CN104130490A - Thermoplastic vulcanized rubber based on polylactic acid, and preparation method thereof - Google Patents
Thermoplastic vulcanized rubber based on polylactic acid, and preparation method thereof Download PDFInfo
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses thermoplastic vulcanized rubber based on polylactic acid, and a preparation method thereof. The rubber comprises the raw materials of, by weight, 50-90 parts of ethylene-vinyl acetate rubber, 10-50 parts of polylactic acid, 0.1-3 parts of peroxide, 0.1-5 parts of a free radical stabilizing agent, 0.05-1 part of an antioxidant, 0.1-3 parts of an anti-aging agent, and 1-20 parts of a plasticizer. With the preparation method provided by the invention, the obtained thermoplastic vulcanized rubber has the characteristics of high biomass content, high strength, high elongation rate, good resilience, partial biodegradability, excellent thermoplasticity, and the like. The preparation method is simple, and industrialization can be easily realized.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of Thermoplastic Vulcanizate based on poly(lactic acid) and preparation method thereof.
Background technology
Along with the development of automobile industry, production and the usage quantity of traditional rubber, plastics grow with each passing day.Meanwhile, a kind of novel high polymer material, Thermoplastic Vulcanizate (TPV), because its advantage that has conventional plastic and rubber concurrently is rapidly developed.TPV at room temperature shows the character of rubber, at high temperature can be as plastics melt-processed, can fast, economical and machine-shaping easily, and can recycle after using, become a kind of very important novel high polymer material.
Thermoplastic Vulcanizate (TPV) is mainly made up of two parts, and the one, plastics, as external phase, the 2nd, crosslinked rubber is as disperse phase.The rubber that TPV selects at present mainly contains natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, acrylic elastomer, ethylene/vinyl acetate rubber, terpolymer EP rubber, chloroprene rubber or their blend, and the plastics of selecting mainly comprise polypropylene, polyethylene, polymeric amide, styrene-acrylonitrile copolymer, polystyrene, polycarbonate or their mixture.Publication number is that the patent of CN 1944497A discloses and a kind ofly adopts double peroxide vulcanization system to prepare the method for Thermoplastic Vulcanizate based on above-mentioned rubber and plastics.Current most typical TPV is terpolymer EP rubber 5 PDM) with polypropylene (PP) through dynamic vulcanization and making, be a large amount of solid cures EPDM microparticulate continuous PP mutually in the macromolecular elastomer material of formation.Conventionally EPDM content in TPV is 60-70wt%.Dynamic vulcanization makes the EPDM particle diameter disperseing in PP plastic substrate lower than 2 microns, and the characteristic of rubber and plastics is well combined, and obtains the elastomer material of excellent combination property.But traditional EPDM/PP thermoplastic elastomer tensile strength is not high, the tensile strength of for example EPDM/PP (60/40, wt/wt) Thermoplastic Vulcanizate is even lower than 10MPa.
Using in a large number and discarding of tradition TPV not only causes the day by day in short supply of petroleum resources, but also ecotope is done great damage.Poly(lactic acid) (PLA) is a kind of novel biodegradable plastic, can be that starting material are made by non-grain starch.Starch obtains glucose through saccharification, then makes lactic acid by glucose and certain strain fermentation, then is synthesized the poly(lactic acid) of certain molecular weight by lactic acid.PLA has good biodegradability, can be degradable by occurring in nature microorganism after use, finally generate carbonic acid gas and water, and can not cause any pollution to environment, be a kind of novel environment friendly plastics.But the Thermoplastic Vulcanizate based on poly(lactic acid) rarely has report.Recently, the patent that publication number is CN102827465A discloses a kind of degradable thermoplastic vulcanized rubber that comprises 50～80 parts of polyester type bio-based elastomericss and 50～20 parts of poly(lactic acid).The elastomerics adopting in this patent is the polyester type elastomer body of not yet large-scale production.Good degradation property is the advantage of polyester type elastomer body, but degraded is still not clear the impact of polyester type elastomer body rubber characteristic in TPV use procedure.
It is one of essential condition of the Thermoplastic Vulcanizate of processability excellence that rubber and plastics have excellent compatibility.Vinyl acetate polymer (PVAc) is completely compatible with PLA, and therefore ethylene-vinyl acetate rubber and PLA have good consistency, and consistency can obtain by the content that regulates vinyl-acetic ester in rubber.Ethylene-vinyl acetate rubber has good high temperature resistant, oil resistant, ageing-resistant performance, and can adopt peroxide cure.Therefore by ethylene-vinyl acetate rubber and poly(lactic acid) dynamic crosslinking under superoxide exists, can develop a kind of new bio base and part biological degradable thermoplastic vulcanized rubber of excellent performance.
