CN114350101B - Thermoplastic elastomer material, preparation method thereof and coated biodegradable resin product - Google Patents
Thermoplastic elastomer material, preparation method thereof and coated biodegradable resin product Download PDFInfo
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- CN114350101B CN114350101B CN202210079447.7A CN202210079447A CN114350101B CN 114350101 B CN114350101 B CN 114350101B CN 202210079447 A CN202210079447 A CN 202210079447A CN 114350101 B CN114350101 B CN 114350101B
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 73
- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004626 polylactic acid Substances 0.000 claims abstract description 32
- FOKFMXDJUSUVDA-UHFFFAOYSA-N C(CCC(=C)C=C)=C(C)CCC=C(C)C.C=CC1=CC=CC=C1 Chemical class C(CCC(=C)C=C)=C(C)CCC=C(C)C.C=CC1=CC=CC=C1 FOKFMXDJUSUVDA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920001400 block copolymer Polymers 0.000 claims abstract description 26
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920005586 poly(adipic acid) Polymers 0.000 claims abstract description 13
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 17
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 9
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 claims description 8
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- -1 polybutylene adipate Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 8
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
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- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
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- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
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- 238000013329 compounding Methods 0.000 description 2
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- 230000005484 gravity Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
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Abstract
The invention discloses a thermoplastic elastomer material, a preparation method thereof and a coated biodegradable resin product. The thermoplastic elastomer material is prepared from the following raw materials in parts by mass: 50-70 parts of hydrogenated styrene-beta-farnesene block copolymer; 0-40 parts of biodegradable resin; 20-30 parts of inorganic filler; and 0.25-0.5 part of auxiliary agent, wherein the biodegradable resin is at least one selected from polylactic acid and poly (adipic acid)/butylene terephthalate. The components with specific mass ratio are matched with each other to form the thermoplastic elastomer material with excellent adhesion with the biodegradable resin through synergistic effect, and the thermoplastic elastomer material has low hardness and excellent elasticity.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a thermoplastic elastomer material, a preparation method thereof and a coated biodegradable resin product.
Background
With the development of human society economy, energy shortage leads to rapid energy price rise, environmental problems brought by waste of plastic products become a current focus, and biodegradable resin materials become an important research direction at the present stage. However, the hardness of the common biodegradable resin materials such as polylactic acid (PLA), poly (adipic acid)/poly (butylene terephthalate) (PBAT) is larger, generally larger than 70A, and further adding a plasticizer for toughening can lead to oil production of the product, and some products require softer hand feeling such as keys or handles, so that the application range of the biodegradable resin materials is greatly limited.
Therefore, it is necessary to coat a layer of soft material with high elasticity on the surface of the biodegradable resin material by a secondary injection bonding process or the like, so as to further improve the soft touch feeling of the biodegradable resin material product. Thermoplastic elastomer materials (TPE) are commonly used two-shot adhesive coated materials, which have both rubber and thermoplastic properties, and are a class of plasticized and molded polymeric materials that have rubber elasticity at normal temperature and are flowable at high temperatures. The high polymer chain of the thermoplastic elastomer (TPE) consists of a plastic section (hard section) and a rubber section (elastic soft section), wherein the plastic section has reversibility, forms a physical cross-linking point at normal temperature, plays a role in restraining macromolecular components and reinforcing, loses restraining force at high temperature, is plastic, and is a high-elasticity chain section with larger free rotation capacity. However, the solubility parameters of biodegradable resin materials such as polylactic acid (PLA) and poly (butylene adipate/terephthalate) (PBAT) are greatly different from those of conventional thermoplastic elastomer materials, and the two materials are difficult to be compatible, so that the thermoplastic elastomer is difficult to adhere to the surface of the biodegradable resin materials such as polylactic acid (PLA) and poly (butylene adipate/terephthalate) (PBAT).
Thus, there is a need in the art for improvement.
Disclosure of Invention
Based on this, the present invention provides a thermoplastic elastomer material which has a low hardness, a high elasticity, and an excellent adhesion to a biodegradable resin, a method for producing the same, and a coated biodegradable resin article.
The technical scheme of the invention is as follows.
