CN111171301A - Preparation method and application of nitrogenous copolymerized polylactic acid - Google Patents
Preparation method and application of nitrogenous copolymerized polylactic acid Download PDFInfo
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- CN111171301A CN111171301A CN202010087909.0A CN202010087909A CN111171301A CN 111171301 A CN111171301 A CN 111171301A CN 202010087909 A CN202010087909 A CN 202010087909A CN 111171301 A CN111171301 A CN 111171301A
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- polylactic acid
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- retardant
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
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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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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Abstract
The invention belongs to the field of flame-retardant fibers, and discloses a preparation method of nitrogenous copolymerized polylactic acid, which comprises the steps of taking nitrogenous carboxylic acid compounds and lactide, and carrying out polymerization reaction to obtain the nitrogenous copolymerized polylactic acid; the invention also discloses an application of the nitrogenous copolymerization polylactic acid prepared by the preparation method, and the nitrogenous copolymerization polylactic acid is fused, blended and spun with polylactic acid, tin dioxide-loaded zirconium phosphate and alkyl phosphinic acid metal salt to prepare the flame-retardant fiber. The flame-retardant fiber prepared by the method can quickly form a compact carbon layer during combustion, and form the nano ceramic microspheres in the carbon layer, so that the strength of the carbon layer is effectively improved, the transfer of heat and oxygen is inhibited, and the high-efficiency flame retardance of the fiber is realized. The flame-retardant fiber has the limiting oxygen index of more than or equal to 30 and the UL94 flame-retardant grade of V0, and solves the problem of low flame-retardant property of polylactic acid prepared by a chemical copolymerization method in the prior art. The nitrogenous copolymerized polylactic acid prepared by the invention is used for preparing flame-retardant fibers, and the flame-retardant fibers are used for producing textiles or fiber products.
Description
Technical Field
The invention belongs to the field of flame-retardant fibers, relates to preparation of flame-retardant bio-based polymer fibers, and particularly relates to a preparation method and application of nitrogenous copolymerized polylactic acid.
Background
Polylactic acid is bio-based Polyester (PLA), has good thermal stability and biocompatibility, also has certain antibacterial property and ultraviolet resistance, can be used for manufacturing packaging materials, fibers and non-woven fabrics, and is applied to various fields of clothing, construction, forestry, agriculture, paper making, medical treatment and health care and the like.
The limiting oxygen value refers to the volume fraction concentration of oxygen in the oxygen and nitrogen mixture when just burning the support fabric. The level of the limiting oxygen value is one of important reference indexes for evaluating the flammability performance of the fabric material. The limit oxygen index of polyester fiber is about 20-22%, and its flammability limits the application range of polylactic acid.
The existing polylactic acid flame-retardant modification methods mainly comprise three methods, including: physical blending and chemical copolymerization. The physical blending method has the problems of poor compatibility of the flame retardant, high addition amount, easy agglomeration and the like, which destroy the service performance of the material; the chemical copolymerization method has the advantages of good compatibility, lasting function and the like, but also has the problems of low flame retardant property, poor durability and the like.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogenous copolymerized polylactic acid, which aims to solve the problem that polylactic acid prepared by a chemical copolymerization method in the prior art has low flame retardant property;
another object of the present invention is to provide the use of the above-mentioned nitrogen-containing copolymerized polylactic acid.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of nitrogenous copolymerized polylactic acid is to take nitrogenous carboxylic acid compounds and lactide to carry out polymerization reaction to obtain the nitrogenous copolymerized polylactic acid.
As a limitation, the nitrogen content in the nitrogen-containing copolymerized polylactic acid is 3-9%;
the weight ratio of the nitrogen-containing carboxylic acid compound to the lactide is 1: 0.5 to 2;
the polymerization reaction is carried out for 6-10h at 170-200 ℃ under vacuum condition.
