CN112920565B - High-melt-strength biodegradable polyester material and preparation method thereof - Google Patents
High-melt-strength biodegradable polyester material and preparation method thereof Download PDFInfo
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- CN112920565B CN112920565B CN202110130953.XA CN202110130953A CN112920565B CN 112920565 B CN112920565 B CN 112920565B CN 202110130953 A CN202110130953 A CN 202110130953A CN 112920565 B CN112920565 B CN 112920565B
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- biodegradable polyester
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- coupling agent
- silane coupling
- silicon dioxide
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 106
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 57
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 39
- -1 polybutylene succinate adipate Polymers 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000498 cooling water Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000004626 polylactic acid Substances 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 6
- 229920000954 Polyglycolide Polymers 0.000 claims description 5
- 239000004633 polyglycolic acid Substances 0.000 claims description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 5
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 4
- HTCRKQHJUYBQTK-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-yloxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)CC HTCRKQHJUYBQTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 4
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 4
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 2
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 claims description 2
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 claims description 2
- SYXTYIFRUXOUQP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)C SYXTYIFRUXOUQP-UHFFFAOYSA-N 0.000 claims 2
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 claims 2
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 claims 2
- 229920000728 polyester Polymers 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 22
- 229920002961 polybutylene succinate Polymers 0.000 description 17
- 239000004631 polybutylene succinate Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 10
- 239000000155 melt Substances 0.000 description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 8
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- SKVOYPCECYQZAI-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-ylperoxy carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)CC SKVOYPCECYQZAI-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical group CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 2
- CKXDKAOBYWWYEK-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1CCC(=O)OCCCCO1 CKXDKAOBYWWYEK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000021270 cold food Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000021268 hot food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a high melt strength biodegradable polyester material, which is characterized by being prepared from the following raw materials in parts by weight: 91.00-99.88% of biodegradable polyester; 0.01 to 1.00 percent of organic peroxide; 0.01 to 3.00 percent of silane coupling agent; 0.10-5.00% of silica particles. The invention also provides a preparation method of the high-melt-strength biodegradable polyester material. The high-melt-strength biodegradable polyester material has high melt strength, is green and environment-friendly, and can completely meet the requirements of a processing and forming mode related to melt stretching.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high melt strength biodegradable polyester material and a preparation method thereof.
Background
In recent years, the problem of "white contamination" caused by conventional plastics has become more severe and has become a global environmental problem. At present, "plastic restriction" has become a global consensus, and a plurality of countries and regions continue to have corresponding "plastic restriction" and "plastic prohibition" policies, including China, Korea, Thailand, Germany, France and other member countries of the European Union. Under the background, biodegradable green materials are receiving more and more attention from various enterprises in society.
Currently, biodegradable materials mainly include thermoplastic polyesters such as polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene terephthalate succinate (PBST), polybutylene terephthalate adipate (PBAT), Polyhydroxybutyrate (PHB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polypropylene carbonate (PPC), polyglycolic acid (PGA), and Polycaprolactone (PCL). The biodegradable polyester can be completely degraded into carbon dioxide and water, and the large-scale popularization of the biodegradable polyester has important significance for solving the problem of white pollution caused by non-degradable plastics. Wherein, polylactic acid, Polyhydroxyalkanoate (PHA), polyvinyl alcohol resin (PVA) and the like have higher modulus and strength, and meet the use requirements of hard products such as disposable spoons, lunch boxes, daily necessities, automotive upholsteries and the like; the poly (butylene succinate), the poly (butylene succinate adipate), the poly (butylene terephthalate), and the like have excellent flexibility and stretchability, have mechanical properties similar to polyethylene, and meet the use requirements of soft products such as shopping bags and agricultural mulching films; the polyhydroxyalkanoate, the polybutylene succinate and the like have excellent heat resistance and meet the packaging requirements of cold and hot foods; polylactic acid, polyglycolic acid, polycaprolactone and the like have excellent biocompatibility and can be applied to the product fields of surgical sutures, bone nails, sustained-release drugs and the like. Therefore, the biodegradable polyester has wide application prospect in the fields of food packaging products, disposable tableware, shopping bags, agricultural mulching films, daily necessities, automotive interior parts, medicines and the like.
