CN111748100A - Polymer, preparation method and application - Google Patents
Polymer, preparation method and application Download PDFInfo
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- CN111748100A CN111748100A CN202010690328.6A CN202010690328A CN111748100A CN 111748100 A CN111748100 A CN 111748100A CN 202010690328 A CN202010690328 A CN 202010690328A CN 111748100 A CN111748100 A CN 111748100A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
- C08J2485/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polymer, a preparation method and application thereof, and provides a polymer with a structural formula shown as the following formula (I), wherein R is1Is composed of
Or
Physically mixing the polymer with the structural formula of the formula (I) and a base material to obtain a flame-retardant molded product, and improving the compatibility of the flame retardant and the polymer and the mutual coordinationAnd the flame retardant property of the polymer is improved by the same action.
Description
Technical Field
The invention relates to a polymer, a preparation method and application thereof.
Background
Since the advent of the polymer material, its flammability has become an inevitable drawback in its use, and it releases a large amount of smoke and toxic gases during combustion, causing secondary damage. However, due to the excellent properties of polymer materials, polymer materials have to be used in large quantities, so that how to reduce the flammability of polymer materials has become a major issue.
The flame retardant property of the high polymer material is improved, and the experiment is mainly carried out by adding a flame retardant into a composite material system and synthesizing a novel material with a flame retardant group, namely, inorganic matters and organic matters containing chemical elements with a flame retardant effect are introduced into the composite material system, wherein the elements mainly comprise nitrogen, phosphorus, chlorine, bromine and the like.
At present, the halogen-containing flame retardant is the organic flame retardant with the largest yield in the world, especially the bromine-containing flame retardant product, and is most widely used in the field of electronic and electric appliances. However, the halogen flame retardant can generate a large amount of corrosive and toxic gases in the using and recycling processes, which causes pollution to the environment and also can cause serious influence on the performance of precision instrument elements, and the development of novel low-smoke low-toxicity halogen-free environment-friendly flame retardant and flame retardant polymer material to replace the halogen flame retardant is urgently needed.
Polymeric flame retardants are receiving increasing attention due to their safety and environmental protection. The polymer flame retardant is also a high molecular polymer, so that the compatibility of the polymer flame retardant with materials is good, and the original physical and mechanical properties of the high polymer can be maintained. Secondly, the structure of the long-chain macromolecules of the flame retardant enables the flame retardant not to be easy to migrate. Because of these advantages, macromolecular flame retardants are the focus of current research.
Therefore, the invention provides a polymer, a preparation method and application thereof, and the provided polymer can be used as a good polymeric flame retardant.
Disclosure of Invention
The invention provides a polymer, a preparation method and application thereof, wherein the polymer has a structural formula shown as the following formula (I):
wherein R is1Is composed of
The aforementioned n is the polymerization degree of the polymer and is 1-900, preferably 150-250.
The term "degree of polymerization" refers to the ratio of weight average molecular weight to unit average molecular weight.
The term "weight average molecular weight" is a statistical average molecular weight by mass, a molecular weight obtained on average per unit weight, and is a conversion value with respect to standard polystyrene measured by GPC (gel permeation chromatography).
R mentioned above1Is composed of
When n is 205 to 215.
R mentioned above1Is composed of
When n is 200 to 210.
R mentioned above1Is composed of
When n is 175 to 185.
The number average molecular weight of the polymer is 240-222000g/mol, preferably 36000-60000 g/mol; and/or
The polymer has a polymer dispersibility index of 1.0 to 1.1, preferably 1.00 to 1.05.
Wherein the number average molecular weight, degree of polymerization, and Polymer Dispersibility Index (PDI) are measured by Gel Permeation Chromatography (GPC) and the mobile phase measured by gel permeation chromatography is water at a rate of 0.8 ml/min. The gel permeation chromatography method uses polystyrene as a standard sample to obtain the number average molecular weight, the weight average molecular weight and the like. The PDI is the ratio of the weight average molecular weight to the number average molecular weight.
