1. A halogen flame-retardant reinforced polyketone material is characterized by comprising the following components in percentage by weight:

wherein the main flame retardant is at least one of decabromodiphenylethane, brominated epoxy resin and brominated polystyrene;

the auxiliary flame retardant is selected from at least one of antimony trioxide and sodium antimonate.

2. The halogen flame retardant reinforced polyketone material of claim 1 wherein said filled reinforcement is short glass fibers.

3. The halogenated flame-retardant reinforced polyketone material as claimed in claim 1, wherein the antioxidant is prepared by mixing a main antioxidant and a secondary antioxidant in a weight ratio of 1: 1;

preferably, the primary antioxidant is selected from hindered phenol type antioxidants;

preferably, the secondary antioxidant is selected from hindered phenol type antioxidants;

preferably, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester;

preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite.

4. The halogen flame retardant reinforced polyketone material of claim 1 wherein said lubricant is selected from at least one of N, N' -bis ethylene stearyl amide, stearic amide, paraffin wax, polyethylene wax, polypropylene wax and silicone.

5. A halogen flame retardant reinforced polyketone material as in claim 1, wherein said nucleating agent is selected from at least one of long carbon chain linear saturated carboxylic acid sodium salt NAV101 and long carbon chain linear saturated carboxylic acid calcium salt CAV 102.

6. A process for preparing a halogen flame retardant reinforced polyketone material according to any one of claims 1 to 5, comprising the steps of:

(1) weighing polyketone raw materials, and drying at the temperature of 100-120 ℃ for 4-10h for later use;

(2) adding the dried polyketone into a telling mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing treatment for 1-2min to obtain a mixed material A;

(3) putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer, mixing for 2-4min, adding the mixed material A, and continuously mixing for 2-3min to obtain a mixed material B;

(4) drying the mixed material B at the temperature of 90-100 ℃ for 2-3h for later use;

(5) and putting the dried mixed material B and the auxiliary agent into a double-screw extruder, adding glass fiber, performing reinforced filling extrusion, and performing granulation treatment to obtain the halogen flame-retardant reinforced polyketone material.

7. The method for preparing a halogen flame retardant reinforced polyketone material according to claim 6, wherein the temperature of each section of the twin-screw extruder in the step (5) is set as follows:

the temperature of the first zone is 140-170 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 230-240 ℃, the temperature of the fifth zone is 220-230 ℃, the temperature of the sixth zone is 200-220 ℃, the temperature of the seventh zone is 200-220 ℃, the temperature of the eighth zone is 200-220 ℃, and the temperature of the head is 230-250 ℃.

8. The preparation method of the halogen flame-retardant reinforced polyketone material as claimed in claim 6, wherein the residence time of the dried mixed material B in the twin-screw extruder is 1-2 minutes;

preferably, the pressure in the double-screw extruder is 12-18 MPa.

9. The preparation method of the halogen flame retardant reinforced polyketone material as claimed in claim 6, wherein the main flame retardant is at least one selected from decabromodiphenylethane, brominated epoxy resin and brominated polystyrene;

preferably, the auxiliary flame retardant is selected from at least one of antimony trioxide and sodium antimonate;

preferably, the filler reinforcement is short glass fibers;

preferably, the antioxidant is formed by mixing a main antioxidant and a secondary antioxidant according to the weight ratio of 1: 1;

preferably, the primary antioxidant is selected from hindered phenol type antioxidants;

preferably, the secondary antioxidant is selected from hindered phenol type antioxidants;

preferably, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester;

preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite;

preferably, the lubricant is selected from at least one of N, N' -bis-ethylene-stearyl fatty acid amide, stearic acid amide, paraffin wax, polyethylene wax, polypropylene wax, and silicone;

preferably, the nucleating agent is selected from at least one of long carbon chain linear saturated carboxylic acid sodium salt NAV101 and long carbon chain linear saturated carboxylic acid calcium salt CAV 102.

10. Use of a halogenated flame retardant reinforced polyketone material as defined in any one of claims 1 to 5 or a halogenated flame retardant reinforced polyketone material prepared according to any one of claims 6 to 9 in automotive materials.

