CN115197270A - Self-catalytic functional reaction monomer, self-catalytic polymerization and self-catalytic depolymerization functional copolymer, and preparation method and application thereof - Google Patents

Self-catalytic functional reaction monomer, self-catalytic polymerization and self-catalytic depolymerization functional copolymer, and preparation method and application thereof Download PDF

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CN115197270A
CN115197270A CN202110391482.8A CN202110391482A CN115197270A CN 115197270 A CN115197270 A CN 115197270A CN 202110391482 A CN202110391482 A CN 202110391482A CN 115197270 A CN115197270 A CN 115197270A
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copolymer
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王玉忠
倪延朋
陈琳
付腾
吴万寿
曹杏
汪秀丽
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Sichuan University
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Abstract

The invention discloses an autocatalytic functional reaction monomer, an autocatalytic polymerization and autocatalytic depolymerization functional copolymer and a preparation method thereof. The functional copolymer of the self-catalytic polymerization and the self-catalytic depolymerization has no small molecular catalyst residue, and consists of structural units represented by I, II and III or I, II and IV, and under the condition of not adding a traditional catalyst, the self-catalytic functional reaction monomer can be simultaneously used as a catalyst and a third reaction monomer for polymerization with various polymers such as polyester, polycarbonate and the like, and is polymerized into a corresponding copolymer through melting polycondensation. And the obtained copolymer can carry out self-depolymerization reaction under proper conditions without adding a depolymerization catalyst, so as to obtain reaction monomers again and realize the chemical recovery of the copolymer. Meanwhile, the introduction of the autocatalytic functional reaction monomer can endow the obtained copolymer with rich functionality, such as flame retardance, antistatic property, antibacterial property, cationic dyeability and the like, and can simultaneously realize autocatalytic polymerization, multi-functionalization and autopolymerization chemical recovery of melt polycondensation of various polymers.

Description

Self-catalytic functional reaction monomer, self-catalytic polymerization and self-catalytic depolymerization functional copolymer, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional reaction monomers, functional copolymers and preparation thereof, and particularly relates to a novel autocatalytic functional reaction monomer, an autocatalytic polymerization and autocatalytic depolymerization functional copolymer and a preparation method thereof. That is to say, the compound can be used as a polymerization catalyst and a third reaction monomer at the same time without adding a traditional catalyst, and can catalyze the melt copolymerization of the compound and raw material monomers of polymers such as polyester or polycarbonate, so that the copolymer such as copolyester or copolycarbonate without small molecular catalyst residues and with a preset monomer introduction amount is synthesized, and the copolymer can carry out self-depolymerization reaction under a proper condition without adding a depolymerization catalyst, so as to obtain the reaction monomer again, and realize the chemical recovery of the copolymer. Meanwhile, the introduction of the self-catalytic polymerization monomer can also endow the polymer with multiple functions, thereby realizing the self-catalytic melt polymerization, the multiple functions and the self-depolymerization chemical recovery of the copolymer.
Background
Melt polycondensation, a conventional polymerization method, has been widely used for the industrial production of various polymers, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene succinate (PBS), polybutylene adipate/terephthalate (PBAT), and polyethylene furan dicarboxylate (PEF), etc. In recent years, the application of melt polycondensation to non-phosgene green Polycarbonate (PC) production technologies and products has also been receiving increasing market attention. In the melt polycondensation process, a proper catalyst can greatly improve the production efficiency of products, such as an antimony catalyst used in polyester production, a small molecule catalyst used in polycarbonate production and the like. However, small molecule catalysts remaining in the polymer matrix often affect the safety of use and ecological safety of the polymer, especially some heavy metal-based catalysts. With the enhancement of environmental awareness of people, the green catalyst has become an important factor influencing the sustainable development of the melt polycondensation polymer industry. However, the existing green catalysts with higher catalytic activity and lower toxicity still have many problems in the aspects of stability of storage and use links, balance of polymerization activity and selectivity, controllability of polymer production process and performance quality and the like, for example, titanium catalysts developed for polyester generally have the defects of poor stability, aggravated side reaction and the like, so that the hue of synthesized PET is poor and the quality is reduced; particularly, when a titanium catalyst coexists with a large amount of phosphorus-containing compounds, side reactions are more easily aggravated, so that the color of the phosphorus-containing copolymer catalyzed and synthesized by the titanium catalyst is generally yellow, the b value is particularly high, the high-end application cannot be met, and the titanium catalyst is not beneficial to the chemical recovery of polymers. In addition, the presence of residual small-molecule catalyst in the resin can cause some adverse effects on the performance quality of the polymer, such as reduced thermal stability, and the like, and the application is limited.
On the other hand, the polymer material and the product thereof bring convenience to the life of people, and the generation and improper disposal of a large amount of waste macromolecules also bring serious problems of environmental pollution and resource waste. Therefore, the recovery and comprehensive utilization of waste macromolecules have become one of the main problems affecting the environment and the sustainable development of human beings worldwide. The existing waste high polymer recovery method mainly comprises a physical method, a physical chemical method and a chemical method, wherein the chemical method can realize the closed-loop recovery of polymer-monomer-polymer to obtain high-valued regeneration products, and is particularly suitable for the high-valued recovery of polycondensation high polymers such as polyester and the like. However, in the process of chemically recovering monomers, catalysts are additionally added for depolymerization of polymers, which not only faces the problem of depolymerization efficiency, but also causes great difficulty in separation and purification of monomers due to catalyst residues. In addition, the heavy metal or small molecule catalyst native in the material also faces the problem of environmental pollution or unstable property in the recovery process, thereby bringing adverse effect to the separation and purification of the monomer. These are only the problems of chemical recovery of simple polymer systems. In the practical use process of the polymer material, due to the defects or the defects of the performance of the polymer material, the functional modification is needed according to the requirements of the application occasions. At present, the most common way for the functional modification of the polymer is to add the functional additives directly into the base material by physical blending during the polymerization or processing of the polymer. The chemical recovery of the complex polymer material system based on the blending functionalization modification also needs to solve the separation and purification problems of various functional additives and reaction monomers, increases the chemical recovery difficulty of the material, further increases the environmental pollution and resource consumption in the recovery process, and is not beneficial to the cyclic utilization and sustainable development of the polymer material.
In view of the above, the present inventors have desired to develop a copolymer having the following characteristics: the polymer uses a polymerizable compound with autocatalysis polymerization activity (namely an autocatalysis functional reaction monomer) as a polymerization catalyst and a third monomer, so that the polymerizable compound can be connected into a molecular chain of the polymer in the polymerization process, and the obtained resin has no residue of a small molecular catalyst; in the chemical recovery process of the polymer, a depolymerization catalyst is not required to be added, the obtained copolymer can be subjected to self-depolymerization reaction under a proper condition to obtain a reaction monomer again, and the third monomer can be directly used for repolymerization of the copolymer without separation and purification; the third monomer structure used in the polymer has specific functionality, and the polymer can endow the obtained copolymer with certain functionality after being introduced into a polymer macromolecular chain. Therefore, the copolymer can simultaneously realize autocatalytic melt polymerization, multifunctionality and autopolymerization chemical recovery of various polymers.
Disclosure of Invention
One of the objects of the present invention is to provide a class of autocatalytically functional reactive monomers.
The second purpose of the invention is to provide a functional copolymer of autocatalytic polymerization and autocatalytic depolymerization.
It is a further object of the present invention to provide a process for the preparation of functional copolymers by autocatalytic polymerization and autocatalytic depolymerization.
The fourth purpose of the invention is to provide the application of the functional copolymer of autocatalytic polymerization and autocatalytic depolymerization.
The invention provides an autocatalytic functional reaction monomer which is characterized in that the structural general formula of the reaction monomer is as follows:
Figure BDA0003016906720000031
Figure BDA0003016906720000041
in the formula, Z 1 、Z 2 Is carboxyl, ester group, amino, hydroxyl, acyloxy with polycondensation polymerization activity or a is an integer of 1 to 12, Z 1 、
Figure BDA0003016906720000042
Z 2 The same or different; z is a linear or branched member 3 、Z 4 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, Z 3 、Z 4 The same or different; z 5 、Z 6 Is H atom, C1-C12 alkyl, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl, substituted aryl, ester group, carboxyl, hydroxyl, amino, acyloxy or
Figure BDA0003016906720000043
a is an integer of 1 to 12; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl group, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl group, nitrogen ethyl group or amide group; when the reactive monomer structure is A-S, M n+ Is an organic cation; when the reactive monomer structure is T-W, M n+ Is an organic cation or an alkali metal ion.
The ester group in the structural general formula of the autocatalytic functional reaction monomer is any one of a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group or a hexyl ester group after esterification of monohydric alcohol, or a phenyl ester group after esterification of monohydric phenol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a diethylene glycol ester group, a glycerol ester group or a pentaerythritol ester group after esterification of polyhydric alcohol.
The organic cation M in the structural general formula of the autocatalytic functional reaction monomer n+ Is any one of cations having the following structural formula, n is an integer of 1 to 2:
Figure BDA0003016906720000044
Figure BDA0003016906720000051
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z is a linear or branched member 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z is a linear or branched member 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
The invention provides a preparation method of the self-catalytic functional reaction monomer, which is to add a precursor containing phosphonic acid groupWith alkali metal ions or containing B 1 -B 8 Performing neutralization reaction on hydroxide, bicarbonate or acetate of the organic cation according to a conventional molar ratio to prepare a target reaction monomer; or the corresponding sodium salt, potassium salt or silver salt of the precursor containing phosphonic acid group and the precursor containing B 1 -B 8 The target reaction monomer is prepared by carrying out ion exchange reaction on chlorine salt, bromine salt or p-toluenesulfonate with an organic cation structure in an organic solvent according to a conventional molar ratio.
The precursor containing phosphonic acid group and corresponding salt used in the preparation method of the self-catalytic functional reaction monomer can be referred to Inorganic Chemistry 2016,55,7928-7943; polymer Chemistry,2014,5,1982-1991; journal of the American Chemical Society,2005,127,8,2398-2399; the preparation is carried out by the method disclosed in Journal of Polymer Part A, polymer Chemistry,2012,50,4977-4982, and the like.