In one aspect, the invention provides a thermoplastic elastomer material, which is prepared from the following raw materials in parts by mass:
Wherein the biodegradable resin is at least one selected from polylactic acid and poly (adipic acid)/butylene terephthalate.
In some embodiments, the biodegradable resin is 10 parts to 20 parts by mass.
In some of these embodiments, the biodegradable resin is poly (adipic acid)/butylene terephthalate.
In some of these embodiments, the hydrogenated styrene- β -farnesene block copolymer has a β -farnesene molar content of not less than 70wt%, a Shore A hardness of not greater than 35, and a melt index at 230℃under a pressure of 10kg of greater than 30.
In some of these embodiments, the polybutylene adipate/terephthalate has a melt index of greater than 10, a tensile strength of greater than 10MPa, and an elongation at break of no less than 300% at 190 ℃ under a pressure of 2.16 kg; and/or
The melt index of the polylactic acid at 210 ℃ and under the pressure of 2.16kg is more than 5, the tensile strength is more than 50Mpa, and the hardness is less than 85D.
In some of these embodiments, the inorganic filler is selected from at least one of calcium carbonate, carbon black, and silica; the particle size of the inorganic filler is 0.1-5 mu m.
In some embodiments, the auxiliary agent comprises an antioxidant and an ultraviolet absorber, wherein the antioxidant is 0.15-0.3 part by weight, and the ultraviolet absorber is 0.1-0.2 part by weight.
In another aspect of the present invention, there is provided a method of preparing a thermoplastic elastomer material comprising the steps of:
the respective raw materials of the thermoplastic elastomer material described above are mixed and extruded to obtain the thermoplastic elastomer material.
In yet another aspect of the present invention, there is provided a coated biodegradable resin article comprising a biodegradable resin substrate and a coating layer coated on the surface of the biodegradable resin substrate, wherein the material of the coating layer comprises the thermoplastic elastomer material as described above.
In some of these embodiments, the biodegradable resin substrate is selected from at least one of polylactic acid and poly (adipic acid)/poly (butylene terephthalate).
The raw materials of the thermoplastic elastomer material comprise specific parts by weight of hydrogenated styrene-beta-farnesene block copolymer, specific types of biodegradable resin, inorganic filler and auxiliary agent, wherein the hydrogenated styrene-beta-farnesene block copolymer is taken as a main base material, lower hardness can be achieved without oil filling and plasticizing, and meanwhile, the thermoplastic elastomer material has high elasticity, and has synergistic effect with other components to form the thermoplastic elastomer material with excellent adhesion with the biodegradable resin, and the thermoplastic elastomer material has low hardness and excellent elasticity.
The thermoplastic elastomer material has excellent adhesion with biodegradable resin, especially with biodegradable resin such as polylactic acid (PLA), poly (adipic acid)/butylene terephthalate (PBAT), etc., and can be well coated on the surface of the biodegradable resin.
Further, the mass portion of the biodegradable resin is 10-20, and by further optimizing the mass portion of the biodegradable resin, the melt index of the thermoplastic elastomer material is further improved while the thermoplastic elastomer material and the biodegradable resin are ensured to have better adhesive property, lower hardness and excellent elasticity, so that the processing of the thermoplastic elastomer material is facilitated.
Further, the biodegradable resin is butylene terephthalate, the types of the biodegradable resin in the raw materials are further regulated, the thermoplastic elastomer material is ensured to have lower hardness and excellent elasticity, and meanwhile, the melt index is further improved, so that the thermoplastic elastomer material and the biodegradable resin have better adhesive property.
In the preparation method of the thermoplastic elastomer, specific raw materials are adopted, and the components with specific mass ratios are matched with each other to realize synergistic effect, so that the thermoplastic elastomer material with excellent cohesiveness with biodegradable resin can be obtained without an oil filling step, and the thermoplastic elastomer material with high elasticity and low hardness is simple in process flow and low in equipment requirement.
The coated biodegradable resin product comprises a biodegradable resin base material and a coating layer coated on the surface of the biodegradable resin base material, wherein the raw material of the coating layer comprises the thermoplastic elastomer material. The coated biodegradable resin product has excellent elasticity and lower hardness, and the coating layer has good adhesion with the resin base material, high elasticity, low hardness, soft touch feeling and biodegradability.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
An embodiment of the invention provides a thermoplastic elastomer material, which is prepared from the following raw materials in parts by mass:
Wherein the biodegradable resin is at least one selected from polylactic acid and poly (adipic acid)/poly (butylene terephthalate).