However, the existing biodegradable polyesters have linear molecular structures, which results in that the intermolecular entanglement force of the biodegradable polyesters is so weak that the melt strength of the biodegradable polyesters is particularly low. As a result, the biodegradable polyester exhibits significant strain softening behavior during melt drawing, so that it is difficult for the biodegradable polyester to meet the production requirements of stretch flow field-based process forming processes, such as film blowing, bottle blowing, thermoforming, foaming, and rapid spinning. Therefore, the low melt strength of the biodegradable polyester greatly limits the processing and forming mode of the biodegradable polyester, and further weakens the competitiveness of the biodegradable polyester to the traditional non-degradable plastic product. Therefore, the improvement of the melt strength has important significance for improving the processing performance of the biodegradable polyester and promoting the industrial popularization of the biodegradable polyester.
It is reported that the melt strength of the polymer can be remarkably improved by introducing a long-chain branched structure into the molecular chain of the polymer. At present, the reported preparation methods of biodegradable long-chain branched polyester mainly comprise copolymerization technology, chain extension technology, radiation induction technology and organic peroxide induction technology. Wherein, the copolymerization technology is to adopt a branched monomer to introduce a long-chain branch into a polymer molecular chain in the polymerization process. However, the copolymerization technology has the problems of low molecular weight of the product, low production efficiency and easy environmental pollution caused by the solvent, and is not suitable for large-scale production. The chain extension technology mainly refers to that reactive compounds such as polyfunctional epoxy groups, isocyanate groups and the like are adopted as chain extenders to carry out chemical reaction with biodegradable polyester in the melt processing process. Because the reactivity of the chain extender is low, the sufficient reaction of the chain extender and the polyester needs a long time, and the chain extender is not suitable for continuous production. Also, isocyanate compounds have a large toxicity, which may limit the application of biodegradable in the field of products in contact with food. The radiation induction technology is that biodegradable polyester and multifunctional branching promoter are first mixed and then radical grafting reaction is induced with high energy ray, such as gamma ray, to form long branched chain structure. However, radiation-induced techniques suffer from the problems of step processing, non-uniform branching in the surface and interior of the product, expensive radiation equipment, and safety hazards for personnel. The organic peroxide induction technology is that organic peroxide is adopted to induce biodegradable polyester to perform free radical grafting reaction and generate a long branched chain structure in the melt processing process. However, the organic peroxide is used in a large amount, and on one hand, the organic peroxide reacts violently, so that the polyester is easy to generate a large amount of gel, and the processing fluidity of the polyester is poor; on the other hand, the organic peroxide decomposes to generate a large amount of irritant volatiles and remains in the long-chain branched polyester, which limits the application of the long-chain branched polyester to the field of food-contact products. Therefore, how to realize the high melt strength biodegradable polyester material which accords with the safety certification of food contact products has important significance for developing the biodegradable polyester material which relates to the processing and forming of a stretching flow field and expanding the application field of biodegradable polyester.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-melt-strength biodegradable polyester material which has high melt strength and is environment-friendly and can completely meet the requirement of a processing and forming mode related to melt stretching. The technical scheme is as follows:
a high melt strength biodegradable polyester material is characterized by being prepared from the following raw materials in parts by weight: 91.00-99.88% of biodegradable polyester; 0.01 to 1.00 percent of organic peroxide; 0.01 to 3.00 percent of silane coupling agent; 0.10-5.00% of silica particles.
Preferably, the high melt strength biodegradable polyester material is prepared from the following raw materials in parts by weight: 97.20 to 99.57 percent of biodegradable polyester; 0.03-0.30% of organic peroxide; 0.10 to 1.00 percent of silane coupling agent; 0.30-1.50% of silica particles.
The biodegradable polyester is a biodegradable polyester polymer material.