Summary of the invention
In view of this, the object of the invention is to propose a kind of preparation method of the Thermoplastic Vulcanizate based on poly(lactic acid), to obtain, biomass content is high, intensity is high, elongation is large, stretching permanentset is little, part biological degradable, thermoplastic property excellence, the far-ranging Thermoplastic Vulcanizate of use temperature.
Based on above-mentioned purpose, a kind of Thermoplastic Vulcanizate based on poly(lactic acid) provided by the invention is made up of according to weight part proportioning separately following raw material: 50～90 parts of ethylene-vinyl acetate rubbers, 10～50 parts of poly(lactic acid), 0.1～3 part of superoxide, 0.1～5 part of free radical stabilizer, 0.05～1 part, oxidation inhibitor, 0.1～3 part, anti-aging agent, 1～20 part, softening agent.
Preferably, in described ethylene-vinyl acetate rubber, the weight percentage of vinyl-acetic ester is 45%-75%.
Preferably, the transformation period of described superoxide at 100 DEG C is not less than 1 hour, is no more than 10 minutes 170 DEG C of half-life, and can ensure under low temperature blend time, superoxide, substantially regardless of solution, at high temperature decomposes completely when dynamic vulcanization.
Alternatively, described free radical stabilizer is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound, the existence of free radical stabilizer can be in the time of superoxide fast decoupled Mulberry Extract, avoid local excessive crosslinked and cause the decline of TPV mechanical property, and the free radical being captured at the same temperature can be slowly released again, thereby reach better, more uniform cure efficiency.
Alternatively, described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010, can stop or reduce the thermooxidative degradation of ethylene-vinyl acetate rubber and poly(lactic acid) in dynamic vulcanization process.
Alternatively, described anti-aging agent is at least one in 2,2,4 trimethyl 1,2 dihydroquinoline polymer, CPPD N cyclohexyl N' phenyl p phenylene diamine and N-(1,3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine.
Alternatively, described softening agent is ester plasticizer, comprises at least one in Octyl adipate, citrate, Uniflex DBS, dioctyl sebacate and trioctyl trimellitate.Ester plasticizer and poly(lactic acid) and ethylene-vinyl acetate rubber have good consistency, therefore can improve to a greater extent prepared thermoplastic sulfurized rubber elasticity, regulate its hardness, simultaneously can also reduce its cost.
The present invention also provides a kind of preparation method of the described Thermoplastic Vulcanizate based on poly(lactic acid), comprises the following steps:
First ethylene-vinyl acetate rubber, superoxide, free radical stabilizer and anti-aging agent are mixed and obtained rubber unvulcanizate by two roller mills or Banbury mixer or screw extrusion press at 40 DEG C～100 DEG C according to weight part proportioning, calendering process is identical with traditional rubber mixing-milling technique; Then by above-mentioned rubber unvulcanizate, poly(lactic acid), oxidation inhibitor and softening agent according to weight part proportioning at 165 DEG C～200 DEG C by Banbury mixer or screw extrusion press melt blending 5～25 minutes, finally obtain a kind of taking poly(lactic acid) as matrix, cross-linked ethylene-vinyl-acetic ester rubber is the Thermoplastic Vulcanizate of disperse phase.
Alternatively, 30～200 revs/min of described closed-smelting machine rotor rotating speeds, preferably 50～100 revs/min.
Alternatively, described screw extrusion press rotating speed 80-300 rev/min, preferably 100～200 revs/min.
