阅读说明：本技术 一种高分子化工材料及其制备方法 (A kind of macromolecule chemical industry material and preparation method thereof ) 是由 苏明阳 陈晓东 杨轶 李姗珊 王旭 于 2019-09-17 设计创作，主要内容包括：本发明涉及高分子材料技术领域,具体来说是一种高分子化工材料及其制备方法,由以下质量份数的原料组成：芳香二酐30.4-50.65份、芳香二胺30-50份、卤代醇15-25份、聚氯乙烯树脂15-25份、金属钠15-25份、分散剂5-10份。本发明先制备得到了聚酰亚胺预聚体,然后在聚酰亚胺预聚体上接枝了卤代醇,并得到了分子链上含有羟基的接枝预聚体,此时接枝预聚体上的羟基与金属钠反应后,再与聚氯乙烯反应,使耐腐蚀的聚氯乙烯接枝在聚酰亚胺预聚体上,并在高温下使得聚酰亚胺预聚体发生失水聚合,形成了高分子量的聚合物,制备得到的高分子化工材料在化工反应釜外及化工反应釜内实现了耐腐蚀且保温的性能。(The present invention relates to technical field of polymer materials, a kind of specifically macromolecule chemical industry material and preparation method thereof, is made of the raw material of following mass fraction: 30.4-50.65 parts of aromatic dianhydride, 30-50 parts of aromatic diamines, 15-25 parts of halohydrin, 15-25 parts of Corvic, 15-25 parts of metallic sodium, 5-10 parts of dispersing agent.Polyimide prepolymer has first been prepared in the present invention, then halohydrin has been grafted on polyimide prepolymer, and the grafting performed polymer on strand containing hydroxyl is obtained, after the hydroxyl being grafted on performed polymer at this time is reacted with metallic sodium, again with pvc response, make corrosion resistant polyvinyl chloride graft on polyimide prepolymer, and make polyimide prepolymer that dehydration polymerization occur at high temperature, the polymer for foring high molecular weight, the macromolecule chemical industry material being prepared realize corrosion-resistant and heat preservation performance outside chemical reaction kettle and in chemical reaction kettle.)

1. a kind of macromolecule chemical industry material, which is characterized in that be made of the raw material of following mass fraction: aromatic dianhydride 30.4- 50.65 parts, 30-50 parts of aromatic diamines, 15-25 parts of halohydrin, 15-25 parts of Corvic, 15-25 parts of metallic sodium, dispersion 5-10 parts of agent.

2. macromolecule chemical industry material according to claim 1, which is characterized in that the dispersing agent is dodecyl benzene sulfonic acid The mixed liquor of sodium, lauric acid and POLYPROPYLENE GLYCOL, with molar ratio computing, neopelex: lauric acid: POLYPROPYLENE GLYCOL=1-2: 1:1。

3. a kind of macromolecule chemical industry material according to claim 1, which is characterized in that the aromatic dianhydride is selected from equal four benzene Tetracid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and 4,4 '-(hexafluoros One of isopropyl) double phthalic anhydrides.

4. a kind of macromolecule chemical industry material according to claim 1, which is characterized in that the aromatic diamines are selected from diamino Diphenyl ether or p-phenylenediamine.

5. a kind of macromolecule chemical industry material according to claim 1, which is characterized in that the halohydrin be ethylene chlorhydrin, One of 4- fluoro butanol, 2- bromopropyl alcohol.

6. a kind of preparation method of macromolecule chemical industry material according to claim 1, which is characterized in that including walking as follows It is rapid:

(1) raw material preparation: weigh following raw material by mass fraction: 30.4-50.65 parts of aromatic dianhydride, 30-50 parts of aromatic diamines, 15-25 parts of halohydrin, 15-25 parts of Corvic, 15-25 parts of metallic sodium, 5-10 parts of dispersing agent, it is spare；

(2) preparation of polyimide prepolymer: aromatic diamines are made to be dissolved completely in polarity under stirring condition at 0-20 DEG C non- In proton solvent, and aromatic dianhydride equivalent is repeatedly added in the polar aprotic solvent of aromatic diamines, is warming up to 50-60 DEG C And 3-4h is stirred, it filters, washing obtains polyimide prepolymer；

Wherein the addition number of aromatic dianhydride is 8-10 times, and total addition time of aromatic dianhydride is 0.5-1h；

(3) grafting of halohydrin: after polyimide prepolymer and the halohydrin mixing that step (2) is prepared, and it is completely molten Solution stirs 2-3h in polar non-solute, and at 60-80 DEG C, filters, washing, obtains grafting performed polymer；

(4) preparation of polymer: the grafting performed polymer that step (3) is prepared is first dissolved in polar non-solute, then Metallic sodium is added and is reacted, Corvic is added after sodium all merges and generates there is no bubble, in 90-110 It after reacting 1-2h at DEG C, is cooled to room temperature, filters, washing obtains polymer；

(5) preparation of macromolecule chemical industry material: the polymer that step (4) is prepared is dissolved in esters solvent, and is added Then dispersing agent carries out ultrasound, obtains macromolecule chemical industry material.

