CN112795154A - Foaming-grade biodegradable polyester material and preparation method thereof - Google Patents
Foaming-grade biodegradable polyester material and preparation method thereof Download PDFInfo
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- CN112795154A CN112795154A CN202110130954.4A CN202110130954A CN112795154A CN 112795154 A CN112795154 A CN 112795154A CN 202110130954 A CN202110130954 A CN 202110130954A CN 112795154 A CN112795154 A CN 112795154A
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- biodegradable polyester
- foaming
- tert
- silicon dioxide
- percent
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 119
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 119
- 239000000463 material Substances 0.000 title claims abstract description 92
- 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 123
- 238000005187 foaming Methods 0.000 claims abstract description 77
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 37
- 238000001125 extrusion Methods 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 32
- 239000000314 lubricant Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims description 39
- -1 polybutylene succinate adipate Polymers 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 239000000498 cooling water Substances 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 11
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 10
- 239000004626 polylactic acid Substances 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 6
- 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 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 5
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 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
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000954 Polyglycolide Polymers 0.000 claims description 4
- 229920000331 Polyhydroxybutyrate Polymers 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
- 239000004633 polyglycolic acid Substances 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-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 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 claims description 2
- 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
- FSEJJKIPRNUIFL-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-octadecanoyloxypropyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCCCCCCCCCCCC FSEJJKIPRNUIFL-UHFFFAOYSA-N 0.000 claims description 2
- FWCDLNRNBHJDQB-UHFFFAOYSA-N [2-(hydroxymethyl)-3-octadecanoyloxy-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC FWCDLNRNBHJDQB-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- UHUSDOQQWJGJQS-UHFFFAOYSA-N glycerol 1,2-dioctadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCCCC UHUSDOQQWJGJQS-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
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-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
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 229920002961 polybutylene succinate Polymers 0.000 description 14
- 239000004631 polybutylene succinate Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 239000004088 foaming agent Substances 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 8
- 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 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000011109 contamination Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005859 coupling reaction Methods 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
- 239000006261 foam material Substances 0.000 description 2
- 230000036541 health Effects 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
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 238000012545 processing 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
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a foaming-level biodegradable polyester material which is characterized by being prepared from the following raw materials in parts by weight: 88.00-99.87% 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; 0.01 to 3.00 percent of lubricant. The invention also provides a preparation method of the foaming-grade biodegradable polyester material. The foaming-level biodegradable polyester material has high melt strength and excellent foamability, and can meet the process requirements of continuous extrusion foaming, kettle pressure foaming, mould pressing foaming and injection molding foaming.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a foaming-level biodegradable polyester material and a preparation method thereof.
Background
In recent years, the problem of "white pollution" caused by traditional plastics is becoming more and more serious, causing serious damage to the ecological environment, particularly the marine ecosystem, and seriously harming the safety and health of marine organisms and even human beings. Among these, non-degradable foams are one of the most major sources of contamination causing "white contamination". This is because the foam materials are so light in weight that they are difficult to recycle that they are expensive to recycle, ultimately resulting in a vast majority of the foam articles being disposed of, landfilled, or incinerated after use. Therefore, aiming at the field of foam products, the development of biodegradable foam materials is one of effective means for solving the problem of white pollution. In this context, biodegradable foams are gaining increasing interest in the business, academic and social industries.
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), and polyglycolic acid (PGA). However, the biodegradable polyester materials are all linear molecular structures, which results in low melt strength of the biodegradable polyester materials and difficulty in meeting the production requirements of the foam molding process. Therefore, improving the melt strength of the biodegradable polyester material is one of the key technologies for preparing biodegradable polyester foam products. The long-chain branched polyester material is prepared by introducing a long-chain branched structure into a biodegradable polyester molecular chain, so that the melt strength of the biodegradable polyester material can be effectively improved. The long-chain branched polyester material prepared by adopting the reaction technology has the advantages of continuous production, high production efficiency and low processing cost, and is most suitable for industrial large-scale production. At present, a great deal of documents and patents report that organic peroxide is used for inducing and preparing long-chain branched polyester materials so as to improve the melt strength of biodegradable polyester materials. However, this technique has a problem that the amount of the organic peroxide used is so high that the long-chain branched polyester material contains a large amount of irritant volatiles formed by the decomposition of the organic peroxide, which limits the use of the long-chain branched polyester material in the field of contact products with foods and medicines. Therefore, how to reduce the dosage of the organic peroxide to ensure that the prepared long-chain branched polyester material completely meets the food and medicine safety certification is significant for developing biodegradable polyester foam products.
