CN116041694A - Preparation method for improving oxidation resistance of polyamide - Google Patents
Preparation method for improving oxidation resistance of polyamide Download PDFInfo
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- CN116041694A CN116041694A CN202211681591.4A CN202211681591A CN116041694A CN 116041694 A CN116041694 A CN 116041694A CN 202211681591 A CN202211681591 A CN 202211681591A CN 116041694 A CN116041694 A CN 116041694A
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- antioxidant
- polyamide
- chain fatty
- carbon chain
- oxidation resistance
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention belongs to the technical field of polymer materials, and particularly relates to a preparation method for improving oxidation resistance of polyamide. The invention relates to a preparation method for improving the oxidation resistance of polyamide, which comprises the following steps: adding long carbon chain fatty dibasic acid, long carbon chain fatty diamine, antioxidant and water in proper proportion into a salifying kettle, heating under the protection of inert gas for salifying reaction for 1-3 h, press-filtering, heating to 230-260 ℃ under the protection of inert gas, reacting for 4-7 h under the pressure of less than 1.5MPa, and granulating under water to obtain the finished polyamide. The preparation method adopts the method that the raw materials are added into a salifying kettle before polymerization reaction, are uniformly mixed, have good antioxidant effect, and can greatly improve the antioxidant property of the product; the preparation method of the invention has simple operation, consistent and even material mixing, and the prepared resin product has better antioxidant effect when the additive amount is equal.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a preparation method for improving oxidation resistance of polyamide.
Background
Polyamide (PA) is commonly called Nylon, which is a thermoplastic resin general term containing repeating amide groups —nhco ] on a molecular main chain, and is the earliest developed variety in engineering plastics, and is widely applied to the fields of chemical industry, electric appliances, automobiles and other mechanical manufacturing due to the characteristics of high strength, high modulus, excellent chemical resistance, wear resistance, high melting point, low friction coefficient and the like.
The molecular chain end of the polyamide resin part is amino (-NH) 2 ) Is easy to oxidize and affects the stability and use of the polyamide material. In order to prevent the polyamide from being oxidized, an antioxidant adding method is generally adopted to protect the amino group of the polyamide, and the polymer antioxidant generally adopts copper salt compounds, phenolic antioxidants, hindered amine stabilizers, phosphite antioxidants, triazine stabilizers, ultraviolet light absorbers or the like, wherein the amine antioxidants are used as auxiliary stabilizers when being used for the polyamide, the copper salt compounds are generally matched with iodine compounds, otherwise, the antioxidant effect is poor, and the auxiliary agents have an important disadvantage of easy color development; phosphite antioxidants are also used together with the main antioxidants to exert synergistic effect, and meanwhile, phosphite esters have poor hydrolysis resistance and cannot be added in the salification process; the triazine stabilizer and the ultraviolet light absorber have better effect on photooxidation, but have insignificant effect on thermal oxidation and thermal oxidation aging; in addition, the heat resistance of the hindered phenol antioxidant 1010, antioxidant 1076, and the like is generally poor due to the relatively high temperature during processing of the polyamide resin.
At present, two main methods for adding the antioxidant are as follows: 1) The polyamide product is added during the molding processing; 2) The polyamide resin is added during modification processing. In the first method, the polyamide product is molded and processed by a multi-purpose single screw extruder for mixing extrusion or injection molding equipment, and the antioxidant is added to the equipment and is difficult to mix uniformly, so that the obtained product has unsatisfactory antioxidant effect; the second method generally uses a twin-screw extruder for mixing, and although the mixing effect is better than that of the first method, the mixing effect is difficult to be uniform and the operation is complicated.
Therefore, in order to improve the oxidation resistance of the polyamide resin, it is necessary to find an excellent antioxidant auxiliary and a suitable addition method.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method for improving the oxidation resistance of polyamide. The preparation method adopts the method that the raw materials are added into a salifying kettle before polymerization reaction, are uniformly mixed, have good antioxidant effect, and can greatly improve the antioxidant property of the product. The preparation method of the invention has simple operation, consistent and even mixing and better effect.
In order to achieve the technical purpose, the technical scheme adopted by the embodiment of the invention is as follows:
a preparation method for improving the oxidation resistance of polyamide comprises the following steps: adding long carbon chain fatty dibasic acid, long carbon chain fatty diamine, antioxidant and water in proper proportion into a salifying kettle, heating under the protection of inert gas for salifying reaction for 1-3 h, press-filtering, heating to 230-260 ℃ under the protection of inert gas, reacting for 4-7 h under the pressure of less than 1.5MPa, and granulating under water to obtain the finished polyamide.