As another limitation, the nitrogen-containing carboxylic acid compound is prepared by carrying out nucleophilic addition reaction on succinic anhydride and phenylenediamine for 1.5-3.5h at room temperature.
By way of further limitation, the solvent of the nucleophilic addition reaction is toluene; the molar ratio of succinic anhydride to phenylenediamine is 2-2.5: 1.
the invention also provides an application of the nitrogenous copolymerized polylactic acid, which is used for preparing flame-retardant fibers after melt blending and spinning with polylactic acid, tin dioxide-loaded zirconium phosphate and alkyl phosphinic acid metal salt at 220-250 ℃;
the spinning speed is 2000-3200 m/min.
As a limitation, the tin dioxide-loaded zirconium phosphate is prepared by chelating zirconium phosphate and tin tetrachloride under the action of a chelating agent through a metal ion chelating method.
The metal ion chelating method is characterized in that zirconium phosphate and a chelating agent react for 3-5h at the temperature of 35-45 ℃, tin tetrachloride is added for reaction for 3-5h at the temperature of 55-65 ℃, and then the mixture is roasted for 2-4h at the temperature of 350-450 ℃ under the protection of inactive gas.
As a further limitation, the tin dioxide in the tin dioxide-loaded zirconium phosphate has the particle size of 10-80nm and the content of 5-20%;
the chelating agent is EDTA or phytic acid;
the weight ratio of the zirconium phosphate to the tin tetrachloride to the chelating agent is 1: 0.8-1.2: 0.8-1.2;
as a second limitation, the limit oxygen index of the flame-retardant fiber is more than or equal to 30vol%, the UL94 flame-retardant grade reaches V0 grade, the mechanical property of the fiber is 2.9-3.4cN/dtex, and the elongation at break is 8-18%.
As a third limitation, the metal alkyl phosphinate is aluminum diethyl phosphinate and/or zinc diethyl phosphinate;
the weight ratio of the nitrogenous copolymerized polylactic acid to the polylactic acid, the alkyl phosphinic acid metal salt and the tin dioxide-loaded zirconium phosphate is 1: 0.4-2: 0.04-0.08: 0.005-0.02.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
the invention successfully introduces nitrogen element in the copolymerized polylactic acid by taking the nitrogenous carboxylic acid compound as the raw material, thereby increasing the flame retardant effect. The flame-retardant fiber prepared by melt blending of the copolymerized polylactic acid, the phosphorus-containing organic flame retardant and the tin dioxide-loaded zirconium phosphate can realize the nitrogen and phosphorus synergistic flame-retardant effect, and simultaneously, the nano germanium oxide is introduced to synchronously realize the polycondensation catalysis effect and the synergistic flame-retardant effect;
the flame-retardant fiber prepared by the method can quickly form a compact carbon layer during combustion, and form the nano ceramic microspheres in the carbon layer, so that the strength of the carbon layer is effectively improved, the transfer of heat and oxygen is inhibited, and the high-efficiency flame retardance of the fiber is realized. The limit oxygen index of the flame-retardant fiber is more than or equal to 30vol%, and the UL94 flame-retardant grade reaches V0 grade.
The preparation method can directly prepare the nitrogenous copolymerized polylactic acid, the prepared nitrogenous copolymerized polylactic acid can be used for preparing flame-retardant fibers, and the prepared flame-retardant fibers can be used for producing textiles such as cloth, clothes, decorative articles, national defense and military fabrics and other fiber products.