In some embodiments, the thermoplastic elastomer material comprises the following preparation raw materials in parts by weight:
In some embodiments, the biodegradable resin is 5-30 parts by mass.
In some embodiments, the biodegradable resin is 10 to 20 parts by mass.
By further optimizing the mass fraction of the biodegradable resin, the melt index of the thermoplastic elastomer material is further improved while the better adhesive property, lower hardness and excellent elasticity of the thermoplastic elastomer material and the biodegradable resin are ensured, thereby being beneficial to processing the thermoplastic elastomer material.
In some embodiments, the biodegradable resin is selected from polylactic acid or polybutylene adipate/terephthalate.
By further regulating the types of the biodegradable resin in the raw materials, the thermoplastic elastomer material is ensured to have lower hardness and excellent elasticity, and meanwhile, the thermoplastic elastomer material and the biodegradable resin are further improved in better adhesive property and melt index.
The hydrogenated styrene-beta-farnesene segmented copolymer is a bio-based material extracted from sugarcane, and has the advantages of plasticity, high elasticity and excellent mechanical property. The skilled person in the present invention found during the exploration: the hydrogenated styrene-beta-farnesene segmented copolymer has good compatibility with biodegradable materials such as polylactic acid (PLA), poly (adipic acid)/butylene terephthalate (PBAT), and the like, and has lower hardness without oil-filling treatment. The theory is that the block structure of the hydrogenated styrene-beta-farnesene block copolymer and the beta-farnesene can endow the copolymer with good interfacial compatibility with biodegradable materials such as polylactic acid (PLA) and poly (adipic acid)/butylene terephthalate (PBAT).
It will be appreciated that the hydrogenated styrene-beta-farnesene block copolymer described above is an oil-free hydrogenated styrene-beta-farnesene block copolymer.
In some of these embodiments, the hydrogenated styrene- β -farnesene block copolymer has a β -farnesene molar content of not less than 70wt%, a Shore A hardness of not greater than 35, and a melt index at 230℃and a pressure of 10kg of greater than 30.
It will be understood that the above-mentioned molar content of β -farnesene refers to the percentage of the number of moles of β -farnesene contained in the styrene- β -farnesene block copolymer to the total number of moles of monomers contained in the styrene- β -farnesene block copolymer.
In one embodiment, the hydrogenated styrene- β -farnesene block copolymer is selected from at least one of SF904 and SF901 of japan kuraray.
In a specific example, the hydrogenated styrene- β -farnesene block copolymer has SF904, a β -farnesene monomer content of 79% in SF904, a 15wt% toluene solution viscosity of 32mpa.s (test standard ASTM D445), a hardness of 21 (Shore A, test standard ASTM D2240), a tensile strength of 5.8MPa (test standard ASTM D412), and an elongation at break of 900% (test standard ASTM D412).
In another specific example, the hydrogenated styrene- β -farnesene block copolymer is SF901, the β -farnesene monomer content in SF901 is 70%, the viscosity of a 15wt% toluene solution thereof is 31mpa.s (test standard ASTM D445), the hardness is 26 (Shore A, test standard ASTM D2240), the tensile strength is 8Mpa (test standard ASTM D412), and the elongation at break is 640% (test standard ASTM D412).
The polylactic acid PLA is a polyester polymer obtained by taking lactic acid as a main raw material and is a novel biodegradable material. The PLA has good thermal stability, good solvent resistance and good processing performance; the poly (butylene adipate/terephthalate) PBAT is a copolymer of butylene adipate and butylene terephthalate, has good ductility and elongation at break, good heat resistance and impact property, and good biodegradability; the polylactic acid PLA and/or the polybutylene adipate/terephthalate PBAT and other components such as the hydrogenated styrene-beta-farnesene segmented copolymer can form a thermoplastic elastomer material with excellent cohesiveness with biodegradable resin, and simultaneously has low hardness, high elasticity and higher fluidity, and excellent processability.