Further, the long carbon chain fatty diamine is decanediamine, and the long carbon chain fatty diamine is decanediamine.
Further, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, and the temperature resistance of the main antioxidant is more than 250 ℃.
Further, the primary antioxidant is an antioxidant 1098, and the auxiliary antioxidant is one of phosphorous acid, sodium hydrogen phosphite or sodium hypophosphite.
Further, the mass ratio of the main antioxidant to the auxiliary antioxidant in the antioxidants is 1:0.2 to 0.6.
As described above, the main antioxidant 1098 is selected, and the antioxidant 1098 is not discolored, has good heat resistance and is hydrolysis-resistant, so that the antioxidant 1098 is used in a polymerization kettle (more than 250 ℃), the property of the antioxidant 1098 is not changed, the effect is excellent, and the antioxidant is high in free radical capturing capacity; on the other hand, because the antioxidation participates in salification and polymerization, the consistency and homogenization effect are good;
as described above, the auxiliary antioxidant is selected from one of phosphorous acid, sodium hydrogen phosphite or sodium hypophosphite, and the phosphorous acid, sodium hydrogen phosphite or sodium hypophosphite are all phosphorus antioxidants, and the replacement 168 and the antioxidant 1098 are matched for use and have synergistic effect; it should be noted that 168 and 1098 are normally selected and used because the antioxidant 168 is phosphate and is not hydrolysis-resistant.
Further, the mass ratio of the total amount of the long carbon chain fatty dibasic acid and the long carbon chain fatty diamine to water is 46-48: 52 to 54.
Because the water salt system formed by the long carbon chain fatty dibasic acid, the long carbon chain fatty diamine and the water is transferred from the salt forming kettle to the polymerization kettle in a filter pressing mode, the purpose is to remove solid particle impurities. Therefore, materials in the water salt system must be completely dissolved into a homogeneous solution, and when the water content in the water salt system is more than 52%, the main antioxidant 1098 can be completely dissolved, and because the higher the water content in the water salt system is, the lower the polyamide salt content is, the higher the energy consumption is, and the less economical is, the mass ratio of the total amount of the long carbon chain fatty dibasic acid and the long carbon chain fatty diamine to water is 46-48: 52-54.
Further, the antioxidant comprises the following components in percentage by mass: antioxidant + long carbon chain fatty diacid + long carbon chain fatty diamine = 0.2-1.0: 100, preferably 0.3 to 0.6:100.
further, the temperature of the salification reaction is 120-130 ℃.
The total amount of the salt formed by 48% of long-carbon-chain fatty dibasic acid and long-carbon-chain fatty diamine and 52% of water can not be completely dissolved at the temperature lower than 120 ℃, the equipment requirement is correspondingly increased when the temperature is too high, the energy consumption is increased, the cost is increased, the salt forming reaction temperature is 120-130 ℃, and the antioxidant can be completely dissolved under the condition.
Compared with the prior art, the invention has the following advantages:
(1) The process for adding the antioxidant during the molding processing of the polyamide product adopts a single screw extruder for mixing extrusion, the antioxidant is not uniformly mixed, and the performance of the product is reduced; the preparation method adopts the method that the raw materials are added into a salifying kettle before polymerization reaction, are uniformly mixed, have good antioxidant effect, and can greatly improve the antioxidant property of the product.
(2) Compared with mixing and adding by a double-screw extruder, the preparation method provided by the invention is simple and convenient to operate, consistent and uniform in material mixing and better in effect.
(3) Because the antioxidants are uniformly mixed in the preparation method, the resin product obtained by the method has better antioxidant effect when the antioxidants are added in the same amount.
(4) The main antioxidant used in the preparation of the invention has strong capability of capturing free radicals, does not change color, resists thermal oxidation and hydrolysis, is suitable for polyamide products, and has better antioxidant effect than other antioxidants; in addition, the selected auxiliary antioxidants have outstanding color protection effect, and the mixed antioxidants have synergistic effect, so that the effect is better than that of the single antioxidant.