Background

Polyketone (PK) is a novel green material which is successfully polymerized and produced in large quantities in 10 years by the Korea Xiaoxing group. The material is a polymer obtained by absorbing carbon monoxide in air and copolymerizing the carbon monoxide with ethylene and propylene. The material has very few branched chains on the molecular chain, and has no hydrophilic and lipophilic groups, so the material has extremely excellent chemical resistance. The polyketone material has the following advantages that 1, the specific gravity of the polyketone material is 1.24g/cm³Is heavier than nylon, but lighter than PBT and POM, has chemical resistance equivalent to PPS, can bear strong acid and strong alkali, and has excellent chemical resistance; 2. the wear resistance of the polyketone is 14 times of that of the traditional POM, and the resin material can perfectly replace the POM, thereby not only improving the wear resistance, but also greatly reducing the weight; 3. the polyketone has outstanding high and low temperature performance, and can be directly used at the temperature of between 30 ℃ below zero and 105 ℃. The material is hydrolysis-resistant and glycol solution-resistant, and has great potential in the automobile industry. However, since the star group mainly comprises PK resin polymerization, and new application of PK is blank in China, how to provide a modified polyketone material with good fluidity, low cost, excellent mechanical property, flame retardance of V-0 and excellent processing formability is a problem to be solved urgently.

Disclosure of Invention

The invention aims to provide a halogen flame-retardant reinforced polyketone material, a preparation method and application thereof, so as to overcome the defects of poor flowability, high cost, poor mechanical property and low flame-retardant grade of the polyketone material in the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the halogen flame-retardant reinforced polyketone material comprises the following components in percentage by weight:

wherein the main flame retardant is at least one of decabromodiphenylethane, brominated epoxy resin and brominated polystyrene;

the auxiliary flame retardant is selected from at least one of antimony trioxide and sodium antimonate.

Optionally, the upper limit of the amount of the polyketone PK is selected from 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts; the lower limit of the amount of the polyketone PK is selected from 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts and 51 parts.

Optionally, the primary flame retardant is present in an amount of 9 parts.

Optionally, the primary flame retardant is present in an amount of 10 parts.

Optionally, the primary flame retardant is present in an amount of 11 parts.

Optionally, the secondary flame retardant is present in an amount of 3 parts.

Optionally, the secondary flame retardant is present in an amount of 4 parts.

Optionally, the upper filling enhancement amount limit is selected from 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, and the lower filling enhancement amount limit is selected from 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts.

Optionally, the antioxidant is present in an amount of 0.2 parts.

Optionally, the antioxidant is present in an amount of 0.3 parts.

Optionally, the antioxidant is present in an amount of 0.4 parts.

Optionally, the antioxidant is present in an amount of 0.5 parts.

Optionally, the antioxidant is present in an amount of 0.6 parts.

Optionally, the lubricant is present in an amount of 0.2 parts.

Optionally, the lubricant is present in an amount of 0.3 parts.

Optionally, the lubricant is present in an amount of 0.4 parts.

Optionally, the lubricant is present in an amount of 0.5 parts.

Optionally, the lubricant is present in an amount of 0.6 parts.

Optionally, the lubricant is present in an amount of 0.7 parts.

Optionally, the lubricant is present in an amount of 0.8 parts.

Optionally, the nucleating agent is present in an amount of 0.3 parts.

Optionally, the nucleating agent is present in an amount of 0.4 parts.

Optionally, the nucleating agent is present in an amount of 0.5 parts.

Optionally, the nucleating agent is present in an amount of 0.6 parts.

Optionally, the filling reinforcement is short glass fibers.

Optionally, the antioxidant is prepared by mixing a main antioxidant and a secondary antioxidant according to a weight ratio of 1: 1.

Optionally, the primary antioxidant is selected from hindered phenol type antioxidants.

Optionally, the secondary antioxidant is selected from hindered phenol type antioxidants.

Optionally, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester.

Optionally, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite.

Optionally, the lubricant is selected from at least one of N, N' -bis-ethylene-stearyl fatty acid amide, stearic acid amide, paraffin wax, polyethylene wax, polypropylene wax, and silicone.

Optionally, the nucleating agent is selected from at least one of a long carbon chain linear saturated carboxylic acid sodium salt NAV101 and a long carbon chain linear saturated carboxylic acid calcium salt CAV 102.

