阅读说明：本技术 一种氘代超分子聚合物及其制备方法 (Deuterated supramolecular polymer and preparation method thereof ) 是由 谭欣欣 杜杰 王丽萍 宋智蓉 把静文 杨锁龙 郭彪 于 2020-03-24 设计创作，主要内容包括：本发明提供一种氘代超分子聚合物,属于超分子聚合物技术领域。所述氘代超分子聚合物是将由氘代环烯开环易位聚合后得到的以氘代聚合物为间隔基的双官能度单体,通过四重氢键或金属配位键这两类非共价相互作用形成的四重氢键型氘代超分子聚合物或金属配位型氘代超分子聚合物。本发明还提供所述氘代超分子聚合物的制备方法。本发明氘代超分子聚合物主链通过非共价作用相互连接,具有自修复、加工性能好的优点。本发明氘代超分子聚合物的制备原料来源简单,工艺流程简单,可通过调节氘代环烯的种类与摩尔比,实现不饱和碳与饱和碳比例可控的氘代超分子聚合物的制备,结合氢同位素加成反应可调节饱和产物中氢同位素的比例。(The invention provides a deuterated supramolecular polymer, belonging to the technical field of supramolecular polymers. The deuterated supramolecular polymer is a quadruple hydrogen bond type deuterated supramolecular polymer or a metal coordination type deuterated supramolecular polymer formed by the non-covalent interaction of a quadruple hydrogen bond or a metal coordination bond of a bifunctional monomer which is obtained by ring-opening metathesis polymerization of deuterated cycloalkene and takes the deuterated polymer as a spacer. The invention also provides a preparation method of the deuterated supramolecular polymer. The main chains of the deuterated supramolecular polymer are mutually connected through non-covalent interaction, and the deuterated supramolecular polymer has the advantages of self-repairing and good processing performance. The preparation method of the deuterated supramolecular polymer has the advantages of simple raw material source and simple process flow, can realize the preparation of the deuterated supramolecular polymer with controllable proportion of unsaturated carbon and saturated carbon by adjusting the type and the molar ratio of deuterated cycloalkene, and can adjust the proportion of hydrogen isotopes in saturated products by combining with hydrogen isotope addition reaction.)

1. The deuterated supramolecular polymer is a quadruple-hydrogen bonded deuterated supramolecular polymer or a metal-coordinated deuterated supramolecular polymer formed by the noncovalent interaction of a quadruple hydrogen bond or a metal-coordinated bond of a bifunctional monomer which is obtained by ring-opening metathesis polymerization of deuterated cycloalkene and takes a deuterated polymer as a spacer.

2. The deuterated supramolecular polymer as claimed in claim 1, wherein the quaternary hydrogen bond type deuterated supramolecular polymer has the following structural formula i:

in the formula I, R is one of H, D, methyl, ethyl and heptyl; m is 20 to 500; n increases with increasing concentration.

3. The deuterated supramolecular polymer as recited in claim 1, wherein said metal-coordinated deuterated supramolecular polymer has the formula ii:

in the formula II, M is one of Zn, Fe, Co or Ni; m is 20 to 500; n increases with increasing concentration.

4. The deuterated supramolecular polymer as claimed in claim 2, wherein the molecular structural formula of the saturated product after the addition of the deuterated supramolecular polymer in the quaternary hydrogen bond type is shown as the following formula III:

in the formula III, R is one of H, D, methyl, ethyl and heptyl; q is one of H, D or T; m is 20 to 500; n increases with increasing concentration.

5. The deuterated supramolecular polymer as recited in claim 3, wherein the saturated product obtained after the addition of the metal-coordinated deuterated supramolecular polymer has the following molecular structure formula IV:

in the formula IV, Q is one of H, D or T; m is one of Zn, Fe, Co or Ni; m is 20 to 500; n increases with increasing concentration.

6. The method of any of claims 1 to 5, comprising the steps of:

1) adding non-deuterated cycloalkene into heavy water, adding a catalyst and a lower alcohol additive, heating for reaction for a period of time, and performing hydrogen-deuterium exchange to obtain deuterated cycloalkene;

2) adding a chain transfer agent, a catalyst and an organic solvent into the deuterated cycloalkene, heating to react for a period of time, removing the solvent to obtain a bifunctional monomer taking the deuterated polymer as a spacer, and obtaining the deuterated supramolecular polymer through the non-covalent interaction between the bifunctional monomers.