Preferably, the biodegradable polyester is one or more of polylactic acid, polyglycolic acid, polybutylene succinate adipate, polybutylene terephthalate adipate, polyhydroxybutyrate or poly (3-hydroxybutyrate-co-3-hydroxyvalerate).
Preferably, the organic peroxide is one or more of alkyl peroxide, aryl peroxide, diaryl peroxide, peroxyketal, peroxyester, peroxycarbonate and cyclic peroxide.
Still more preferably, the organic peroxide is t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (t-butylperoxy) valerate, ethyl-3, 3-di (t-butylperoxy) butyrate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxy-2-ethylhexyl carbonate, di (2-ethylhexyl) peroxydicarbonate, di- (tetradecyl) peroxydicarbonate, di- (hexadecyl) peroxydicarbonate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane and 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane or the combination of a plurality of the same.
Still further preferably, the organic peroxide is a combination of a peroxyester and a peroxycarbonate, wherein the peroxyester is one or a combination of more of t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (t-butylperoxy) valerate and ethyl-3, 3-di (t-butylperoxy) butyrate, and the peroxycarbonate is one or a combination of more of t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate and t-amyl peroxy-2-ethylhexyl carbonate.
Preferably, the silane coupling agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane and gamma-methacryloxypropyl trimethoxysilane.
Preferably, the silica particles are one or a combination of two of micron-sized silica particles, submicron-sized silica particles and nano-sized silica particles. More preferably, the silica particles are one or a combination of two of submicron silica particles and nanoscale silica particles. Still more preferably, the silica particles are nanoscale silica particles.
The invention also provides a preparation method of the high-melt-strength biodegradable polyester material, which is characterized by comprising the following steps of:
(1) the following raw materials are prepared by weight: 91.00-99.88% of biodegradable polyester, 0.01-1.00% of organic peroxide, 0.01-3.00% of silane coupling agent and 0.10-5.00% of silicon dioxide particles;
(2) drying the biodegradable polyester at 45-120 deg.C for 60-120min to make the water content of the biodegradable polyester less than 200ppm, and cooling to 10-30 deg.C;
(3) adding organic peroxide and a silane coupling agent which accounts for 1/3-2/3 of the total amount of the silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at the temperature of 100-150 ℃ for 60-120min to ensure that the moisture content of the silica particles is less than 200ppm, and cooling to 10-30 ℃;
(5) spraying the rest silane coupling agent on the surface of the silicon dioxide particles, and mixing for 10-30 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion on the mixed material obtained in the step (6) through a double-screw extruder to form strips, water cooling and granulating to obtain the granular biodegradable polyester with high melt strength.
The silane coupling agent is added in two times: the first addition is carried out in the step (3), and the addition amount of the silane coupling agent is 1/3-2/3 of the total amount of the silane coupling agent prepared in the step (1); and (3) performing second addition in the step (5), wherein the addition amount of the silane coupling agent is 2/3-1/3 of the total amount of the silane coupling agent prepared in the step (1).
Since the surface of the silica particle itself contains a large number of hydroxyl groups, the silane coupling agent is sprayed on the surface of the silica particle in the step (5) in order to make the silane coupling agent and the silica particle fully contact with each other, thereby facilitating the subsequent hydrolytic coupling reaction between the silane coupling agent and the silica particle.
Preferably, the length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 36:1 to 52: 1.
It is preferable that the temperature of the twin-screw extruder in the above step (7) is 75 to 220 ℃.
Preferably, the cooling water tank used for cooling in the step (7) has a length of 2 to 15m and the cooling water has a temperature of 40 to 90 ℃.