The preparation method of the halogen flame-retardant reinforced polyketone material comprises the following steps:

(1) weighing polyketone raw materials, and drying at the temperature of 100-120 ℃ for 4-10h for later use;

(2) adding the dried polyketone into a telling mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing treatment for 1-2min to obtain a mixed material A;

(3) putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer, mixing for 2-4min, adding the mixed material A, and continuously mixing for 2-3min to obtain a mixed material B;

(4) drying the mixed material B at the temperature of 90-100 ℃ for 2-3h for later use;

(5) and putting the dried mixed material B and the auxiliary agent into a double-screw extruder, adding glass fiber, performing reinforced filling extrusion, and performing granulation treatment to obtain the halogen flame-retardant reinforced polyketone material.

Optionally, the temperature of each section of the twin-screw extruder in the step (5) is set as follows: the temperature of the first zone is 140-170 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 230-240 ℃, the temperature of the fifth zone is 220-230 ℃, the temperature of the sixth zone is 200-220 ℃, the temperature of the seventh zone is 200-220 ℃, the temperature of the eighth zone is 200-220 ℃, and the temperature of the head is 230-250 ℃.

Optionally, the residence time of the dried mixed material B in the twin-screw extruder is 1-2 minutes.

Optionally, the pressure in the twin-screw extruder is 12-18 MPa.

The halogen flame-retardant reinforced polyketone material or the prepared halogen flame-retardant reinforced polyketone material is applied to automobile materials.

Compared with the prior art, the invention has the advantages that: the application provides a halogen flame-retardant reinforced polyketone material, which adopts a proper main flame retardant to retard flame and modify polyketone, can achieve excellent flame retardance and can keep good mechanical properties. The auxiliary flame retardant is added and compounded with the main flame retardant, so that the flame retardant effect is greatly improved, the weight of the main flame retardant is reduced, and the cost is reduced. In addition, the special glass fiber is selected, and the glass fiber is well compatible with the polyketone resin, so that the mechanical property of the material is greatly improved, and a solid foundation is laid for other subsequent research and development work of the polyketone. The preparation method of the halogen flame-retardant reinforced polyketone material is simple and easy to implement, has no pollution to the environment, and is a green and environment-friendly preparation process.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.

The halogen flame-retardant reinforced polyketone material comprises the following components in percentage by weight:

wherein the main flame retardant is at least one of decabromodiphenylethane, brominated epoxy resin and brominated polystyrene;

the auxiliary flame retardant is selected from at least one of antimony trioxide and sodium antimonate.

Optionally, the upper limit of the amount of the polyketone PK is selected from 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts; the lower limit of the amount of the polyketone PK is selected from 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts and 51 parts.

Optionally, the primary flame retardant is present in an amount of 9 parts.

Optionally, the primary flame retardant is present in an amount of 10 parts.

Optionally, the primary flame retardant is present in an amount of 11 parts.

Optionally, the secondary flame retardant is present in an amount of 3 parts.

Optionally, the secondary flame retardant is present in an amount of 4 parts.

Optionally, the upper filling enhancement amount limit is selected from 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, and the lower filling enhancement amount limit is selected from 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts.

Optionally, the antioxidant is present in an amount of 0.2 parts.

Optionally, the antioxidant is present in an amount of 0.3 parts.

Optionally, the antioxidant is present in an amount of 0.4 parts.

Optionally, the antioxidant is present in an amount of 0.5 parts.

Optionally, the antioxidant is present in an amount of 0.6 parts.

Optionally, the lubricant is present in an amount of 0.2 parts.

Optionally, the lubricant is present in an amount of 0.3 parts.

Optionally, the lubricant is present in an amount of 0.4 parts.

Optionally, the lubricant is present in an amount of 0.5 parts.

Optionally, the lubricant is present in an amount of 0.6 parts.

Optionally, the lubricant is present in an amount of 0.7 parts.

Optionally, the lubricant is present in an amount of 0.8 parts.

Optionally, the nucleating agent is present in an amount of 0.3 parts.

Optionally, the nucleating agent is present in an amount of 0.4 parts.

Optionally, the nucleating agent is present in an amount of 0.5 parts.

Optionally, the nucleating agent is present in an amount of 0.6 parts.

Optionally, the filling reinforcement is short glass fibers.

Optionally, the antioxidant is prepared by mixing a main antioxidant and a secondary antioxidant according to a weight ratio of 1: 1.

Optionally, the primary antioxidant is selected from hindered phenol type antioxidants.

Optionally, the secondary antioxidant is selected from hindered phenol type antioxidants.

Optionally, the primary antioxidant is selected from the group consisting of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester.

Optionally, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite.