As can be seen from above, the preparation method of a kind of Thermoplastic Vulcanizate based on poly(lactic acid) provided by the invention can realize on traditional processing of high molecular material equipment, and cost is low, environmental friendliness, easily realize suitability for industrialized production.The Thermoplastic Vulcanizate obtaining according to preparation method provided by the invention has the features such as biomass content is high, rebound resilience good, part biological degradable, intensity is high, thermoplastic property is excellent, can be directly used in extrusion moulding, compression molding to prepare various thermoplastic elastomer goods.In addition, the additive of trace, such as tinting material, processing aid etc. can not affect the fundamental property of this bio-based Thermoplastic Vulcanizate.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
The ethylene-vinyl acetate rubber 300g that is 50% by vinyl acetate content, dicumyl peroxide 3g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 2.5g, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline polymkeric substance 2.5g mixes and within 10 minutes, obtains rubber unvulcanizate (blending condition: temperature is 80 DEG C with Banbury mixer, rotor speed is 50 revs/min), then by rubber unvulcanizate and poly(lactic acid) 200g, Uniflex DBS 15g, 1010 oxidation inhibitor 2.5g and 168 oxidation inhibitor 0.5g melt blending in Banbury mixer obtains Thermoplastic Vulcanizate (blending condition: temperature is 170 DEG C for 10 minutes, rotor speed is 50 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Embodiment 2
The ethylene-vinyl acetate rubber 350g that is 70% by vinyl acetate content, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane 7g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 1.5g, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline polymkeric substance 2.5g obtains rubber unvulcanizate for mixing 10 minutes at 40-60 DEG C with two roller mills, then by rubber unvulcanizate and poly(lactic acid) 150g, Octyl adipate 15g and 1010 oxidation inhibitor 1.5g melt blending in Banbury mixer obtains Thermoplastic Vulcanizate (blending condition: temperature is 180 DEG C for 12 minutes, rotor speed is 100 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Embodiment 3
The ethylene-vinyl acetate rubber 300g that is 50% by vinyl acetate content, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane 6g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 1g, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline polymkeric substance 1g mixes and within 10 minutes, obtains rubber unvulcanizate (blending condition: temperature is 80 DEG C with Banbury mixer, rotor speed is 50 revs/min), then by rubber unvulcanizate and poly(lactic acid) 200g, tributyl citrate 10g, 1010 oxidation inhibitor 1g and 168 oxidation inhibitor 1g melt blending in Banbury mixer obtains Thermoplastic Vulcanizate (blending condition: temperature is 180 DEG C for 10 minutes, rotor speed is 50 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Embodiment 4
The ethylene-vinyl acetate rubber 300g that is 60% by vinyl acetate content, dicumyl peroxide 2.5g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 5g, N-(1, 3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine 6g mixes and within 10 minutes, obtains rubber unvulcanizate (blending condition: temperature is 70 DEG C with Banbury mixer, rotor speed is 60 revs/min), then by rubber unvulcanizate and poly(lactic acid) 200g, dioctyl sebacate 25g and 1010 oxidation inhibitor 1g melt blending in Banbury mixer obtains Thermoplastic Vulcanizate (condition: temperature is 170 DEG C for 12 minutes, rotor speed is 80 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Embodiment 5
The ethylene-vinyl acetate rubber 350g that is 60% by vinyl acetate content, dicumyl peroxide 4g, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound 4g, 2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance 2.0g obtains rubber unvulcanizate for mixing 10 minutes at 40-60 DEG C with two roller mills, then rubber unvulcanizate and poly(lactic acid) 150g, dioctyl sebacate 10g and 1010 oxidation inhibitor 4g melt blending in Banbury mixer are obtained to Thermoplastic Vulcanizate (blending condition: temperature is 170 DEG C, rotor speed is 60 revs/min) for 12 minutes.Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Embodiment 6
The ethylene-vinyl acetate rubber 600g that is 50% by vinyl acetate content, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane 12g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 5g, N-(1, 3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine 5g mixes and within 8 minutes, obtains rubber unvulcanizate (blending condition: temperature is 80 DEG C with Banbury mixer, rotor speed is 100 revs/min), then by rubber unvulcanizate and poly(lactic acid) 400g, tributyl citrate 100g, 1010 oxidation inhibitor 2g and 168 oxidation inhibitor 2g melt extrude by twin screw extruder, obtain a kind of Thermoplastic Vulcanizate, wherein forcing machine is respectively 30 DEG C from feeding section to a mouthful temperature for mould section, 165 DEG C, 170 DEG C, 175 DEG C and 180 DEG C, screw speed is 150rpm.Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Comparative example 1
By ethylene-propylene rubber (EPDM) 300g, dicumyl peroxide 3g, 2, 2, 6, 6-tetramethyl piperidine-nitrogen-oxide compound 2.5g, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline polymkeric substance 2.5g mixes and within 10 minutes, obtains rubber unvulcanizate (blending condition: temperature is 80 DEG C with Banbury mixer, rotor speed is 50 revs/min), then by rubber unvulcanizate and poly(lactic acid) 200g, Uniflex DBS 15g, 1010 oxidation inhibitor 2.5g and 168 oxidation inhibitor 0.5g melt blending in Banbury mixer obtains Thermoplastic Vulcanizate (blending condition: temperature is 170 DEG C for 10 minutes, rotor speed is 50 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Comparative example 2
Ethylene-vinyl acetate rubber 300g, the poly(lactic acid) 200g, 2 that are 50% by vinyl acetate content, 5-dimethyl-2,5-bis-(t-butylperoxy) hexane 6g, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound 1g, 2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance 1g, tributyl citrate 10g, 1010 oxidation inhibitor 1g and 168 oxidation inhibitor 1g disposable in Banbury mixer melt blending within 10 minutes, obtain Thermoplastic Vulcanizate (blending condition: temperature is 180 DEG C, rotor speed is 50 revs/min).Thermoplastic Vulcanizate is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
Comparative example 3
The ethylene-vinyl acetate rubber 300g that is 50% by vinyl acetate content and poly(lactic acid) 200g melt blending in Banbury mixer obtains blend (blending condition: temperature is 180 DEG C, rotor speed is 50 revs/min) for 10 minutes.Blend is hot-forming by vulcanizing press, obtain the sheet Thermoplastic Vulcanizate of 1 mm thick, and be cut into standard batten for Mechanics Performance Testing according to relevant criterion, every test result is listed in table 1.
