CN111500061A - High-temperature-resistant P L A/PA bio-based composite material - Google Patents
High-temperature-resistant P L A/PA bio-based composite material Download PDFInfo
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- CN111500061A CN111500061A CN202010452980.4A CN202010452980A CN111500061A CN 111500061 A CN111500061 A CN 111500061A CN 202010452980 A CN202010452980 A CN 202010452980A CN 111500061 A CN111500061 A CN 111500061A
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- 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
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a high-temperature-resistant P L A/PA bio-based composite material which comprises, by weight, 0.1-5.0 parts of ethylene-vinyl acetate copolymer, 0.1-1.0 part of ADR chain extender, 0.1-0.3 part of antioxidant, 0.1-1.0 part of nucleating agent, 0.1-1.0 part of anti-hydrolysis stabilizer, 0-0.2 part of low-melting point white oil, 10-81.5 parts of P L A and 10-81.5 parts of PA.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-temperature-resistant P L A/PA bio-based composite material.
Background
The first generation polylactic acid material (P L A) takes corn starch as a raw material, is hydrolyzed into glucose, the glucose is fermented into lactic acid by microorganisms, the lactic acid is chemically synthesized into P L A, the second generation P L A mainly takes straw fibers as a raw material, the glucose is hydrolyzed into the glucose, the glucose is fermented into the lactic acid by the microorganisms, the lactic acid is chemically synthesized into P L A. P L A has transparency and can be subjected to thermoplastic molding processing, the performance of the material is similar to that of polypropylene in traditional plastics, the material is mainly used for manufacturing sheet materials, plastic uptake disposable tableware, injection molding products and the like, the material is widely used for medical biological materials, packaging products, engineering plastics of automobiles and the like, 3D printing wires and the like, the glass transition temperature of the P L A material is only 55-70 ℃, the material can be used in products which are not sensitive to temperature, such as packaging plastic uptake sheet materials, PBAT and other composite materials are used in the fields of household garbage bags, mulching films and the like, but the application in the field of electrical equipment injection molding accessories with temperature resistance requirements or petrochemical engineering has.
The production of bio-based Polyhexamethylene Adipamide (PA) mainly comprises two process routes of castor oil cracking and glucose biological fermentation. Castor oil is a fatty oil extracted by pressing castor beans, is also called as green petroleum, can be a hundred percent of plant sources, and is chemically synthesized. The PA has the common characteristics of flame resistance, good electrical insulation, excellent mechanical property, high mechanical strength, good toughness, good self-lubricating property, good friction resistance, good corrosion resistance, no mildew, no moth damage, alkali resistance, no acid and oxidant resistance and small relative density of only 1.04-1.14.
The heat resistance of the P L A is limited in many aspects due to the non-temperature resistance, at present, methods such as adding a crystallization nucleating agent and blending modification with PBS are mainly used for improving the heat resistance of the P L A material, the heat resistance is difficult to solve by adding the crystallization nucleating agent singly, the PBS is not one hundred percent of bio-based, the price is not low, the temperature resistance is limited to a certain degree and is difficult to reach more than 95 ℃, the PA has high hygroscopicity, the defects of insufficient dimensional stability and the like, and the degradation speed is slow due to the structural reason of a molecular structure.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a high-temperature-resistant P L A/PA bio-based composite material.
In order to achieve the aim, the invention adopts the technical scheme that the high-temperature-resistant P L A/PA bio-based composite material comprises, by weight, 0.1-5.0 parts of ethylene-vinyl acetate copolymer, 0.1-1.0 part of ADR chain extender, 0.1-0.3 part of antioxidant, 0.1-1.0 part of nucleating agent, 0.1-1.0 part of anti-hydrolysis stabilizer, 0-0.2 part of low-melting-point white oil, 10-81.5 parts of P L A and 10-81.5 parts of PA.
Further, the ethylene-vinyl acetate copolymer adopts LL 2505 of WAKER company of Germany or 7320M of Taiwan platicized stone of China, is a hydrolysable plasticizing material and increases the compatibility between the polymers P L A and PA.
Furthermore, the ADR chain extender adopts 4370 of Shanxi province chemical research institute (Co., Ltd.) or 4370F of Pasteur petrochemical industry, is a high-efficiency chain extender with reactivity, and increases the compatibility between the polymer P L A and the polymer PA.
Further, the antioxidant adopts 245 of Brassisted Germany or 245 of double bond chemistry of Taiwan, and prevents the thermal oxidative degradation of the polymers P L A and PA during the processing process.
Furthermore, the nucleating agent adopts TMC300 of Shanxi province chemical research institute (Co., Ltd.) or TMP3000 of Hangzhou Xianmao New Material science and technology Co., Ltd.) to improve the crystallinity of the polymer P L A and PA composite material.