7. a kind of preparation method of macromolecule chemical industry material according to claim 6, which is characterized in that the step (2)- Polar non-solute used in step (4) are as follows: N, N '-dimethyl formamide, N, N '-dimethyl acetamide, pyrrolidines One of ketone, tetrahydrofuran, dimethyl sulfoxide.

8. a kind of preparation method of macromolecule chemical industry material according to claim 6, which is characterized in that the step (5) In esters solvent be ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether propionate and isopropyl acetate One of ester.

9. a kind of preparation method of macromolecule chemical industry material according to claim 6, which is characterized in that the step (5) The condition of middle ultrasound are as follows: under the supersonic frequency of 50-100Hz, ultrasonic 2-3h.

Technical field

The present invention relates to technical field of polymer materials, specifically a kind of macromolecule chemical industry material and its preparation side Method.

Background technique

Corrosion refers to that material reacts caused material damage or deterioration with the external world, and developed country's corrosion loss averagely accounts for its people Economic total income 2-4%, the U.S. show that the corrosion loss of chemical industry is beautiful up to 82,900,000,000 and damage is being corroded in China in nineteen ninety investigation It loses aspect and also did investigation, l988 is estimated as hundred million RMB of 270-500.In recent years, a large number of applications at home and abroad show that high score Sub- material shows increasing effect in enterprise's corrosion-resistant field, and with its easily molded processing.At a certain temperature, high Molecular material inorganic acid resistance, alkali, salt corrosive nature better than metal material and being carried out in a deep going way with research work, macromolecule material Expect that bigger effect will be played in anticorrosion field.

Reaction kettle is widely used in petroleum, chemical industry, rubber, pesticide, dyestuff, medicine, food, for complete vulcanization, nitrification, Pressure vessel of the technical process such as hydrogenation, hydrocarbonylation, polymerization, condensation, such as reactor, reaction pot, decomposition pot, polymeric kettle etc.；Material Matter generally has carbon manganese steel, stainless steel, zirconium, nickel-base alloy and other composite materials, and reaction kettle is comprehensive reaction vessel, and reaction kettle It is contacted for a long time with chemical raw material, shortens the service life of reaction kettle.

Summary of the invention

In view of the deficiency of the prior art, the object of the present invention is to provide a kind of macromolecule chemical industry material and its Preparation method, the present invention have first been prepared polyimide prepolymer, halohydrin have then been grafted on polyimide prepolymer, And the grafting performed polymer on strand containing hydroxyl has been obtained, after the hydroxyl being grafted on performed polymer at this time is reacted with metallic sodium, then With pvc response, make corrosion resistant polyvinyl chloride graft on polyimide prepolymer, and makes polyamides sub- at high temperature Dehydration polymerization occurs for amine performed polymer, forms the polymer of high molecular weight, this polymer had not only had the performance of heat preservation, but also had resistance to The performance of corrosion, the macromolecule chemical industry material being prepared realize corrosion-resistant and heat preservation performance inside and outside chemical reaction kettle.

In order to solve the above technical problems, the present invention adopts the following technical scheme:

A kind of macromolecule chemical industry material, is made of the raw material of following mass fraction: 30.4-50.65 parts of aromatic dianhydride, fragrance 30-50 parts of diamines, 15-25 parts of halohydrin, 15-25 parts of Corvic, 15-25 parts of metallic sodium, 5-10 parts of dispersing agent.

Preferably, the dispersing agent is the mixed liquor of neopelex, lauric acid and POLYPROPYLENE GLYCOL, with molar ratio Meter, neopelex: lauric acid: POLYPROPYLENE GLYCOL=1-2:1:1.

Preferably, the aromatic dianhydride is selected from equal four acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 3, One of 3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and 4,4 '-(hexafluoro isopropyl) double phthalic anhydrides.

Preferably, the aromatic diamines are selected from diaminodiphenyl ether or p-phenylenediamine.

Preferably, the halohydrin is one of ethylene chlorhydrin, 4- fluoro butanol, 2- bromopropyl alcohol.