Optionally, the lubricant is selected from at least one of N, N' -bis-ethylene-stearyl fatty acid amide, stearic acid amide, paraffin wax, polyethylene wax, polypropylene wax, and silicone.

Optionally, the nucleating agent is selected from at least one of a long carbon chain linear saturated carboxylic acid sodium salt NAV101 and a long carbon chain linear saturated carboxylic acid calcium salt CAV 102.

The preparation method of the halogen flame-retardant reinforced polyketone material comprises the following steps:

(1) weighing polyketone raw materials, and drying at the temperature of 100-120 ℃ for 4-10h for later use;

(2) adding the dried polyketone into a telling mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing treatment for 1-2min to obtain a mixed material A;

(3) putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer, mixing for 2-4min, adding the mixed material A, and continuously mixing for 2-3min to obtain a mixed material B;

(4) drying the mixed material B at the temperature of 90-100 ℃ for 2-3h for later use;

(5) and putting the dried mixed material B and the auxiliary agent into a double-screw extruder, adding glass fiber, performing reinforced filling extrusion, and performing granulation treatment to obtain the halogen flame-retardant reinforced polyketone material.

Optionally, the temperature of each section of the twin-screw extruder in the step (5) is set as follows: the temperature of the first zone is 140-170 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 230-240 ℃, the temperature of the fifth zone is 220-230 ℃, the temperature of the sixth zone is 200-220 ℃, the temperature of the seventh zone is 200-220 ℃, the temperature of the eighth zone is 200-220 ℃, and the temperature of the head is 230-250 ℃.

Optionally, the residence time of the dried mixed material B in the twin-screw extruder is 1-2 minutes.

Optionally, the pressure in the twin-screw extruder is 12-18 MPa.

The halogen flame-retardant reinforced polyketone material or the prepared halogen flame-retardant reinforced polyketone material is applied to automobile materials.

The invention adopts polyketone, and is assisted with filling reinforcement, flame retardant, antioxidant, lubricant and nucleating agent to modify the polyketone in a molten state. Wherein the polyketone is crystalline material, and is low viscosity food grade green PK resin M930F provided by Xiaoxing Corp Korea.

The flame retardant can enable the material to achieve a good flame retardant effect, due to the uniformity of the molecular chain of the PK material, the flame retardant effect of V-0 can be achieved by adding less flame retardant, the cost is greatly reduced by compounding the main flame retardant and the auxiliary flame retardant, the addition of the flame retardant has an effect of increasing the fluidity of the PK material, and the processing difficulty is better reduced. The flame retardant used in the invention is decabromodiphenylethane produced by Shandong Shouguang company, brominated epoxy resin produced by Shandong Shouguang company, brominated polystyrene (621) produced by Yabao company in America, and the auxiliary flame retardant is conventional antimony trioxide (Sb203) in Hunan Chenzhou and sodium antimonate (SA-F) in Chengdu Fei.

The filling reinforcement is made of glass fiber commonly used in modified production, and the addition of the glass fiber can greatly improve the comprehensive performance of the material, which is common knowledge. However, the Chongqing composite material short glass fiber 301HP is selected for carrying out reinforcement modification research, so that the polyketone modified material with high performance is obtained.

The addition of the antioxidant is to prevent the addition of the auxiliary agent which is added due to the fact that the material is easy to decompose and the material generates heat in a machine screw due to friction in the machine screw so as to cause decomposition of some auxiliary agents or thermal-oxidative decomposition of raw materials in the processing process of the material, and can better catalyze modification and enable modification processing to be easier. The antioxidant adopted by the invention is divided into a main antioxidant and an auxiliary antioxidant according to the weight ratio of 1:1, wherein the main antioxidant is hindered phenol antioxidant tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (code: 1010), and the secondary antioxidant is hindered phenol antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (code: 168).

The lubricant is mainly added into the material to enable other auxiliary agents and raw materials to be better dispersed, and comprises an internal lubricant and an external lubricant or a composite lubricant formed by the internal lubricant and the external lubricant. Wherein the internal lubricant may be a fatty acid amide type lubricant or a hydrocarbon type lubricant and the external lubricant may be a non-polar lubricant. Fatty acid amide lubricants include N, N' -diethenylstearyl fatty acid amide (TAF), stearic acid amide; hydrocarbon lubricants include paraffin wax, polyethylene wax or polypropylene wax; the non-polar lubricant may be a silicone.