The invention provides a copolymer with self-catalytic polymerization and self-depolymerization functions, which is a copolymer of wholly aromatic polyester, semi-aromatic polyester, aliphatic-aromatic polyester, bio-based polyester, polycarbonate, polyester elastomer, nylon elastomer or a modified polymer of the above polymers and a self-catalytic functional reaction monomer, wherein the self-catalytic functional reaction monomer is completely connected to a molecular chain of the copolymer and consists of the following structural units I, II and III or I, II and IV:
Figure BDA0003016906720000052
in the formula, R 1 Represents an arylene, C2-C12 alkylene or alkylidene group, a 2, 5-furyl group, a carboxylic acid or an ester group-terminated polyamide segment;
Figure BDA0003016906720000061
in the formula, R 2 Represents an arylene group, a C2-C12 alkylene group or an alkylidene group, 4' -isopropylidenediphenylA radical (bisphenol A radical), a 4,4 '-diphenylmethyl radical (bisphenol F radical), a 4,4' -diphenylsulfone radical (bisphenol S radical), an isosorbide radical, a polyether radical (polyether polyol radical) or an alcohol-terminated polyester radical (polyester polyol radical);
Figure BDA0003016906720000062
Figure BDA0003016906720000071
in the formula, R 3 、R 4 Is a carbonyl group, a secondary amino group, an O atom or
Figure BDA0003016906720000072
a is an integer of 1 to 12, R 3 、R 4 The same or different; r 5 、R 6 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, R 5 、R 6 The same or different; r 7 Is H atom, C1-C12 alkyl, hydroxyl, C1-C12 alkoxy, secondary amino, tertiary amino, aryl or substituted aryl; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl group, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl group, nitrogen ethyl group or amide group; cation M n+ Is any one of alkali metal ions or organic cations having the following structural formula:
Figure BDA0003016906720000073
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z is a linear or branched member 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino,Tertiary amino, amido, aryl or substituted aryl groups; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
Figure BDA0003016906720000074
Figure BDA0003016906720000081
In the formula, R 3 Is a carbonyl group, a secondary amino group, an O atom or
Figure BDA0003016906720000082
a is an integer of 1 to 12; r 5 、R 6 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, R 5 、R 6 The same or different; r 7 Is H atom, C1-C12 alkyl, hydroxyl, C1-C12 alkoxy, secondary amino, tertiary amino, aryl or substituted aryl; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl, nitrogen ethyl or amide group; cation M n+ Is any one of alkali metal ions or organic cations having the following structural formula:
Figure BDA0003016906720000083
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
Wherein the number of the structural units of [ III ] is 0.05-99% of the number of the structural units of [ I ]; the number of the structural units of the copolymer is 0.05-40 percent of that of the structural units of the copolymer, the intrinsic viscosity [ eta ] of the copolymer is 0.16-2.10 dL/g, the limited oxygen index is 22.5-57.0 percent, the vertical combustion grade is V-2-V-0 grade, the antibacterial rate of staphylococcus aureus is 30-99.99 percent, and the antibacterial rate of escherichia coli is 30-99.99 percent.
The functional copolymer of the self-catalytic polymerization and the self-catalytic depolymerization can carry out the self-depolymerization chemical reaction when the temperature is raised to 120 to 280 ℃ in an alcohol reaction medium under normal pressure or the temperature is raised to 120 to 280 ℃ in an alcohol reaction medium under pressure, and the target monomer is recovered and obtained again, and can be directly used for the repolymerization of the copolymer without separation and purification.
When the number of the structural units of the [ III ] is preferably 0.1 to 60% of the number of the structural units of the [ I ]; the number of the structural units of the copolymer is 0.1 to 30 percent of the number of the structural units of the copolymer, and the intrinsic viscosity [ eta ] of the copolymer is 0.20 to 2.10dL/g; the limiting oxygen index is 23.5-53.0%, the vertical combustion grade is V-2-V-0 grade, the antibacterial rate of staphylococcus aureus is 40-99.99%, and the antibacterial rate of escherichia coli is 40-99.99%.
The autocatalytic functional reaction monomer in the functional copolymer of autocatalytic polymerization and autocatalytic depolymerization is at least one of the following structural general formulas:
Figure BDA0003016906720000091
Figure BDA0003016906720000101
in the formula, Z 1 、Z 2 Is carboxyl, ester group, amino, hydroxyl, acyloxy or carboxyl with polycondensation polymerization activity
Figure BDA0003016906720000102
a is an integer of 1 to 12, Z 1 、Z 2 The same or different; z is a linear or branched member 3 、Z 4 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, Z 3 、Z 4 The same or different; z is a linear or branched member 5 、Z 6 Is H atom, C1-C12 alkyl, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, ester group, carboxyl, hydroxyl, amino, acyloxy or
Figure BDA0003016906720000103
a is an integer of 1 to 12; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl group, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl group, nitrogen ethyl group or amide group; m is a group of n+ Is alkali metal ion or organic cation, and n is an integer of 1-3.
In the structural general formula of the autocatalytic functional reaction monomer, the ester group is any one of a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group or a hexyl ester group after monohydric alcohol esterification, or a phenyl ester group after monohydric phenol esterification, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol group, a neopentyl glycol ester group, a diethylene glycol ester group, a glycerol ester group or a pentaerythritol ester group after polyhydric alcohol esterification.
Cation M in the structural general formula of the autocatalytic functional reaction monomer n+ Is an alkali metal ion or has the following B 1 -B 8 Any one of the organic cations of the general structural formula:
Figure BDA0003016906720000111
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z is a linear or branched member 11 Is C2-C16 alkylene or arylene; z is a linear or branched member 12 Is C1-C16 alkyl, aryl or substituted aryl; z 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, or secondary aminoTertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
The autocatalytic functional reaction monomers used above can be found in Polymer Chemistry,2014,5,1982-1991; polymer,2015,60,50-61; the method disclosed in Journal of the American Chemical Society,2005,127,8,2398-2399, and the like.
The invention provides a method for preparing functional copolymer of self-catalyzed polymerization and self-catalyzed depolymerization, which is prepared by mixing dicarboxylic acid or dicarboxylic acid ester and polymer monomer of dihydric alcohol or phenol according to the conventional proportion, performing esterification or ester exchange by adopting the conventional direct esterification method or ester exchange method, and performing melt polycondensation reaction or further performing solid phase polycondensation, and is characterized in that before the esterification or ester exchange reaction or before the polycondensation after the esterification reaction, a double-polymerization functional group accounting for 0.05-99% of the mole number of the dicarboxylic acid or dicarboxylic acid ester in the polymer monomer or a single-polymerization functional group self-catalyzed functional reaction monomer accounting for 0.05-40% of the mole number of the dicarboxylic acid or dicarboxylic acid ester in the polymer monomer is added into a reaction system; preferably 0.1 to 60 percent of double-polymerization functional group or 0.1 to 30 percent of single-polymerization functional group self-catalysis functional reaction monomer.
The autocatalytic functional reaction monomer used in the above autocatalytic polymerization method has obvious catalytic action on esterification reaction, ester exchange reaction and polycondensation reaction, and is suitable for polymerization processes such as direct esterification-melt polycondensation, ester exchange-melt polycondensation, solid phase polycondensation and melt polycondensation-solid phase polycondensation.
The polymerization process steps and conditions of the conventional direct esterification method, the melt polycondensation by the ester exchange method and the solid phase polycondensation adopted by the invention are as follows:
the direct esterification method comprises the following steps: adding polymer monomer (dicarboxylic acid, dihydric alcohol or phenol) and self-catalytic polymerization monomer in a reaction kettle according to a conventional ratio, pressurizing and heating to 120-240 ℃ to perform esterification reaction for 0.5-8 hours; after the esterification is finished, pre-polycondensing for 0.5-2 hours at 160-270 ℃ under low vacuum, then polycondensing for 1-8 hours at 200-300 ℃ under high vacuum, extruding the polymer melt by using inert gas (preferably adopting nitrogen), and cooling the melt by water to obtain the target polymer. Wherein, the self-catalyzed polymerization functional reaction monomer can be added into the reaction kettle before esterification or before polycondensation after esterification.
An ester exchange method: adding polymer monomer (ester of dicarboxylic acid, dihydric alcohol or phenol) and self-catalyzed polymerization monomer in a reaction kettle according to a conventional ratio, and carrying out ester exchange reaction at 120-240 ℃ for 0.5-8 hours under normal pressure; after the ester exchange is finished, pre-polycondensing for 0.5-2 hours at 160-270 ℃ under low vacuum, then polycondensing for 1-8 hours at 200-300 ℃ under high vacuum, extruding the polymer melt by using inert gas (preferably adopting nitrogen), and cooling the melt by water to obtain the target polymer.
Solid phase polycondensation: firstly, preparing a polymer with relatively low molecular weight by melt polycondensation through the ester exchange method or the direct esterification method, drying and pre-crystallizing the obtained polymer with relatively low molecular weight under the protection of nitrogen, putting a sample into a solid phase polycondensation reaction device, continuously polycondensing for 0.5 to 15 hours at 120 to 240 ℃ under high vacuum, cooling and granulating to obtain the target polymer.
The autocatalytic functional reaction monomer used in the above autocatalytic polymerization method can be used alone as an esterification, transesterification, or polycondensation catalyst, or can be used as a main catalyst in combination with an auxiliary agent such as a cocatalyst, a stabilizer, an antioxidant, a matting agent, a toner, or the like.
Because the introduced self-catalytic functional reaction group has the function of catalyzing ester exchange, the chemical recovery of self-catalytic depolymerization of the copolymer is suitable for the recovery methods such as hydrolysis, alcohol (or phenol) hydrolysis, aminolysis and alcoholysis-ester exchange combined method which take water, alcohol, phenol or amine as reaction media.
The invention provides an application of a functional copolymer of autocatalytic polymerization and autocatalytic depolymerization, which is independently applied in the fields of fibers and products thereof, non-woven fabrics, engineering plastics, membrane materials, container materials, packaging materials, biomedical materials, shape memory materials or 3D printing materials, and is used for modifying high molecular materials as a functional additive.
Compared with the prior art, the invention has the following advantages:
1. the functional copolymer of the autocatalytic polymerization and the autocatalytic depolymerization provided by the invention utilizes the autocatalytic functional reaction monomer as the catalyst and the third monomer for melt polycondensation at the same time, so that the functional reaction monomer can catalyze the melt copolymerization of the functional reaction monomer and the polymer raw material monomer without adding other catalysts and is connected into a macromolecular chain of the copolymer to obtain the corresponding copolymer, thereby fundamentally eliminating the catalyst residue and the emigration in the corresponding polymer prepared by the existing method and the possible health and ecological environment problems, and providing a new solution for realizing the green synthesis and the safe use of various polymers.
2. The functional copolymer of the autocatalytic polymerization and the autocatalytic depolymerization, provided by the invention, takes a specific functional structure into consideration during design, and after a certain content of functional reaction monomers are connected to a macromolecular chain of the copolymer, the performance of the copolymer can be changed, so that the autocatalytic polymerization can be realized, and meanwhile, the polymer is endowed with good flame retardance, molten drop resistance, antistatic property, antibacterial property, easy dyeing and other functionalities, has a good application prospect, and meets the huge development requirements of the polyester industry.
3. Since the autocatalytic functional reaction monomer used in the autocatalytic polymerization method provided by the present invention has a significant catalytic effect on transesterification, esterification, melting, and solid phase polycondensation reactions, the autocatalytic polymerization method provided by the present invention is suitable for a polymerization method such as direct esterification-melt polycondensation, transesterification-melt polycondensation, solid phase polycondensation, and melt polycondensation-solid phase polycondensation of various aromatic, aliphatic, or oligomeric dicarboxylic acids (or esters) and various aromatic, aliphatic, or oligomeric diols (or phenols) as raw materials, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), aromatic polyester type Liquid Crystal Polymer (LCP), polybutylene succinate (PBS), polybutylene adipate/terephthalate (PBAT), polyethylene furan dicarboxylate (PEF), polylactic acid (PLA), polycarbonate (PC), modified polycarbonate (LCP), or modified polycarbonate (TPEE), and thermoplastic elastomer (nylon elastomer).
