CN112266609A - Fully renewable toughened nylon and preparation method and application thereof - Google Patents
Fully renewable toughened nylon and preparation method and application thereof Download PDFInfo
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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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
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention relates to a fully renewable toughened nylon and a preparation method and application thereof. Comprises nylon, a liquid toughening agent, an antioxidant and an initiator, wherein a-CH 2-chain segment of the nylon is connected with a double bond graft of the liquid toughening agent; the liquid flexibilizer is ricinoleic acid butyl ester or epoxidized soybean oil. The liquid toughening agent is adopted for modification, so that the precipitation of the toughening agent on the surface of the nylon is effectively inhibited, the utilization efficiency of the toughening agent is improved, and the impact performance of the nylon material is improved.
Description
Technical Field
The invention belongs to the technical field of nylon material preparation, and particularly relates to a fully renewable toughened nylon and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Nylon is a kind of engineering plastics with excellent performance, and the commonly used nylon includes 6 and 66, but both materials are derived from petroleum resources, and the application of the nylon materials is limited along with the exhaustion of the petroleum resources. Nylon raw materials derived from renewable resources are receiving attention, such as nylon 11, nylon 1010, nylon 1012, and the like.
Similar to nylon 6 and 66 derived from petroleum resources, renewable nylon materials have good mechanical properties, heat resistance, abrasion resistance, chemical solvent resistance, and self-lubricity, but have poor impact properties, limiting their applications.
In order to improve the impact property of nylon materials, a method of adding a polyolefin toughening agent is generally adopted, but the toughening agent is also derived from petroleum resources, and maleic anhydride with high toxicity is often adopted as a grafting monomer in the preparation process.
The liquid toughening agent can improve the impact property of the nylon material, and is a good method for replacing a polyolefin toughening agent. However, the inventors found that when the amount of such a toughening agent added is large, the toughening agent is likely to precipitate on the surface of nylon, which affects the use of the material, and most of the liquid toughening agents are derived from petroleum resources.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a fully renewable toughened nylon and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the fully renewable toughened nylon comprises nylon, a liquid toughening agent, an antioxidant, an initiator and-CH of the nylon2The chain segment is grafted with the double bond of the liquid toughening agent or other active matrix;
the liquid flexibilizer is ricinoleic acid butyl ester or epoxidized soybean oil.
The toughening nylon is modified by adopting a liquid toughening agent, and compared with the existing polyolefin toughening agent, the source of the selected liquid toughening agent is different, and toxic maleic anhydride is not required to be used as a grafting monomer in the preparation process.
The selected liquid toughening agent is a renewable liquid toughening agent with double bonds, epoxy, carboxyl and hydroxyl. Epoxy, carboxyl and hydroxyl contained in the liquid toughening agent react with carboxyl and amido at the tail end of a nylon chain segment, and most importantly, the double bond in the toughening agent is opened by using an initiator and is grafted to-CH of the nylon material2And on the chain segment, the toughening agent is firmly anchored in the nylon material by using a chemical bond, so that the precipitation of the toughening agent on the surface of the nylon is effectively inhibited, the utilization efficiency of the toughening agent is improved, and the impact performance of the nylon material is improved.
In some embodiments of the present invention, the weight parts of the raw materials of the fully renewable toughened nylon are as follows: 94.8-66 parts of nylon, 5-30 parts of liquid toughening agent, 0.1-2 parts of antioxidant and 0.1-2 parts of initiator.
Further, the weight parts of the raw materials of the fully renewable toughened nylon are as follows: 78-70 parts of nylon, 20-25 parts of liquid toughening agent, 0.5-1 part of antioxidant and 1.5-1.8 parts of initiator. The species and proportion of the raw materials can influence the grafting effect of the reaction, and further influence the mechanical properties of the obtained fully renewable toughened nylon.