Drawings
FIG. 1 is a comparison of mechanical properties of the flame retardant fiber obtained in example 1 of the present invention and polylactic acid;
FIG. 2 is a comparison of the nitrogen-containing copolymerized polylactic acid (b) and polylactic acid (a) obtained in example 1 of the present invention after combustion.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1 preparation method and application of nitrogenous copolymerized polylactic acid
1) Preparation of nitrogen-containing carboxylic acid compounds
Respectively dissolving 1.00kg (22mol) of succinic anhydride and 1.08kg (10mol) of p-phenylenediamine in 5L of toluene to obtain a succinic anhydride toluene solution and a p-phenylenediamine toluene solution;
mixing the succinic anhydride toluene solution and the p-phenylenediamine toluene solution, carrying out nucleophilic addition reaction for 2h at normal temperature, and filtering to obtain a crude product A of the nitrogenous carboxylic acid compound1And then washed 3 times with 5L of acetone, respectively, to obtain 1.8kg of nitrogen-containing carboxylic acid compound B1。
2) Preparation of nitrogenous copolymerized polylactic acid
10kg of nitrogenous carboxylic acid compound B was taken1Mixing with 5kg lactide to obtain a polymerization system, and reacting the polymerization system at 180 ℃ for 8h under a vacuum condition to obtain 15kg of nitrogen-containing copolymerized polylactic acid with the nitrogen content of 6%.
3) Preparation of tin dioxide-loaded zirconium phosphate
Dispersing 1kg of lamellar zirconium phosphate with particle size of about 500nm in 100L of water, adding 1kg of phytic acid, and reacting at 40 deg.C for 4h (hereinafter referred to as "L" for reaction)1Reaction), adding 1kg of stannic chloride, and reacting at 60 deg.C for 4h (hereinafter referred to as "L" for the reaction)2Reaction ") to obtain a supported substance C115L water clean load C1Then placing the mixture into a 400 ℃ muffle furnace, and roasting the mixture for 3 hours at the temperature of 400 ℃ under the protection of nitrogen to prepare 1.7kg of tin dioxide-loaded zirconium phosphate, wherein the particle size of tin dioxide is 40nm, and the content of tin dioxide is 10%.
4) Preparation of flame-retardant fibers
10kg of nitrogenous copolymerized polylactic acid, 4.1kg of polylactic acid, 0.1kg of tin dioxide-loaded zirconium phosphate and 0.8kg of alkyl phosphinic acid metal salt are melted and blended at 240 ℃ and spun at a spinning speed of 3000m/min to prepare 15kg of flame-retardant fiber with 4 percent of nitrogen content, the limited oxygen index is 33vol percent, and the UL94 flame-retardant grade reaches V0 grade. The mechanical properties of the obtained flame-retardant fiber and polylactic acid are tested, and as can be seen from figure 1, the mechanical properties of the obtained flame-retardant fiber are 3.46cN/dtex, and the elongation at break can reach 16.5%, and compared with the mechanical properties of the polylactic acid fiber which are 3.65cN/dtex and the elongation at break can reach 12%, the mechanical properties of the fiber are slightly reduced, and the elongation at break is increased.
The obtained nitrogenous copolymerized polylactic acid and polylactic acid are compared after being combusted, and referring to fig. 2, the obtained nitrogenous copolymerized polylactic acid is obviously enhanced in flame retardant effect.
The prepared nitrogenous copolymerized polylactic acid can be used for preparing flame-retardant fibers, and the prepared flame-retardant fibers can be used for producing textiles such as cloth clothing, decorative articles, national defense and military fabrics and other fiber products.
Example 2-9 preparation method and application of Nitrogen-containing copolymerized polylactic acid
Examples 2 to 9 are a method for preparing a nitrogenous copolymerized polylactic acid and its use, respectively, and the steps are substantially the same as those of example 1, except for differences in process parameters, which are detailed in table 1:
TABLE 1 summary of the process parameters of examples 2-9
The contents of other portions of examples 2 to 9 are the same as those of example 1.
The embodiments 1 to 9 are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and any person skilled in the art can not use the above technical content as a teaching to make changes or modifications to the equivalent embodiments with equivalent changes, but all simple modifications, equivalent changes and modifications made to the above embodiments without departing from the technical spirit of the present invention, and still all the modifications, equivalent changes and modifications of the embodiments are within the scope of the present invention as claimed in the present invention.