4. Because the autocatalysis functional reaction monomer used in the autocatalysis polymerization method provided by the invention has stable chemical property and good compatibility with a polymer reaction system, the autocatalysis functional reaction monomer used in the method has good storage stability, hydrolysis resistance, thermal stability, reaction activity and matrix compatibility.
5. Because the autocatalytic functional reaction monomer used in the autocatalytic polymerization method provided by the invention is of a phosphonate-containing structure and can also play a role of a stabilizer besides being used as a catalyst, the occurrence of side reactions can be inhibited, the performance quality (especially the b value of a polymer) of the obtained copolymer is improved, and compared with a pure polymer and copolymer system using an additive catalyst, the obtained copolymer has higher thermal stability and better hue.
6. The functional copolymer of the autocatalytic polymerization and the autocatalytic depolymerization provided by the invention contains phosphonate ionic groups similar to sulfonate, so that the copolymer also shows good antistatic performance and affinity with cationic dyes.
7. The functional copolymer of autocatalytic polymerization and autocatalytic depolymerization provided by the invention is not added with any additive which influences fiber preparation, so that the copolymer has good spinnability, not only can be directly used as a polymer raw material for fibers, but also can be used for obtaining corresponding films, plates, packaging materials, engineering plastics and the like through processing modes such as injection molding, film blowing, tape casting and the like.
8. Since the autocatalytic functional groups in the autocatalytic polymerization and autocatalytic depolymerization functional copolymer provided by the invention have the function of catalyzing ester exchange, the copolymer can be subjected to an autopolymerization reaction under a proper condition without adding a depolymerization catalyst, and is completely depolymerized into a reaction monomer.
9. Because the functional copolymer of the autocatalytic polymerization and the autocatalytic depolymerization provided by the invention can be completely autopolymerized into a reaction monomer, compared with a non-autocatalytic copolymer system, the chemical recovery of the copolymer not only has mild conditions and high depolymerization and conversion rate, but also can reduce the separation and purification problems caused by a primary small molecular catalyst and an additional depolymerization catalyst, and a third monomer can remain in the recovered monomer without separation and purification and can be reused for synthesizing the copolymer.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of autocatalytic functional reaction monomer 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphinate prepared in example 1 of the present invention. The peaks at 7.27, 7.92ppm and 8.25ppm in the hydrogen spectrum are assigned to the hydrogen on the anthraceneoxa ring, the peaks at 9.21, 7.79 and 7.70ppm are assigned to the hydrogen on the imidazole ring, the peaks at 3.87ppm are assigned to the hydrogen of the methyl ester, the peaks at 4.42, 4.16 and 1.44ppm are assigned to the hydrogen of the methyl and methylene groups on the imidazole ring, and the remaining peaks are the solvent peak and the water peak. The nuclear magnetic hydrogen spectrum result shows that the target monomer is successfully prepared.
FIG. 2 is a nuclear magnetic phosphorus spectrum of an autocatalytic functional reaction monomer 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene hypophosphite prepared in example 1 of the present invention. The chemical shift of the spectrum has only one peak: 13.7ppm, indicating that only one phosphorus environment is present, and also indicating that the target monomer has been successfully prepared.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the autocatalytic polymerized and autocatalytic depolymerized functional copolymer prepared in example 23 of the present invention. The hydrogen spectrum showed a peak around 8.22ppm corresponding to hydrogen on the benzene ring in the copolymer structural unit, a peak at 4.94ppm corresponding to hydrogen on the ethylene glycol unit of the copolymer main chain, and peaks at 9.10, 8.92 and 8.02ppm corresponding to hydrogen on the autocatalytically reactive monomer structural unit of the copolymer. Indicating that the autocatalytic functional reaction monomer has been successfully introduced into the molecular chain of the copolymer.
FIG. 4 shows the nuclear magnetic phosphorus spectra of the functional copolymer prepared by the autocatalytic polymerization and the autocatalytic depolymerization in example 23 of the present invention. The peak near 2.3ppm in the phosphorus spectrogram corresponds to the phosphorus element in the structural unit of the autocatalytic functional reaction monomer in the copolymer, and the result further proves that the autocatalytic functional reaction monomer is successfully introduced into the molecular chain of the copolymer.
FIG. 5 is a thermogravimetric plot of the autocatalytically functional reactant monomer prepared in example 1 of the present invention. The figure shows that the prepared self-catalyzed functional reaction monomer can maintain good thermal stability in the melt polycondensation process.
FIG. 6 is a thermogravimetric plot of polymers prepared in example 41 of the present invention and comparative examples 1 and 2. It can be seen that the thermal stability of the polymer obtained by autocatalytic polymerization is significantly higher than that of the same polymer prepared by other catalysts.
FIG. 7 is a graph of the heat release of the copolymer prepared in example 53 of the present invention and PET prepared in comparative example 1. The results show that the functional copolymer prepared by self-catalytic polymerization and self-catalytic depolymerization shows different combustion behaviors, the heat release rate is obviously reduced, the peak heat release rate is reduced by more than half compared with that of pure PET, and the excellent flame retardant property is shown.
FIG. 8 is a graph of the smoke density of the autocatalytic polymerized and autocatalytic depolymerized functional copolymer prepared in example 53 of the present invention and PET prepared in comparative example 1. The results show that the smoke density of the copolymer is remarkably reduced along with the introduction of the autocatalytic functional reaction monomer, and the smoke density is only about 30 percent of that of pure PET, thereby showing extremely excellent smoke suppression performance. This shows that the introduction of the autocatalytic functional reaction monomer well suppresses the amount of smoke generated by the copolymer.
FIG. 9 is a graph showing the absorbance of dye liquors after dyeing of an autocatalytically polymerized and autocatalytically depolymerized functional copolymer fiber prepared in example 56 of the present invention and a PET fiber prepared in comparative example 1. As can be seen from the results, the absorbance of the dye solution obtained in example 56 after dyeing the copolymer fiber is significantly lower than that of the dye solution obtained after dyeing the pure PET fiber, indicating that more dye is adsorbed to the surface of the copolymer fiber during the dyeing process. This result indicates that the copolymer has excellent cationic dyeing ability.
Detailed Description
The following examples are given to further illustrate the invention. It is necessary to point out here that the following examples are not to be construed as limiting the scope of the invention, which is intended to be covered by the present invention if a person skilled in the art would make insubstantial modifications and adaptations of the invention in light of the above teachings.
In addition, it is worth mentioning that: intrinsic viscosity [. Eta. ] of the copolymers obtained in the following examples and of the comparative example copolymer]Phenol/1, 2-tetrachloroethane (1, v; the limiting oxygen indices are all determined according to ASTM D2863-97; the vertical burning test was carried out in accordance with UL-94 standard, and the specimen size was 125X 12.7X 3.2mm 3 (ii) a The cone calorimetric test is carried out according to ISO 5660-1 standard to make it 100X 3mm 3 The standard sample strip of (1), measured on an FTT cone calorimeter; the antibacterial property test is carried out according to the QB-T2591-2018 standard; the fiber dyeing performance test uses methylene blue as a cationic dye, 1g of fiber sample is weighed for a dyeing test, an ultraviolet-visible spectrophotometer is used for dye liquor absorbance test, and the absorbance of the fiber sample at the position of 665nm of the wavelength is taken as the maximum absorbance.
Example 1
In a reaction vessel, 696g of [2, 8-bis (methoxy) carbonyl ] anthracenexanthenephosphoric acid and 3L of ethanol were added, followed by uniformly mixing with stirring and slowly raising the temperature to 50 ℃, then 256g of 1-ethyl-3-methylimidazole hydroxide (equimolar amount) was slowly dropped, and stirring was carried out for 2 hours. Removing the solvent and drying to obtain the 1-ethyl-3-methylimidazole [2, 8-di (methoxy) carbonyl ] anthracene xanthene hypophosphite.
Example 2
In a reaction vessel, 6966 g of [2, 8-bis (methoxy) carbonyl ] anthracene xanthene phosphoric acid was dispersed in 3L of ethanol, 200g of potassium hydrogencarbonate was added thereto, and the reaction was carried out for 2 hours, followed by removal of the solvent to obtain potassium [2, 8-bis (methoxy) carbonyl ] anthracene xanthene phosphate. 386g of the product obtained in the previous step was weighed out and added to an ethanol solution containing 174.7g of 1-butyl-3-methylimidazole chloride, and the mixture was stirred for 4 hours. Filtering, removing solvent from filtrate, recrystallizing the obtained white solid with mixed solution of diethyl ether and ethanol, and drying to obtain 1-butyl-3-methylimidazole [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphate.
Example 3
In the reaction vessel, 696g of (2, 8-dicarboxy) anthracenexanthene phosphoric acid was first dispersed in 3L of ethanol, 168g of sodium hydrogencarbonate was added, reaction was carried out for 2 hours, and the solvent was removed to obtain sodium (2, 8-dicarboxy) anthracenexanthene phosphate. 370g of the product obtained in the previous step is weighed and added into an ethanol solution dissolved with 216.1g of N-butylpyridine bromide, the mixture is stirred for 4 hours, filtered, the solvent is removed from the filtrate, and the obtained white solid is recrystallized by a mixed solution of diethyl ether and ethanol and dried to obtain N-butylpyridine (2, 8-dicarboxy) anthracene xanthene phosphinate.
Example 4
In a reaction kettle, 856.64g of 2-carboxyethylphenyl phosphinic acid is firstly dissolved in 2L of ethylene glycol, stirred, reacted at 190 ℃ for 4 hours, and cooled for standby. And then, at room temperature, continuously adding 512g of 1-ethyl-3-methylimidazole hydroxide to perform a neutralization reaction, stirring for 4 hours, collecting the obtained solution to obtain an ethylene glycol solution of 1-ethyl-3-methylimidazole 2- (2-hydroxyethoxycarbonyl) ethylphenyl hypophosphite, and drying for later use.
Example 5
In the reaction vessel, 856.64g of 2-carboxyethylphenylphosphinic acid and 20mL of concentrated sulfuric acid were first dissolved in 1L of methanol, and the reaction was carried out under reflux for 6 hours. After the reaction is finished, adding sodium bicarbonate to neutralize sulfuric acid, filtering, removing the solvent from the filtrate to obtain 2- (2-methoxycarbonyl) ethyl phenyl hypophosphorous acid, and drying for later use. Weighing 228g of the product in the previous step, adding the product into an ethanol solution dissolved with 198g of 1-butyl-3-methylimidazole acetate, stirring for 6 hours, removing the solvent, and recrystallizing to obtain the 1-butyl-3-methylimidazole 2- (2-methoxycarbonyl) ethylphenyl hypophosphite.