The nucleating agent is added to accelerate the crystallization rate of the material, and although PK is a crystalline material, the crystallinity is reduced due to the influence of the auxiliary agent in the modification process, so that if the material can obtain higher crystallinity in the modification process, the mechanical property of the material can be greatly improved, and meanwhile, the temperature resistance of the material can be greatly improved, so that the material can be applied in wider fields. The nucleating agent adopted by the invention is mainly one of long carbon chain linear saturated carboxylic acid sodium salt NAV101 and long carbon chain linear saturated carboxylic acid calcium salt CAV 102.

The technical solution of the present invention is further explained below with reference to several examples.

Each of the materials in the examples of the present invention is commercially available.

Example 1

Weighing 43 parts of polyketone (PKM930F), 9 parts of decabromodiphenylethane serving as a main flame retardant, 33 parts of Sb2O serving as an auxiliary flame retardant, 40 parts of short glass fiber 301HP, 0.3 parts of antioxidants 1010 and 168, 0.3 part of TAF serving as a lubricant and 0.3 part of siloxane serving as a nucleating agent CAV 1020.3. Preparing the halogen flame-retardant reinforced PK material.

The composite material was prepared by the following method:

a. weighing raw materials including polyketone (at 100 ℃ for 4h), and respectively drying the raw materials;

b. adding the dried polyketone into a high-speed mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing for about 2 min;

c. putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer for mixing for about 2min, adding the mixed flame retardant into the mixed materials for fully mixing for about 3min after mixing, and putting the mixed materials into a drying oven for drying for 3h at the temperature of 100 ℃;

d. and (3) putting the fully mixed and dried raw materials and the auxiliary agent into a double-screw extruder, adding glass fiber for reinforcing, filling, extruding and granulating to prepare the halogen flame-retardant reinforced polyketone reinforcing material.

The temperature of each section of the twin-screw extruder is set as follows: the temperature of the first zone is 140 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 200 ℃ and the temperature of the head is 240 ℃. The residence time in the twin-screw extruder was 1 minute and the pressure was 15 megapascals (MPa).

Example 2

46 parts of polyketone (PK M930F), 10 parts of a main flame retardant decabromodiphenylethane, 3 parts of an auxiliary flame retardant SA-F, 40 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, 0.3 part of lubricant TAF and siloxane and 1020.3 parts of a nucleating agent CAV. Preparing the halogen flame-retardant reinforced PK material.

The composite material was prepared by the following method:

a. weighing raw materials including polyketone (110 ℃ for 3h), and respectively drying the raw materials;

b. adding the dried polyketone into a high-speed mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing for about 1 min;

c. putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer for mixing for about 3min, adding the mixed flame retardant into the mixed materials for fully mixing for about 3min after mixing, and putting the mixed materials into a drying oven for drying for 3h at the temperature of 100 ℃;

d. and (3) putting the fully mixed and dried raw materials and the auxiliary agent into a double-screw extruder, adding glass fiber for reinforcing, filling, extruding and granulating to prepare the high-performance halogen flame-retardant reinforced PK material.

The temperature of each section of the twin-screw extruder is set as follows:

the temperature of the first zone is 150 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 200 ℃, the temperature of the seventh zone is 200 ℃, the temperature of the eighth zone is 210 ℃ and the temperature of the head is 240 ℃. According to the preparation method, the residence time in the double-screw extruder is 2 minutes, and the pressure in the double-screw extruder is 14 MPa.

Example 3

Weighing 50 parts of polyketone (PK M930F), 62110 parts of main flame retardant, Sb2O34 parts of auxiliary flame retardant, 30 parts of short glass fiber 301HP, 0.3 part of antioxidant 1010 and 168, 0.3 part of lubricant TAF and siloxane, 1020.3 parts of nucleating agent CAV, and halogen flame retardant reinforced polyketone material.

The composite material was prepared by the following method:

a. weighing raw materials including polyketone (110 ℃ for 4h), and respectively drying the raw materials;

b. adding the dried polyketone into a high-speed mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing for about 2 min;

c. putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer for mixing for about 2min, adding the mixed flame retardant into the mixed materials for fully mixing for about 3min after mixing, and putting the mixed materials into a drying oven for drying for 2.5h at 90 ℃;

d. and (3) putting the fully mixed and dried raw materials and the auxiliary agent into a double-screw extruder, adding glass fiber for reinforcing, filling, extruding and granulating to prepare the high-performance halogen flame-retardant reinforced PK material.