In conclusion, the invention has the advantages of simple operation, high reliability, good antioxidant effect and uniform quality.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method for improving the oxidation resistance of polyamide comprises the following steps:
48.13kg of sebacic acid, 40.98kg of decanediamine, 1098.53 kg of antioxidant, 0.16kg of sodium hydrogen phosphite and 96.8kg of water are put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen, the temperature is raised to 125 ℃, the pressure is filtered and the mixture is filtered into a polymerization kettle, the temperature is raised to 250 ℃ under the protection of nitrogen, the pressure is 1.45MPa, the reaction is carried out for 6 hours, and the finished polyamide is obtained after underwater pelleting.
Example 2
A preparation method for improving the oxidation resistance of polyamide comprises the following steps:
48.13kg of sebacic acid, 40.98kg of decanediamine, 1098.38 kg of antioxidant, 0.16kg of phosphorous acid and 96.8kg of water are put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen, the mixture is pressed and filtered into a polymerizing kettle, the mixture is heated to 250 ℃ under the protection of nitrogen, the pressure is 1.45MPa, the mixture is reacted for 6 hours, and the finished polyamide is obtained after underwater pelleting.
Example 3
A preparation method for improving the oxidation resistance of polyamide comprises the following steps:
48.13kg of sebacic acid, 40.98kg of decanediamine, 1098.53 kg of antioxidant, 0.22kg of sodium hypophosphite and 96.8kg of water are put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen, the mixture is pressed and filtered into a polymerization kettle, the mixture is heated to 250 ℃ under the protection of nitrogen, the pressure is 1.45MPa, the mixture is reacted for 6 hours, and the finished polyamide is obtained after underwater pelleting.
Example 4
A preparation method for improving the oxidation resistance of polyamide comprises the following steps:
48.13kg of sebacic acid, 40.98kg of decanediamine, 1098.38 kg of antioxidant, 0.22kg of phosphorous acid and 96.8kg of water are put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen, the mixture is pressed and filtered into a polymerizing kettle, the mixture is heated to 250 ℃ under the protection of nitrogen, the pressure is 1.45MPa, the mixture is reacted for 6 hours, and the finished polyamide is obtained after underwater pelleting.
Comparative example 1 (no auxiliary antioxidant added)
A process for the preparation of a polyamide comprising the steps of:
48.13kg of sebacic acid, 40.98kg of decanediamine, 1098.0.53 kg of antioxidant and 96.8kg of water are taken and put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen and the temperature is raised to 125 ℃, the mixture is pressed and filtered into a polymerizing kettle, the temperature is raised to 250 ℃ under the protection of nitrogen and the pressure is less than 1.5MPa, the reaction is carried out for 6 hours, and the finished polyamide is obtained after underwater pelleting.
Comparative example 2 (no primary antioxidant and auxiliary antioxidant added)
A process for the preparation of a polyamide comprising the steps of:
48.13kg of sebacic acid, 40.98kg of decanediamine and 96.8kg of water are taken and put into a salifying kettle, after the salifying reaction is carried out for 2 hours under the protection of nitrogen and the temperature is raised to 125 ℃, the mixture is pressed and filtered into a polymerizing kettle, the temperature is raised to 250 ℃ under the protection of nitrogen and the pressure is less than 1.5MPa, the mixture is reacted for 6 hours, and the finished polyamide is obtained after underwater granulating.
Examples 1 to 4And the materials obtained in comparative examples 1 to 2 were subjected to an antioxidant property test, a property test method: 100g of polyamide is cut into particles and placed for 200cm 2 In a tray, the tray is tiled, placed in a constant temperature drying oven at 150 ℃ for 48 hours, taken out and measured by a CR-400/410 color difference meter. The results are shown in table 1 below:
as can be seen from the test results of the above examples, the polyamide prepared by the invention has good antioxidation effect, and the composite antioxidant composed of the antioxidant 1098 and one of the phosphorous acid, sodium hydrogen phosphite or sodium hypophosphite has better effect than the single antioxidant 1098, so that the invention has better antioxidation performance, and the main antioxidant and the auxiliary antioxidant adopted by the embodiment of the invention have synergistic effect.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (9)
1. The preparation method for improving the oxidation resistance of the polyamide is characterized by comprising the following steps of: adding long carbon chain fatty dibasic acid, long carbon chain fatty diamine, antioxidant and water in proper proportion into a salifying kettle, heating under the protection of inert gas for salifying reaction for 1-3 h, press-filtering, heating to 230-260 ℃ under the protection of inert gas, reacting for 4-7 h under the pressure of less than 1.5MPa, and granulating under water to obtain the finished polyamide.
2. The method for preparing the polyamide with improved oxidation resistance according to claim 1, wherein the long carbon chain fatty diamine is decanediamine and the long carbon chain fatty diamine is decanedioic acid.
