CN108976795A - A kind of polyarylphosphorus ether radiation protection composite material and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of polymer materials, in particular to a polyarylene sulfide/nano metal oxide composite material with good gamma ray protection performance and a preparation method thereof. The invention provides a polyarylene sulfide-based radiation protection composite material, which comprises the following components: polyarylene sulfide matrix resin, processing aid, radiation protection functional filler and coupling agent, the ratio of each component It is: 40-90 parts by weight of polyarylene sulfide base resin, 1-10 parts by weight of processing aid, 10-50 parts by weight of radiation protection functional filler, and the amount of coupling agent is 0.5% of the mass of polyarylene sulfide resin ~5%; Wherein, the processing aid is the same low molecular weight polyarylene sulfide resin as the base resin. The obtained polyarylene sulfide-based radiation protection composite material has good processability, heat resistance, mechanical properties and radiation protection, and its preparation process is simple, which is convenient for industrial production.

Description

A polyarylene sulfide-based radiation protection composite material and its preparation method

technical field

The invention relates to the technical field of polymer materials, in particular to a polyarylene sulfide/nano metal oxide composite material with good gamma ray protection performance and a preparation method thereof.

Background technique

With the rapid development of nuclear science and the extensive application of nuclear technology, traditional ionizing radiation protection materials, such as anti-nuclear radiation concrete and lead alloys, have been difficult to meet the needs of new mobile nuclear facilities, nuclear waste storage containers, and spacecraft. Practical needs for radiation protection.

At present, many polymer-based ionizing radiation protection materials that use organic polymers as the matrix and are filled with fine powders with radiation protection functions have gradually become an indispensable type of radiation protection materials due to their advantages such as low density and easy processing and molding. However, the polymer matrices commonly used in such materials, such as polyolefins, epoxy resins, and polyurethanes, are difficult to meet the requirements of mechanical properties, heat resistance, corrosion resistance, and radiation stability. On the other hand, in order to obtain excellent radiation protection effect, composite materials are often filled with a large number of particles with radiation protection ability. This often leads to difficult processing and poor mechanical properties of composite materials.

Contents of the invention

In view of the above defects, the present invention aims to provide a radiation protection composite material with good processability and shielding performance and a preparation method thereof.

Technical scheme of the present invention:

The first technical problem to be solved by the present invention is to provide a polyarylene sulfide-based radiation protection composite material, which includes the following components: polyarylene sulfide matrix resin, processing aids, radiation protection functional fillers and Coupling agent, the ratio of each component is: 40-90 parts by weight of polyarylene sulfide base resin, 1-10 parts by weight of processing aid, 10-50 parts by weight of radiation protection functional filler, the amount of coupling agent is poly 0.5%-5% (preferably 2%) of the mass of the arylsulfide resin; wherein, the processing aid is the same low molecular weight polyarylene sulfide resin as the base resin.

Furthermore, the weight average molecular weight of the low molecular weight polyarylene sulfide resin ranges from 15000 g/mol to 25000 g/mol.

Further, the weight average molecular weight of the polyarylene sulfide matrix resin is in the range of 40000g/mol-70000g/mol.

Further, the polyarylene sulfide resin is at least one of polyphenylene sulfide (PPS), polyarylene sulfide sulfone (PASS) or polyarylene sulfide ketone (PASK).

Further, the radiation protection functional filler is nano rare earth oxide; further, the radiation protection functional filler is at least one of nano gadolinium oxide, nano cerium oxide, nano samarium oxide or nano lanthanum oxide.

Further, the coupling agent is γ-glycidoxypropyltrimethoxysilane (KH560) or γ-aminopropyltriethoxysilane (KH550).

Preferably, the polyarylene sulfide matrix resin is polyphenylene sulfide, the radiation protection functional filler is nanometer gadolinium oxide, and the coupling agent is γ-glycidyl etheroxypropyltrimethoxysilane (KH560) .

The second technical problem to be solved by the present invention is to provide the preparation method of the above-mentioned polyarylene sulfide-based radiation protection composite material. , extrusion and injection molding polyarylene sulfide-based radiation protection composites.

Preferably, the preparation method of the polyarylene sulfide-based radiation protection composite material is: first mix the polyarylene sulfide matrix resin and the radiation protection functional filler to obtain a mixture, and then spray the diluted coupling The blended material is obtained by mixing the agent, and finally the dried blended material and the processing aid are mixed, extruded and injection molded to obtain a polyarylene sulfide-based radiation protection composite material.

Further, the preparation method of the above-mentioned polyarylene sulfide-based radiation protection composite material comprises the following steps:

1) First mix the polyarylene sulfide base resin and the radiation protection functional filler with a high-speed mixer (generally, it takes about 20 minutes);

2) Then add the coupling agent into the high-speed mixer by spraying after dilution (diluted 10 times), and continue to mix at a high speed for 10-30 minutes (preferably 20 minutes). Preferably at 120°C) for drying for 8 to 10 hours;

3) Continue to mix the dried blended material and processing aid in a high-speed mixer for 15 to 20 minutes, then take it out, and extrude and granulate through a twin-screw extruder;

4) Drying the extrusion-granulated pellets at 100-140° C. (preferably 120° C.) for 8-10 hours, and then injection molding to obtain a polyarylene sulfide-based radiation protection composite material.