It should be noted that, poly(lactic acid) used in above each embodiment and comparative example, ethylene-vinyl acetate rubber and EPDM be all vacuum-drying 12 hours at 50 DEG C before using.Poly(lactic acid) used is the product P LA2003D of Natureworks LLC company of the U.S., and ethylene-vinyl acetate rubber used is German Lanxess Corporation product, and EPDM used is Dow Chemical company product.Other chemical assistants are commercially available prod, and purity is more than 97%.
The step of the prepared compacting of the thermoplastic elastic material based on poly(lactic acid) sheet material comprises: first the prepared thermoplastic elastic material based on poly(lactic acid) is put into mould hot pressing on vulcanizing press (180 DEG C of hot pressing temperatures, hot pressing time 4min, hot pressing pressure 15MPa) cold pressing again that (time 5min colds pressing, pressure 15MPa colds pressing), make the sheet material that thickness is 1mm, for tensile property and hardness test.
Wherein adopt electronic tensile test machine (Instron5967) at room temperature by the tensile property of standard GB/T/T528-2009 test sample, draw speed is 200mm/min; Adopt Shao Shi D type hardness tester meter according to the hardness of standard GB/T/T531.1-2008 test sample.It is to record under 100Hz condition at 200 DEG C with oscillation frequency that complex viscosity utilizes dull and stereotyped torque rheometer (TA Instruments, DHR-2).
The performance perameter of the thermoplastic elastic material based on poly(lactic acid) in table 1 embodiment and comparative example
The Thermoplastic Vulcanizate based on poly(lactic acid) obtaining by the present invention has the advantages such as biomass content is high, part biological degradable, intensity is high, rebound resilience is good compared with current traditional Thermoplastic Vulcanizate, can meet at cushioning material, car internal and external ornament product, medical equipment, the application of the aspects such as sports shoes.Compared with the Thermoplastic Vulcanizate that adopts traditional EPDM rubber to prepare with poly(lactic acid) dynamic vulcanization in comparative example 1, the Thermoplastic Vulcanizate tensile strength based on poly(lactic acid) obtaining in embodiment 1～6 has improved approximately 1～2 times, 100% tensile modulus has improved 2～4 times, simultaneously elongation at break is higher, and complex viscosity is lower at 200 DEG C.Compared with the Thermoplastic Vulcanizate based on poly(lactic acid) that adopts a step melt-blending process to prepare in comparative example 2, the Thermoplastic Vulcanizate tensile strength based on poly(lactic acid), 100% tensile modulus and the elongation at break etc. that in embodiment 1～6, obtain have and significantly improve, and complex viscosity reduces at 200 DEG C simultaneously.Compared with ethylene-vinyl acetate rubber/polylactic acid blend than not adopting dynamic vulcanization to prepare in embodiment 3, the Thermoplastic Vulcanizate tensile strength based on poly(lactic acid) obtaining in embodiment 1～6 improves 1～3 times, 100% tensile modulus has improved 4～9 times, and hardness significantly improves simultaneously.Therefore, content of the present invention is a breakthrough in composition of raw materials and performance to traditional Thermoplastic Vulcanizate.The complex viscosity of thermoplastic elastic material based on poly(lactic acid) provided by the invention under high frequency is lower, can be directly used in extrusion moulding or hot-forming, to prepare various thermoplastic elastomer goods.In addition, trace or a small amount of additive, such as processing aid, tinting material, hydrolysis-resisting agent etc. can shadow described in the fundamental property of bio-based thermoplastic elastic material.