The preparation method is characterized in that the temperature of each section of the double-screw extruder is set as follows:

the temperature of the first zone is 160 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 200 ℃ and the temperature of the machine head is 250 ℃. According to the preparation method, the residence time in the double-screw extruder is 2 minutes, and the pressure in the double-screw extruder is 15 MPa.

Example 4

Weighing 48 parts of polyketone (PK M930F), 6219 parts of main flame retardant, 33 parts of auxiliary flame retardant Sb2O, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, 0.3 part of lubricant TAF and siloxane and 1020.3 parts of nucleating agent CAV according to parts by weight, and preparing the halogen flame-retardant reinforced polyketone material.

The composite material was prepared by the following method:

a. weighing raw materials including polyketone (at 120 ℃ for 4h), and respectively drying the raw materials;

b. adding the dried polyketone into a high-speed mixer, adding a lubricant, a nucleating agent and an antioxidant, and carrying out high-speed mixing for about 2 min;

c. putting the main flame retardant and the auxiliary flame retardant into a high-speed mixer for mixing for about 3min, adding the mixed flame retardant into the mixed materials for fully mixing for about 2min after mixing, and putting the mixed materials into a drying oven for drying for 3h at the temperature of 100 ℃;

d. and (3) putting the fully mixed and dried raw materials and the auxiliary agent into a double-screw extruder, adding glass fiber for reinforcing, filling, extruding and granulating to obtain the halogen flame-retardant reinforced polyketone material.

The preparation method is characterized in that the temperature of each section of the double-screw extruder is set as follows:

the temperature of the first zone is 160 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 200 ℃, the temperature of the eighth zone is 200 ℃ and the temperature of the head is 245 ℃. According to the preparation method, the residence time in the double-screw extruder is 1 minute, and the pressure in the double-screw extruder is 14 MPa.

Example 5

52 parts of polyketone (PK M930F), 10 parts of brominated epoxy resin serving as a main flame retardant, 3 parts of SA-F serving as an auxiliary flame retardant, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, 0.3 part of TAF serving as a lubricant and 0.3 part of siloxane serving as a nucleating agent and 1020.3 parts of CAV serving as a nucleating agent to prepare the halogen flame-retardant reinforced polyketone material.

The preparation method is the same as that of example 1.

Example 6

Weighing 44 parts of polyketone (PK M930F), 11 parts of a main flame retardant brominated epoxy resin, 4 parts of an auxiliary flame retardant SA-F, 35 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, 0.3 part of a lubricant TAF and siloxane and 1020.3 parts of a nucleating agent CAV, and preparing the halogen flame-retardant reinforced polyketone material.

The preparation method is the same as that of example 1.

Example 7

Weighing 44 parts of polyketone (PK M930F), 62110 parts of main flame retardant, SA-F4 parts of auxiliary flame retardant, 301HP 35 parts of short glass fiber, 0.2 parts of antioxidant 1010 and 168, 0.6 part of lubricant TAF and siloxane and 1020.3 parts of nucleating agent CAV, and preparing the halogen flame-retardant reinforced polyketone material.

The preparation method is the same as that of example 1.

Example 8

Weighing 45 parts of polyketone (PK M930F), 11 parts of a main flame retardant decabromodiphenylethane, 3 parts of an auxiliary flame retardant SA-F, 35 parts of short glass fiber 301HP, 0.5 part of antioxidants 1010 and 168, 0.3 part of stearic acid amide and siloxane and 1010.3 parts of a nucleating agent NAV, and preparing the halogen flame-retardant reinforced polyketone material.

The preparation method is the same as that of example 1.

Example 9

52 parts of polyketone (PK M930F), 11 parts of a main flame retardant decabromodiphenylethane, 3 parts of an auxiliary flame retardant SA-F, 30 parts of short glass fiber 301HP, 0.6 part of antioxidants 1010 and 168, 0.8 part of polyethylene wax and siloxane and 1010.6 parts of a nucleating agent NAV, are weighed according to the parts by weight, and the halogen flame-retardant reinforced polyketone material is prepared.

The preparation method is the same as that of example 1.

Example 10

51 parts of polyketone (PK M930F), 62111 parts of main flame retardant, SA-F3 parts of auxiliary flame retardant, 301HP 40 parts of short glass fiber, 0.4 part of antioxidant 1010 and 168 parts of polypropylene wax and siloxane, and 0.5 part of nucleating agent CAV1020.4 parts are weighed according to the parts by weight to prepare the halogen flame-retardant reinforced polyketone material.

