阅读说明：本技术 具有中子吸收功能的含硼二维聚芳硫醚材料及制备方法 (Boron-containing two-dimensional polyarylene sulfide material with neutron absorption function and preparation method thereof ) 是由 严永刚 焦雪菲 任浩浩 李鹏程 严大卫 张刚 杨杰 于 2019-10-23 设计创作，主要内容包括：本发明涉及耐高温耐腐蚀具有中子吸收功能和防核辐射的二维聚芳硫醚材料及其制备方法,属于功能聚合物材料领域。本发明提供一种具有中子吸收功能的含硼二维聚芳硫醚材料,所述二维聚芳硫醚材料的结构式如式I所示,式I中,m1与m2的摩尔比为1～50：99～50。本发明所得耐高温耐腐蚀具有中子吸收功能和防核辐射的二维聚芳硫醚薄膜熔点大于280℃,200℃以下没有溶剂,其薄膜重叠到8CM厚度其快中子吸收系数为0.9,抗伽马射线可达10<Sup>9</Sup>,其抗拉伸强度大于60MPa、抗弯曲强度达到80MPa,是一种具有吸收和屏蔽高能射线的新型特种高分子材料。<Image he="570" wi="700" file="DDA0002243668220000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a high-temperature-resistant corrosion-resistant two-dimensional polyarylene sulfide material with a neutron absorption function and nuclear radiation prevention and a preparation method thereof, belonging to the field of functional polymer materials. The invention provides a boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function, wherein the structural formula of the two-dimensional polyarylene sulfide material is shown as a formula I, and in the formula I, the molar ratio of m1 to m2 is 1-50: 99 to 50. The melting point of the high-temperature-resistant corrosion-resistant two-dimensional polyarylene sulfide film with neutron absorption function and nuclear radiation prevention is higher than 280 ℃, no solvent is used below 200 ℃, and the film is overlapped to the thickness of 8CM in the filmThe sub-absorption coefficient is 0.9, and the gamma ray resistance can reach 10 9 The tensile strength is more than 60MPa, the bending strength reaches 80MPa, and the high-strength high-molecular material is a novel special high-molecular material capable of absorbing and shielding high-energy rays.)

1. A boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function is characterized in that the structural formula of the two-dimensional polyarylene sulfide material is shown as a formula I:

in the formula I, the molar ratio of m1 to m2 is 1-50: 99-50;

Ar₁selected from:

Ar₂selected from:

z is selected from:

wherein X is Cl or Br.

2. The boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function according to claim 1, wherein the weight average molecular weight of the boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function is 15000 to 100000.

3. The boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function according to claim 1 or 2, wherein the boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function has a melt index of 10-1000/10 min and a melting point of 240-370 ℃.

4. The method for preparing the boron-containing two-dimensional polyarylene sulfide material with neutron absorption function according to any one of claims 1 to 3, which comprises the following steps: taking a polar aprotic solvent as a medium, and carrying out polymerization reaction on a dihalogenated aromatic compound containing double active groups, a dihalogenated aromatic compound and sodium sulfide or sodium hydrosulfide under the action of a catalyst and alkali at the temperature of 180-300 ℃ to obtain polyarylene sulfide containing active side groups; and then reacting the polyarylene sulfide containing the active side group with a boron-containing compound, and connecting linear molecular chains of the polyarylene sulfide containing the active side group into a two-dimensional structure through boron to obtain the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function.

5. The method for preparing boron-containing two-dimensional polyarylene sulfide material with neutron absorption function according to claim 4, wherein the boron-containing active compound is selected from: dihalophenylborane, dihaloalkylborane, boron trihalide, or boric acid.

6. The method for preparing boron-containing two-dimensional polyarylene sulfide material with neutron absorption function according to claim 4 or 5, wherein the polyarylene sulfide containing active side groups is reacted with a boron-containing compound by the following method: adding polyarylene sulfide containing active side groups into an anhydrous aprotic solvent, adding a boron-containing active compound under the protection of inert gas while stirring, stirring and heating to 60-190 ℃, reacting for 2-12 hours, and then filtering, washing and drying to obtain a boron-containing two-dimensional structure polyarylene sulfide material with a nuclear radiation protection function;

further, the mass ratio of the polyarylene sulfide containing the active side group to the boron-containing active compound is as follows: 50-150 parts of polyarylene sulfide containing active side groups and 1-50 parts of boron-containing active compounds.