Example 6
In a reaction vessel, 580g of 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene phosphinic acid was first dispersed in 3L of ethanol, 84g of sodium hydrogencarbonate was added thereto, reaction was carried out for 4 hours, and the solvent was removed to obtain sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene phosphinate. Weighing 301g of the product in the previous step, adding the weighed 301g of the product into a methanol solution in which 102.5g of 1, 2-dimethyl-3-ethylimidazole bromine salt is dissolved, reacting for 6 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained solid with ethanol, and drying to obtain 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzimidazole-2-yl) anthracene xanthene hypophosphite.
Example 7
In the reaction vessel, 581g of 2, 8-bis (5-methoxycarbonyl-benzoxazol-2-yl) anthracenexanthenephosphoric acid was first dispersed in 3L of ethanol, 84g of sodium hydrogencarbonate was added and the reaction was carried out for 4 hours, and the solvent was removed to give sodium 2, 8-bis (5-methoxycarbonyl-benzoxazol-2-yl) anthracenexanthenephosphate. Weighing 301.5g of the product obtained in the previous step, adding the product into a methanol solution dissolved with 102.5g of 1, 2-dimethyl-3-ethylimidazole bromine salt, reacting for 6 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained solid by using ethanol, and drying to obtain the 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-benzoxazol-2-yl) anthracene xanthene hypophosphite.
Example 8
In a reaction vessel, 597g of 2, 8-bis (5-methoxycarbonyl-benzothiazol-2-yl) anthracene xanthene phosphinic acid was first dispersed in 3L of ethanol, 84g of sodium bicarbonate was added, reaction was carried out for 4 hours, and the solvent was removed to obtain sodium 2, 8-bis (5-methoxycarbonyl-benzothiazol-2-yl) anthracene xanthene phosphinate. Weighing 309.5g of the product obtained in the previous step, adding the product into a methanol solution dissolved with 102.5g of 1, 2-dimethyl-3-ethylimidazole bromine salt, reacting for 6 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained solid by using ethanol, and drying to obtain the 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-benzothiazole-2-yl) anthracene xanthene hypophosphite.
Example 9
246g of 3, 5-dicarboxyphenylphosphonic acid, 332g of methyl 3, 4-diaminobenzoate, 394g of EDCI, 80g of HOBT and 1000mL of DMF are added into a reaction kettle, and the mixture is reacted for 24 hours at normal temperature, the solvent is removed, and the product is washed twice and dried. The resulting solid was reacted in 250ml of glacial acetic acid under reflux for 12 hours and filtered to give 3, 5-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) phenylphosphonic acid. Weighing 101.2g of the product obtained in the previous step, dispersing the product in ethanol, adding 51.2g of 1-ethyl-3-methylimidazole hydroxide, reacting for 4 hours at the temperature of 60 ℃, removing the solvent, and drying to obtain the bis (1-ethyl-3-methylimidazole) 3, 5-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) phenylphosphonate.
Example 10
856g of 2-carboxyethyl phenyl hypophosphorous acid and 608g of 3, 4-diaminobenzoic acid are firstly added into 2L of hydrochloric acid solution (4 mol/L) in a reaction kettle, reflux reaction is carried out for 8 hours, the solution is adjusted to be neutral by ammonia water, filtration is carried out, a filter cake is washed twice by hot water and dried, and 2- (5-methoxycarbonyl-1H-benzimidazole-2-yl) ethyl phenyl hypophosphorous acid is obtained. 330g of the product of the previous step and 84g of sodium bicarbonate were added to ethanol and reacted for 6 hours. Adding 216.1g of N-butylpyridine bromide, reacting for 4 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid with diethyl ether, and drying to obtain the N-butylpyridine 2- (5-methoxycarbonyl-1H-benzimidazole-2-yl) ethyl phenyl hypophosphite.
Example 11
In the reaction kettle, 865g of (4-aminophenyl) phosphonic acid is firstly added into 3L of ethanol, 530g of sodium carbonate is added, the reaction is carried out for 8 hours, and after the solvent is removed, disodium (4-aminophenyl) phosphonate is obtained. Weighing 78g of the product obtained in the previous step, adding the weighed product into an acetone solution dissolved with 197.7g of 1-hexyl-3-methylimidazolium bromide, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid with ethylene glycol diethyl ether, and drying to obtain the di (1-hexyl-3-methylimidazole) (4-aminophenyl) phosphonate.
Example 12
In the reaction vessel, 870g of (4-hydroxyphenyl) phosphonic acid was first dissolved in 2L of DMF, 392g of acetyl chloride was slowly added dropwise thereto, and the reaction was carried out for 10 hours to remove the solvent, thereby obtaining [4- (acetoxy) phenyl ] phosphonic acid. 648g of the product of the previous step and 504g of sodium bicarbonate were weighed out and added to 1L of ethanol, reacted for 8 hours, filtered, the solvent was removed from the filtrate, and dried to obtain disodium [4- (acetoxy) phenyl ] phosphonate. Weighing 260g of the product obtained in the previous step, adding the product into an ethanol solution dissolved with 606g of 1-decyl-3-methylimidazolium bromide, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid with acetone, and drying to obtain the di (1-decyl-3-methylimidazole) [4- (acetoxyl) phenyl ] phosphonate.
Example 13
In the reaction vessel, 864g (4-methoxycarbonylphenyl) phosphonic acid was added to 2L ethanol, 672g sodium bicarbonate was added, reaction was carried out for 4 hours, and the solvent was removed to obtain disodium (4-methoxycarbonylphenyl) phosphonate, which was dried for use. 780g of the product obtained in the previous step is weighed and added into an isopropanol solution dissolved with 880g of 1-ethyl-3-methylimidazole chloride for reaction for 10 hours, the reaction solution is filtered, the solvent is removed from the filtrate, the obtained white solid is recrystallized by acetone, and the white solid is dried to obtain the di (1-ethyl-3-methylimidazole) (4-methoxycarbonylphenyl) phosphonate.
Example 14
920g of (4-methoxycarbonyl-3-methylphenyl) phosphonic acid was added to 2L of ethanol in a reaction vessel, 672g of sodium bicarbonate was added, reaction was carried out for 4 hours, the solvent was removed to obtain disodium (4-methoxycarbonyl-3-methylphenyl) phosphonate, and drying was carried out. 822g of the product obtained in the previous step is weighed and added into an isopropanol solution dissolved with 1098g of 1,1'- (1, 3-trimethylene) bis-3-methylimidazolium dibromide salt for reaction for 10 hours, the filtration is carried out, the solvent is removed from the filtrate, the obtained white solid is recrystallized by acetone and dried, and then the 1,1' - (1, 3-trimethylene) bis-3-methylimidazolium (4-methoxycarbonylphenyl) phosphonate is obtained.
Example 15
822g of 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is added into 2L of ethanol in a reaction kettle, 504g of sodium bicarbonate is added, the reaction is carried out for 4 hours, the solvent is removed, and the disodium 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is obtained and dried for later use. Weighing 636g of the product obtained in the previous step, adding the weighed product into an isopropanol solution dissolved with 586.7g of chlorinated 1-ethyl-3-methylimidazole, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid with diethyl ether, and drying to obtain the bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate.
Example 16
822g of 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is added into 2L of ethanol in a reaction kettle, 504g of sodium bicarbonate is added, the reaction is carried out for 4 hours, the solvent is removed, and the disodium 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is obtained and dried for later use. Weighing 636g of the product obtained in the previous step, adding the weighed product into n-butyl alcohol solution dissolved with 1356g of tetra-n-butylphosphine bromide, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained solid with ethanol, and drying to obtain the di (tetra-n-butylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate.
Example 17
822g of 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is added into 2L of ethanol in a reaction kettle, 600g of potassium bicarbonate is added, the reaction lasts for 4 hours, the solvent is removed, and dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate is obtained and dried for standby. Weighing 700g of the product obtained in the previous step, adding the product into a methanol solution dissolved with 1581.8g of tributyl n-octyl phosphine bromide, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid with ethanol, and drying to obtain the di (tributyl n-octyl phosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate.
Example 18
822g of 3, 5-bis (methoxycarbonyl) phenylphosphonic acid is added into 2L of ethanol in a reaction kettle, 600g of potassium bicarbonate is added, the reaction lasts for 4 hours, the solvent is removed, and dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate is obtained and dried for standby. 350g of the product obtained in the previous step is weighed and added into a methanol solution dissolved with 360g of N, N '- (1, 3-trimethylene) bipyridine for reaction for 10 hours, filtration is carried out, the solvent is removed from the filtrate, the obtained white solid is recrystallized by acetone and dried, and the N, N' - (1, 3-trimethylene) bipyridine 3, 5-bis (methoxycarbonyl) phenylphosphonate can be obtained.
Example 19
264.95g of 2, 5-dibromo-p-xylene and 5g of nickel bromide are added into a reaction kettle, 520g of triethyl phosphite is slowly dropped into the reaction kettle under the protection of nitrogen, reflux reaction is carried out at 180 ℃ for 10 hours, extraction and liquid separation are carried out by using dichloromethane and water, the solvent is removed, the obtained oily substance is refluxed and hydrolyzed in concentrated hydrochloric acid for 10 hours, and filtration is carried out to obtain white solid. Weighing 216g of white solid, dissolving the white solid in a sodium hydroxide aqueous solution, adding 345g of potassium permanganate for oxidation, reacting at 80 ℃ for 6 hours, filtering, acidifying the filtrate to obtain the white solid, and washing twice. The obtained product is put into a methanol/concentrated sulfuric acid system for methyl esterification, then potassium bicarbonate is added for neutralization, filtration is carried out, and filtrate is recrystallized to obtain 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium.
Example 20
822g of 2, 5-bis (methoxycarbonyl) phenylphosphonic acid is added into 2L of ethanol in a reaction kettle, 504g of sodium bicarbonate is added, the reaction is carried out for 4 hours, the solvent is removed, and 3, 5-bis (methoxycarbonyl) phenylphosphonic acid disodium is obtained and is dried. Weighing 318g of the product obtained in the previous step, adding the weighed product into an isopropanol solution in which 648.4g of brominated 1,1'- (1, 6-hexamethylene) bis (tributylphosphine) is dissolved, reacting for 10 hours, filtering, removing the solvent from the filtrate, recrystallizing the obtained white solid by using ethanol, and drying to obtain the 1,1' - (1, 6-hexamethylene) bis (tributylphosphine) 2, 5-bis (methoxycarbonyl) phenylphosphonate.
Example 21
415g of terephthalic acid, 225mL of ethylene glycol and 11.45g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphinate are added into a reaction kettle, nitrogen is filled to remove air in the kettle, and the pressure is increased to 0.1MPa; heating to 240 ℃ within 2 hours, starting esterification reaction, controlling the pressure in the kettle to be 0.3-0.4 MPa, maintaining for 2 hours, gradually increasing the temperature to 260 ℃, vacuumizing after the esterification reaction is finished, carrying out low-vacuum polycondensation for 0.5-2 hours at 260-270 ℃, heating to 270 ℃, and discharging after carrying out high-vacuum (the pressure is less than 80 Pa) polycondensation reaction for 1-4 hours.