In some embodiments of the invention, the nylon is nylon 11, nylon 12, nylon 1010, nylon 1012, nylon 1212, or the like; nylon 11, nylon 1010, and nylon 1012 are preferable. The raw material of the nylon is selected as a nylon raw material of renewable resources, compared with nylon 6 and nylon 66, the renewable nylon raw material has slightly better impact performance but still lower impact performance, and the fully renewable toughened nylon prepared by the invention improves the impact performance of the renewable nylon raw material.
In some embodiments of the invention, the antioxidant is one or a mixture of pentaerythrityl [ tetrakis (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), octadecyl-3- (3, 5-di-tert-butyl-4-hydroxy) propene (antioxidant 1076), hexamethylenediamine N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoyl) (antioxidant 1098), 2, 6-di-tert-butyl-4-cresol (antioxidant 264), 2,4, 6-tri-tert-butylphenol (antioxidant 246), and triester 2, 4-di-tert-butylphenyl (antioxidant 168). The antioxidant is used for preventing the mechanical property reduction of the nylon raw material caused by oxidation in the extrusion process.
In some embodiments of the invention, the initiator is dicumyl peroxide, dibenzoyl peroxide, or the like. The initiator acts to open the double bonds of the liquid toughener and then to promote grafting to the-CH of the nylon2-in the chain segment. The choice of the type of initiator has an influence on the grafting effect, affecting the number and length of the graft segments.
In a second aspect, a method for preparing fully renewable toughened nylon comprises the following steps:
mixing raw materials of nylon, a liquid toughening agent, an antioxidant and an initiator, then putting the mixture into an extruder for extrusion, and obtaining the fully renewable toughened nylon composite material by drawing, drying and dicing the extrudate.
In some embodiments of the invention, the conditions under which the mixture is extruded in the extruder are: the temperature is 200-330 ℃, the rotating speed of the main screw is 5-300 r/min, and the rotating speed of the feeding screw is 1-50 r/min.
Furthermore, the temperature of the mixture in the extruder is 230-280 ℃, the rotating speed of the main screw is 60-150 r/min, and the rotating speed of the feeding screw is 10-40 r/min. Further preferably, the temperature of the mixture in the extruder is 250-280 ℃, the rotating speed of the main screw is 100-150 r/min, and the rotating speed of the feeding screw is 20-40 r/min.
In a third aspect, the fully renewable toughened nylon is applied to spinning, injection molding, films and the like.
One or more technical schemes of the invention have the following beneficial effects:
the renewable nylon and the liquid toughening agent are used as main raw materials to prepare the fully renewable toughened nylon material, all the raw materials are derived from renewable resources, in order to inhibit the precipitation of the liquid toughening agent, the toughening agent and the nylon raw materials are linked through chemical bonds by adopting a chemical grafting method, the precipitation of the toughening agent is well limited, and the impact performance of the prepared nylon material is superior to that of the polyolefin toughening agent.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1
Weighing nylon, a liquid toughening agent (butyl ricinoleate), an initiator (dicumyl peroxide) and an antioxidant (antioxidant 1076) according to parts by weight, wherein the nylon 1188 parts, the liquid toughening agent 10 parts, the antioxidant 0.5 part and the initiator 1.5 parts are mixed in a high-speed mixer for 30 min. And then placing the mixture into a hopper of an extruder, extruding at 230 ℃, the rotating speed of a main screw rod is 60 revolutions per minute, and the rotating speed of a feeding screw rod is 10 revolutions per minute, and drawing, cooling, drying and granulating the extrudate to obtain the toughened nylon composite material.
Example 2
Weighing nylon, a liquid toughening agent (butyl ricinoleate), an initiator (dicumyl peroxide) and an antioxidant (antioxidant 1076) according to parts by weight, wherein 1178 parts of nylon, 20 parts of liquid toughening agent, 0.5 part of antioxidant and 1.5 parts of initiator are mixed in a high-speed mixer for 30 min. And then placing the mixture into a hopper of an extruder, extruding at 230 ℃, the rotating speed of a main screw rod is 60 revolutions per minute, and the rotating speed of a feeding screw rod is 10 revolutions per minute, and drawing, cooling, drying and granulating the extrudate to obtain the toughened nylon composite material.