7. The method for preparing the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function according to any one of claims 4 to 6, wherein the polyarylene sulfide containing the active side group is prepared by the following method: firstly, 40-300 parts by weight of dihalogenated aromatic compound containing double active groups, 500-1000 parts by weight of sodium sulfide, 10-100 parts by weight of catalyst, 10-50 parts by weight of alkali and 1000-5000 parts by weight of polar aprotic solvent are added into a reaction kettle, and the mixture is reacted and dehydrated at the temperature of 150-205 ℃ under the protection of inert gas; then adding 500-1000 parts by weight of dihalogenated aromatic compound, and reacting at 180-280 ℃ for 1-6 hours; and then heating to 200-280 ℃ to continue reacting for 1-6 hours, finally cooling to 100-180 ℃, adding deionized water while stirring, filtering, washing and drying to obtain the polyarylene sulfide containing the active side group.

8. The method for preparing the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function according to any one of claims 4 to 7, wherein the dihalogen aromatic compound containing double active groups is selected from: dihalosalicylic acid, dihalobenzenediol, dichlorobiphenyldiol, dihalobenzenedicarboxylic acid, dichloronaphthalenedicarboxylic acid or dihalonaphthalenediol;

preferably, the dihalo aromatic compound containing a double active group is selected from: 2, 5-dichloroterephthalic acid, 3, 6-dibromophthalic anhydride, 4, 8-dibromo-1H, 3H-benzo [1,2-C:4,5-C' ] difuran-1, 3,5, 7-tetraone, 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2, 5-dichlorohydroquinone, 2, 6-dichlorohydroquinone, 4, 6-dichlororesorcinol, 3, 5-dichlororesorcinol, 3, 6-dichlorop-hydroxybenzoic acid or 3, 5-dibromo-2-hydroxybenzoic acid.

9. The method for producing a boron-containing two-dimensional polyarylene sulfide material having a neutron absorption function according to any one of claims 4 to 8, wherein the dihalogenated aromatic compound is a p-dihalogenated or m-dihalogenated aromatic compound;

further, the dihaloaromatic compound is selected from: 1, 4-dihalobenzene, 2, 4-dihalobenzene, 3, 5-dihalobenzene, 4,4 '-dihalobiphenyl, 4,4' -dihalodiphenylsulfone, 4,4 '-dihalobenzophenone or 4,4' -dihalodiphenylether;

preferably, the dihaloaromatic compound is 1, 4-dichlorobenzene, 2, 4-m-dichlorobenzene, 4 '-dichlorodiphenyl sulfone or 4,4' -dichlorobenzophenone.

10. The method for preparing boron-containing two-dimensional polyarylene sulfide material with neutron absorption function according to any one of claims 4 to 9,

the polar aprotic solvent is selected from sulfones or sulfones compounds, amine compounds or lactam compounds; further, the polar aprotic solvent is selected from: n-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolone, hexamethylphosphoramide, N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethylsulfoxide, or sulfolane; or:

the catalyst is selected from amino or amino carboxylate compounds, hydroxy carboxylate compounds or organic phosphorus salt compounds; further, the amino or amino carboxylate compound is sodium aminotriacetate, ethylenediamine tetraacetate or diethylenetriamine pentacarboxylate; preferably trisodium (or tetrasodium) ethylenediaminetetraacetate, as in ethylenediaminetetraacetate; the hydroxy carboxylate compound is tartaric acid, heptonate, sodium gluconate or sodium alginate; preferably sodium alginate; the organic phosphorus salt compound is ethylenediamine tetra (methylene) phosphate, diethylenetriamine penta (methylene) phosphonate or amine trimethylene phosphate; preferably, the sodium ethylene diamine tetra (methylene) phosphate; or:

the alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or barium bicarbonate.