7. The method of claim 6, wherein in step 1), the catalyst is RuCl₂(PPh₃)₃The lower alcohol additive is methanol or ethanol; the temperature of the heating reaction is 120-200 ℃, and the time is 0.2-12 h; the non-deuterated cycloalkene is one of cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cyclopentadecene, 1, 3-cyclooctadiene, 1,3, 5-cyclooctatriene and 1,3, 5-cycloheptatriene.

8. The method of claim 6, wherein in step 2), the chain transfer agent is a chain transfer agent with both ends being 2-urea-4-pyrimidone derivatives or a chain transfer agent with both ends being terpyridine (or derivatives thereof); the catalyst is a Grubbs second generation catalyst or a Grubbs third generation catalyst; the organic solvent is dichloromethane or chloroform; the temperature of the heating reaction is 25-60 ℃, and the time is 6-36 h; the solvent is removed by evaporation under reduced pressure or by settling in methanol.

9. The method of claim 8, wherein the chain transfer agent having 2-urea-4-pyrimidinone derivatives at both ends is used to obtain a deuterated polymer having 2-urea-4-pyrimidinone derivatives at both ends, wherein the deuterated polymer having supramolecular groups at both ends can be used as a monomer and further coupled to each other via quadruple hydrogen bonds to obtain a quadruple hydrogen bonding deuterated supramolecular polymer.

10. The method of claim 8, wherein the chain transfer agent having terpyridine (or a derivative thereof) at both ends is used to obtain a deuterated polymer having terpyridine (or a derivative thereof) at both ends, and wherein the deuterated polymer having the supramolecular groups at both ends is used as a monomer and further connected to each other via a metal coordination bond to obtain a metal-coordinated deuterated supramolecular polymer.

Technical Field

The invention belongs to the technical field of supramolecular polymers, and particularly relates to a deuterated supramolecular polymer and a preparation method thereof.

Background

Inertial Confinement Fusion (ICF) is one of the most promising ways to realize controllable fusion power generation so as to solve energy crisis at present, and a material with higher deuterium and tritium atomic density is required to be used as an ICF target fuel. On one hand, the deuterated polymer can be used as a target pill to be filled with thermonuclear fuel (such as deuterium-tritium ice); on the other hand, the conventional low-temperature frozen deuterium-tritium target fuel has various problems including the use of a low-temperature freezing system, the preparation of a target pill, the encapsulation of deuterium-tritium, the homogenization and layering of deuterium-tritium ice and the like, and great challenges are brought to the engineering application of ICF. The deuterium (tritium) substituted polymer also has a material with higher deuterium (tritium) atom density, and compared with deuterium-tritium ice, the deuterium (tritium) substituted polymer has the advantages of no need of a complex cooling system, stable property, easiness in storage and transportation and the like, and is an ICF target fuel with great prospect.

In addition, the deuterated polymers also have important application in the fields of low-loss polymer optical fibers, neutron scattering characterization and the like.

At present, the types and preparation methods of deuterated polymers which are publicly reported at home and abroad are few, related research is limited in the field of covalent polymerization, and deuterated supramolecular polymers based on non-covalent interaction are not reported yet. The covalent deuterated polymers currently reported: firstly, from the material preparation method, the most common preparation method of the deuterated polymer at present is a deuterated monomer covalent polymerization method, and the methods usually need to synthesize the deuterated monomer through multi-step reactions, so that the method has the disadvantages of multiple operation steps, complex process, easy occurrence of side reaction, and great difficulty in separation and purification. Secondly, in the conventional preparation process of deuterated monomers with various steps, various deuterated reagents easily absorb water vapor in the air to generate hydrogen-deuterium exchange reaction, so that the deuteration rate is reduced. Therefore, a novel simple and efficient preparation method of the deuterated polymer is developed, and the deuterated polymer is expanded from the field of the traditional covalent polymer to the field of the supramolecular polymer, so that the method has important significance for implementation and development of inertial confinement fusion experiments.

