositions

Info

Publication number: CN107513262B
Application number: CN201610451382.9A
Authority: CN
Inventors: 杨桂生; 范继贤; 吴安琪; 费彬; 姚晨光
Original assignee: Hefei Genius New Materials Co Ltd
Current assignee: Hefei Genius New Materials Co Ltd
Priority date: 2016-06-18
Filing date: 2016-06-18
Publication date: 2021-03-26
Anticipated expiration: 2036-06-18
Also published as: CN107513262A

Abstract

The invention discloses a polyketone composition, which is prepared from the following components in parts by weight: 90-100 parts of polyketone resin, 0.1-1 part of graphene, 0-0.5 part of antioxidant, 0.2-1 part of liquid assistant, 0-1 part of stabilizer and 0-0.5 part of lubricant. The invention provides a new way for improving the UV degradation resistance of polyketone resin; the application range of the graphene is widened; the invention has simple design and easy realization, and can increase the proportion of some components to be made into master batches which are directly mixed with polyketone resin to be injected into products.

Description

Polyketone compositions

Technical Field

The invention belongs to the technical field of high molecular materials, and particularly relates to a polyketone polymer composition containing a stabilizer with an anti-UV (ultraviolet) photodegradation effect.

Background

Polyketone (POK) is a copolymer obtained by polymerizing monomers such as carbon monoxide and propylene, and has been industrially produced by british shell company for the first time, and it is reported that polyketone has an impact resistance 3 times stronger than nylon, a chemical stability 1.4 to 2.5 times stronger than nylon, and is harder than Polyoxymethylene (POM), which is the hardest material at present, by 14 times or more. Polyketones also have excellent heat resistance, chemical resistance, impact resistance, and abrasion resistance. Because of its many advantages, it is used in many industrial fields, but its application range is limited because of the existence of ketone group, so that it has poor light ageing resistance, so that it has many researches on light ageing resistance, such as adding 2- (hydroxyaryl) -1,3, 5-triazine to polyketone to raise its UV resistance, as proposed in patent CN1181771A, and also in patent US-A-4954584, it is proposed that the mixture of carbon black and diphenylamine stabilizer is preferable, and in patent US-A-5149733, it is proposed that the mixture of carbon black and hindered thiobisphenol stabilizer is used as A method for raising UV resistance of polyketone, and these methods are favorable for raising UV resistance of polyketone polymer, so that its application range is further enlarged.

Graphene is a novel nanomaterial, which has many excellent properties, such as the strongest strength, and thus is considered to be applicable in many fields; meanwhile, people are also continuously researching new characteristics of the graphene, so that the graphene is expected to be applied to more fields, for example, when Li Mei Ming of university of Yunnan researches the optical properties of graphene with different structures, the graphene is found to have strong absorption and reflection in ultraviolet and visible light bands and strong absorption in ultraviolet light bands, so that the graphene is expected to be applied to solar cells and other materials.

Disclosure of Invention

The invention aims to prepare a composition for improving the UV resistance of polyketone polymer by utilizing the optical characteristics of graphene and increase the application range of the graphene.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the composition is prepared from the following components in parts by weight: :

the melt flow rate of the polyketone resin is 6-200 g/10min under the test conditions of 240 ℃ and 2.16 kg.

The graphene is divided into a plurality of types, such as one or more of graphene oxide, reinforced graphene and conductive graphene, and the graphene oxide is preferred in the patent.

The antioxidant is selected from one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (Irganox1010), N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide (S-EED), N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098), preferably S-EED.

The liquid auxiliary agent is one or more of propylene glycol, glycerin, sorbitol and mannitol, and sorbitol is preferred in the patent. The liquid assistant is mainly convenient for graphene to be mixed into the polyketone resin, and the graphene is a nano material and has small particle size, so that simple blending is not easy to add into the polyketone resin; the choice of liquid auxiliaries has furthermore the object of improving the melt processing stability of the polyketone resins by combining them with other auxiliaries.

The stabilizer is one or more of aluminum phosphate, aluminum borate and aluminum silicate, and aluminum phosphate is preferred.

The lubricant is selected from one or more of ethylene bis stearamide, calcium stearate, silicone, polyethylene wax or pentaerythritol stearate, and preferably ethylene bis stearamide.

The preparation method of the composition comprises the following steps:

weighing polyketone resin, adding the polyketone resin into a high-speed mixer, adding a liquid auxiliary agent while stirring, stirring for 30 seconds after the addition, sequentially adding an antioxidant, a lubricant and a stabilizer into the high-speed mixer, mixing for 1-2 minutes, stopping the mixing, and adding the mixed polyketone mixture into a hopper of an extruder; extruding at 220-245 ℃ by a twin-screw extruder, discharging in the form of strands, granulating by a granulator, drying the granules in an oven at 110 ℃ for 4 hours, and then respectively forming standard bars according to ASTM D638 and ASTM D6110 by an injection molding machine.