The intrinsic viscosity [ eta ] of the copolymer is 0.57dL/g; the limiting oxygen index is 25.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 76%, and the antibacterial rate of escherichia coli is 79%.
Example 22
415g of terephthalic acid, 230mL of ethylene glycol and 34.35g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.62dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 86%, and the antibacterial rate of escherichia coli is 82%.
Example 23
415g of terephthalic acid, 240mL of ethylene glycol and 57.25g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.68dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 91 percent, and the antibacterial rate of escherichia coli is 92 percent.
Example 24
415g of terephthalic acid, 250mL of ethylene glycol and 80.15g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.72dL/g; the limiting oxygen index is 31.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 92%, and the antibacterial rate of escherichia coli is 93%.
Example 25
415g of terephthalic acid, 260mL of ethylene glycol and 114.5g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.78dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 94 percent, and the antibacterial rate of escherichia coli is 95 percent.
Example 26
415g of terephthalic acid, 280mL of ethylene glycol and 229g of 1-ethyl-3-methylimidazo [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphinate were added into a reaction kettle, and esterification and polycondensation reactions were performed according to the procedures and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.80dL/g; the limiting oxygen index is 36.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 97%, and the antibacterial rate of escherichia coli is 96%.
Example 27
415g of terephthalic acid, 320mL of ethylene glycol and 343.5g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.89dL/g; the limiting oxygen index is 39.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 98%, and the antibacterial rate of escherichia coli is 99%.
Example 28
415g of terephthalic acid, 240mL of ethylene glycol and 85.05g of 1-butyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphinate were charged into a reaction vessel, and after esterification and polycondensation reactions were performed according to the procedure and conditions of example 21, the materials were discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.71dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 96 percent, and the antibacterial rate of escherichia coli is 99 percent.
Example 29
415g of terephthalic acid, 240mL of ethylene glycol and 89.95g of 1-hexyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.69dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99.1%, and the antibacterial rate of escherichia coli is 99.2%.
Example 30
415g of terephthalic acid, 250mL of ethylene glycol and 99.75g of 1-decyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.65dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99.9 percent, and the antibacterial rate of escherichia coli is 99.9 percent.
Example 31
415g of terephthalic acid, 220mL of ethylene glycol and 0.1g of trimethyl phosphate (stabilizer) are added into a reaction kettle, esterification is carried out according to the steps and conditions of the example 21, after the esterification is finished, under the protection of nitrogen, an ethylene glycol solution dissolved with 60.52g of N-butylpyridine [2, 8-di (methoxy) carbonyl ] anthracene xanthene hypophosphite is added into the reaction kettle, the temperature is controlled at 240 ℃, nitrogen is stopped to be introduced after the addition is finished, vacuumizing is started, low-vacuum polycondensation is carried out for 0.5 to 2 hours at 260 to 270 ℃, then the temperature is increased to 270 ℃, and high-vacuum polycondensation is carried out for 1 to 3 hours (the pressure is less than 100 Pa), and then discharging is carried out.
The intrinsic viscosity [ eta ] of the copolymer is 0.76dL/g; the limiting oxygen index is 31.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 94 percent, and the antibacterial rate of escherichia coli is 98 percent.
Example 32
485g of dimethyl terephthalate, 280mL of ethylene glycol and 59.40g of 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzimidazole-2-yl) anthracene xanthene phosphinate are added into a reaction kettle, nitrogen is filled to remove air in the kettle, ester exchange reaction is carried out for 2 to 4 hours at 190 to 210 ℃, the temperature is raised to 240 ℃ after the ester exchange is finished, vacuum pumping is carried out, low vacuum polycondensation reaction is carried out for 0.5 to 2 hours at 240 to 260 ℃, then the temperature is raised to 270 ℃ for 1 to 3 hours under high vacuum (the pressure is less than 80 Pa), and then the materials are discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.67dL/g; the limiting oxygen index is 28.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 88 percent, and the antibacterial rate of escherichia coli is 91 percent.
Example 33
485g of dimethyl terephthalate, 290mL of ethylene glycol and 118.8g of 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene phosphinate were charged into a reaction vessel, subjected to transesterification and polycondensation according to the procedures and conditions described in example 32, and then discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.74dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 94 percent, and the antibacterial rate of escherichia coli is 96 percent.
Example 34
485g of dimethyl terephthalate, 280mL of ethylene glycol and 120.8g of 1, 2-dimethyl-3-ethylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzoxazol-2-yl) anthracenexanthene phosphinate were charged into a reaction vessel, and after the ester exchange and polycondensation reactions were carried out by the procedures and conditions in example 32, the product was discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.72dL/g; the limiting oxygen index is 31.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 95%, and the antibacterial rate of escherichia coli is 95%.
Example 35
485g of dimethyl terephthalate, 280mL of ethylene glycol and 6.08g of 1-butyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and after the ester exchange and polycondensation reactions were carried out by the procedure and conditions of example 32, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.45dL/g; the limiting oxygen index is 24.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 75%, and the antibacterial rate of escherichia coli is 74%.
Example 36
415g of terephthalic acid, 220mL of ethylene glycol and 1.27g of 1, 4-dimethyl terephthalate-2, 5-disodium diphosphonate were added to the reaction kettle, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.45dL/g; the antibacterial rate of staphylococcus aureus is 40 percent, and the antibacterial rate of escherichia coli is 40 percent.
Example 37
415g of terephthalic acid, 220mL of ethylene glycol and 0.63g of disodium 1, 4-dimethylterephthalate-2, 5-diphosphonate were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out in accordance with the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.31dL/g; the antibacterial rate of staphylococcus aureus is 30 percent, and the antibacterial rate of escherichia coli is 30 percent.
Example 38
The polymer obtained in the embodiment 35 is dried under the protection of nitrogen, and then a sample is subjected to pre-crystallization treatment for 0.25 to 4 hours at the temperature of between 80 and 180 ℃ under the protection of normal pressure and nitrogen, and then the sample is placed in a solid phase polycondensation reaction device to be continuously polycondensed for 2 to 8 hours at the temperature of between 180 and 240 ℃ under high vacuum, so that the target polymer is obtained.
The intrinsic viscosity [ eta ] of the copolymer is 1.12dL/g; the limiting oxygen index is 24.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 75%, and the antibacterial rate of escherichia coli is 74%.
Example 39
The polymer obtained in the example 36 is dried under the protection of nitrogen, and then a sample is subjected to pre-crystallization treatment for 0.25 to 4 hours at the temperature of between 80 and 180 ℃ under the protection of normal pressure and nitrogen, and then the sample is placed in a solid phase polycondensation reaction device to be continuously polycondensed for 2 to 8 hours at the temperature of between 180 and 240 ℃ under high vacuum, so that the target polymer is obtained.
The intrinsic viscosity [ eta ] of the copolymer is 0.90dL/g; the limiting oxygen index is 23.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 40 percent, and the antibacterial rate of escherichia coli is 40 percent.
Example 40
The polymer obtained in the example 37 is dried under the protection of nitrogen, and then a sample is subjected to pre-crystallization treatment for 0.25 to 4 hours at the temperature of 80 to 180 ℃ under the protection of normal pressure nitrogen, and then the sample is placed in a solid phase polycondensation reaction device to be continuously polycondensed for 2 to 8 hours at the temperature of 180 to 240 ℃ under high vacuum, so as to obtain the target polymer.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.72dL/g; the limiting oxygen index is 22.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 30 percent, and the antibacterial rate of escherichia coli is 30 percent.
Example 41
415g of terephthalic acid, 230mL of ethylene glycol and 18.98g of 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium salt were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.74dL/g; the limiting oxygen index is 25.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 40 percent, and the antibacterial rate of escherichia coli is 40 percent.
Example 42
485g of dimethyl terephthalate, 240mL of ethylene glycol and 25.30g of 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium salt were added to the reaction vessel, and ester exchange and polycondensation reactions were carried out by the procedure and conditions of example 32, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.82dL/g; the limiting oxygen index is 28%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 42 percent, and the antibacterial rate of escherichia coli is 43 percent.
Example 43
485g of dimethyl terephthalate, 240mL of ethylene glycol and 63.25g of 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium salt were charged into a reaction vessel, and ester exchange and polycondensation reactions were carried out by the procedure of example 32, followed by discharge.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.89dL/g; the limiting oxygen index is 31%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 48%, and the antibacterial rate of escherichia coli is 47%.
Example 44
485g of dimethyl terephthalate, 280mL of ethylene glycol and 75.80g of tetra-n-butylphosphine [2, 8-di (methoxy) carbonyl ] anthracene xanthene phosphinate were charged into a reaction vessel, and subjected to ester exchange and polycondensation reactions by the procedure of example 32, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.70dL/g; the limiting oxygen index is 31%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 96%, and the antibacterial rate of escherichia coli is 97%.
Example 45
415g terephthalic acid, 225mL ethylene glycol and 25.35g 1-ethyl-3-methyl imidazole 2- (2-methoxy carbonyl) ethyl phenyl hypophosphite into the reaction kettle, according to the embodiment of 21 process esterification and polycondensation, discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.70dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 79 percent, and the antibacterial rate of escherichia coli is 90 percent.
Example 46
415g terephthalic acid, 230mL ethylene glycol and 42.25g 1-ethyl-3-methyl imidazole 2- (2-methoxy carbonyl) ethyl phenyl hypophosphorous acid were added into the reaction kettle, and esterification and polycondensation reactions were carried out by the procedure of example 21, and then the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.65dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 90%, and the antibacterial rate of escherichia coli is 94%.
Example 47
415g terephthalic acid, 220mL ethylene glycol and 0.4225g 1-ethyl-3-methyl imidazole 2- (2-methoxy carbonyl) ethyl phenyl hypophosphorous acid were added into the reaction kettle, and esterification and polycondensation reactions were carried out by the process of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.16dL/g; the limiting oxygen index is 22.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 30 percent, and the antibacterial rate of escherichia coli is 30 percent.
Example 48
415g terephthalic acid, 290mL ethylene glycol and 338g 1-ethyl-3-methyl imidazole 2- (2-methoxy carbonyl) ethyl phenyl hypophosphorous acid were added to the reaction kettle, and esterification and polycondensation reactions were carried out by the procedure of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.35dL/g; the limiting oxygen index is 57%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99.9 percent, and the antibacterial rate of escherichia coli is 99.9 percent.
Example 49
415g of terephthalic acid, 225mL of ethylene glycol and 19.95g of potassium 2- (2-methoxycarbonyl) ethylphenylphosphinate were charged into a reaction kettle, and after esterification and polycondensation reactions were carried out by the process of example 21, the reaction product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.71dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 45%, and the antibacterial rate of escherichia coli is 45%.
Example 50
415g terephthalic acid, 225mL ethylene glycol, 0.1g trimethyl phosphate (stabilizer) and 38.96g 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium were added to the reaction kettle, and esterification and polycondensation reactions were carried out by the process of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.84dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99%, and the antibacterial rate of escherichia coli is 99.1%.