In one embodiment, the poly (butylene adipate/terephthalate) has a melt index of greater than 10, a tensile strength of greater than 10MPa, and an elongation at break of not less than 300% at 190℃under a pressure of 2.16kg
In some embodiments, the poly (butylene adipate/terephthalate) PBAT can be selected from BASFAt least one of S BX 7025 and vinca group PBAT resin ECO-A20.
In some embodiments, the polylactic acid has a melt index of greater than 5, a tensile strength of greater than 50Mpa, and a hardness of less than 85D at 210 ℃ under a pressure of 2.16 kg.
In some embodiments, the polylactic acid is selected from at least one of PLA BX 8145 of us natureworks PLA 2003D and BASF.
The inorganic filler can reduce the production cost, improve the flexural modulus, tensile strength, ductility, shearing strength, impact resistance, compressive strength and other properties of the product, and has the most remarkable effect of providing better creep resistance and reducing compression set. Further, the inorganic filler is an inorganic mineral filler.
In some embodiments, the inorganic filler is at least one selected from the group consisting of calcium carbonate, carbon black, and silica.
Further, the particle size of the inorganic filler is 0.1 μm to 5. Mu.m.
The above-mentioned auxiliary agents may be functional auxiliary agents commonly used in the art, including but not limited to: antioxidants, anti-ultraviolet agents, and the like.
In some of these embodiments, the above-described adjuvants include antioxidants and ultraviolet absorbers; further, the antioxidant is 0.15 to 0.3 part by weight, and the ultraviolet absorber is 0.1 to 0.2 part by weight.
The antioxidant can prevent the oxidation of the polymer material from changing during the processing and using process, and the ultraviolet absorber can absorb the ultraviolet light during the processing and using process of the polymer material, so as to prevent the polymer material from changing and decomposing due to the ultraviolet irradiation during the processing and using process. The antioxidant and the ultraviolet absorber may be those commonly used in the art.
In some embodiments, the antioxidant is selected from at least one of tris (2, 4-di-tert-butylphenyl) phosphite, n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Further preferably, the antioxidant is compounded by compounding the 168 and 1076 of basf according to the mass ratio of 2:1.
In some embodiments, the ultraviolet light absorber is selected from at least one of bis (2, 6-tetramethyl-4-piperidinyl) sebacate (UV-770), 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole (UV-P), 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole (UV-326).
An embodiment of the present invention also provides a method for preparing a thermoplastic elastomer material, including the following step S10.
And step S10, mixing and extruding the raw materials of the thermoplastic elastomer material to obtain the thermoplastic elastomer material.
In the preparation method of the thermoplastic elastomer, specific raw materials are adopted, and the components with specific mass ratios are matched with each other to realize synergistic effect, so that the thermoplastic elastomer material with excellent cohesiveness with biodegradable resin can be obtained without an oil filling step, and the thermoplastic elastomer material with high elasticity and low hardness is simple in process flow and low in equipment requirement.
In some embodiments, the step of mixing includes steps S11-S12.
And S11, mixing the hydrogenated styrene-beta-farnesene block copolymer, the inorganic filler and the auxiliary agent to obtain a first mixture.
Step S12, mixing the first mixture with biodegradable resin.
When the mass fraction of the biodegradable resin in the raw material for preparing the thermoplastic elastomer material is 0, the step S12 is not required, and the first mixture is directly subjected to the subsequent extrusion step.
The above-mentioned step of mixing is carried out under stirring conditions, specifically, in a horizontal mixer.
In some embodiments, the stirring speed of the stirring is 20-40 r/min.
In some embodiments, the stirring step is performed at 20-35 ℃ for 5-10 min.
In some of these embodiments, the step of extruding described above is performed in an extruder; further, in a twin screw extruder.
Further, the temperature of the extruder is 220-240 DEG C
Further, the rotating speed of the extruder is 150 r/min-300 r/min.
Further, the aspect ratio of the extruder was (24-48): 1.
In some of these embodiments, after the step of extruding, a step of granulating is also included.
In some of these embodiments, the step of mixing further comprises a step of drying the biodegradable resin prior to the step of mixing.