Further, in the above method, the mixing rate of high-speed mixing in step 1) to step 3) is 800r/min-2000r/min.

Beneficial effects of the present invention:

The polyarylene sulfide resin used in the present invention has excellent heat resistance, corrosion resistance, radiation stability, flame retardancy and excellent mechanical properties, and can be applied to various nuclear technology fields with complex and changeable environments; The nano rare earth oxide can make the composite material have excellent radiation protection performance at a lower content, and further use low molecular weight polyarylene sulfide resin to improve the processing performance of the composite material. The obtained polyarylene sulfide-based radiation protection composite material has good processability, heat resistance, mechanical properties and radiation protection, and its preparation process is simple, which is convenient for industrial production.

Detailed ways

The first technical problem to be solved by the present invention is to provide a polyarylene sulfide-based radiation protection composite material, which includes the following components: polyarylene sulfide matrix resin, processing aids, radiation protection functional fillers and Coupling agent, the ratio of each component is: 40-90 parts by weight of polyarylene sulfide base resin, 1-10 parts by weight of processing aid, 10-50 parts by weight of radiation protection functional filler, the amount of coupling agent is poly 0.5%-5% (preferably 2%) of the mass of the arylsulfide resin; wherein, the processing aid is the same low molecular weight polyarylene sulfide resin as the base resin.

Further, the molecular weight range of the low molecular weight polyarylene sulfide resin is 15000g/mol-25000g/mol.

Further, the molecular weight range of the polyarylene sulfide matrix resin is 40000g/mol-70000g/mol.

The second technical problem to be solved by the present invention is to provide the preparation method of the above-mentioned polyarylene sulfide-based radiation protection composite material. , extrusion and injection molding polyarylene sulfide-based radiation protection composites.

Preferably, the preparation method of the polyarylene sulfide-based radiation protection composite material is: first mix the polyarylene sulfide matrix resin and the radiation protection functional filler to obtain a mixture, and then spray the diluted coupling The blended material is obtained by mixing the agent, and finally the dried blended material and the processing aid are mixed, extruded and injection molded to obtain a polyarylene sulfide-based radiation protection composite material.

Example 1

40wt% polyphenylene sulfide (molecular weight is 50000) and 50wt% nano-gadolinium oxide were mixed at a high speed of 1000r/min for 20 minutes in a high-speed mixer, and then the coupling agent KH560 of 2wt% of the resin matrix quality was diluted 10 times, Add it into the high-speed mixer in the way of spraying, continue to mix at 1000r/min at high speed for 20 minutes, then take it out, and dry the obtained blended material at 120°C for 8 hours; mix the dried blended material with 10wt% low molecular weight polyphenylene sulfide The ether (molecular weight is 15000) is taken out after being mixed at a high speed of 1000r/min for 15 minutes in a high-speed mixer, extruded and granulated through a twin-screw extruder; the screw speed of the extruder is set at 150rpm, and the temperature of the barrel is set as shown in the following table 1; the extruded granulated pellets were dried at 120°C for 8 hours, and then injection molded. The temperature of each section of the injection molding machine is shown in Table 2 below.

Finally, the tensile strength of the polyphenylene sulfide radiation protection composite material is 67.3MPa, the initial decomposition temperature is 494.0℃, and the shielding rate of γ-rays produced by the decay of ¹³⁷ Cs is 47.2%.

Table 1 Process parameters of extrusion temperature control of PPS radiation protection composite materials

Table 2 Process parameters of extrusion temperature control of PPS radiation protection composite materials

Example 2

The polyphenylene sulfide (molecular weight is 40000) of 50wt% and 40wt% nano gadolinium oxide are mixed 20 minutes with 1000r/min high speed in high-speed mixer, then the coupling agent KH550 of 2wt% resin matrix quality is diluted 10 times, Add it into the high-speed mixer by spraying, continue to mix at 1400r/min for 20 minutes and then take it out, and dry the obtained blended material at 120°C for 8 hours; mix the dried blended material with 10wt% low molecular weight polyphenylene sulfide The ether (molecular weight is 20,000) is mixed in a high-speed mixer at a high speed of 1400r/min for 15 minutes and then taken out. After being extruded and granulated by a twin-screw extruder, the extruded and granulated pellets are dried at 120°C for 8 hours. The parameters of injection molding, extrusion and injection molding are shown in Table 1 and Table 2. Finally, the tensile strength of polyphenylene sulfide radiation protection composite material is 64.5 MPa, the initial decomposition temperature is 493.8 ℃, and the shielding rate of γ-rays produced by ¹³⁷ Cs decay is 41.5%.