Example 51
415g terephthalic acid, 220mL ethylene glycol, 0.1g triphenyl phosphate (stabilizer) and dissolved with 49.5g 1-butyl-3-methyl imidazole 2- (2-hydroxy ethoxy carbonyl) ethyl phenyl hypophosphite ethylene glycol solution into the reaction kettle, according to the embodiment of 21 process for esterification and polycondensation reaction, discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.62dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 98%, and the antibacterial rate of escherichia coli is 96%.
Example 52
415g of terephthalic acid, 230mL of ethylene glycol and 55.5g of 1-hexyl-3-methylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedures and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.64dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 96 percent, and the antibacterial rate of escherichia coli is 97 percent.
Example 53
415g of terephthalic acid, 260mL of ethylene glycol and 174g of 1-ethyl-3-methylimidazole 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the reaction vessel was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.72dL/g; the limiting oxygen index is 51.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 98 percent, and the antibacterial rate of escherichia coli is 98.5 percent.
Example 54
415g terephthalic acid, 225mL ethylene glycol and 32.7g di (1-ethyl-3-methyl imidazole) (4-methoxy carbonyl phenyl) phosphonate was added into the reaction kettle, esterification and polycondensation reactions were performed according to the process of example 21, and then the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.82dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 90%, and the antibacterial rate of escherichia coli is 92%.
Example 55
415g of terephthalic acid, 225mL of ethylene glycol, 0.1g of trimethyl phosphate (stabilizer), 21.9g of dipotassium (4-methoxycarbonylphenyl) phosphonate and 10.1g of bis (tributyl-n-octylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and esterification and polycondensation were carried out according to the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.79dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 95 percent, and the antibacterial rate of escherichia coli is 96 percent.
Example 56
415g terephthalic acid, 230mL ethylene glycol and 37.05g bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.72dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 90%, and the antibacterial rate of escherichia coli is 92%.
Example 57
415g of terephthalic acid, 220mL of ethylene glycol, 0.1g of trimethyl phosphate (stabilizer) and 1222.7g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.69dL/g; the limiting oxygen index is 57.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99.9 percent, and the antibacterial rate of escherichia coli is 99.9 percent.
Example 58
415g of terephthalic acid, 300mL of ethylene glycol, 0.1g of trimethyl phosphate (stabilizer) and 370.5g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.74dL/g; the limiting oxygen index is 43.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99%, and the antibacterial rate of escherichia coli is 99%.
Example 59
415g of terephthalic acid, 400mL of ethylene glycol, 0.1g of trimethyl phosphate (stabilizer) and 741g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, subjected to esterification and polycondensation reactions in accordance with the procedures and conditions of example 21, and then discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.74dL/g; the limiting oxygen index is 53.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99.99%, and the antibacterial rate of escherichia coli is 99.99%.
Example 60
415g of terephthalic acid, 230mL of ethylene glycol, 15.3g of dimethyl isophthalate-5-sodium sulfonate and 18.98g of 1, 4-dimethyl terephthalate-2, 5-diphosphonic acid dipotassium salt are added into a reaction kettle, esterification and polycondensation are carried out according to the process of the embodiment 21, and then discharging is carried out, thus obtaining the semi-dull copolyester.
The intrinsic viscosity [ eta ] of the copolymer is 0.78dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 30 percent, and the antibacterial rate of escherichia coli is 30 percent.
Example 61
415g of terephthalic acid, 230mL of ethylene glycol, 12.31g of titanium dioxide (delustering agent) and 17.5g of 3, 5-bis (methoxycarbonyl) benzenephosphonic acid dipotassium salt are added into a reaction kettle, esterification and polycondensation are carried out according to the process of the embodiment 21, and then discharging is carried out, so as to obtain the full-dull copolyester.
The intrinsic viscosity [ eta ] of the copolymer is 0.77dL/g; the limiting oxygen index is 25.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 40%, and the antibacterial rate of escherichia coli is 45%.
Example 62
415g of terephthalic acid, 240mL of ethylene glycol, 0.1g of trimethyl phosphate (stabilizer), 0.55g of titanium dioxide (delustering agent) and 59.3g of bis (tetra-n-butylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate are added into a reaction kettle, esterification and polycondensation are carried out according to the process of the embodiment 21, and then discharging is carried out, so as to obtain the light copolyester.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.88dL/g; the limiting oxygen index is 28.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 96 percent, and the antibacterial rate of escherichia coli is 96 percent.
Example 63
415g of terephthalic acid, 400mL of ethylene glycol, 262.5g of dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 427.5g of 1-decyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were added to the reaction vessel, and esterification and polycondensation reactions were carried out by the procedures and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.69dL/g; the limiting oxygen index is 53.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99.99%, and the antibacterial rate of escherichia coli is 99.99%.
Example 64
415g terephthalic acid, 590mL ethylene glycol, 700g dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 270.75g 1-decyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.61dL/g; the limiting oxygen index is 57.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99.99%, and the antibacterial rate of escherichia coli is 99.99%.
Example 65
200g of the copolymer obtained in example 24 is weighed and placed in a reaction kettle containing 240mL of ethylene glycol, and reacted for 3 hours at 180 ℃ under the protection of nitrogen, the copolymer is completely depolymerized, no solid residue exists, and a solution system is clear and transparent and has no discoloration. The excess ethylene glycol was removed and the product obtained was a mixture of 1, 4-ethylene terephthalate-2, 5-diphosphonic acid dipotassium salt, ethylene terephthalate, which mixture was used for repolymerization without further isolation and purification.
Example 66
200g of the copolymer obtained in example 42 is weighed and placed in a reaction kettle filled with 240mL of ethylene glycol, and the reaction is carried out for 2 hours at 180 ℃ under the protection of nitrogen, the copolymer is completely depolymerized, no solid residue exists, and the solution system is clear and transparent and has no color change. The excess ethylene glycol was removed and the product obtained was a mixture of 1, 4-ethylene terephthalate-2, 5-diphosphonic acid dipotassium salt, ethylene terephthalate, which mixture was used for repolymerization without further isolation and purification.
Example 67
415g of terephthalic acid, 230mL of propylene glycol and 57.25g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.71dL/g; the limiting oxygen index is 24.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 71 percent, and the antibacterial rate of escherichia coli is 75 percent.
Example 68
415g of terephthalic acid, 240mL of propylene glycol, 26.25g of dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 57.25g of 1-ethyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation were carried out by the procedure and conditions of example 21, followed by discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.80dL/g; the limiting oxygen index is 26.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 74%, and the antibacterial rate of escherichia coli is 78%.
Example 69
415g of terephthalic acid, 24wmL of 1, 4-butanediol and 61.75g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate were charged into a reaction vessel, and after esterification and polycondensation reaction were carried out by the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.89dL/g; the limiting oxygen index is 25.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 78%, and the antibacterial rate of escherichia coli is 81%.
Example 70
415g of terephthalic acid, 24wmL 1, 4-butanediol and 60.9g of potassium 2, 8-bis (methoxy) carbonyl xanthenophosphinate were put into a reaction vessel, and esterification and polycondensation were carried out under the same conditions as in example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.84dL/g; the limiting oxygen index is 24.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 45%, and the antibacterial rate of escherichia coli is 40%.
Example 71
415g of terephthalic acid, 250mL1, 4-butanediol, 9.25g of sodium 2, 8-bis (methoxy) carbonyl ] anthracenexanthene hypophosphite and 68.75g of bis (1-butyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out in accordance with the procedures and conditions of example 21, they were discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.89dL/g; the limiting oxygen index is 25.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 80%, and the antibacterial rate of escherichia coli is 85%.
Example 72
540g of 2, 6-naphthalenedicarboxylic acid, 260mL of ethylene glycol and 96.05g of bis (1-butyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, subjected to esterification and polycondensation by the procedure of example 21, and discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.86dL/g; the limiting oxygen index is 27.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 90%, and the antibacterial rate of escherichia coli is 87%.
Example 73
540g of 2, 6-naphthalenedicarboxylic acid, 270mL1, 4-butanediol, 39.75g of disodium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 37.05g of bis (1-hexyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out under the same conditions as in example 21, followed by discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.81dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 92%, and the antibacterial rate of escherichia coli is 88%.
Example 74
415g of terephthalic acid, 395g of 1, 4-cyclohexanedimethanol and 86.5g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged in a reaction vessel, and esterification and polycondensation were carried out by the procedure of example 21.
The intrinsic viscosity [ eta ] of the copolymer is 0.64dL/g; the limiting oxygen index is 25.5.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 90%, and the antibacterial rate of escherichia coli is 87%.
Example 75
468g of 2, 5-furandicarboxylic acid, 270mL of ethylene glycol and 86.45g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were added to a reaction vessel, and the pressure was increased to 0.1MPa under nitrogen protection; reacting for 2-5 hours at 160-210 ℃, controlling the pressure in the kettle to be 0.3-0.4 MPa, vacuumizing after the esterification is completed, performing low-vacuum polycondensation for 1-2 hours at 220-240 ℃, then heating to 250 ℃, performing high-vacuum polycondensation for 1-8 hours (the pressure is less than 80 Pa), and discharging.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.87dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 76%, and the antibacterial rate of escherichia coli is 79%.
Example 76
Adding 552.3g of furan-2, 5-dicarboxylic acid dimethyl ester, 520mL of ethylene glycol and 52.5g of 3, 5-bis (methoxycarbonyl) benzenephosphonic acid dipotassium into a reaction kettle, reacting for 2-5 hours at 160-210 ℃ under the protection of nitrogen, vacuumizing after ester exchange is completed, carrying out low-vacuum polycondensation for 1-2 hours at 220-240 ℃, then heating to 250 ℃, and carrying out high-vacuum (pressure is less than 80 Pa) polycondensation for 1-8 hours, and then discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.77dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 45%, and the antibacterial rate of escherichia coli is 40%.
Example 77
552.3g of dimethyl furan-2, 5-dicarboxylate, 520mL of ethylene glycol, 0.05g of trimethyl phosphate (stabilizer) and 76g of 1-hexyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, subjected to esterification and polycondensation reactions under the same conditions as in example 76, and discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.73dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99%, and the antibacterial rate of escherichia coli is 99%.
Example 78
552.3g of dimethyl furan-2, 5-dicarboxylate, 540mL of ethylene glycol and 135g of bis (tributyl-n-octylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out by the procedure of example 76.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.87dL/g; the limiting oxygen index is 31.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99.9 percent, and the antibacterial rate of escherichia coli is 99.9 percent.
Example 79
552.3g of dimethyl furan-2, 5-dicarboxylate, 600mL1, 4-butanediol and 135g of bis (tributyl-n-octylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate were initially charged in a reaction vessel, subjected to esterification and polycondensation under the same conditions and procedures as in example 76, and discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.93dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 99.9 percent, and the antibacterial rate of escherichia coli is 99.9 percent.
Example 80
241g of adipic acid, 224g of terephthalic acid, 600mL1, 4-butanediol, 0.05g of trimethyl phosphate (stabilizer) and 44.5g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate are added into a reaction kettle, reacted for 2 to 5 hours at 140 to 220 ℃ under the protection of nitrogen, vacuumized after complete esterification, polycondensed for 1 to 2 hours at 220 to 250 ℃ under low vacuum, heated to 255 ℃ and polycondensed for 1.5 to 3 hours under high vacuum (the pressure is less than 50 Pa), and discharged.