Further, the stabilizer against hydrolysis adopts stabaxol-l of Laine chemical Germany or HWV-15CA of Nippon Qingji chemical to prevent the thermal oxidative degradation of the polymers P L A and PA during processing, and the low melting point white oil commercially available improves the molecular mobility of the polymers P L A and PA during processing.
Further, P L a is 4032D manufactured by natureworks, usa, or L175 manufactured by tibin, thailand.
Further, the PA is bio-based PA56 or PA510 of Kaiser (Jinxiang) biomaterials Co.
Further, the preparation method of the P L A/PA bio-based composite material comprises the steps of blending and modifying the components of the ethylene-vinyl acetate copolymer, the ADR chain extender, the antioxidant, the nucleating agent, the hydrolysis-resistant stabilizer, the low-melting-point white oil and the P L A, PA, and carrying out melt plasticizing modification through a double-screw extruder.
Further, the twin-screw extruder adopts 52D of Nanjing Keya company, and the temperature interval of the extruder is as follows: 210-215-215-220-230-235-235-230-225, 220-220-225-225-230-235-240-245-240, 230-235-235-235-240-245-245-240.
The composite material is completely an environment-friendly material from a plant-based source, and aiming at the defect that a P L A material is not high-temperature resistant or not durable, a PA material is introduced, the high temperature resistance of the PA material makes up the non-temperature resistance of a P L A material, and the rapid degradation performance of the P L A material makes up the slow degradation characteristic of the PA material, so that the high temperature resistance and the durability of the composite material can be effectively improved.
Drawings
FIG. 1 is a graph showing temporary plugging effect of the high-temperature resistant P L A/PA bio-based composite material applied to the field of oil exploitation when the temporary plugging material is used.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A high-temperature-resistant P L A/PA bio-based composite material comprises, by weight, 0.1 part of an ethylene-vinyl acetate copolymer, 0.1 part of an ADR chain extender, 0.1 part of an antioxidant, 0.1 part of a nucleating agent, 0.1 part of an anti-hydrolysis stabilizer, 0.2 part of low-melting-point white oil, 10 parts of P L A and 81.5 parts of PA.
The ethylene-vinyl acetate copolymer is prepared from LL 2505 of WAKER company, Germany or 7320M of Taiwan plastic petrochemical company, China, and is a hydrolyzable plasticized material, the compatibility between the polymers P L A and PA is increased, the ADR chain extender is prepared from 4370 of chemical research institute of Shanxi province (limited company) or 4370F of Brazilian petrochemical company, and is a high-efficiency chain extender with reaction activity, the compatibility between the polymers P L A and PA is increased, the antioxidant is prepared from 245 of Pasteur petrochemical company, Germany or 245 of Taiwan double bond chemistry, the polymer P L A and PA are prevented from thermal oxidative degradation during processing, the nucleating agent is prepared from TMC300 of Shanxi chemical research institute (limited company) or TMP3000 of Xiangxi metallocene new material science and technology, Japan, the crystallinity of polymer P L A and PA composite material is increased, the hydrolysis stabilizer is prepared from TMC-l of Laine chemistry, Japanese Qingcheng chemical engineering chemical company HWV-15CA, the polymer P L A and PA 355635 of Taiwan chemical research institute, the polymer P7 is prepared from TMC, the polymer PA 3532A and PA 5635 of Taiwan chemical research institute, the polymer PA 7 is prepared from Taiwan chemical research institute, the Takensu chemical company, the hydrolysis-PA L, the polymer PA 7 is improved, and PA 358 is prepared from Takenotsu bio-PA 7, the polymer PA 7, PA 3, PA 7, PA 3.
The preparation method of the P L A/PA bio-based composite material comprises the steps of blending and modifying ethylene-vinyl acetate copolymer, ADR chain extender, antioxidant, nucleating agent, anti-hydrolysis stabilizer, low-melting point white oil and P L A, PA in component amount, and performing melt plasticizing modification by a double-screw extruder, wherein the double-screw extruder adopts 52D of Nanjing Asia company, and the temperature range of the extruder is 210-215-.
Example two
A high-temperature-resistant P L A/PA bio-based composite material comprises, by weight, 2.5 parts of an ethylene-vinyl acetate copolymer, 0.5 part of an ADR chain extender, 0.2 part of an antioxidant, 0.5 part of a nucleating agent, 0.5 part of an anti-hydrolysis stabilizer, 0.2 part of low-melting-point white oil, 35 parts of P L A and 35 parts of PA.