Specifically, the temperature of the drying treatment is 85 ℃ and the time is 3-4 hours.
The invention also provides a coated biodegradable resin product, which comprises a biodegradable resin base material and a coating layer coated on the surface of the biodegradable resin base material, wherein the material of the coating layer comprises the thermoplastic elastomer material.
The coated biodegradable resin product has excellent elasticity and lower hardness, and the coating layer has good adhesion with the resin base material, low hardness, soft touch feeling and biodegradability.
Specifically, the thermoplastic elastomer material is coated on the surface of the biodegradable resin substrate through two-shot adhesion to form a coating layer.
Such coated biodegradable resin articles include, but are not limited to: keys, handles, etc.
In some embodiments, the resin substrate is at least one of polylactic acid and poly (adipic acid)/poly (butylene terephthalate).
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the appended claims.
Specific examples the parts in the following examples are parts by mass.
Example 1
(1) 70 Parts of hydrogenated styrene-beta-farnesene block copolymer SF904, 0.15 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.2 part of ultraviolet absorber (UV-770) and 30 parts of calcium carbonate are placed into a horizontal stirrer, and stirred for 5min at the normal temperature of 25 ℃ and the stirring rate of 30r/min, so as to obtain a first mixture.
And (3) placing the first mixture into a double-screw extruder with the rotating speed of 300r/min, the length-diameter ratio of 24:1 and the temperature of 220 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
(2) The prepared thermoplastic elastomer material is tested for Shore hardness Shore A, melt index, specific gravity, tensile strength and elongation at break, wherein the Shore hardness Shore A is tested according to ASTM D-2240, the melt index is tested according to ASTM D1238, the specific gravity is tested according to ASTM D-792, and the tensile strength and elongation at break are tested according to ASTM D-412.
Further, the prepared thermoplastic elastomer material forms an injection-bonding coating layer on the PLA resin substrate and the PBAT resin substrate respectively through secondary injection bonding to obtain encapsulated PLA and encapsulated PBAT respectively, wherein the temperature of the secondary injection bonding is 230 ℃. The peel strength of the encapsulated PLA and encapsulated PBAT were then tested, with specific tests being referred to DIN53357-1982.
Example 2
(1) 70 Parts of hydrogenated styrene-beta-farnesene block copolymer SF901, 0.3 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-P) and 20 parts of filling carbon black are placed into a horizontal stirrer, and stirred for 5min under the conditions of normal temperature 25 ℃ and stirring speed of 30r/min, so as to obtain a first mixture.
10 Parts of PBAT resin ECO-A20 is dried at 85 ℃ for 4 hours, then added into the first mixture and stirred for 5 minutes under the condition of stirring speed of 30r/min until the mixture is uniformly mixed, so as to obtain a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Example 3
(1) 70 Parts of hydrogenated styrene-beta-farnesene block copolymer SF901, 0.3 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-P) and 20 parts of filling carbon black are placed into a horizontal stirrer, and stirred for 5min under the conditions of normal temperature 25 ℃ and stirring speed of 30r/min, so as to obtain a first mixture.
10 Parts of PLA resin BX 8145 is dried at 85 ℃ for 4 hours, then added into the first mixture, and stirred for 5 minutes under the condition of stirring speed of 30r/min until the mixture is uniformly mixed, thus obtaining a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Example 4
(1) 50 Parts of hydrogenated styrene-beta-farnesene block copolymer SF904, 0.15 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-326) and 30 parts of silicon dioxide are placed in a horizontal stirrer, and stirred for 5min at the normal temperature of 25 ℃ and the stirring rate of 30r/min, so as to obtain a first mixture.
20 Parts of PBAT resinS BX 7025 is dried at 85 ℃ for 4 hours, then added into the first mixture and stirred for 5 minutes under the condition of stirring speed of 30r/min until the mixture is uniformly mixed, thus obtaining a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Example 5
(1) 50 Parts of hydrogenated styrene-beta-farnesene block copolymer SF904, 0.15 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-326) and 30 parts of silicon dioxide are placed in a horizontal stirrer, and stirred for 5min at the normal temperature of 25 ℃ and the stirring rate of 30r/min, so as to obtain a first mixture.