The high melt strength biodegradable polyester material of the invention has the following advantages:
(1) the invention adopts the organic peroxide with extremely low content to induce the silane coupling agent to carry out the grafting reaction with the biodegradable polyester, thereby ensuring that the modified polyester completely conforms to the food safety certification. In addition, because the polyester has stronger water absorption capacity, the modified polyester material strips extruded by the double-screw extruder can be cooled and can ensure certain water absorption capacity through a water tank at a certain temperature, so that the hydrolysis reaction of the silane coupling agent is met. Therefore, hydrolysis-grafting reaction can be carried out between the silane grafted polyesters (hydrolysis reaction is carried out on the silane grafted polyesters to obtain silanol grafted polyesters, and grafting reaction is carried out between the silanol grafted polyesters), so that a long branched chain structure is introduced into a biodegradable polyester molecular chain. In addition, the silanol grafted polyester can also carry out grafting reaction with silicon dioxide particles with a large number of hydroxyl groups on the surface, on one hand, the silanol grafted polyester is beneficial to promoting the uniform dispersion of the silicon dioxide particles and shows the special physical tackifying effect of the nano particles; on the other hand, after the silica particles can be simultaneously reacted with two or more silanol grafted polyester molecules, the silica particles can be used as physical branch points and can also play a role in enhancing the melt strength. Therefore, under the synergistic effect of the silane coupling agent and the silicon dioxide particles, a large number of long-chain branched structures are successfully introduced into the molecular chain of the biodegradable polyester, so that the entanglement among the molecular chains is greatly improved, and finally, the excellent melt strength is endowed.
The biodegradable polyester, the organic peroxide, the silane coupling agent and the silicon dioxide particles are subjected to the reaction processes of (a) - (g) and the like to obtain SiO 2 The particles are grafted with long-chain branched polyesters, wherein the reactions (a) to (d) are carried out in a twin-screw extruder and the reactions (e) to (g) are carried out during and after water cooling.
The chemical reaction general formula (a) is that organic peroxide is decomposed into small molecular free radicals by heating;
the general formula (b) of the chemical reaction is that micromolecule free radicals induce biodegradation of polyester to form polyester macromolecule free radicals;
the chemical reaction general formula (c) is that the micromolecular free radical induces the silane coupling agent to form the micromolecular free radical of the silane coupling agent;
the general formula (d) of the chemical reaction is that polyester macromolecule free radicals and silane coupling agent micromolecule free radicals are subjected to coupling reaction to form silane grafted polyester;
the general chemical reaction formula (e) is that silane grafted polyester undergoes hydrolysis reaction when meeting water to form silanol grafted polyester;
the chemical reaction general formula (f) is that two silanol grafted polyester molecules are subjected to dehydration condensation reaction to form a four-arm star-shaped structure;
the chemical reaction general formula (g) is that two silanol grafted polyester molecules are respectively reacted with SiO 2 The particles are grafted to form SiO 2 A four-arm star-like structure with particles as centers;
the chemical general formula (h) is SiO finally obtained by repeating the reactions of (f) and (g) for multiple times 2 The particles are grafted with long chain branched polyester.
The branched chain in the general chemical formula (h) is a branched chain produced by random grafting of the product of the general chemical reaction formula (f) with the product of the general chemical reaction formula (g) because the peroxide-induced radical grafting reaction is random.
(2) The invention adopts the double-screw reactive extrusion technology to prepare the high-melt-strength biodegradable polyester material, has the advantages of continuous production, high production efficiency and low processing cost, and can meet the requirement of large-scale production;
(3) the high-melt-strength biodegradable polyester material can be suitable for processing and forming modes based on a stretching field, such as kettle pressure foaming, mould pressing foaming, extrusion foaming, thermal forming, film blowing, blow molding, high-speed spinning and the like, and has important significance for expanding the application field of biodegradable polyester.
Detailed Description
Example 1
In this embodiment, the preparation method of the high melt strength biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: biodegradable polyester 98.05% (poly butylene succinate), organic peroxide 0.15% (tert-butyl peroxy-2-ethyl hexanoate), silane coupling agent 0.80% (vinyl triethoxysilane), silica particles 1.00% (nano silica particles);
(2) drying the biodegradable polyester at 90 ℃ for 90min to ensure that the moisture content of the biodegradable polyester is lower than 200ppm, and cooling to 25 ℃;
(3) adding organic peroxide and 0.40% of silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at 110 deg.C for 120min to make the moisture content of the silica particles less than 200ppm, and cooling to 30 deg.C;
(5) spraying the remaining 0.4% of silane coupling agent on the surface of the silica particles, and mixing for 20 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion on the mixed material obtained in the step (6) through a double-screw extruder to form strips, water cooling and granulating to obtain the granular biodegradable polyester with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 44: 1.