Disclosure of Invention
The invention aims to solve the technical problem of providing a foaming-grade biodegradable polyester material which has high melt strength and excellent foamability and can meet the process requirements of continuous extrusion foaming, kettle pressure foaming, mould pressing foaming and injection molding foaming. The technical scheme is as follows:
a foaming-level biodegradable polyester material is characterized by being prepared from the following raw materials in parts by weight: 88.00-99.87% 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; 0.01 to 3.00 percent of lubricant.
Preferably, the foaming-grade biodegradable polyester material is prepared from the following raw materials in parts by weight: 95.20 to 99.47 percent of biodegradable polyester; 0.03-0.30% of organic peroxide; 0.10 to 1.00 percent of silane coupling agent; 0.30 to 1.50 percent of silicon dioxide particles; 0.10-2.00% of lubricant.
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 and poly (3-hydroxybutyrate-co-3-hydroxyvalerate).
Preferably, the organic peroxide is one or more of alkyl peroxide, aryl peroxide, diaryl acyl 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 tris (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.
Preferably the above lubricant comprises one or a combination of more of ethylene bis stearamide, ethylene bis-12-hydroxystearamide, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monostearate, glycerol tristearate, glycerol distearate, glycerol monostearate, erucamide and oleamide.
The invention also provides a preparation method of the foaming-grade biodegradable polyester material, which is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 88.00-99.87% of biodegradable polyester, 0.01-1.00% of organic peroxide, 0.01-3.00% of silane coupling agent, 0.10-5.00% of silicon dioxide particles and 0.01-3.00% of lubricant;
(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 a lubricant and 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 foaming-level biodegradable polyester.
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 screw length-diameter ratio 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 length of the cooling water tank used for water cooling in the step (7) is 2 to 15m, and the temperature of the cooling water is 40 to 90 ℃.
Adding the obtained granular foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt blending extrusion by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
The foaming-grade biodegradable polyester material has the following advantages:
(1) the invention adopts organic peroxide with extremely low content to induce the silane coupling agent and the biodegradable polyester to carry out grafting reaction. Because the polyester has stronger water absorption capacity, the modified polyester material strips extruded by the double-screw extruder can be cooled through the water tank at a certain temperature, and a certain water absorption capacity can be ensured, 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 function of the nano particles; on the other hand, after the silica particles are reacted with two or more silanol grafted polyester molecules at the same time, the silica particles can be used as physical branch points, and long branch structures can also be introduced into the polyester molecular chains. 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, the silicon dioxide particles have the function of enhancing the viscosity, and finally the polyester is endowed with extremely excellent melt strength, so that the stable growth of the foam holes is met, and the gas overflow is prevented. And the extremely low content of organic peroxide is decomposed to generate few volatile matters, so that the modified polyester contains few volatile matters, the modification completely conforms to the food safety certification, and no health and safety hidden danger exists for final consumers.
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 SiO2The 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 general formula (g) of the chemical reaction is that two silanol grafted polyester molecules are respectively reacted with SiO2The particles are grafted to form SiO2A 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 times2The 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 silane coupling agent and the silicon dioxide particles have good adsorption capacity on the supercritical carbon dioxide, which is not only beneficial to improving the dissolving amount of the supercritical carbon dioxide in a polyester matrix so as to improve the foaming ratio of the final polyester, but also can play a role in cell nucleation so as to improve the cell density of the polyester and improve the appearance fineness of the polyester foam.
(3) The invention adopts the double-screw reactive extrusion technology to prepare the foaming-level 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 foaming-level biodegradable polyester material disclosed by the invention can be suitable for traditional foaming forming modes such as kettle pressure foaming, mould pressing foaming, extrusion foaming and injection molding foaming, and has important significance for expanding the application field of biodegradable polyester.
Detailed Description
Example 1
In this embodiment, the preparation method of the foaming-level biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.75% of biodegradable polyester (poly butylene succinate), 0.15% of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate), 0.80% of silane coupling agent (vinyl triethoxysilane), 1.00% of silica particles (nano silica particles) and 0.30% of lubricant (glycerol monostearate);
(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 a lubricant and 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 foaming-level biodegradable polyester.
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 ℃.
Drying the obtained foaming-level biodegradable polyester at 90 ℃ for 120min, adding the dried foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
Example 2
In this embodiment, the preparation method of the foaming-level biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.80% of biodegradable polyester (polylactic acid), 0.20% of organic peroxide (tert-butyl peroxybenzoate), 0.50% of silane coupling agent (gamma-methacryloxypropyltrimethoxysilane), 0.50% of silica particles (nano-scale silica particles) and 1.00% of lubricant (ethylene bis-12-hydroxystearamide);
(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 a lubricant and 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 foaming-level biodegradable polyester.