20 Parts of PLA resin 2003D was dried at 85℃for 4 hours, then added to the first mixture, and stirred at a stirring rate of 30r/min for 5 minutes until uniformly mixed, to obtain a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Example 6
(1) 50 Parts of hydrogenated styrene-beta-farnesene block copolymer SF904, 0.15 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-326) and 30 parts of silicon dioxide are placed in a horizontal stirrer, and stirred for 5min at the normal temperature of 25 ℃ and the stirring rate of 30r/min, so as to obtain a first mixture.
10 Parts of PBAT resinS BX 7025 and 10 parts of PLA resin 2003D were dried at 85℃for 4 hours, then added to the first mixture, and stirred at a stirring rate of 30r/min for 5 minutes until uniformly mixed, to obtain a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Comparative example 1
(1) 70 Parts of SEBS oil filling material (table rubber SEBS6151 fills oil and table plastic 150N according to the proportion of 1:2), 0.15 part of antioxidant (compounding of 168 and 1076 of Basoff according to the proportion of 2:1), 0.2 part of ultraviolet absorbent (UV-770) and 30 parts of calcium carbonate are placed into a horizontal stirrer, and stirred for 5min under the conditions of normal temperature 25 ℃ and stirring speed of 30r/min, so as to obtain a first mixture.
And (3) putting the first mixture into a double-screw extruder with the rotating speed of 300r/min, the length-diameter ratio of 24:1 and the temperature of 220 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Comparative example 2
(1) 50 Parts of hydrogenated styrene-beta-farnesene block copolymer SF904, 0.15 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.2 part of ultraviolet absorber (UV-770) and 50 parts of calcium carbonate are placed into a horizontal stirrer, and stirred for 5min at normal temperature and stirring speed of 30r/min to obtain a first mixture.
And (3) placing the first mixture into a double-screw extruder with the rotating speed of 300r/min, the length-diameter ratio of 24:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 1.
Comparative example 3
(1) 45 Parts of hydrogenated styrene-beta-farnesene block copolymer SF901, 0.3 part of antioxidant (the mixture of 168 and 1076 of Basoff is compounded according to the mass ratio of 2:1), 0.1 part of ultraviolet absorber (UV-P) and 10 parts of filling carbon black are placed into a horizontal stirrer, and stirred for 5min under the conditions of normal temperature 25 ℃ and stirring speed of 30r/min, so as to obtain a first mixture.
45 Parts of PBAT resin ECO-A20 was dried at 85℃for 4 hours, and then added to the first mixture, and stirred at a stirring rate of 30r/min for 5 minutes until uniformly mixed, to obtain a premix.
And (3) placing the premix into a double-screw extruder with the rotating speed of 150r/min, the length-diameter ratio of 48:1 and the temperature of 240 ℃ for extrusion and granulating to obtain the thermoplastic elastomer material.
Step (2) is the same as step (2) of example 2.
Comparative example 4
Comparative example 4 was identical to example 2 except that 10 parts of the PBAT resin ECO-a20 in example 2 was replaced with 10 parts of polypropylene BX3920 (korean SK copolypp with a melt index of 100 (), hardness of 64D at 230 ℃/2.16 kg). Other conditions were the same as in example 2.
The test results of examples 1 to 6 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
Wherein, peel strength A is the peel strength for the encapsulated PLA test, and peel strength P is the peel strength for the encapsulated PBAT test.
Melt index MFR was measured by referring to ASTM D1238, and the pressure was increased stepwise under the heat-retaining condition of 200 ℃ to flow the thermoplastic elastomer particles under the conditions d= (200 ℃,2.16 KG), f= (200 ℃,1 KG) in example 1 and comparative examples 1-2, which did not flow under the conditions of 200 ℃/1KG, so that the melt index was measured under the conditions D.
In comparative example 2, there was no way to test the peel strength because the material was too brittle, "/" represents no test.