Disclosure of Invention

The invention aims to solve the problems of multiple preparation processes, complex process and the like of the existing deuterated polymer material deuterated monomer raw material, provides a novel preparation method of a deuterated polymer, expands the deuterated polymer from the traditional covalent polymer to the field of supramolecular polymers, and prepares a novel deuterated polymer material, namely a deuterated supramolecular polymer, which has the advantages of self-repairing and easy processing.

The purpose of the invention is realized by the following technical scheme:

the deuterated supramolecular polymer is a quadruple-hydrogen bond type deuterated supramolecular polymer or a metal coordination type deuterated supramolecular polymer formed by the non-covalent interaction of two types of quadruple hydrogen bonds or metal coordination bonds of a bifunctional monomer which is obtained by ring-opening metathesis polymerization of deuterated cycloalkene and takes a deuterated polymer as a spacer.

Further, the structural formula of the quaternary hydrogen bond type deuterated supramolecular polymer is shown as the following formula I:

in the formula I, R is one of H, D, methyl, ethyl and heptyl; m is 20 to 500; n increases with increasing concentration.

In the formula I, m is the average value of the number of repeating units of a corresponding deuterated polymer after ring-opening metathesis polymerization of the deuterated cycloalkene, and is about 20-500, n represents the number of repeating units in a quadruple hydrogen bond type supramolecular polymer formed by a bifunctional monomer taking the deuterated polymer as a spacer, and n increases along with the increase of the concentration.

For convenience of description, the fragment of the structure formula i in which deuterated cyclooctene is ring-opened represents the fragment of the deuterated cycloalkene in the present invention.

Further, the metal coordination type deuterated supramolecular polymer has a structural formula shown as the following formula II:

in the formula II, M is one of Zn, Fe, Co or Ni; m is 20 to 500; n increases with increasing concentration.

In the formula II, m is the average value of the number of repeating units of the corresponding deuterated polymer after ring-opening metathesis polymerization of the deuterated cycloalkene, and is about 20-500, n represents the number of repeating units in the metal coordination type supramolecular polymer formed by the bifunctional monomer taking the deuterated polymer as a spacer, and n increases along with the increase of the concentration.

For convenience of description, the segment of the structural formula ii in which deuterated cyclooctene is opened represents the segment of the deuterated cycloalkene in the present invention.

Further, the molecular structural formula of the saturated product after the addition of the quadruple hydrogen bond type deuterated supramolecular polymer is shown as the following formula III:

in the formula III, R is one of H, D, methyl, ethyl and heptyl; q is one of H, D or T; m is 20 to 500; n increases with increasing concentration.

Further, the molecular structural formula of the saturated product after the metal coordination type deuterated supramolecular polymer is added is shown as the following formula IV:

in the formula IV, Q is one of H, D or T; m is one of Zn, Fe, Co or Ni; m is 20 to 500; n increases with increasing concentration.

A preparation method of a deuterated supramolecular polymer comprises the following steps:

1) adding non-deuterated cycloalkene into heavy water, adding a catalyst and a lower alcohol additive, heating for reaction for a period of time, and performing hydrogen-deuterium exchange to obtain deuterated cycloalkene;

2) adding a chain transfer agent, a catalyst and an organic solvent into the deuterated cycloalkene, heating to react for a period of time, removing the solvent to obtain a bifunctional monomer taking the deuterated polymer as a spacer, and obtaining the deuterated supramolecular polymer through the non-covalent interaction between the bifunctional monomers.

Further, in the step 1), the catalyst is RuCl₂(PPh₃)₃The lower alcohol additive is methanol or ethanol; the temperature of the heating reaction is 120-200 ℃, and the time is 0.2-12 h; the non-deuterated cycloalkene is one of cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cyclopentadecene, 1, 3-cyclooctadiene, 1,3, 5-cyclooctatriene and 1,3, 5-cycloheptatriene.

Further, in the step 1), the mass of the heavy water is 15-100 times of that of the non-deuterated cycloalkene; the addition amount of the catalyst is 2-10% of the mass equivalent of the non-deuterated cycloolefin; the addition amount of the lower alcohol additive is 10-20% of the mass equivalent of the non-deuterated cycloalkene.

Further, in the step 1), deuterated cycloalkene with the deuteration rate of 90-97% can be obtained through primary hydrogen-deuterium exchange, and the product after primary exchange is subjected to secondary exchange in heavy water with the deuteration rate of more than 99.8% under the same condition, so that deuterated cycloalkene with the deuteration rate of 97-99% can be obtained.