Technical Field

The invention relates to a high-temperature-resistant corrosion-resistant two-dimensional polyarylene sulfide material with a neutron absorption function and nuclear radiation prevention and a preparation method thereof, belonging to the field of functional polymer materials.

Background

The Special engineering plastics (Special engineering plastics) are engineering plastics with high comprehensive performance and long-term use temperature of more than 150 ℃, mainly comprise polyphenylene sulfide, polyimide, polyether-ether-ketone, liquid crystal polymers, polysulfone, polyarylate, polyaramide, fluorine-containing polymers and the like, and have various types, excellent performance and high price.

The special engineering plastic PPS has become the first special engineering plastic at present, and the global production capacity is over 7 ten thousand tons/year. Due to the characteristics of excellent corrosion resistance, high temperature resistance, good rigidity, high strength, small specific gravity and the like, the composite material can be used for replacing metal materials, and can be prepared into structural components required by military equipment after modification by various modification means such as blending, filling, reinforcing, forming polymer alloy and the like, wherein the modification means comprises the following steps: the electric tank is characterized by comprising an engine radiator, a vehicle body door, an electric pump and the like, wherein a sea-crossing amphibious tank turret base, a corrosion-resistant rotating gear, a sealing ring, a piston ring, a sealing gasket, an electric injection engine rotor impeller and the like can effectively reduce the weight of the chariot, and improve the maneuverability, reliability, damage safety and riding comfort; the products such as the self-lubricating bearing, the sliding gasket and the like made of the PPS composite material are very suitable for weapons and armored combat vehicles to be used under various severe natural conditions, and the reliability and the wartime attendance rate of the equipment are improved.

However, the modification mainly aims at improving the toughness and the strength of the PPS and has some performances of other materials, the PPS is not functionalized from a main chain structure and endowed with new special functions, and the inherent potential that special engineering plastic molecules can be endowed with new functions is not fully exerted.

Disclosure of Invention

In view of the above, the invention provides linear polyarylene sulfide with active reaction side group in the structure, the polyarylene sulfide with active side group is reacted with boron-containing compound with double active reaction groups, and the linear molecular chains of the polyarylene sulfide with active side group are connected into a two-dimensional structure material through boron (B), and the obtained two-dimensional material (film type) has neutron absorption function and nuclear radiation resistance.

The technical scheme of the invention is as follows:

the first technical problem to be solved by the invention is to provide a boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function, wherein the structural formula of the two-dimensional polyarylene sulfide material is shown as a formula I:

in the formula I, the molar ratio of m1 to m2 is 1-50: 99-50;

Ar₁selected from:

Ar₂selected from:

z is selected from:

wherein X is Cl or Br.

Further, Z and Ar₁The molar ratio of (a) to (b) is 0.1 to 1: 1.

further, the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function has the weight average molecular weight of 15000-100000, the melt index of 10-1000/10 min and the melting point of 240-370 ℃.

The second technical problem to be solved by the present invention is to provide a preparation method of the boron-containing two-dimensional polyarylene sulfide material with neutron absorption function, wherein the preparation method comprises: taking a polar aprotic solvent as a medium, and carrying out polymerization reaction on a dihalogenated aromatic compound containing double active groups, a dihalogenated aromatic compound and sodium sulfide or sodium hydrosulfide under the action of a catalyst and alkali at the temperature of 180-300 ℃ to obtain polyarylene sulfide containing active side groups; and then reacting the polyarylene sulfide containing the active side group with a boron-containing compound, and connecting linear molecular chains of the polyarylene sulfide containing the active side group into a two-dimensional structure through boron (B), thereby obtaining the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function.

Further, the boron-containing active compound is selected from: dihalophenylborane, dihaloalkylborane, boron trihalide, or boric acid.

Further, the reaction of the polyarylene sulfide containing a pendant reactive group with a boron-containing compound is carried out by the following method: adding polyarylene sulfide containing active side groups into an anhydrous aprotic solvent, adding a boron-containing active compound under the protection of inert gas while stirring, stirring and heating to 60-190 ℃, reacting for 2-12 hours, and then filtering, washing and drying to obtain the boron-containing two-dimensional structure polyarylene sulfide material with the nuclear radiation protection function. Preferably, the anhydrous aprotic solvent is selected from: n-methylpyrrolidone (NMP), Dimethylacetamide (DMF), Dimethylformamide (DMAC), hexamethylphosphoric triamide (HMPA) or N-cyclohexylpyrrolidone (NCHP).