The term "number average molecular weight", which is a statistical average molecular weight by number of molecules, is a conversion value to standard polystyrene measured using GPC (gel permeation chromatography).
R mentioned above1Is composed of
When the number average molecular weight of the polymer is 49700-52200 g/mol, the polymer dispersion phase index of the polymer is 1.01-1.02;
r mentioned above1Is composed of
When the number average molecular weight of the polymer is 48500-51000 g/mol, the polymer dispersion phase index of the polymer is 1.02-1.03;
r mentioned above1Is composed of
When the number average molecular weight of the polymer is 43000-45500 g/mol, the polymer dispersion phase index of the polymer is 1.02-1.03.
The polymer has the following properties:
polymer Td 5% is 180-250 ℃; and/or
The polymer Td 10% was 200-300 ℃.
Wherein the polymer Td 5% and Td 10% are measured by a method according to the thermogravimetric analyzer, the measured heating rate being 10 ℃/min.
The invention also provides a preparation method of the polymer, which is characterized by comprising the following steps: with methyl phosphorus dichloride and H2N-R1-NH2As raw materials, reacting in the presence of a solvent to obtain a polymer;
wherein R is1As defined in claim 1; the solvent is an inert solvent.
The invention also provides a flame retardant, which comprises the polymer.
The invention also provides a flame-retardant molded product which is obtained by physically mixing the flame retardant and the base material.
The term "shaped article" includes tapes, films, dots, webs, strips, beads and foams.
The term "molding" should be taken in its broadest sense and encompasses any type of molding, e.g., blow molding, rotational molding, extrusion molding, press molding, transfer molding, and the like.
The base material is preferably polycarbonate or nylon.
The physical mixing is melt mixing or dissolving mixing in a solvent. The melt mixing method is to melt the flame retardant and the matrix material together under heating to achieve sufficient mixing effect, and then process the mixture in a specific environment (for example, an extruder-cold water tank) to obtain a corresponding molded product. The mode of dissolving and mixing in the solvent refers to that the flame retardant and the base material are dissolved in the solvent in the presence of the solvent, the mixture is stirred to achieve the effect of full mixing, and then the corresponding product is obtained through the treatment of drying and removing the solvent.
The preparation method of the flame-retardant molded product comprises the following steps:
adding a matrix material and a solvent into a reaction container at a certain temperature, and fully dissolving to obtain a mixed solution; adding the flame retardant into the mixed solution, and continuously stirring; drying; and (5) molding.
The method of the aforementioned molding differs depending on the final molded article.
The polymer provided by the invention can be used as a good polymeric flame retardant, and the flame retardant property of the polymer is improved by improving the compatibility of the flame retardant and the polymer and the mutual synergistic effect.
Detailed Description
EXAMPLE 1 preparation of the Polymer FR-MDP-DDM
The four-necked flask was purged with nitrogen three times, the inside of the flask was kept dry, and a thermometer and a constant pressure dropping funnel were provided. Methylphosphorus dichloride (4g, 0.034mol) and dichloroethane 40ml were charged to a bottle, and 4, 4-diaminodiphenylmethane (DDM, 6.732g, 0.034mol) was dissolved in 20ml of dichloroethane and charged to a constant pressure dropping funnel. Under the protection of nitrogen, the p-phenylenediamine solution is slowly dropped. After the dropwise addition, the temperature is raised to the reflux temperature and the reaction is continued for 4 hours.
After the reaction is finished, the temperature is reduced to room temperature under the protection of nitrogen atmosphere. The mixture was then suction filtered under reduced pressure and the filter cake was washed with dichloroethane. Drying overnight at 80 ℃ under vacuum gave 7.2g (labeled FR-MDP-DDM) of a white solid in 75.8% yield.
The infrared test analysis result shows that the 1062cm-1 part is an absorption peak of P-N-C, the 3200cm-1 part is a stretching vibration peak of N-H, and the P-N group and the N-H vibration are determined in the product, thereby proving that the target product is obtained.