Example 3
Weighing nylon, a liquid toughening agent (butyl ricinoleate), an initiator (dicumyl peroxide) and an antioxidant (antioxidant 1076) according to parts by weight, wherein the nylon 101088 parts, the liquid toughening agent 10 parts, the antioxidant 0.5 part and the initiator 1.5 parts are mixed in a high-speed mixer for 30 min. And then placing the mixture into a hopper of an extruder, extruding at the temperature of 250 ℃, at the rotating speed of a main screw rod of 100 revolutions per minute and at the rotating speed of a feeding screw rod of 20 revolutions per minute, and drawing, cooling, drying and granulating the extrudate to obtain the toughened nylon composite material.
Example 4
Weighing nylon, a liquid toughening agent (butyl ricinoleate), an initiator (dicumyl peroxide) and an antioxidant (antioxidant 1076) according to parts by weight, wherein 101078 parts of nylon, 20 parts of the liquid toughening agent, 0.5 part of the antioxidant and 1.5 parts of the initiator are mixed in a high-speed mixer for 30 min. And then placing the mixture into a hopper of an extruder, extruding at the temperature of 250 ℃, at the rotating speed of a main screw rod of 100 revolutions per minute and at the rotating speed of a feeding screw rod of 20 revolutions per minute, and drawing, cooling, drying and granulating the extrudate to obtain the toughened nylon composite material.
Example 5
Weighing nylon, a liquid toughening agent (butyl ricinoleate), an initiator (dicumyl peroxide) and an antioxidant (antioxidant 1076) according to parts by weight, wherein 101278 parts of nylon, 20 parts of the liquid toughening agent, 0.5 part of the antioxidant and 1.5 parts of the initiator are mixed in a high-speed mixer for 20 min. And then placing the mixture into a hopper of an extruder, extruding at the conditions of 280 ℃, 150 revolutions per minute of the main screw and 40 revolutions per minute of the feeding screw, and drawing, cooling, drying and granulating the extrudate to obtain the toughened nylon composite material.
Comparative example 1
Compared with the embodiment 5, the preparation method is the same as the embodiment 5 by replacing the butyl ricinoleate with the maleic anhydride grafted ethylene octene copolymer, so that the toughened nylon composite material is obtained.
The toughened nylon composite materials obtained in examples 1 to 5 and comparative example 1 were subjected to a tensile strength test in accordance with ISO 527-21/1A/50, notched impact strength test in accordance with ISO 179/1eA, and the results of the performance tests of the toughened nylon composite materials obtained in examples 1 to 5 and comparative example 1 are shown in Table 1.
Table 1 results of performance testing
| Tensile strength/MPa | Impact strength KJ/m2 | |
| Example 1 | 55.3 | 45.6 |
| Example 2 | 45.7 | 90.8 |
| Example 3 | 51.1 | 54.4 |
| Example 4 | 43.8 | 105.8 |
| Example 5 | 40.9 | 115.0 |
| Comparative example 1 | 41.5 | 85.3 |
From Table 1, it can be seen that the impact strength of the nylon material can be remarkably improved after the ricinoleic acid butyl ester is added into the nylon 11, 1010 and 1012, and the impact strength of the pure nylon 11, 1010 and 1012 is 5-8 KJ/m2When 10% of ricinoleic acid butyl ester is added, the notch impact strength of the blend is improved by 7-10 times, and when 20% of ricinoleic acid butyl ester is added, the notch impact strength of the blend is up to 115.0KJ/m2The super-tough nylon reaches the level of super-tough nylon, and compared with the traditional maleic anhydride grafted toughening agent (comparative example 1), the notch impact strength is 5-30 KJ/m higher than that of the traditional maleic anhydride grafted toughening agent under the condition of the same addition amount of the toughening agent2The renewable nylon toughening agent technology provided by the invention can obviously improve the impact property of the material, and simultaneously the tensile strength is close to that of the material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A fully renewable toughened nylon is characterized in that: comprises nylon, a liquid toughening agent, an antioxidant and an initiator, wherein a-CH 2-chain segment of the nylon is connected with a double bond graft of the liquid toughening agent;
the liquid flexibilizer is ricinoleic acid butyl ester or epoxidized soybean oil.