3. The method for preparing the polyamide with improved oxidation resistance according to claim 1, wherein the antioxidant comprises a primary antioxidant and an auxiliary antioxidant, and the temperature resistance of the primary antioxidant is more than 250 ℃.
4. The method for improving the oxidation resistance of a polyamide according to claim 3, wherein the primary antioxidant is an antioxidant 1098 and the secondary antioxidant is one of phosphorous acid, sodium hydrogen phosphite or sodium hypophosphite.
5. The method for improving the oxidation resistance of polyamide according to claim 3, wherein the mass ratio of the primary antioxidant to the secondary antioxidant in the antioxidants is 1:0.2 to 0.6.
6. The preparation method for improving the oxidation resistance of the polyamide according to claim 1, wherein the mass ratio of the total amount of the long carbon chain fatty dibasic acid and the long carbon chain fatty diamine to water is 46-48: 52 to 54.
7. The method for improving the oxidation resistance of polyamide according to claim 1, wherein the antioxidant comprises the following components in mass ratio: antioxidant + long carbon chain fatty diacid + long carbon chain fatty diamine = 0.2-1.0: 100.
8. the method for improving the oxidation resistance of polyamide according to claim 1, wherein the antioxidant comprises the following components in mass ratio: antioxidant + long carbon chain fatty diacid + long carbon chain fatty diamine = 0.3-0.6: 100.
9. the method for improving the oxidation resistance of a polyamide according to claim 1, wherein the salt forming reaction is carried out at a temperature of 120 to 130 ℃.
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| CN202211681591.4A CN116041694A (en) | 2022-12-27 | 2022-12-27 | Preparation method for improving oxidation resistance of polyamide |
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| CN202211681591.4A CN116041694A (en) | 2022-12-27 | 2022-12-27 | Preparation method for improving oxidation resistance of polyamide |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1737036A (en) * | 2005-09-07 | 2006-02-22 | 无锡殷达尼龙有限公司 | Polyamide 1010 resin production process |
| CN106832264A (en) * | 2017-02-20 | 2017-06-13 | 中仑塑业（福建）有限公司 | A kind of copolymerization transparent nylon and its synthetic method |
| CN111040722A (en) * | 2019-12-29 | 2020-04-21 | 无锡殷达尼龙有限公司 | Preparation method of high-adhesion-strength polyamide hot melt adhesive |
| CN112280032A (en) * | 2020-11-03 | 2021-01-29 | 北京化工大学 | Preparation method of long carbon chain nylon material |
| CN113061247A (en) * | 2021-03-31 | 2021-07-02 | 上海庚彩新材料科技有限公司 | High-temperature-resistant and easy-to-process polyamide copolymer and preparation method thereof |
| CN114426665A (en) * | 2020-10-28 | 2022-05-03 | 华峰集团有限公司 | Antioxidant polyamide material and preparation method thereof |
| CN115010922A (en) * | 2022-07-22 | 2022-09-06 | 山东东辰瑞森新材料科技有限公司 | Long-carbon-chain high-temperature-resistant nylon and preparation method and application thereof |
-
2022
- 2022-12-27 CN CN202211681591.4A patent/CN116041694A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1737036A (en) * | 2005-09-07 | 2006-02-22 | 无锡殷达尼龙有限公司 | Polyamide 1010 resin production process |
| CN106832264A (en) * | 2017-02-20 | 2017-06-13 | 中仑塑业（福建）有限公司 | A kind of copolymerization transparent nylon and its synthetic method |
| CN111040722A (en) * | 2019-12-29 | 2020-04-21 | 无锡殷达尼龙有限公司 | Preparation method of high-adhesion-strength polyamide hot melt adhesive |
| CN114426665A (en) * | 2020-10-28 | 2022-05-03 | 华峰集团有限公司 | Antioxidant polyamide material and preparation method thereof |
| CN112280032A (en) * | 2020-11-03 | 2021-01-29 | 北京化工大学 | Preparation method of long carbon chain nylon material |
| CN113061247A (en) * | 2021-03-31 | 2021-07-02 | 上海庚彩新材料科技有限公司 | High-temperature-resistant and easy-to-process polyamide copolymer and preparation method thereof |
| CN115010922A (en) * | 2022-07-22 | 2022-09-06 | 山东东辰瑞森新材料科技有限公司 | Long-carbon-chain high-temperature-resistant nylon and preparation method and application thereof |
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