Further, the mass ratio of the polyarylene sulfide containing the active side group to the boron-containing active compound is as follows: 50-150 parts of polyarylene sulfide containing active side groups and 1-50 parts of boron-containing active compounds.

Further, in the above method for preparing a boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function, the polyarylene sulfide containing an active side group is prepared by the following method: firstly, 40-300 parts by weight of dihalogenated aromatic compound containing double active groups, 500-1000 parts by weight of sodium sulfide, 10-100 parts by weight of catalyst, 10-50 parts by weight of alkali and 1000-5000 parts by weight of polar aprotic solvent are added into a reaction kettle, and the mixture is reacted and dehydrated at the temperature of 150-205 ℃ under the protection of inert gas; then adding 500-1000 parts by weight of dihalogenated aromatic compound, and reacting at 180-280 ℃ for 1-6 hours; and then heating to 200-280 ℃ to continue reacting for 1-6 hours, finally cooling to 100-180 ℃, adding deionized water while stirring, filtering, washing and drying to obtain the polyarylene sulfide containing the active side group.

Further, in the above method for preparing a boron-containing two-dimensional polyarylene sulfide material having a neutron absorption function, the dihalo aromatic compound containing a double active group is selected from: dihalosalicylic acid, dihalobenzenediol, dichlorobiphenyldiol, dihalobenzenedicarboxylic acid, dichloronaphthalenedicarboxylic acid or dihalonaphthalenediol.

Preferably, the dihalo aromatic compound containing a double active group is selected from: 2, 5-dichloroterephthalic acid, 3, 6-dibromophthalic anhydride, 4, 8-dibromo-1H, 3H-benzo [1,2-C:4,5-C' ] difuran-1, 3,5, 7-tetraone, 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2, 5-dichlorohydroquinone, 2, 6-dichlorohydroquinone, 4, 6-dichlororesorcinol, 3, 5-dichlororesorcinol, 3, 6-dichlorop-hydroxybenzoic acid or 3, 5-dibromo-2-hydroxybenzoic acid; the structural formula is as follows:

further, in the above method for producing a boron-containing two-dimensional polyarylene sulfide material having a neutron absorbing function, the dihalogenated aromatic compound is a para-dihalogenated or meta-dihalogenated aromatic compound.

Still further, the dihaloaromatic compound is selected from: 1, 4-dihalobenzene, 2, 4-dihalobenzene, 3, 5-dihalobenzene, 4,4 '-dihalobiphenyl, 4,4' -dihalodiphenylsulfone, 4,4 '-dihalobenzophenone or 4,4' -dihalodiphenylether; the structural formula is as follows:

preferably, the dihaloaromatic compound is 1, 4-dichlorobenzene, 2, 4-m-dichlorobenzene, 4 '-dichlorodiphenyl sulfone or 4,4' -dichlorobenzophenone.

Further, in the preparation method of the boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function, the polar aprotic solvent is selected from sulfone or sulfone compounds, amine compounds or lactam compounds.

Preferably, in the above method for preparing a boron-containing two-dimensional polyarylene sulfide material having a neutron absorption function, the polar aprotic solvent is selected from: n-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolone (DMI), Hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

Further, in the above method for preparing a boron-containing two-dimensional polyarylene sulfide material having a neutron absorption function, the catalyst is selected from an amino or amino carboxylate compound, a hydroxy carboxylate compound, or an organophosphate compound.