2. The fully renewable toughened nylon of claim 1 wherein: the weight portions of the raw materials of the fully renewable toughened nylon are as follows: 94.8-66 parts of nylon, 5-30 parts of liquid toughening agent, 0.1-2 parts of antioxidant and 0.1-2 parts of initiator.
3. The fully renewable toughened nylon of claim 2 wherein: the weight portions of the raw materials of the fully renewable toughened nylon are as follows: 78-70 parts of nylon, 20-25 parts of liquid toughening agent, 0.5-1 part of antioxidant and 1.5-1.8 parts of initiator.
4. The fully renewable toughened nylon of claim 1 wherein: the nylon is nylon 11, nylon 12, nylon 1010, nylon 1012, nylon 1212, etc.; nylon 11, nylon 1010, and nylon 1012 are preferable.
5. The fully renewable toughened nylon of claim 1 wherein: the antioxidant is one or a mixture of more of [ tetra (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3- (3, 5-di-tert-butyl-4-hydroxy) propylene octadecyl ester (antioxidant 1076), N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2, 6-di-tert-butyl-4-cresol, 2,4, 6-tri-tert-butylphenol and (2, 4-di-tert-butylphenyl) phosphite triester.
6. The fully renewable toughened nylon of claim 1 wherein: the initiator is dicumyl peroxide or dibenzoyl peroxide.
7. The process for preparing fully renewable toughened nylon according to any one of claims 1 to 6, characterized in that: mixing raw materials of nylon, a liquid toughening agent, an antioxidant and an initiator, then putting the mixture into an extruder for extrusion, and obtaining the fully renewable toughened nylon composite material by drawing, drying and dicing the extrudate.
8. The method of preparing a fully renewable toughened nylon according to claim 7 wherein: the conditions under which the mixture is extruded in the extruder are: the temperature is 200-330 ℃, the rotating speed of the main screw is 5-300 r/min, and the rotating speed of the feeding screw is 1-50 r/min.
9. The method of claim 8, wherein: the temperature of the mixture in the extruder is 230-280 ℃, the rotating speed of a main screw is 60-150 revolutions per minute, and the rotating speed of a feeding screw is 10-40 revolutions per minute;
preferably, the temperature of the mixture in the extruder is 250-280 ℃, the rotating speed of a main screw is 100-150 r/min, and the rotating speed of a feeding screw is 20-40 r/min.
10. Use of the fully renewable toughened nylon according to any one of claims 1 to 6 in spinning, injection moulding, film and the like.
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| CN110724377A (en) * | 2019-11-06 | 2020-01-24 | 山东科华赛邦新材料股份有限公司 | High-impact-resistance toughened nylon material at ultralow temperature and preparation method thereof |
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2020
- 2020-10-28 CN CN202011174858.1A patent/CN112266609B/en active Active
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|---|---|---|---|---|
| US4957966A (en) * | 1987-06-10 | 1990-09-18 | Sumitomo Chemical Company, Ltd. | Thermoplastic resin composition |
| US5017652A (en) * | 1987-09-18 | 1991-05-21 | Sumitomo Chemical Co., Ltd. | Process for making a thermoplastic resin composition |
| US5506305A (en) * | 1991-07-22 | 1996-04-09 | Sumitomo Chemical Company Limited | Thermoplastic resin compositions comprising polyphenylene ether, polyamide and block copolymers |
| US5389714A (en) * | 1991-12-27 | 1995-02-14 | Ge Plastics, Japan, Ltd. | Blends of polyphenylphene ether, polyamide, elastomeric substances and needle shaped titanium oxide treated with organopolysiloxanes |
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