The temperature of the twin-screw extruder in the above step (7) was 165 ℃.
The length of the cooling water tank used for water cooling in the step (7) is 4 meters, and the temperature of the cooling water is 70 ℃.
Example 2
In this embodiment, the preparation method of the high melt strength biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 98.80% of biodegradable polyester (polylactic acid), 0.20% of organic peroxide (tert-butyl peroxybenzoate), 0.50% of silane coupling agent (gamma-methacryloxypropyltrimethoxysilane), and 0.50% of silica particles (nano-scale silica particles);
(2) drying the biodegradable polyester at 100 ℃ for 120min to ensure that the moisture content of the biodegradable polyester is lower than 200ppm, and cooling to 20 ℃;
(3) adding organic peroxide and 0.30% of silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at 120 deg.C for 100min to make the moisture content of the silica particles less than 200ppm, and cooling to 20 deg.C;
(5) spraying the remaining 0.2% of silane coupling agent on the surface of the silicon dioxide particles, and mixing for 15 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion on the mixed material obtained in the step (6) through a double-screw extruder to form strips, water cooling and granulating to obtain the granular biodegradable polyester with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 48: 1.
The temperature of the twin-screw extruder in the above step (7) was 195 ℃.
The length of the cooling water tank used for water cooling in the step (7) is 5 meters, and the temperature of the cooling water is 80 ℃.
Example 3
In this embodiment, the preparation method of the high melt strength biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: biodegradable polyester 98.60% (poly (3-hydroxybutyrate-co-3-hydroxyvalerate)), organic peroxide 0.30% (t-amyl peroxy-2-ethylhexyl carbonate), silane coupling agent 0.60% (gamma-methacryloxypropyl trimethoxysilane), silica particles 0.50% (nanoscaled silica particles);
(2) drying the biodegradable polyester at 95 ℃ for 80min to ensure that the moisture content of the biodegradable polyester is lower than 200ppm, and cooling to 25 ℃;
(3) adding organic peroxide and 0.2% of silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at 100 ℃ for 100min to ensure that the moisture content of the silica particles is less than 200ppm, and cooling to 20 ℃;
(5) spraying the remaining 0.4% of silane coupling agent on the surface of the silica particles, and mixing for 10 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion, strip forming, water cooling and grain cutting on the mixed material obtained in the step (5) by using a double-screw extruder to obtain the granular biodegradable polyester with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 40: 1.
The temperature of the twin-screw extruder in the above step (7) was 180 ℃.
The length of the cooling water tank used for water cooling in the step (7) is 3 meters, and the temperature of the cooling water is 80 ℃.
Example 4
In this embodiment, the preparation method of the high melt strength biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.80% of biodegradable polyester (polybutylene terephthalate adipate), 0.20% of organic peroxide (0.10% of tert-butyl peroxybenzoate and 0.10% of tert-amyl peroxy-2-ethyl hexyl carbonate), 1.00% of silane coupling agent (vinyl trimethoxy silane), and 1.00% of silica particles (nanoscale silica particles);
(2) drying the biodegradable polyester at 80 ℃ for 120min to ensure that the moisture content of the biodegradable polyester is lower than 200ppm, and cooling to 20 ℃;
(3) adding organic peroxide and 0.50% of silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at 120 deg.C for 90min to make the moisture content of the silica particles less than 200ppm, and cooling to 30 deg.C;
(5) spraying the remaining 0.5% of silane coupling agent on the surface of the silica particles, and mixing for 15 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion, strip forming, water cooling and grain cutting on the mixed material obtained in the step (6) by using a double-screw extruder to obtain the granular biodegradable polyester with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 44: 1.
The temperature of the twin-screw extruder in the above step (7) was 170 ℃.