The intrinsic viscosity [ eta ] of the copolymer is 1.37dL/g; the limiting oxygen index is 25.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 85%, and the antibacterial rate of escherichia coli is 87%.
Example 81
241g of adipic acid, 224g of terephthalic acid, 600mL1, 4-butanediol, 31.5g of dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 15.5g of 1-hexyl-3-methylimidazol [2, 8-di (methoxy) carbonyl ] anthracenexanthene xanthene phosphinate were charged into a reaction vessel, and esterification and polycondensation reactions were carried out under the same conditions and in the same steps as in example 80 to discharge the product.
The intrinsic viscosity [ eta ] of the copolymer is 1.31dL/g; the limiting oxygen index is 24%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 89%, and the antibacterial rate of escherichia coli is 90%.
Example 82
Adding 472g of succinic acid, 430mL of 1, 4-butanediol, 0.05g of trimethyl phosphate (stabilizer) and 47.2g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate into a reaction kettle, reacting for 2-5 hours at 120-180 ℃ under the protection of nitrogen, vacuumizing after esterification is completed, carrying out low-vacuum polycondensation for 1-2 hours at 200-220 ℃, then heating to 230 ℃, carrying out high-vacuum polycondensation for 1.5-8 hours (the pressure is less than 50 Pa), and discharging.
The intrinsic viscosity [. Eta. ] of the copolymer is 1.97dL/g; the limiting oxygen index is 24%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 86%, and the antibacterial rate of escherichia coli is 88%.
Example 83
472g of succinic acid, 430mL of 1, 4-butanediol, 0.05g of trimethyl phosphate (stabilizer), 42g of dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 19.76g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction kettle, and esterification and polycondensation were carried out under the same conditions as in example 82 to discharge the product.
The intrinsic viscosity [ eta ] of the copolymer is 2.10dL/g; the limiting oxygen index is 24.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 75%, and the antibacterial rate of escherichia coli is 78%.
Example 84
415g of isophthalic acid, 230mL of ethylene glycol and 26.25g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were added to the reaction vessel, and after esterification and polycondensation reactions were carried out by the procedure of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.84dL/g; the limiting oxygen index is 24.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 76%, and the antibacterial rate of escherichia coli is 78%.
Example 85
382g terephthalic acid, 33g isophthalic acid, 230mL ethylene glycol, 34.25g bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were added to the reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.81dL/g; the limiting oxygen index is 25.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 81%, and the antibacterial rate of escherichia coli is 83%.
Example 86
415g terephthalic acid, 182g isosorbide, 180mL ethylene glycol, 37.05g bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were added to a reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.78dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 79%, and the antibacterial rate of escherichia coli is 86%.
Example 87
354g of succinic acid, 177g of isosorbide, 140ml of 1, 4-butanediol and 37.05g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate are added into a reaction kettle, and esterification and polycondensation are carried out according to the steps and conditions of example 82, and then discharging is carried out.
The intrinsic viscosity [ eta ] of the copolymer is 1.08dL/g; the limiting oxygen index is 23.5%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 79%, and the antibacterial rate of escherichia coli is 86%.
Example 88
485g of dimethyl terephthalate, 300mL1, 4-butanediol, 520g of polytetramethylene ether glycol (polytetrahydrofuran glycol, PTMEG, mn = 1000), 0.2g of Irganox1098 (antioxidant) and 68.05g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate are added into a reaction kettle, reacted for 2 to 5 hours at 160 to 220 ℃ under the protection of nitrogen, vacuumized after complete ester exchange, subjected to low vacuum polycondensation for 0.5 to 2 hours at 220 to 240 ℃, then heated to 250 ℃, subjected to high vacuum (pressure less than 50 Pa) polycondensation for 1.5 to 4 hours, and discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 1.28dL/g; the limiting oxygen index is 24.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 76%, and the antibacterial rate of escherichia coli is 78%.
Example 89
485g of dimethyl terephthalate, 300mL1, 4-butanediol, 150g of polytetramethylene ether glycol (polytetrahydrofuran, PTMEG, mn = 1000), 0.2g of Irganox1098 (antioxidant), 49.55g of potassium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthenophosphinate and 12.3g of bis (1-hexyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate were added to the reaction vessel. After the transesterification and polycondensation reaction according to the procedure of example 82, the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 1.18dL/g; the limiting oxygen index is 24.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 97%, and the antibacterial rate of escherichia coli is 98%.
Example 90
600g of caprolactam, 47g of adipic acid and 16mL of water are added into a reaction kettle together, the ring opening polymerization of caprolactam is carried out at 240 ℃ under the protection of nitrogen, the reaction is carried out for 4 hours, and then the carboxyl-terminated polyamide prepolymer is obtained and dried. Weighing 300g of the obtained polyamide prepolymer, 140g of polyethylene glycol (Mn = 1000), 0.2g of Irganox1098 (antioxidant) and 20.55g of bis (1-hexyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate, adding into a reaction kettle, reacting at 240-260 ℃ for 2-3 hours under the protection of nitrogen, then vacuumizing, carrying out low-vacuum polycondensation at 260 ℃ for 0.5 hour, then heating to 280 ℃, carrying out polycondensation at high vacuum (the pressure is less than 100 Pa) for 1.5-4 hours, and then discharging.
The intrinsic viscosity [ eta ] of the copolymer is 1.09dL/g; the limiting oxygen index is 28.0%; the antibacterial rate of staphylococcus aureus is 81% and the antibacterial rate of escherichia coli is 86% when the vertical combustion grade is V-2 grade.
Example 91
A polyamide prepolymer was prepared by following the procedure and conditions of example 90. Then, 300g of the polyamide prepolymer, 140g of polytetramethylene ether glycol (Mn = 1000), 0.2g of Irganox1098 (antioxidant), 18.55g of potassium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene phosphinate and 16.3g of bis (1-hexyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were weighed out and added into a reaction kettle. After the transesterification and polycondensation were carried out in the same manner and under the same conditions as in example 90, the reaction mixture was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 1.14dL/g; the limiting oxygen index is 27.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 96 percent, and the antibacterial rate of escherichia coli is 97 percent.
Example 92
600g of laurolactam, 36g of adipic acid and 16mL of water are added into a reaction kettle together, under the protection of nitrogen, the ring opening polymerization of caprolactam is carried out at 240 ℃ for 4 hours, and then the carboxyl-terminated polyamide prepolymer is obtained and dried. 300g of the obtained polyamide prepolymer, 140g of polypropylene glycol (Mn = 1000), 0.2g of Irganox1098 (antioxidant) and 20.55g of bis (1-butyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were weighed out and charged into a reaction vessel. After the transesterification and polycondensation were carried out in the same manner and under the same conditions as in example 90, the reaction mixture was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 1.03dL/g; the limiting oxygen index is 26.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 87%, and the antibacterial rate of escherichia coli is 84%.
Example 93
300g of PA66 polyamide prepolymer (Mn = 1000), 140g of polypropylene glycol (Mn = 1000), 0.2g of Irganox1098 (antioxidant), 20.55g of bis (1-butyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate were charged to the reactor. After the transesterification and polycondensation were carried out in the same manner and under the same conditions as in example 90, the reaction mixture was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 1.23dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 86%, and the antibacterial rate of escherichia coli is 85%.
Example 94
457g of bisphenol A, 450g of diphenyl carbonate and 29.6g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate are charged to the reaction vessel. Under the protection of nitrogen, carrying out ester exchange reaction for 0.5-3 hours at 160-180 ℃; then starting to vacuumize, carrying out low-vacuum polycondensation for 0.5-2 hours at the temperature of 210-260 ℃, then heating, carrying out high-vacuum polycondensation reaction for 1-3 hours at the temperature of 270-300 ℃ under the pressure of less than 50Pa, and discharging.
The intrinsic viscosity [ eta ] of the copolymer is 0.62dL/g; the limiting oxygen index is 37.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 79%, and the antibacterial rate of escherichia coli is 85%.
Example 95
457g of bisphenol A, 450g of diphenyl carbonate and 7.4g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate are charged to the reaction vessel. The transesterification and polycondensation reactions were carried out and the product was discharged by the procedure of example 94.
The intrinsic viscosity [ eta ] of the copolymer is 0.58dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-1 grade; the antibacterial rate of staphylococcus aureus is 74 percent, and the antibacterial rate of escherichia coli is 81 percent.
Example 96
457g of bisphenol A, 450g of diphenyl carbonate and 11.1g of sodium 2, 8-bis (5-methoxycarbonyl-1H-benzimidazol-2-yl) anthracenexanthene xanthene hypophosphite were charged into the reaction vessel. The transesterification and polycondensation reactions were carried out and the product was discharged by the procedure of example 94.
The intrinsic viscosity [ eta ] of the copolymer is 0.58dL/g; the limiting oxygen index is 33.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 45%, and the antibacterial rate of escherichia coli is 55%.
Example 97
457g of bisphenol A, 450g of diphenyl carbonate, 3.5g of dipotassium 3, 5-bis (methoxycarbonyl) phenylphosphonate and 4.9g of bis (1-decyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into the reaction vessel. The transesterification and polycondensation were carried out under the same conditions and procedures as in example 94, and the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.55dL/g; the limiting oxygen index is 31.0%; the vertical combustion grade is V-1 grade; the antibacterial rate of staphylococcus aureus is 98%, and the antibacterial rate of escherichia coli is 99%.
Example 98
445g of bisphenol A, 450g of diphenyl carbonate and 1.6g of bis (tetra-n-butylphosphino) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into the reaction vessel. The transesterification and polycondensation were carried out under the same conditions and procedures as in example 94, and the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.59dL/g; the limiting oxygen index is 30.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 82%, and the antibacterial rate of escherichia coli is 90%.
Example 99
401g of bisphenol F, 450g of diphenyl carbonate and 7.4g of bis (1-ethyl-3-methylimidazole) 3, 5-bis (methoxycarbonyl) benzenephosphonate were charged to the reaction vessel. The transesterification and polycondensation reactions were carried out by the procedure of example 94 and the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.63dL/g; the limiting oxygen index is 29.0%; the vertical combustion grade is V-2 grade; the antibacterial rate of staphylococcus aureus is 72 percent, and the antibacterial rate of escherichia coli is 80 percent.
Example 100
501g of bisphenol S, 450g of diphenyl carbonate and 15.8g of bis (tetra-n-butylphosphine) 3, 5-bis (methoxycarbonyl) phenylphosphonate were charged into a reaction vessel. The transesterification and polycondensation were carried out by the procedure and conditions of example 95, and the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.60dL/g; the limiting oxygen index is 32.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 92%, and the antibacterial rate of escherichia coli is 90%.
Example 101
438g of isosorbide, 675g of diphenyl carbonate and 26.1g of bis (tributyl-n-octylphosphine) 3, 5-bis (methoxycarbonyl) benzenephosphonate were added to the reaction vessel. The transesterification and polycondensation reactions were carried out by the procedure of example 95 and the product was discharged.