The ethylene-vinyl acetate copolymer is prepared from LL 2505 of WAKER company, Germany or 7320M of Taiwan plastic petrochemical company, China, and is a hydrolyzable plasticized material, the compatibility between the polymers P L A and PA is increased, the ADR chain extender is prepared from 4370 of chemical research institute of Shanxi province (limited company) or 4370F of Brazilian petrochemical company, and is a high-efficiency chain extender with reaction activity, the compatibility between the polymers P L A and PA is increased, the antioxidant is prepared from 245 of Pasteur petrochemical company, Germany or 245 of Taiwan double bond chemistry, the polymer P L A and PA are prevented from thermal oxidative degradation during processing, the nucleating agent is prepared from TMC300 of Shanxi chemical research institute (limited company) or TMP3000 of Xiangxi metallocene new material science and technology, Japan, the crystallinity of polymer P L A and PA composite material is increased, the hydrolysis stabilizer is prepared from TMC-l of Laine chemistry, Japanese Qingcheng chemical engineering chemical company HWV-15CA, the polymer P L A and PA 355635 of Taiwan chemical research institute, the polymer P7 is prepared from TMC, the polymer PA 3532A and PA 5635 of Taiwan chemical research institute, the polymer PA 7 is prepared from Taiwan chemical research institute, the Takensu chemical company, the hydrolysis-PA L, the polymer PA 7 is improved, and PA 358 is prepared from Takenotsu bio-PA 7, the polymer PA 7, PA 3, PA 7, PA 3.
The preparation method of the P L A/PA bio-based composite material comprises the steps of blending and modifying ethylene-vinyl acetate copolymer, ADR chain extender, antioxidant, nucleating agent, anti-hydrolysis stabilizer, low-melting point white oil and P L A, PA in component amount, and performing melt plasticizing modification by a double-screw extruder, wherein the double-screw extruder adopts 52D of Nanjing Asia company, and the temperature range of the extruder is 210-215-.
EXAMPLE III
A high-temperature-resistant P L A/PA bio-based composite material comprises, by weight, 5.0 parts of an ethylene-vinyl acetate copolymer, 1.0 part of an ADR chain extender, 0.3 part of an antioxidant, 1.0 part of a nucleating agent, 1.0 part of an anti-hydrolysis stabilizer, 0.2 part of low-melting-point white oil, 81.5 parts of P L A and 81.5 parts of PA.
The ethylene-vinyl acetate copolymer is prepared from LL 2505 of WAKER company, Germany or 7320M of Taiwan plastic petrochemical company, China, and is a hydrolyzable plasticized material, the compatibility between the polymers P L A and PA is increased, the ADR chain extender is prepared from 4370 of chemical research institute of Shanxi province (limited company) or 4370F of Brazilian petrochemical company, and is a high-efficiency chain extender with reaction activity, the compatibility between the polymers P L A and PA is increased, the antioxidant is prepared from 245 of Pasteur petrochemical company, Germany or 245 of Taiwan double bond chemistry, the polymer P L A and PA are prevented from thermal oxidative degradation during processing, the nucleating agent is prepared from TMC300 of Shanxi chemical research institute (limited company) or TMP3000 of Xiangxi metallocene new material science and technology, Japan, the crystallinity of polymer P L A and PA composite material is increased, the hydrolysis stabilizer is prepared from TMC-l of Laine chemistry, Japanese Qingcheng chemical engineering chemical company HWV-15CA, the polymer P L A and PA 355635 of Taiwan chemical research institute, the polymer P7 is prepared from TMC, the polymer PA 3532A and PA 5635 of Taiwan chemical research institute, the polymer PA 7 is prepared from Taiwan chemical research institute, the Takensu chemical company, the hydrolysis-PA L, the polymer PA 7 is improved, and PA 358 is prepared from Takenotsu bio-PA 7, the polymer PA 7, PA 3, PA 7, PA 3.
The preparation method of the P L A/PA bio-based composite material comprises the steps of blending and modifying ethylene-vinyl acetate copolymer, ADR chain extender, antioxidant, nucleating agent, anti-hydrolysis stabilizer, low-melting point white oil and P L A, PA in component amount, and performing melt plasticizing modification by a double-screw extruder, wherein the double-screw extruder adopts 52D of Nanjing Asia company, and the temperature range of the extruder is 210-215-.
In specific implementation, the invention is applied in the field of oil exploitation, when the temporary plugging material is used: the GX-01 well shale oil reservoir has the vertical depth of about 4500m, the formation temperature of about 150 ℃ and the formation pressure of about 63 MPa; the perforation well section is 4503-4506m/4612-4515m, the construction displacement is 8.0m3/min, the construction liquid amount is 1200m3/min, and the construction pressure is 68-80 MPa. The composite material temporary plugging diversion agent is adopted to carry out interlayer temporary plugging diversion construction, 500kg of temporary plugging agent is added, the construction pressure before temporary plugging is 69.5MPa, the construction pressure after temporary plugging is 75.5MPa, the pressure amplitude before and after temporary plugging is about 6MPa, and the temporary plugging effect is obvious.