Further, the amine or amino carboxylate compound is sodium aminotriacetate (NTA), ethylenediamine tetraacetate (EDTA salt) or diethylenetriamine pentacarboxylate (DTPA); preferably trisodium (or tetrasodium) ethylenediaminetetraacetate, as in ethylenediaminetetraacetate; the hydroxy carboxylate compound is tartaric acid, heptonate, sodium gluconate or sodium alginate; preferably sodium alginate; the organic phosphorus salt compound is ethylenediamine tetra methylene sodium phosphate (EDTMPS), diethylenetriamine penta methylene phosphonate (DETPMS) or amine trimethylene phosphate; preferably sodium Ethylene Diamine Tetra Methylene Phosphate (EDTMPS).

Further, in the above preparation method of the boron-containing two-dimensional polyarylene sulfide material with a neutron absorption function, the base is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or barium bicarbonate.

Further, in the preparation method of the boron-containing two-dimensional polyarylene sulfide material with the neutron absorption function, the pH value of a reaction system is kept at 8-12, preferably 8.5-11.5 in the preparation process of the polyarylene sulfide containing the active side group.

In the invention, the raw materials are in parts by weight except for special specifications.

The invention has the beneficial effects that:

the invention designs a high-temperature-resistant corrosion-resistant two-dimensional polyarylene sulfide film with a neutron absorption function and nuclear radiation prevention, which can enhance the neutron absorption capability of a material and strengthen the shielding effect of high-energy rays by combining the synergistic effect of carbon, hydrogen and boron on a molecular level. The melting point of the high-temperature-resistant corrosion-resistant two-dimensional polyarylene sulfide film with neutron absorption function and nuclear radiation resistance is more than 280 ℃, no solvent is used below 200 ℃, the film is overlapped to the thickness of 8CM, the fast neutron absorption coefficient is 0.9, and the gamma ray resistance can reach 10⁹The tensile strength is more than 60MPa, the bending strength reaches 80MPa, and the high-strength high-molecular material is a novel special high-molecular material capable of absorbing and shielding high-energy rays.

The invention also has the following remarkable characteristics:

(1) the alkaline complex catalysis increases the activity of sulfur in sodium hydrosulfide, dissociates crystal water in sodium hydrosulfide, makes water easier to be removed, and shortens the reaction period. The used alkaline complex catalyst can maintain the pH value of the whole reaction, ensure that the pH value is between 8 and 12, stabilize a solution system and stably perform the reaction, and is beneficial to the improvement of molecular weight;

(2) the strong alkaline complexing emulsification can prevent early dehydration and later reaction from depositing and agglomerating on the wall of the reaction kettle at high temperature and fully disperse reactants to form a uniform reaction system;

(3) the obtained polyarylene sulfide contains active side groups and can react with boron-containing active monomers in the next step to form a two-dimensional polyarylene sulfide film raw material;

(4) the yield of the synthesized high molecular weight polyarylene sulfide containing the active side group is up to more than 90%, and the weight average molecular weight is 15000-100000; the melt index is 10-1000/10 min, and the melting point can be more than or equal to 290 ℃;

(5) the synthesized high molecular weight polyarylene sulfide containing active side groups can react with the boron-containing active Z to further form a corresponding two-dimensional polyarylene sulfide film, and the two-dimensional polyarylene sulfide film becomes a novel high-temperature-resistant corrosion-resistant neutron and gamma-ray-absorbing high-efficiency nuclear protection functional material.

Detailed Description

The reaction process of the invention is as follows:

further, the general reaction formula is as follows:

b boron is an element with the maximum neutron absorption coefficient in the periodic table of elements, the boron enters a PPS structure and can be endowed with a brand new neutron absorption function, and HO-B-OH groups can continue to react with metal ions which can efficiently absorb X rays, such as tantalum ions, tungsten ions and the like, so that boron-containing polyarylene sulfide which can absorb neutrons and shield X rays is formed; in addition, as the HO-B-OH group has-OH active groups, the unit fraction and the molecular weight of the HO-B-OH group are controlled, the HO-B-OH group can be further bonded with metal oxide and metal fiber and further functionalized into novel functional special engineering plastic which has high temperature resistance, corrosion resistance, high strength and high rigidity and has X-ray and neutron absorption and protection.

The above-mentioned contents of the present invention will be further described in detail by the following specific embodiments of examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and conventional practice in the art are intended to be included within the scope of the present invention without departing from the technical spirit of the present invention as described above.