The intrinsic viscosity [ eta ] of the copolymer is 0.64dL/g; the limiting oxygen index is 33.0%; the vertical combustion grade is V-0 grade; the antibacterial rate of staphylococcus aureus is 99%, and the antibacterial rate of escherichia coli is 99%.
Comparative example 1
415g terephthalic acid, 250mL ethylene glycol and 0.2g ethylene glycol antimony into the reaction kettle, according to the embodiment of the steps and conditions for esterification and polycondensation reaction, discharge.
The intrinsic viscosity [ eta ] of the copolymer is 0.65dL/g; the limiting oxygen index is 21.0%; the vertical combustion grade is stepless; the antibacterial rate of staphylococcus aureus is 20%, and the antibacterial rate of escherichia coli is 19%.
Comparative example 2
415g of terephthalic acid, 250mL of ethylene glycol and 0.1g of tetrabutyl titanate were charged into a reaction vessel, and after esterification and polycondensation reactions were carried out according to the procedure and conditions of example 21, the product was discharged.
The intrinsic viscosity [. Eta. ] of the copolymer is 0.72dL/g; the limiting oxygen index is 21.0%; the vertical combustion grade is stepless; the antibacterial rate of staphylococcus aureus is 20%, and the antibacterial rate of escherichia coli is 19%.

Claims (10)

1. An autocatalytic functional reaction monomer, which is characterized in that the structural general formula of the autocatalytic functional reaction monomer is as follows:
Figure FDA0003016906710000011
Figure FDA0003016906710000021
in the formula, Z 1 、Z 2 Is carboxyl, ester group, amino, hydroxyl, acyloxy or carboxyl with polycondensation polymerization activity
Figure FDA0003016906710000022
a is an integer of 1 to 12, Z 1 、Z 2 The same or different; z is a linear or branched member 3 、Z 4 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, Z 3 、Z 4 The same or different; z 5 、Z 6 Is H atom, C1-C12 alkyl, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl, substituted aryl, ester group, carboxyl, hydroxyl, amino, acyloxy or
Figure FDA0003016906710000023
a is an integer of 1 to 12; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl, nitrogen ethyl or amide group; when the reactive monomer structure is A-S, M n+ Is an organic cation; when the reactive monomer structure is T-W, M n+ Is an organic cation or an alkali metal ion; organic cation M n+ Has the following B 1 -B 8 Any one of cations of the general structural formula, n is an integer from 1 to 2:
Figure FDA0003016906710000024
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z is a linear or branched member 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
2. The autocatalytic functional reactive monomer of claim 1, wherein the ester group in the structural formula of the autocatalytic functional reactive monomer is any one of methyl ester group, ethyl ester group, propyl ester group, butyl ester group, pentyl ester group or hexyl ester group after esterification of monohydric alcohol, or phenyl ester group after esterification of monohydric phenol, or ethylene glycol ester group, propylene glycol ester group, butylene glycol group, neopentyl glycol ester group, diethylene glycol ester group, glycerol ester group or pentaerythritol ester group after esterification of polyhydric alcohol.
3. A functional copolymer of autocatalytic polymerization and autocatalytic depolymerization is characterized in that the copolymer is a copolymer of wholly aromatic polyester, semi-aromatic polyester, aliphatic-aromatic polyester, bio-based polyester, polycarbonate, polyester elastomer, nylon elastomer or a modified polymer of the above polymers and an autocatalytic functional reaction monomer, and the autocatalytic functional reaction monomer is completely connected into a molecular chain of the copolymer and consists of the following structural units I, II and III or structural units I, II and IV:
Figure FDA0003016906710000031
in the formula, R 1 Represents an arylene, C2-C12 alkylene or alkylidene group, a 2, 5-furyl group, a carboxylic acid or an ester group-terminated polyamide segment;
Figure FDA0003016906710000032
in the formula, R 2 Represents an arylene group, a C2-C12 alkylene group or an alkylidene group, a 4,4' -isopropylidenediphenyl group, a 4,4' -diphenylmethylene group, a 4,4' -diphenylsulfone group, an isosorbide group, a polyether polyol group or a polyester polyol group;
Figure FDA0003016906710000033
Figure FDA0003016906710000041
in the formula, R 3 、R 4 Is a carbonyl group, a secondary amino group, an O atom or
Figure FDA0003016906710000042
a is an integer of 1 to 12, R 3 、R 4 The same or different; r 5 、R 6 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, R 5 、R 6 The same or different; r is 7 Is H atom, C1-C12 alkyl, hydroxyl, C1-C12 alkoxy, secondary amino, tertiary amino, aryl or substituted aryl; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl group, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl group, nitrogen ethyl group or amide group; cation M n+ Is an alkali metal ion or has the following B 1 -B 8 Any one of the organic cations of the general structural formula:
Figure FDA0003016906710000043
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z is a linear or branched member 11 Is C2-C16 alkylene or arylene; z is a linear or branched member 12 Is C1-C16 alkyl, aryl or substituted aryl; z 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl,
Figure FDA0003016906710000051
in the formula, R 3 Is a carbonyl group, a secondary amino group, an O atom or
Figure FDA0003016906710000052
a is an integer of 1 to 12; r is 5 、R 6 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, R 5 、R 6 The same or different; r 7 Is H atom, C1-C12 alkyl, hydroxyl, C1-C12 alkoxy, secondary amino, tertiary amino, aryl or substituted aryl; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl, nitrogen ethyl or amide group; cation M n+ Is an alkali metal ion or has the following B 1 -B 8 Any one of the organic cations of the general structural formula:
Figure FDA0003016906710000061
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z is a linear or branched member 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z is a linear or branched member 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl,
wherein the number of the structural units of [ III ] is 0.05-99% of the number of the structural units of [ I ]; the number of the structural units of the copolymer is 0.05-40 percent of that of the structural units of the copolymer, the intrinsic viscosity [ eta ] of the copolymer is 0.16-2.10 dL/g, the limited oxygen index is 22.5-57.0 percent, the vertical combustion grade is V-2-V-0 grade, the antibacterial rate of staphylococcus aureus is 30-99.99 percent, and the antibacterial rate of escherichia coli is 30-99.99 percent.
4. The functional copolymer of self-catalyzed polymerization and self-catalyzed depolymerization as claimed in claim 3, wherein the copolymer can be heated to 120-280 ℃ in alcohol reaction medium under normal pressure or heated to 120-280 ℃ under pressure to carry out self-depolymerization chemical reaction, and the target monomer is recovered and obtained, and can be directly used for re-polymerization of the copolymer without separation and purification.
5. The functional copolymer of autocatalytic polymerization and autocatalytic depolymerization according to claim 3, characterized in that the number of structural units of said copolymer [ III ] is 0.1 to 60% of the number of structural units of [ I ]; the number of the structural unit of [ IV ] is 0.1-30% of the number of the structural unit of [ I ], and the intrinsic viscosity [ eta ] of the copolymer is 0.20-2.10 dL/g; the limiting oxygen index is 23.5-53.0%, the vertical combustion grade is V-2-V-0 grade, the antibacterial rate of staphylococcus aureus is 40-99.99%, and the antibacterial rate of escherichia coli is 40-99.99%.
6. A method for preparing the functional copolymer of self-catalytic polymerization and self-catalytic depolymerization as claimed in claim 3, which is prepared by mixing dicarboxylic acid or dicarboxylic acid ester with polymer monomer of dihydric alcohol or phenol at a conventional ratio, performing esterification or ester exchange by conventional direct esterification or ester exchange method, and performing melt polycondensation reaction or further performing solid phase polycondensation, and is characterized in that before the esterification or ester exchange reaction or before the polycondensation after the esterification reaction, a double-polymerization functional group self-catalytic functional reaction monomer or a single-polymerization functional group self-catalytic functional reaction monomer with 0.05-99% by mole of the dicarboxylic acid or the dicarboxylic acid ester in the polymer monomer is added into the reaction system.
7. The method for preparing the functional copolymer of autocatalytic polymerization and autocatalytic depolymerization according to claim 6, wherein the mole number of the diacid or diacid ester compound added to the polymer monomer is 0.1-60% of the double-polymerized functional group autocatalytic functional reaction monomer or 0.1-30% of the single-polymerized functional group autocatalytic functional reaction monomer.
8. The method for preparing the functional copolymer by autocatalytic polymerization and autocatalytic depolymerization according to claim 6 or 7, wherein the autocatalytic functional reaction monomer used in the method is at least one of the following structural formulas:
Figure FDA0003016906710000071
Figure FDA0003016906710000081
in the formula, Z 1 、Z 2 Is carboxyl, ester, amino, hydroxyl, acyloxy or
Figure FDA0003016906710000082
a is an integer of 1 to 12, Z 1 、Z 2 The same or different; z 3 、Z 4 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl, Z 3 、Z 4 The same or different; z 5 、Z 6 Is H atom, C1-C12 alkyl, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl, substituted aryl, ester group, carboxyl, hydroxyl, amino, acyloxy or
Figure FDA0003016906710000083
a is an integer of 1 to 12; x is O atom, S atom, secondary amino group, nitrogen methyl or nitrogen ethyl group, W is O atom or S atom, Y is O atom, S atom, secondary amino group, nitrogen methyl group, nitrogen ethyl group or amide group; cation M n+ Is an alkali metal ion or has the following B 1 -B 8 Any one of organic cations of the general structural formula, n isAn integer of 1 to 3:
Figure FDA0003016906710000084
in the formula, Z 7 、Z 8 、Z 9 、Z 10 Is C2-C16 alkyl, aryl or substituted aryl, which can be the same or different; z 11 Is C2-C16 alkylene or arylene; z 12 Is C1-C16 alkyl, aryl or substituted aryl; z is a linear or branched member 13 Is H atom, C1-C12 alkyl, cyano, C1-C12 alkoxy, secondary amino, tertiary amino, amido, aryl or substituted aryl; x is O atom, S atom, C1-C16 nitrogen alkyl or nitrogen aryl.
9. The method for preparing the functional copolymer of autocatalytic polymerization and autocatalytic depolymerization according to claim 8, wherein the ester group in the autocatalytic functional reaction monomer structure used in the method is a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group or a hexyl ester group after esterification of monohydric alcohol, or a phenyl ester group after esterification of monohydric phenol, or any one of an ethylene glycol ester group, a propylene glycol ester group, a butylene glycol group, a neopentyl glycol ester group, a diethylene glycol ester group, a glycerol ester group or a pentaerythritol ester group after esterification of polyhydric alcohol.
10. The use of the functional copolymer of claim 3 in the fields of fibers and products thereof, non-woven fabrics, engineering plastics, film materials, container materials, packaging materials, biomedical materials, shape memory materials or 3D printing materials, or as a functional additive for modifying high molecular materials.
CN202110391482.8A 2021-04-13 2021-04-13 Self-catalytic functional reaction monomer, self-catalytic polymerization and self-catalytic depolymerization functional copolymer, and preparation method and application thereof Pending CN115197270A (en)

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