Analysis of the above test data shows that: the peel strength of the encapsulated PBAT is higher than that of PLA, because the melting point of PBAT is lower than that of PLA, the PLA and PBAT solubility parameters are close, and the two can be directly blended without a compatilizer, and as can be seen from the comparison of example 2 and example 3 and the comparison of example 4 and example 5, the magnitude of the peel strength is determined to be mainly related to the melt index, and the higher the melt index, the greater the peel strength; example 1 compared to comparative example 1 shows that HSFC (hydrogenated styrene-beta-farnesene block copolymer) has some compatibility with PLA/PBAT and HSBC (SEBS) is substantially absent; comparative example 3 the hardness was very fast in the case of increasing the proportion of degradable material, and the peel strength was very fast in comparative example 4 in which the degradable material was replaced with conventional PP material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The thermoplastic elastomer material is characterized by comprising the following preparation raw materials in parts by mass:
50-70 parts of hydrogenated styrene-beta-farnesene block copolymer;
10-20 parts of biodegradable resin;
20-30 parts of inorganic filler; and
0.25-0.5 Part of auxiliary agent;
Wherein the biodegradable resin is at least one of polylactic acid and poly (adipic acid)/butylene terephthalate, and the auxiliary agent comprises an antioxidant and an ultraviolet absorber;
The molar content of beta-farnesene in the hydrogenated styrene-beta-farnesene block copolymer is not less than 70wt%, the Shore A hardness is not more than 35, and the melt index at 230 ℃ and 10kg pressure is more than 30.
2. Thermoplastic elastomer material according to claim 1, characterized in that the biodegradable resin is poly (adipic acid)/butylene terephthalate.
3. Thermoplastic elastomer material according to claim 1, characterized in that the melt index of the polybutylene adipate/terephthalate at 190 ℃ and 2.16kg pressure is greater than 10, the tensile strength is greater than 10MPa and the elongation at break is not less than 300%.
4. The thermoplastic elastomer material according to any one of claims 1 to 3, wherein the polylactic acid has a melt index of more than 5, a tensile strength of more than 50Mpa and a hardness of less than 85D at 210 ℃ under a pressure of 2.16 kg.
5. A thermoplastic elastomer material according to any one of claims 1 to 3, characterized in that the hydrogenated styrene- β -farnesene block copolymer is SF904.
6. A thermoplastic elastomer material according to any one of claims 1 to 3, wherein the inorganic filler is selected from at least one of calcium carbonate, carbon black and silica; the particle size of the inorganic filler is 0.1-5 mu m.
7. The thermoplastic elastomer material according to any one of claims 1 to 3, wherein the antioxidant is 0.15 to 0.3 parts by mass and the ultraviolet absorber is 0.1 to 0.2 parts by mass.
8. A method of preparing a thermoplastic elastomer material, comprising the steps of:
The thermoplastic elastomer material according to any one of claims 1 to 7, wherein the thermoplastic elastomer material is obtained by mixing and extruding the respective raw materials.
9. A coated biodegradable resin article comprising a biodegradable resin substrate and a coating layer coated on the surface of the biodegradable resin substrate, wherein the material of the coating layer comprises the thermoplastic elastomer material according to any one of claims 1 to 7.
10. The coated biodegradable resin article according to claim 9, characterized in that said biodegradable resin base material is at least one selected from the group consisting of polylactic acid and poly (adipic acid)/poly (butylene terephthalate).
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| CN110770297A (en) * | 2017-06-16 | 2020-02-07 | 普立万公司 | Thermoplastic elastomer compound with high biorenewable content for overmolding on non-elastomeric polymer substrates |
| DE102019204322A1 (en) * | 2019-03-28 | 2020-10-01 | Tesa Se | Shock-absorbing and flexible pressure-sensitive adhesive |
| CN113039243A (en) * | 2018-11-16 | 2021-06-25 | 艾维恩股份有限公司 | Overmolding thermoplastic elastomer compounds having high biobased content |
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| CN105001603A (en) * | 2014-11-25 | 2015-10-28 | 江苏天仁生物材料有限公司 | Fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and preparation method thereof |
| CN110770297A (en) * | 2017-06-16 | 2020-02-07 | 普立万公司 | Thermoplastic elastomer compound with high biorenewable content for overmolding on non-elastomeric polymer substrates |
| CN113039243A (en) * | 2018-11-16 | 2021-06-25 | 艾维恩股份有限公司 | Overmolding thermoplastic elastomer compounds having high biobased content |
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