Claims (10)
1. The preparation method of the nitrogenous copolymerized polylactic acid is characterized in that nitrogenous carboxylic acid compounds and lactide are polymerized to obtain the nitrogenous copolymerized polylactic acid.
2. The method for producing a nitrogen-containing copolymerized polylactic acid according to claim 1,
the nitrogen content in the nitrogenous copolymerized polylactic acid is 3-9%;
the weight ratio of the nitrogen-containing carboxylic acid compound to the lactide is 1: 0.5 to 2;
the polymerization reaction is carried out for 6-10h at 170-200 ℃ under vacuum condition.
3. The method for preparing a nitrogenous copoly (lactic acid) according to claim 1 or 2, wherein the nitrogenous carboxylic acid compound is prepared by a nucleophilic addition reaction of succinic anhydride and phenylenediamine.
4. The method for preparing a nitrogen-containing copolymerized polylactic acid according to claim 3, wherein the solvent for the nucleophilic addition reaction is toluene; the molar ratio of succinic anhydride to phenylenediamine is 2-2.5: 1.
5. the application of the nitrogen-containing copolymerized polylactic acid is characterized in that the nitrogen-containing copolymerized polylactic acid is prepared by the preparation method of any one of claims 1 to 4, and is used for preparing the flame-retardant fiber after the nitrogen-containing copolymerized polylactic acid, tin dioxide-loaded zirconium phosphate and alkyl phosphinic acid metal salt are subjected to melt blending and spinning.
6. The application of the nitrogen-containing polylactic acid copolymer as claimed in claim 5, wherein the tin dioxide-loaded zirconium phosphate is prepared by chelating zirconium phosphate with tin tetrachloride under the action of a chelating agent through a metal ion chelating method.
7. The application of the nitrogen-containing copolymerized polylactic acid according to claim 6, wherein the metal ion chelating method is to react zirconium phosphate with a chelating agent at 35-45 ℃ for 3-5h, then add tin tetrachloride at 55-65 ℃ for 3-5h, and then calcine at 350-450 ℃ for 2-4h under the protection of inactive gas.
8. The use of the nitrogen-containing copolymerized polylactic acid according to claim 6 or 7,
the particle size of tin dioxide in the tin dioxide-loaded zirconium phosphate is 10-80nm, and the content of the tin dioxide is 5-20%;
the chelating agent is EDTA or phytic acid;
the weight ratio of the zirconium phosphate to the tin tetrachloride to the chelating agent is 1: 0.8-1.2: 0.8-1.2.
9. The use of the nitrogenous copoly (lactic acid) according to any one of claims 5 to 7, wherein the flame-retardant fiber has a limiting oxygen index of not less than 30vol%, a UL94 flame-retardant rating of V0, a fiber mechanical property of 2.9 to 3.4cN/dtex, and an elongation at break of 8 to 18%.
10. The use of the nitrogen-containing copolymerized polylactic acid according to any one of claims 5 to 7,
the metal alkyl phosphinate is aluminum diethyl phosphinate and/or zinc diethyl phosphinate;
the weight ratio of the nitrogenous copolymerized polylactic acid to the polylactic acid, the alkyl phosphinic acid metal salt and the tin dioxide-loaded zirconium phosphate is 1: 0.4-2: 0.04-0.08: 0.005-0.02.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887854A (en) * | 2006-06-16 | 2007-01-03 | 中国科学院长春应用化学研究所 | Aniline oligomer, its aliphatic polyester copolymer and their prepn |
| CN101054439A (en) * | 2007-04-24 | 2007-10-17 | 上海同杰良生物材料有限公司 | High molecular weight degradation polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1887854A (en) * | 2006-06-16 | 2007-01-03 | 中国科学院长春应用化学研究所 | Aniline oligomer, its aliphatic polyester copolymer and their prepn |
| CN101054439A (en) * | 2007-04-24 | 2007-10-17 | 上海同杰良生物材料有限公司 | High molecular weight degradation polymer and preparation method thereof |
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