EXAMPLE 2 preparation of the Polymer FR-MDP-DDE
The four-necked flask was purged with nitrogen three times, the inside of the flask was kept dry, and a thermometer and a constant pressure dropping funnel were provided. Methylphosphorus dichloride (4g, 0.034mol) and dichloroethane 40ml were charged to a bottle, and 4, 4' -diaminodiphenyl ether (DDE, 6.8g, 0.034mol) was dissolved in 20ml of dichloroethane, which was charged to a constant pressure dropping funnel. Under the protection of nitrogen, the p-phenylenediamine solution is slowly dropped. After the dropwise addition, the temperature is raised to the reflux temperature and the reaction is continued for 4 hours.
After the reaction is finished, the temperature is reduced to room temperature under the protection of nitrogen atmosphere. The mixture was then suction filtered under reduced pressure and the filter cake was washed with dichloroethane. Drying overnight at 80 ℃ under vacuum gave 7.0g (labeled FR-MDP-DDE) of a white solid in 73.2% yield.
The infrared test analysis result shows that the 1062cm-1 part is an absorption peak of P-N-C, the 3200cm-1 part is a stretching vibration peak of N-H, and the P-N group and the N-H vibration are determined in the product, thereby proving that the target product is obtained.
EXAMPLE 3 preparation of the Polymer FR-MDP-ODA
The four-necked flask was purged with nitrogen three times, the inside of the flask was kept dry, and a thermometer and a constant pressure dropping funnel were provided. Methylphosphorus dichloride (4g, 0.034mol) and dichloroethane 40ml were charged to a bottle, and 3, 4' -diaminodiphenyl ether (ODA, 6.8g, 0.034mol) was dissolved in 20ml of dichloroethane, and charged to a constant pressure dropping funnel. Under the protection of nitrogen, the p-phenylenediamine solution is slowly dropped. After the dropwise addition, the temperature is raised to the reflux temperature and the reaction is continued for 4 hours.
After the reaction is finished, the temperature is reduced to room temperature under the protection of nitrogen atmosphere. The mixture was then suction filtered under reduced pressure and the filter cake was washed with dichloroethane. Vacuum drying at 80 deg.C overnight gave 7.05g (labeled FR-MDP-ODA) as a white solid in 73.7% yield
The infrared test analysis result shows that the 1062cm-1 part is an absorption peak of P-N-C, the 3200cm-1 part is a stretching vibration peak of N-H, and the P-N group and the N-H vibration are determined in the product, thereby proving that the target product is obtained.
The polymer products obtained in examples 1-3 were characterized by the following properties:
(1) gel permeation chromatography, GPC: the molecular weight and molecular weight distribution of the product were determined
(2) Thermogravimetric analyzer: the product was tested for thermal stability
Application examples 1 to 3
At normal temperature, the three-necked flask was fixed in a water bath and the temperature of the water bath was adjusted to 50 ℃. At this temperature, tetrahydrofuran and Polycarbonate (PC) were added to the flask in this order, and stirred well. After the PC is completely dissolved in the tetrahydrofuran, 1g of the polymer flame retardant (the product obtained in example 1-3) is added into the solution, the mixture is continuously stirred for 1h, and the mixture is placed in a culture dish and then placed in a vacuum oven to be dried into a film, wherein the drying temperature is 80 ℃.
Application examples 1 'to 3'
At normal temperature, the three-necked flask was fixed in a water bath and the temperature of the water bath was adjusted to 50 ℃. At this temperature, formic acid and nylon 66(PA) were added to the flask in this order, and stirred well. After PA was completely dissolved in formic acid, 1g of a polymeric flame retardant (product obtained in example 1-3) was added to the solution, the mixture was stirred for 1 hour, and the mixture was placed in a petri dish and then dried in a vacuum oven to form a film at a drying temperature of 80 ℃.
The film-formed articles obtained in application examples 1 to 3 and application examples 1 'to 3' were subjected to flame retardancy tests, and the results are shown in the following table.