The present invention also protects a kind of preparation method of macromolecule chemical industry material, includes the following steps:

(1) raw material preparation: following raw material: 30.4-50.65 parts of aromatic dianhydride, aromatic diamines 30-50 is weighed by mass fraction Part, 15-25 parts of halohydrin, 15-25 parts of Corvic, 15-25 parts of metallic sodium, 5-10 parts of dispersing agent are spare；

(2) preparation of polyimide prepolymer: aromatic diamines are made to be dissolved completely in pole under stirring condition at 0-20 DEG C In property aprotic solvent, and aromatic dianhydride equivalent is repeatedly added in the polar aprotic solvent of aromatic diamines, is warming up to 50- 60 DEG C and 3-4h is stirred, filtered, washing obtains polyimide prepolymer；

Wherein the addition number of aromatic dianhydride is 8-10 times, and total addition time of aromatic dianhydride is 0.5-1h；

(3) grafting of halohydrin: after polyimide prepolymer and the halohydrin mixing that step (2) is prepared, and it is complete Fully dissolved stirs 2-3h in polar non-solute, and at 60-80 DEG C, filters, washing, obtains grafting performed polymer；

(4) preparation of polymer: the grafting performed polymer that step (3) is prepared is first dissolved in polar non-solute, Then metallic sodium is added and is reacted, Corvic is added after sodium all merges and generates there is no bubble, in 90- It after reacting 1-2h at 110 DEG C, is cooled to room temperature, filters, washing obtains polymer；

(5) preparation of macromolecule chemical industry material: the polymer that step (4) is prepared is dissolved in esters solvent, and Dispersing agent is added, then carries out ultrasound, obtains macromolecule chemical industry material.

Preferably, polar non-solute used in the step (2)-step (4) are as follows: N, N '-dimethyl formyl Amine, N, one of N '-dimethyl acetamide, pyrrolidones, tetrahydrofuran, dimethyl sulfoxide.

Preferably, the esters solvent in the step (5) is ethyl cellosolve acetate, propylene glycol methyl ether acetate, third One of glycol monomethyl ether propionic ester and isopropyl acetate.

Preferably, condition ultrasonic in the step (5) are as follows: under the supersonic frequency of 50-100Hz, ultrasonic 2-3h.

Compared with prior art, the invention has the advantages that:

1, the present invention first carries out amidation polymerization reaction by aromatic dianhydride and aromatic diamines, has obtained polyimides pre-polymerization Body contains H element on the imino group of polyimide prepolymer, at this time the halogen in the H element and halohydrin on imino nitrogen atom Atom reacts, and not only hydroxyl has been grafted on polyimide prepolymer and has obtained grafting performed polymer, but also has made H element It is precipitated in the form of HCl with halogen atom, and chemical materials is highly susceptible to soda acid and organic solvent in the long-term use Corrosion, therefore high temperature resistant and corrosion resistant feature need to be met in the coating of chemical field, it is based on above-mentioned theory, the present invention is prepared into To grafting performed polymer reacted again with sodium, replace the H on hydroxyl by Na element, form sodium alkoxide structure, then again Corrosion resistant Corvic is added, reacts the chlorine element on Corvic with the sodium element on sodium alkoxide, and will gather Vinyl Graft makes polyimide prepolymer dehydration at high temperature on macromolecular chain, while under high temperature, forms polyimides Structure, since the miscellaneous structure of virtue in polyimide molecule is formed by conjugated system, ladder and half hierarchic structure, so that strand With very strong rigidity, cause polyimide material that there is very high glass transition temperature, higher fusing point or softening point, this When polyimides have excellent thermal insulation property, and the polyethylene structure in Corvic have excellent anticorrosive property Can, high temperature resistant and etch-proof polymer have been obtained at this time, then form colloidal sol after polymer is dispersed in esters solvent, just In the outer surface and inner surface that are coated in reaction kettle.

2, polyimides is one of optimal high-molecular organic material of comprehensive performance, can make it at a temperature of 600 DEG C It decomposes, and low temperature resistant temperature reaches -200 DEG C, no sharp melting point, high insulating property；Polyvinyl resin is not only soft, Er Qienai Corrosive nature is strong, alkali is also insoluble in insoluble in acid, and have excellent characteristic resistant to high temperature, at this point, the grafting of polyvinyl chloride makes Polyimides high temperature resistance it is more excellent, therefore high temperature resistant, low temperature resistant and corrosion resistant polymeric membrane has been prepared, And the coating being prepared can be applied to reaction kettle.

3, the macromolecule chemical industry material that is prepared of the present invention can be coated on the inner wall or outer wall of chemical reaction kettle, and So that solvent is volatilized under room temperature, so that chemical materials forms a film, forms the membrane structure with anticorrosion and heat insulation function, it is of the invention Macromolecule chemical industry material is suitable for reaction of the heat-preserving range between -200-750 DEG C, and the present invention is on polyimide prepolymer The side chain for introducing large volume increases polyimides so that the side chain of polyimide prepolymer main chain two sides can not be symmetrical at this time Solubility property in a solvent, while polyethylene structure is also easily soluble in esters solvent, polyethylene structure also facilitates polyamides The solubility property of imines, after adding dispersing agent, polymer can be dissolved in esters solvent and form colloidal sol.

Specific embodiment

In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.