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 adopted for water cooling in the step (7) is 5 meters, and the temperature of the cooling water is 80 ℃.
Drying the obtained foaming-level biodegradable polyester at 100 ℃ for 120min, adding the dried foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
Example 3
In this embodiment, the preparation method of the foaming-level biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: biodegradable polyester 98.10% (poly (3-hydroxybutyrate-co-3-hydroxyvalerate)), organic peroxide 0.30% (t-amyl peroxy-2-ethyl hexyl carbonate), silane coupling agent 0.60% (gamma-methacryloxypropyl trimethoxysilane), silica particles 0.50% (nano silica particles), lubricant 0.50% (pentaerythritol tetrastearate);
(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 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 0.4% of silane coupling agent on the surface of the silica particles, and mixing for 10 min;
(6) adding a lubricant and 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 foaming-level biodegradable polyester.
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 adopted for water cooling in the step (7) is 3 meters, and the temperature of the cooling water is 80 ℃.
Drying the obtained foaming-level biodegradable polyester at 95 ℃ for 120min, adding the dried foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
Example 4
In this embodiment, the preparation method of the foaming-level biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: biodegradable polyester 97.40% (polybutylene terephthalate adipate), organic peroxide 0.20% (wherein t-butyl peroxybenzoate 0.10%, t-amyl peroxy-2-ethyl hexyl carbonate 0.10%), silane coupling agent 1.00% (vinyltrimethoxysilane), silica particles 1.00% (nanoscale silica particles), lubricant 0.40% (erucamide);
(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 a lubricant and 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 foaming-level biodegradable polyester.
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 ℃.
Drying the obtained foaming-level biodegradable polyester at 80 ℃ for 120min, adding the dried foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
Example 5
In this embodiment, the preparation method of the foaming-level biodegradable polyester material sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.60 percent of biodegradable polyester (wherein the content of the biodegradable polyester is 77.60 percent, the content of polylactic acid is 20.00 percent), 0.30 percent of organic peroxide (wherein the content of n-butyl-4, 4-di (tert-butylperoxy) valerate is 0.10 percent, the content of tert-amyl peroxy-2-ethyl hexyl carbonate is 0.20 percent), 0.60 percent of silane coupling agent (wherein the content of vinyl triethoxysilane is 0.40 percent, the content of gamma-methacryloxypropyl trimethoxysilane is 0.20 percent), 0.50 percent of nano silica particles and 1.00 percent of lubricant (wherein the content of ethylene bis stearamide is 0.50 percent, and the content of ethylene bis-12-hydroxy stearamide is 0.50 percent);
(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 a lubricant and 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 foaming-level biodegradable polyester.
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 ℃.
Drying the obtained foaming-level biodegradable polyester at 90 ℃ for 120min, adding the dried foaming-level biodegradable polyester into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the biodegradable polyester foaming material.
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).
Drying the four polyester materials at 90 ℃ for 120min, then respectively adding the four polyester materials into an extrusion foaming production line, and carrying out melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the polyester foamed sheet.
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: 98.75 percent of poly butylene succinate, 0.15 percent of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate), 0.80 percent of silane coupling agent (vinyl triethoxysilane), and 0.30 percent of lubricant (glycerol monostearate);
(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) adding organic peroxide and 0.40% of silane coupling agent into polybutylene succinate, and uniformly mixing to obtain a mixed material;
(4) adding a lubricant into polybutylene succinate, and uniformly mixing to obtain a mixed material;
(5) and (3) performing melt extrusion on the mixed material through a double-screw extruder to form strips, cooling and granulating to obtain granular modified poly (butylene succinate).
The length-diameter ratio of the screw of the twin-screw extruder in the step (5) is 44: 1.
The temperature of the twin-screw extruder in the above step (5) was 165 ℃.
The cooling method in the step (5) is to cool the water by using a cooling water tank, wherein the length of the cooling water tank is 4 meters, and the temperature of the cooling water is 70 ℃.
Adding the obtained modified poly (butylene succinate) into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the modified poly (butylene succinate) foaming sheet.
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: 98.55% of polybutylene succinate, 0.15% of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate), 1.00% of silica particles (nano-scale silica particles) and 0.30% of lubricant (glycerol monostearate);
(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 a lubricant and the silicon dioxide particles obtained in the step (3) into polybutylene succinate, and uniformly mixing; and (5) carrying out melt extrusion on the mixed material through a double-screw extruder to form strips, cooling and granulating to obtain granular modified poly (butylene 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 cooling method in the step (7) is to cool the water by using a cooling water tank, wherein the length of the cooling water tank is 4 meters, and the temperature of the cooling water is 70 ℃.