Example 3

Mix 28wt% polyphenylene sulfide (molecular weight is 50000), 12wt% polyarylene sulfide sulfone and 50wt% nano samarium oxide in a high-speed mixer at a high speed of 1000r/min for 20 minutes, then mix 2wt% of the resin matrix mass The coupling agent KH560 was diluted 10 times, added to the high-speed mixer by spraying, and then mixed at a high speed of 1000r/min for 20 minutes, then taken out, and the obtained blended material was dried at 120°C for 8 hours; the dried blended The material and 10wt% low-molecular-weight polyphenylene sulfide (molecular weight is 15000) are taken out after mixing at a high speed of 1000r/min for 15 minutes in a high-speed mixer, and then extruded and granulated by a twin-screw extruder; the screw speed of the extruder is set The temperature of the barrel is set at 160 rpm, and the temperature of the barrel is set as shown in Table 3 below; the pellets extruded and granulated are dried at 120°C for 8 hours, and then injection molded. The temperature of each section of the injection molding machine is shown in Table 4 below.

Finally, the tensile strength of polyphenylene sulfide radiation protection composite material is 62.1MPa, the initial decomposition temperature is 493.5℃, and the shielding rate of γ-rays produced by ¹³⁷ Cs decay is 46.4%.

Table 3 Extrusion temperature control process parameters of PPS/PASS radiation protection composites

Table 4 Extrusion temperature control process parameters of PPS/PASS radiation protection composites

Although the present invention has been described above with reference to the embodiments, it will be apparent to those skilled in the art that various modifications can be made to the above embodiments without departing from the spirit and scope of the claims.

Claims (10)

1. polyarylphosphorus ether radiation protection composite material, which is characterized in that the composite material includes following component: poly arylidene thio-ester Class matrix resin, processing aid, radiation protection functional stuffing and coupling agent, the ratio of each component are as follows: polyarylphosphorus ethers matrix tree 40~90 parts by weight of rouge, 1~10 parts by weight of processing aid, 10~50 parts by weight of radiation protection functional stuffing, the dosage of coupling agent It is the 0.5%~5% of poly arylidene thio-ester resinoid quality；Wherein, the processing aid is low molecular weight identical with matrix resin Poly arylidene thio-ester resinoid.

2. polyarylphosphorus ether radiation protection composite material according to claim 1, which is characterized in that the low molecular weight is poly- The weight average molecular weight of aromatic sulfide resinoid is 15000g/mol~25000g/mol.

3. polyarylphosphorus ether radiation protection composite material according to claim 1 or 2, which is characterized in that the polyarylphosphorus The weight average molecular weight of ethers matrix resin is 40000g/mol~70000g/mol.

4. described in any item polyarylphosphorus ether radiation protection composite materials according to claim 1~3, which is characterized in that described Poly arylidene thio-ester resinoid is at least one of polyphenylene sulfide, polyaryl thioether sulfone or polyarylene sulfide ketone.

5. polyarylphosphorus ether radiation protection composite material according to any one of claims 1 to 4, which is characterized in that described Radiation protection functional stuffing is oxide nano rare earth；Further, the radiation protection functional stuffing is nano oxidized gadolinium, nanometer At least one of cerium oxide, nano oxidized samarium or nano lanthanum oxide.

6. described in any item polyarylphosphorus ether radiation protection composite materials according to claim 1~5, which is characterized in that described Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane or gamma-aminopropyl-triethoxy-silane.

7. the preparation method of the described in any item polyarylphosphorus ether radiation protection composite materials of claim 1~6, feature exist In, the preparation method is that: by polyarylphosphorus ethers matrix resin, processing aid, radiation protection functional stuffing and coupling agent through mixed Even, extrusion and injection molding obtain polyarylphosphorus ether radiation protection composite material.

8. the preparation method of polyarylphosphorus ether radiation protection composite material according to claim 7, which is characterized in that described Polyarylphosphorus ether radiation protection composite material the preparation method comprises the following steps: first polyarylphosphorus ethers matrix resin and radiation protection function are filled out Material mixes to obtain mixture, then sprays the coupling agent diluted into mixture and mix that material is blended, finally by being total to after drying It mixes material and processing aid and obtains polyarylphosphorus ether radiation protection composite material through mixing, extrusion and injection molding.

9. the preparation method of polyarylphosphorus ether radiation protection composite material according to claim 7 or 8, which is characterized in that The preparation method of the polyarylphosphorus ether radiation protection composite material the following steps are included:

1) first polyarylphosphorus ethers matrix resin and radiation protection functional stuffing are mixed using high-speed mixer；

2) then coupling agent is added in high-speed mixer in a manner of sprinkling through diluting, is further continued for 10~30min of mixed at high speed After take out, obtained blending material is 8~10 hours dry in 100~140 DEG C；

3) the blending material after drying is continued to mixed at high speed 15~take out after twenty minutes in a high speed mixer with processing aid, By double screw extruder extruding pelletization；

4) pellet of extruding pelletization is 8~10 hours dry in 100~140 DEG C, by injection molding, obtain polyarylphosphorus ether spoke Penetrate protection composite material.

10. the preparation method of polyarylphosphorus ether radiation protection composite material according to claim 9, which is characterized in that step It is rapid 1)~step 3) high speed mixing mixing rate be 800r/min~2000r/min.