Further, in the step 2), the chain transfer agent is a chain transfer agent of which both ends are 2-urea-4-pyrimidone derivatives or a chain transfer agent of which both ends are terpyridine (or derivatives thereof); the catalyst is a Grubbs second generation catalyst or a Grubbs third generation catalyst; the organic solvent is dichloromethane or chloroform; the temperature of the heating reaction is 25-60 ℃, and the time is 6-36 h; the solvent is removed by evaporation under reduced pressure or by settling in methanol.

Further, in the step 2), the molar ratio of the deuterated cycloalkene to the chain transfer agent is 10: 1-250: 1; the addition amount of the Grubbs second-generation catalyst or the Grubbs third-generation catalyst is 0.1 per thousand molar equivalent of the deuterated cycloalkene, and the volume ratio of the organic solvent to the deuterated cycloalkene is 1: 1-10: 1.

Further, when a chain transfer agent with both ends being 2-urea-4-pyrimidone derivatives is adopted, a deuterated polymer with both ends being supramolecular groups of the 2-urea-4-pyrimidone derivatives can be obtained, the deuterated polymer with both ends being supramolecular groups can be used as a monomer, and further connected with each other through quadruple hydrogen bonds, so that a quadruple hydrogen bond type deuterated supramolecular polymer is obtained.

Further, when a chain transfer agent having both ends of terpyridine (or a derivative thereof) is used, a deuterated polymer having both ends of a supramolecular group of terpyridine (or a derivative thereof) can be obtained, and the deuterated polymer having both ends of a supramolecular group can be used as a monomer and further connected with each other through a metal coordination bond, thereby obtaining a metal coordination type deuterated supramolecular polymer.

The invention obtains deuterated cycloalkene with high deuteration rate by carrying out hydrogen-deuterium exchange reaction on non-deuterated cycloalkene, then carrying out ring-opening metathesis polymerization on the deuterated cycloalkene by using a chain transfer agent of which both ends are 2-urea-4-pyrimidone derivatives or both ends are terpyridine (or derivatives thereof) to obtain bifunctional monomers with a deuterated polymer as a spacer group, and mutually connecting the monomers by non-covalent bond interaction to obtain a quadruple-hydrogen bond type or coordination type deuterated supramolecular polymer, wherein the main chain of the deuterated supramolecular polymer contains unsaturated carbon, and the deuterated supramolecular polymer can be subjected to addition reaction with hydrogen isotope gas under the action of a catalyst to obtain a corresponding saturated product. By adjusting the molar ratio of different kinds of deuterated cycloalkenes, the molar ratio of unsaturated carbon (namely carbon combined with double bonds) to saturated carbon (namely carbon with only single bonds) in the deuterated supramolecular polymer can be adjusted, and further the hydrogen isotope ratio in saturated products can be adjusted.

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

the invention provides a novel deuterated polymer based on non-covalent interaction, namely a deuterated supramolecular polymer. Compared with the traditional deuterated covalent polymer, the main chains of the deuterated supramolecular polymer are mutually connected through non-covalent interaction, and the deuterated supramolecular polymer has the advantages of self-repairing and good processing performance.

Compared with the traditional method that the raw material deuterated monomer needs to be subjected to multi-step synthesis, separation and purification and other processes, the invention provides the preparation method of the deuterated supramolecular polymer, which has the advantages of simple raw material source and wide selectable range, can directly obtain the cycloalkene with high deuteron rate through one or two hydrogen-deuterium exchange reactions, effectively reduces the occurrence of side reactions and multi-step separation and purification steps, greatly simplifies the process flow, and reduces the operation difficulty and the production cost.

The preparation method can realize the preparation of the deuterated supramolecular polymer with the controllable ratio (0.07-6) of unsaturated carbon to saturated carbon by adjusting the species and the molar ratio of deuterated cycloalkene, can adjust the ratio of hydrogen isotopes in saturated products by combining with hydrogen isotope addition reaction, and has the controllable ratio of hydrogen to deuterium (or the ratio of tritium to deuterium) of 0-0.75.

The preparation method of the deuterated supramolecular polymer has a great application value in the fields of inertial confinement fusion target material preparation and the like.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.