The diameter of a double screw of the double screw extruder is 35mm, and the length-diameter ratio is 35.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1. according to the invention, the UV degradation resistance of the polyketone resin is improved by adding the graphene into the polyketone resin;

2. the application range of the graphene is widened;

3. the invention has simple design and easy realization, and can increase the proportion of some components to be made into master batches which are directly mixed with polyketone resin to be injected into products.

Detailed Description

The invention will now be further illustrated by reference to the following examples.

A is polyketone resin: M-230A of the Korean Xiaoxing

B, graphene: graphene oxide SE2430 of Heizhou sixth element

C, antioxidant:

S-EED

d, liquid auxiliary agent: sorbitol

E, stabilizer: aluminium phosphate

F, lubricant: commercial EBS

The preparation method of the polyketone composition of each embodiment of the invention comprises the following steps:

In the examples (example 4 is a comparative example), the percentages (% by weight) of the components are shown in table 1:

TABLE 1 proportion of each component of the examples

The above component proportions are subjected to the above composition preparation steps to obtain pellets, these pellets are injection molded into tensile test specimens and notched impact test specimens according to ASTM standards, and these test specimens are subjected to accelerated UV aging; accelerated aging was carried out by exposing the specimens to a fluorescent lamp source in an ultraviolet aging apparatus equipped with UV-340A fluorescence or the like, the accelerated aging experimental conditions being continuous UV exposure without any water condensation stage, and the experimental blackboard temperature being 50 ℃.

The photodegradation of polyketone polymers results in a decrease in the elongation of the polymer part and a decrease in the notched impact strength, and thus the stabilization effect can be determined by testing its relative retention.

TABLE 2 elongation at break change before and after QUV Exposure to aging

TABLE 3 notched Izod impact Strength Change before and after QUV Exposure to aging

By the properties of each of the samples listed in tables 2 and 3, the polyketone polymer retains better elongation at break and impact strength, thus demonstrating that greater UV resistance is provided to the polyketone polymer by the stabilizers of the present invention.

The stabilized polyketone polymers formed in this way are also used in glass fibre reinforced or mineral filled polyketone polymers and also for the production of fibres, sheets, films and the like for given applications, which can be produced by conventional shaping means, such as extrusion, injection moulding and thermoforming. The composition is suitable for applications where the final product may be directly exposed to ultraviolet light, such as automotive interior and exterior parts that require photoaging.

The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The polyketone composition is prepared from the following components in parts by weight:

90-100 parts of polyketone resin,

0.1-1 part of graphene,

0 to 0.5 part of an antioxidant,

0.2 to 1 part of liquid auxiliary agent,

0 to 1 part of a stabilizer,

0-0.5 part of lubricant.

2. The polyketone composition according to claim 1, wherein the polyketone resin has a melt flow rate of 6 to 200g/10min at 240 ℃ under a test condition of 2.16 kg.

3. The polyketone composition of claim 1, wherein the graphene is one or more of graphene oxide, reinforced graphene, and conductive graphene.

4. The polyketone composition of claim 1, wherein the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.

5. The polyketone composition of claim 1, wherein the liquid adjuvant is one or more of propylene glycol, glycerol, sorbitol, and mannitol.

6. The polyketone composition of claim 1 wherein the stabilizer is one or more of aluminum phosphate, aluminum borate and aluminum silicate.

7. The polyketone composition of claim 1 wherein the lubricant is selected from one or more of ethylene bis stearamide, calcium stearate, silicone, polyethylene wax and pentaerythritol stearate.

8. A process for the preparation of a polyketone composition as claimed in any one of claims 1 to 7, characterised by the steps of:

weighing polyketone resin, adding the polyketone resin into a high-speed mixer, adding a liquid auxiliary agent while stirring, sequentially adding an antioxidant, a lubricant and a stabilizer into the high-speed mixer, mixing for 1-2 minutes, stopping mixing, and adding the mixed polyketone mixture into a hopper of an extruder; extruding at 220-245 ℃ by a double-screw extruder, discharging in the form of strands, granulating by a granulator, drying the granules in an oven at 110 ℃ for 4 hours, and preparing the strands by an injection molding machine.

9. The method of preparing a polyketone composition according to claim 8, wherein the twin screw extruder has a twin screw diameter of 35mm and an aspect ratio of 35.