The degradation principle of the composite material is as follows:
the hydrolysis of P L A mainly includes 4 phenomena, namely water absorption, ester bond fracture, soluble oligomer diffusion and fragment decomposition, the main mode of degradation is bulk erosion, after P L A material is immersed in an aqueous medium or implanted into a human body, the water absorption of the material firstly occurs, the aqueous medium permeates into a polymer matrix, so that polymer molecular chains are loosened, ester bonds begin to be primarily hydrolyzed, molecular weight is reduced, and the polymer molecular chains are gradually degraded into oligomers, the terminal carboxyl groups (generated by polymerization introduction and degradation) of polylactic acid play a catalytic role in the hydrolysis, the terminal carboxyl groups increase in quantity with the progress of degradation, the degradation rate is accelerated, so that the autocatalysis phenomenon is generated, the internal degradation is faster than the surface degradation, the autocatalysis phenomenon is generated due to the fact that degradation products with the terminal carboxyl groups stay in a sample, the autocatalysis effect is generated, as the degradation progresses, more and more carboxyl groups accelerate the degradation of the internal material, the internal and external and internal differences are further increased, when the internal material is completely degraded into the soluble oligomer, and is finally dissolved into the water-insoluble small water-soluble oligomer in the aqueous medium.
The methylene-CH 2-positioned beside the NH group in the PA molecular structure is the weakest link, under the condition of the existence of oxygen at high temperature (more than 120 ℃), oxygen firstly attacks the hydrogen atom in the-CH 2-to form peroxide, the peroxide is easy to crack at high temperature to form free radicals, the free radicals pass back to attack the-CH 2-positioned beside the NH group, and then the molecular chain of the PA is cracked, namely the PA thermo-oxidative degradation process is carried out. PA suffers from hydrolysis at high temperatures in addition to thermal oxygen degradation. This is because the synthesis reaction of PA is a chemical equilibrium process, which is reversible, as shown below: n (CH2)5CH2NH2+ nHOOC- (CH2)5 → - [ (CH2)5-CO-NH-CH2- (CH2)5- ] n + nH2O, which reaction proceeds to the left when water is present at high temperature, i.e. hydrolysis, which also results in the cleavage of the PA molecular chain. When PA is processed in the molten state, the degradation process of PA itself is complex, and both thermal oxidative degradation and hydrolysis are involved.
According to the high-temperature-resistant P L A/PA bio-based composite material, in the thermal-oxidative degradation process, the degradation of P L A generates lactic acid, and the degradation of PA can be accelerated under the acidic condition of lactic acid.
The present invention and the embodiments thereof have been described above, but the description is not limited to the embodiments, but only one of the embodiments of the present invention, and the actual embodiments are not limited thereto. In conclusion, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The high-temperature-resistant P L A/PA bio-based composite material is characterized by comprising, by weight, 0.1-5.0 parts of ethylene-vinyl acetate copolymer, 0.1-1.0 part of ADR chain extender, 0.1-0.3 part of antioxidant, 0.1-1.0 part of nucleating agent, 0.1-1.0 part of anti-hydrolysis stabilizer, 0-0.2 part of low-melting-point white oil, 10-81.5 parts of P L A and 10-81.5 parts of PA.
2. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the ethylene-vinyl acetate copolymer is LL 2505 of WAKER, Germany, or 7320M of Taiwan Tahitian petrochemical, China.
3. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the ADR chain extender is 4370 from Shanxi province chemical research institute (Co., Ltd.) or 4370F from Pasteur petrochemical company.
4. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the antioxidant is 245 of Pasteur petrochemical Germany or 245 of double-bond chemistry Taiwan China.
5. The high temperature resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the nucleating agent is TMC300 from Shanxi institute of chemical technology (Inc.) or TMP3000 from Hangzhou xi New materials science and technology, Inc.
6. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the anti-hydrolysis stabilizer is stabaxol-l of Rlain chemical Germany or HWV-15CA of Qingji chemical Japan.
7. The heat-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the P L A is 4032D from natureworks or L175 from tibin of Thailand.
8. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, wherein the PA is bio-based PA56 or PA510 of Kaiser (Jinxiang) Bio-materials Co.
9. The high-temperature-resistant P L A/PA bio-based composite material as claimed in claim 1, which is prepared by blending and modifying ethylene-vinyl acetate copolymer, ADR chain extender, antioxidant, nucleating agent, anti-hydrolysis stabilizer, low-melting point white oil and P L A, PA in component amounts, and performing melt plasticizing modification by a double-screw extruder.
10. The high temperature resistant P L A/PA bio-based composite material as claimed in claim 9, wherein the double-screw extruder is 52D of Nanjing Asia, and the temperature range of the extruder is 210-215-220-230-235-220-230-220-230-235-240-230-235-240-245-240.
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Application publication date: 20200807 |