The preparation method is the same as that of example 1.

Example 11

The halogen flame-retardant reinforced polyketone material prepared by the above 10 groups of examples can be tested by the following test methods, procedures, conditions and standards.

And (5) evaluating the performance of the material.

Drying the granulated halogen flame-retardant reinforced polyketone material particles in a blast oven at 110-120 ℃ for 3-4 hours, and then carrying out injection molding on the dried particles on an 80T injection molding machine to prepare a sample, wherein the mold temperature is kept between 120-140 ℃ in the sample preparation process.

Tensile strength was tested according to ASTM-D638: specimen type is type I, specimen size (mm): 180 (length) × (12.68 ± 0.2) (neck width) × (3.23 ± 0.2) (thickness), and the drawing speed was 5 mm/min.

Flexural strength and flexural modulus were tested according to ASTM-D790: specimen type is specimen size (mm): (128. + -. 2) × (12.8. + -. 0.2) × (3.21. + -. 0.2), and the bending speed was 2 mm/min.

Notched impact strength was tested according to ASTM-D256: sample type is V-notch type, sample size (mm): (63 ± 2) × (12.58 ± 0.2) × (4.21 ± 0.2); the notch type is V-notch type, and the residual thickness of the notch is 2.44 mm.

Heat distortion temperature was tested according to ASTM-D648, with a load of 1.82MPa, a span of 100mm, specimen size (mm): (128. + -. 2) × (13. + -. 0.2) × (6.4. + -. 0.2), the maximum deformation amount was 0.25 mm.

Flame resistance test checked according to the international UL-94 standard, specimen size (mm): 1/8 splines: (128 ± 2) × (12.8 ± 0.2) × (3.21 ± 0.2); 1/16 splines: (128. + -. 2) × (12.66. + -. 0.2) × (1.59. + -. 0.2).

The performance test and the result of the halogen flame-retardant reinforced polyketone material in the embodiment 1-6 are selected for analysis. For clear comparison, the following table 1 shows the raw material components of the composite materials of examples 1 to 6.

TABLE 1 parts by weight (unit: parts) of the composite materials of examples 1 to 6

The performance of the composite materials of examples 1-6 was evaluated using the above-described test methods and procedures, and the results are shown in table 2 below.

Table 2 composite Performance test results for examples 1-6 and comparative examples

As can be seen from table 2: under the condition that other conditions are unchanged or only change of small fluctuation, different flame retardant systems have larger influence on the comprehensive mechanical property of the whole modified material, and the proper dosage of the proper flame retardant system not only can achieve the excellent flame retardant effect, but also can keep the comprehensive strength of the material as much as possible, so that the comprehensive property of the material is very excellent. Experiments prove that the composition ratio of the example 4 is the best effect: according to parts by weight, 48 parts of Polyketone (PK), 6219 parts of a main flame retardant, 33 parts of an auxiliary flame retardant Sb2O, 30 parts of short glass fiber 301HP, 0.3 part of antioxidants 1010 and 168, 0.3 part of lubricant TAF and siloxane and 1020.3 parts of a nucleating agent CAV. According to the proportion, firstly, the most appropriate and mature glass fiber in China is selected for reinforcement modification, and then, the low-proportion flame retardant (about 16-18 parts of 621 parts is needed if the flame retardant is normal nylon flame retardant V0), so that the cost problem in the material modification process can be greatly reduced, the influence on the mechanical property of the material is minimum, and the most excellent mechanical property is achieved under the condition of low economic cost. Therefore, the proportion combination is the optimal combination to be selected, and simultaneously, the main problems to be discussed by the patent are reflected, and the superiority and novelty of the patent are reflected.

Therefore, through continuous research and development, I successfully develop a series of modified polyketone materials, so that the polyketone materials successfully replace PA, PBT and POM in the traditional meaning in the fields of automobiles, electronics, industry, medical treatment, food, consumer products and the like, and become a new-generation green novel material.

Due to various excellent characteristics of polyketone, the halogen flame-retardant reinforcing material which is excellent and simple in processing performance, green and environment-friendly and meets the European Union standard is prepared by the inventor to fill the blank of the material in domestic modification and make fundamental contribution to the development of the subsequent polyketone material modification.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.