The length of the cooling water tank used for water cooling in the step (7) is 6 meters, and the temperature of the cooling water is 65 ℃.
Example 5
In this embodiment, the preparation method of the high melt strength biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: biodegradable polyester 98.60% (wherein polybutylene succinate is 78.60%, polylactic acid is 20.00%), organic peroxide 0.30% (wherein n-butyl-4, 4-di (tert-butylperoxy) valerate 0.10%, tert-amyl peroxy-2-ethyl hexyl carbonate 0.20%), silane coupling agent 0.60% (wherein vinyltriethoxysilane 0.40%, gamma-methacryloxypropyltrimethoxysilane 0.20%), silica particles 0.50% (nano-silica particles);
(2) drying the biodegradable polyester at 90 ℃ for 120min to ensure that the moisture content of the biodegradable polyester is lower than 200ppm, and cooling to 20 ℃;
(3) adding organic peroxide and 0.40% of silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) drying the silica particles at 120 deg.C for 100min to make the moisture content of the silica particles less than 200ppm, and cooling to 30 deg.C;
(5) spraying the remaining 0.2% of silane coupling agent on the surface of the silica particles, and mixing for 20 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion on the mixed material obtained in the step (6) through a double-screw extruder to form strips, water cooling and granulating to obtain the granular biodegradable polyester with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 48: 1.
The temperature of the twin-screw extruder in the above step (7) was 180 ℃.
The length of the cooling water tank used for water cooling in the step (7) is 4 meters, and the temperature of the cooling water is 75 ℃.
Comparative example 1
In this comparative example, pure polybutylene succinate (PBS), pure polylactic acid (PLA), pure poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) or pure polybutylene terephthalate adipate (PBST).
Comparative example 2
The preparation of modified polybutylene succinate in this comparative example (the main difference from example 1 is that no silica particles are contained):
(1) the following raw materials are prepared by weight: 99.05 percent of poly butylene succinate, 0.15 percent of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate) and 0.80 percent of silane coupling agent (vinyl triethoxysilane);
(2) drying poly (butylene succinate) at 90 ℃ for 90min to ensure that the moisture content of the poly (butylene succinate) is lower than 200ppm, and cooling to 25 ℃;
(3) adding organic peroxide and 0.40% of silane coupling agent into polybutylene succinate, and uniformly mixing to obtain a mixed material;
(4) and (5) carrying out melt extrusion on the mixed material obtained in the step (4) through a double-screw extruder to form strips, cooling and granulating to obtain granular modified polybutylene succinate.
The length-diameter ratio of the screw of the twin-screw extruder in the step (4) is 44: 1.
The temperature of the twin-screw extruder in the above step (4) was 165 ℃.
The length of the cooling water tank adopted for water cooling in the step (4) is 4 meters, and the temperature of the cooling water is 70 ℃.
Comparative example 3
The preparation method of the modified polybutylene succinate in the comparative example (the main difference from the example 1 is that no silane coupling agent is contained):
(1) the following raw materials are prepared by weight: 98.85 percent of poly butylene succinate, 0.15 percent of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate) and 1.00 percent of silicon dioxide particles (nano-scale silicon dioxide particles);
(2) drying poly (butylene succinate) at 90 deg.C for 90min to make the water content of poly (butylene succinate) less than 200ppm, and cooling to 25 deg.C;
(3) drying the silica particles at 110 deg.C for 120min to make the moisture content of the silica particles less than 200ppm, and cooling to 30 deg.C;
(4) adding the silicon dioxide particles obtained in the step (3) into polybutylene succinate, and uniformly mixing;
(5) and (5) carrying out melt extrusion on the mixed material obtained in the step (4) through a double-screw extruder to form strips, cooling and granulating to obtain granular modified polybutylene succinate.
The length-diameter ratio of the screw of the twin-screw extruder in the step (7) is 44: 1.
The temperature of the twin-screw extruder in the above step (7) was 165 ℃.
The length of the cooling water tank adopted for water cooling in the step (7) is 4 meters, and the temperature of the cooling water is 70 ℃.