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. the Thermoplastic Vulcanizate based on poly(lactic acid), it is characterized in that, formed according to weight part proportioning separately by following raw material: 50～90 parts of ethylene-vinyl acetate rubbers, 10～50 parts of poly(lactic acid), 0.1～3 part of superoxide, 0.1～5 part of free radical stabilizer, 0.05～1 part, oxidation inhibitor, 0.1～3 part, anti-aging agent, 1～20 part, softening agent.
2. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, is characterized in that, in described ethylene-vinyl acetate rubber, the weight percentage of vinyl-acetic ester is 45%～75%.
3. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, is characterized in that, the transformation period of described superoxide at 100 DEG C is not less than 1 hour, is no more than 10 minutes 170 DEG C of half-life.
4. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, is characterized in that, described free radical stabilizer is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound.
5. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, is characterized in that, described oxidation inhibitor is at least one in irgasfos 168 and antioxidant 1010.
6. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, it is characterized in that, described anti-aging agent is 2,2,4-trimethylammonium-1, at least one in 2-dihydroquinoline polymkeric substance, CPPD N cyclohexyl N' phenyl p phenylene diamine and N-(1,3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine.
7. a kind of Thermoplastic Vulcanizate based on poly(lactic acid) according to claim 1, is characterized in that, described softening agent is at least one in Octyl adipate, citrate, Uniflex DBS, dioctyl sebacate and trioctyl trimellitate.
8. prepare according to a preparation method for a kind of Thermoplastic Vulcanizate based on poly(lactic acid) described in any one in claim 1～7, it is characterized in that, said method comprising the steps of:
First ethylene-vinyl acetate rubber, superoxide, free radical stabilizer and anti-aging agent are mixed and obtained rubber unvulcanizate by two roller mills or Banbury mixer or screw extrusion press at 40 DEG C～100 DEG C according to weight part proportioning, then above-mentioned rubber unvulcanizate, poly(lactic acid), oxidation inhibitor and softening agent are passed through to Banbury mixer or screw extrusion press melt blending 5～20 minutes according to weight part proportioning at 165 DEG C～200 DEG C, obtain a kind of Thermoplastic Vulcanizate based on poly(lactic acid).
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| CN105585829A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | Environment-friendly flame-retardant polylactic acid composite material |
| CN109851947A (en) * | 2019-01-09 | 2019-06-07 | 青岛海湾化学有限公司 | A kind of PVC3D printed material and preparation method thereof of macromolecule plasticising |
| CN112745587A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Composition for preparing flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, and preparation method and application thereof |
| CN112745588A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Composition for preparing ethylene propylene diene monomer/polylactic acid thermoplastic vulcanized rubber, and preparation method and application thereof |
| CN112759815A (en) * | 2019-11-06 | 2021-05-07 | 中国石油化工股份有限公司 | Composition for preparing ethylene octene copolymer/polylactic acid thermoplastic vulcanized rubber, and preparation method and application thereof |
| CN114874506A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Composition for preparing thermoplastic vulcanized rubber microcellular foam material, and preparation method and application thereof |
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| CN109851947A (en) * | 2019-01-09 | 2019-06-07 | 青岛海湾化学有限公司 | A kind of PVC3D printed material and preparation method thereof of macromolecule plasticising |
| CN112745587A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Composition for preparing flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, and preparation method and application thereof |
| CN112745588A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Composition for preparing ethylene propylene diene monomer/polylactic acid thermoplastic vulcanized rubber, and preparation method and application thereof |
| CN112745587B (en) * | 2019-10-31 | 2022-09-20 | 中国石油化工股份有限公司 | Flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer composition, elastomer, and preparation method and application thereof |
| CN112759815A (en) * | 2019-11-06 | 2021-05-07 | 中国石油化工股份有限公司 | Composition for preparing ethylene octene copolymer/polylactic acid thermoplastic vulcanized rubber, and preparation method and application thereof |
| CN114874506A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Composition for preparing thermoplastic vulcanized rubber microcellular foam material, and preparation method and application thereof |
| CN114874506B (en) * | 2021-02-05 | 2024-06-04 | 中国石油化工股份有限公司 | Composition for preparing thermoplastic vulcanized rubber microporous foam material, preparation method and application thereof |
| CN115403839A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Thermoplastic elastomer microcellular foaming composition, microcellular foaming material, and preparation method and application thereof |
| CN115403839B (en) * | 2021-05-26 | 2024-06-04 | 中国石油化工股份有限公司 | Thermoplastic elastomer microporous foaming composition, microporous foaming material, preparation method and application thereof |
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