The flame retardant property test method comprises the following steps: vertical burning test GB/T2408-.
| Base material | The kind and amount of solvent | Type and amount of polymeric flame retardant | Flame retardant rating | |
| Application example 1 | PC | Tetrahydrofuran, 50ml | FR-MDP-DDM，1g | V-2 |
| Application example 1' | PA | Formic acid, 50ml | FR-MDP-DDM，1g | V-2 |
| Application example 2 | PC | Tetrahydrofuran, 50ml | FR-MDP-DDE，1g | V-2 |
| Application example 2' | PA | Formic acid, 50ml | FR-MDP-DDE，1g | V-2 |
| Application example 3 | PC | Tetrahydrofuran, 50ml | FR-MDP-ODA，1g | V-0 |
| Application example 3' | PA | Formic acid, 50ml | FR-MDP-ODA，1g | V-0 |
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A polymer having the formula (I):
wherein R is1Is composed of
2. The polymer according to claim 1, wherein n is 1 to 900, preferably 150 and 250.
3. The polymer of claim 2, wherein R is1Is composed of
When n is 205 to 215;
the R is1Is composed of
When n is 200-210;
the R is1Is composed of
When n is 175 to 185.
4. The polymer according to claim 1 or 2, characterized in that the number average molecular weight of the polymer is 240-222000g/mol, preferably 36000-60000 g/mol; and/or
The polymer has a polymer dispersibility index of 1.0 to 1.1, preferably 1.00 to 1.05.
5. The polymer of claim 4, wherein R is1Is composed of
When the number average molecular weight of the polymer is 49700-52200 g/mol, the polymer dispersion phase index of the polymer is 1.01-1.02;
R1is composed of
When the number average molecular weight of the polymer is 48500-51000 g/mol, the polymer dispersion phase index of the polymer is 1.02-1.03;
R1is composed of
When the number average molecular weight of the polymer is 43000-45500 g/mol, the polymer dispersion phase index of the polymer is 1.02-1.03.
6. The polymer according to any one of claims 1 to 5, characterized in that it has the following properties:
polymer Td 5% is 180-250 ℃; and/or
The polymer Td 10% was 200-300 ℃.
7. A method for preparing a polymer, comprising the steps of: with methyl phosphorus dichloride and H2N-R1-NH2As raw materials, reacting in the presence of a solvent to obtain a polymer;
wherein R is1As defined in claim 1; the solvent is an inert solvent.
8. A flame retardant comprising the polymer of any one of claims 1 to 7.
9. A flame-retardant shaped article, which is obtained by physically mixing the flame retardant of claim 8 with a base material.
10. A flame retardant shaped article according to claim 9 wherein said base material is preferably selected from polycarbonate or nylon; the physical mixing is melt mixing or dissolving mixing in a solvent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668720A (en) * | 1984-08-17 | 1987-05-26 | Bayer Aktiengesellschaft | Flame resistant moulding compounds based on styrene polymers |
| US4701554A (en) * | 1983-11-25 | 1987-10-20 | Bayer Aktiengesellschaft | Process for the preparation of polyphosphonic acid amides |
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN102757580A (en) * | 2012-07-31 | 2012-10-31 | 广东聚石化学股份有限公司 | Reaction type phosphorus-nitrogen fire retardant and synthesizing method thereof |
| CN102827369A (en) * | 2012-08-17 | 2012-12-19 | 沈阳化工大学 | Synthetic method of phosphorus-nitrogen intumescent flame retardant |
-
2020
- 2020-07-17 CN CN202010690328.6A patent/CN111748100B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701554A (en) * | 1983-11-25 | 1987-10-20 | Bayer Aktiengesellschaft | Process for the preparation of polyphosphonic acid amides |
| US4668720A (en) * | 1984-08-17 | 1987-05-26 | Bayer Aktiengesellschaft | Flame resistant moulding compounds based on styrene polymers |
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN102757580A (en) * | 2012-07-31 | 2012-10-31 | 广东聚石化学股份有限公司 | Reaction type phosphorus-nitrogen fire retardant and synthesizing method thereof |
| CN102827369A (en) * | 2012-08-17 | 2012-12-19 | 沈阳化工大学 | Synthetic method of phosphorus-nitrogen intumescent flame retardant |
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