Comparative example 4
The preparation method of the polyester material in this comparative example (the main difference from example 1 is that organic peroxide, silane coupling agent and silica particles are not contained):
(1) the following raw materials are prepared by weight: 79.60 percent of poly butylene succinate and 20.40 percent of polylactic acid;
(2) drying poly (butylene succinate) and polylactic acid at 90 ℃ for 120min to ensure that the water content is lower than 200ppm, cooling to 20 ℃, and uniformly mixing to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder to form strips, cooling and granulating to obtain the granular polyester material with high melt strength.
The length-diameter ratio of the screw of the double-screw extruder in the step (3) is 48: 1.
The temperature of the twin-screw extruder in the above step (3) was 180 ℃.
The length of the cooling water tank adopted for water cooling in the step (3) is 4 meters, and the temperature of the cooling water is 75 ℃.
The high melt strength biodegradable polyesters obtained in examples 1 to 5 and the high melt strength polyester materials obtained in comparative examples 1 to 4 were dried in a vacuum oven at 80 ℃ for 12 hours, respectively. The Melt Strength (MS) of all samples was measured using a melt strength tester. The test results are shown in tables 1 and 2 below.
Table 1: examples Melt Strength (MS) of the product
Table 2: melt Strength (MS) of comparative example
Table 1 shows the melt strengths of the high melt strength biodegradable polyesters obtained in examples 1 to 5, and Table 2 shows the melt strengths of the high melt strength polyester materials obtained in comparative examples 1 to 4. In the present invention, the high melt strength biodegradable polyesters of examples 1 to 5 have higher melt strength than those of comparative examples 1 to 4. Among them, the high melt-strength biodegradable polyester prepared in example 1 (with the silane coupling agent and the silica particles added simultaneously) has a higher melt strength than the modified polybutylene succinate in comparative examples 2 to 3 (with only the silane coupling agent or the silica particles added, respectively), due to the highly efficient synergistic effect of the silane coupling agent and the silica particles.
The technology disclosed by the patent is not only limited to the preparation of the high-melt-strength biodegradable polyester material, but also is suitable for preparing other long-chain branched high polymer materials, particularly polyester high polymer materials. The embodiments described above are presented to facilitate an understanding and appreciation of the invention by those skilled in the art. Those skilled in the art can apply the above embodiments without inventive modifications and other fields, therefore, the present invention is not limited to the above embodiments, and those skilled in the art can make modifications and variations within the scope of the present invention.
Claims (9)
1. A high melt strength biodegradable polyester material is characterized by being prepared from the following raw materials in parts by weight: 91.00-99.88% of biodegradable polyester; 0.01 to 1.00 percent of organic peroxide; 0.01 to 3.00 percent of silane coupling agent; 0.10 to 5.00 percent of silicon dioxide particles;
the silane coupling agent is one or the combination of more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane;
the preparation method of the high-melt-strength biodegradable polyester material comprises the following steps:
(1) the following raw materials are prepared by weight: 91.00-99.88% of biodegradable polyester, 0.01-1.00% of organic peroxide, 0.01-3.00% of silane coupling agent and 0.10-5.00% of silicon dioxide particles;
(2) drying the biodegradable polyester at 45-120 deg.C for 60-120min to make the water content of the biodegradable polyester less than 200ppm, and cooling to 10-30 deg.C;
(3) adding organic peroxide and a silane coupling agent which accounts for 1/3-2/3 of the total amount of the silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) the silica particles are added at 100-150 DEG C o Drying for 60-120min to make the water content of the silicon dioxide particles less than 200ppm, and cooling to 10-30 o C；
(5) Spraying the rest silane coupling agent on the surface of the silicon dioxide particles, and mixing for 10-30 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion, strip forming, water cooling and grain cutting on the mixed material obtained in the step (6) by using a double-screw extruder to obtain the granular biodegradable polyester with high melt strength.
2. The high melt strength biodegradable polyester material according to claim 1, characterized by being prepared from the following raw materials in parts by weight: 97.20 to 99.57 percent of biodegradable polyester; 0.03-0.30% of organic peroxide; 0.10 to 1.00 percent of silane coupling agent; 0.30-1.50% of silicon dioxide particles.
3. The high melt strength biodegradable polyester material according to claim 1 or 2, characterized in that: the biodegradable polyester is one or the combination of a plurality of polylactic acid, polyglycolic acid, polybutylene succinate adipate, polybutylene terephthalate adipate, polyhydroxybutyrate or poly (3-hydroxybutyrate-co-3-hydroxyvalerate).
4. The high melt strength biodegradable polyester material according to claim 1 or 2, characterized in that: the organic peroxide is one or the combination of more of alkyl peroxide, aryl peroxide, diaryl acyl peroxide, peroxyketal, peroxyester, peroxycarbonate and cyclic peroxide.
5. The high melt strength biodegradable polyester material according to claim 4, characterized in that: the organic peroxide is tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (tert-butylperoxy) valerate, ethyl-3, 3-di (tert-butylperoxy) butyrate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, di (2-ethylhexyl) peroxydicarbonate, di- (tetradecyl) peroxydicarbonate, di- (hexadecyl) peroxydicarbonate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane or the combination of a plurality of the 6, 9-trimethyl-1, 4, 7-triperoxonane.
6. The high melt strength biodegradable polyester material according to claim 5, characterized in that: the organic peroxide is a combination of peroxyester and peroxycarbonate, wherein the peroxyester is one or more of tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (tert-butylperoxy) valerate and ethyl-3, 3-di (tert-butylperoxy) butyrate, and the peroxycarbonate is one or more of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate and tert-amyl peroxy-2-ethylhexyl carbonate.
7. The high melt strength biodegradable polyester material according to claim 1 or 2, characterized in that: the silicon dioxide particles are one or the combination of two of micron-sized silicon dioxide particles, submicron-sized silicon dioxide particles and nanometer-sized silicon dioxide particles.
8. A preparation method of a high melt strength biodegradable polyester material is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 91.00-99.88% of biodegradable polyester, 0.01-1.00% of organic peroxide, 0.01-3.00% of silane coupling agent and 0.10-5.00% of silicon dioxide particles;
the silane coupling agent is one or the combination of more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane; (2) drying the biodegradable polyester at 45-120 deg.C for 60-120min to make the water content of the biodegradable polyester less than 200ppm, and cooling to 10-30 deg.C;
(3) adding organic peroxide and a silane coupling agent which accounts for 1/3-2/3 of the total amount of the silane coupling agent into biodegradable polyester, and uniformly mixing to obtain a mixed material;
(4) the silicon dioxide particles are mixed at 100-150 DEG C o Drying for 60-120min to make the water content of the silicon dioxide particles less than 200ppm, and cooling to 10-30 o C；
(5) Spraying the rest silane coupling agent on the surface of the silicon dioxide particles, and mixing for 10-30 min;
(6) adding the silicon dioxide particles obtained in the step (5) into the mixed material obtained in the step (3), and uniformly mixing;
(7) and (4) carrying out melt extrusion, strip forming, water cooling and grain cutting on the mixed material obtained in the step (6) by using a double-screw extruder to obtain the granular biodegradable polyester with high melt strength.
9. The method of claim 8, wherein the step of preparing the high melt strength biodegradable polyester material comprises:
the length-diameter ratio of the screws of the double-screw extruder in the step (7) is 36:1-52: 1;
the temperature of the twin-screw extruder in the step (7) is 75-220 ℃;
the length of the cooling water tank adopted for water cooling in the step (7) is 2-15m, and the temperature of the cooling water is 40-90 DEG o C。
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| US20240416572A1 (en) * | 2021-09-29 | 2024-12-19 | Kaneka Corporation | Blow-molded article and method for producing the same |
| CN114410091B (en) * | 2022-01-27 | 2023-10-17 | 万华化学（宁波）有限公司 | High-temperature-resistant impact-resistant high-strength modified polylactic acid material and preparation method thereof |
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