Drying the obtained modified poly (butylene succinate) at 90 ℃ for 120min, adding the dried poly (butylene succinate) into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the modified poly (butylene succinate) foamed sheet.
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: 80.00 percent of poly butylene succinate and 20.00 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 melting and extruding the mixed material into strips through a double-screw extruder, cooling and granulating to obtain the granular modified polyester material.
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 ℃.
Adding the obtained modified polyester material into an extrusion foaming production line, and performing melt extrusion foaming by using supercritical carbon dioxide as a foaming agent to finally obtain the modified polyester foamed sheet.
The properties of the foamed-grade biodegradable polyester materials of examples 1-5 and the biodegradable polyesters obtained in comparative examples 1-4 were tested, wherein:
(2) melt Strength (MS) test:
the foamed-grade biodegradable polyester materials obtained in examples 1 to 5 and the biodegradable polyesters obtained in comparative examples 1 to 4 were dried in a vacuum oven at 80 ℃ for 12 hours. The melt strength of all materials was measured using a melt strength tester.
(3) And (3) testing the foaming ratio:
the foam-grade biodegradable polyester materials obtained in examples 1 to 5 and the biodegradable polyesters obtained in comparative examples 1 to 4 were allowed to stand indoors for one week, and the density of each foam sample was measured by a densitometer according to the volume exclusion theory. The expansion ratio is defined as the ratio of the initial density of the polylactic acid to the density of the polylactic acid foam sample.
The results of testing the Melt Strength (MS) and expansion ratio of the foamed-grade biodegradable polyester materials obtained in examples 1 to 5 and the biodegradable polyesters obtained in comparative examples 1 to 4 are shown in Table 1 below.
Table 1: melt Strength (MS) and expansion ratio of the products of examples
Table 2: melt Strength (MS) and expansion ratio of comparative example
From the above test results it can be seen that:
table 1 shows the melt strength and expansion ratio of the biodegradable polyester materials of foaming grade obtained in examples 1 to 5, and Table 2 shows the melt strength and expansion ratio of the biodegradable polyester obtained in comparative examples 1 to 4. In the present invention, the foaming grade biodegradable polyester materials of examples 1-5 have higher melt strength and foaming ratio than the biodegradable polyesters of comparative examples 1-4. Among them, the foaming-grade biodegradable polyester material prepared in example 1 (with the silane coupling agent and the silica particles added simultaneously) has higher melt strength and foaming ratio than the modified polybutylene succinate (with only the silane coupling agent or the silica particles added respectively) in comparative examples 2 to 3, which is attributed to the high-efficiency synergistic effect of the silane coupling agent and the silica particles, and can improve the melt strength and the foaming performance of the foaming-grade biodegradable polyester material more efficiently.
The technology disclosed by the patent is not only limited to preparation of foaming-grade biodegradable polyester materials, but also is suitable for preparation of other foaming-grade high-molecular materials, in particular foaming-grade polyester high-molecular 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 to other fields without inventive modifications, so the present invention is not limited to the above embodiments, and those skilled in the art can make improvements and modifications within the scope of the present invention.
Claims (10)
1. A foaming-level biodegradable polyester material is characterized by being prepared from the following raw materials in parts by weight: 88.00-99.87% 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; 0.01 to 3.00 percent of lubricant.
2. The foaming-grade biodegradable polyester material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight: 95.20 to 99.47 percent of biodegradable polyester; 0.03-0.30% of organic peroxide; 0.10 to 1.00 percent of silane coupling agent; 0.30 to 1.50 percent of silicon dioxide particles; 0.10-2.00% of lubricant.
3. The foam-grade 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 foam-grade 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 foamed-grade 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 foam grade biodegradable polyester material according to claim 5, wherein: 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 foam-grade biodegradable polyester material according to claim 1 or 2, characterized in that:
the silane coupling agent is one or the combination of more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane;
the lubricant comprises one or a combination of more of ethylene bis stearamide, ethylene bis-12-hydroxystearamide, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monostearate, glycerol tristearate, glycerol distearate, glycerol monostearate, erucamide, and oleamide.
8. The foam-grade 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;
the silicon dioxide particles are one or the combination of two of submicron silicon dioxide particles and nanometer silicon dioxide particles;
the silica particles are nanoscale silica particles.
9. A preparation method of a foaming-level biodegradable polyester material is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 88.00-99.87% of biodegradable polyester, 0.01-1.00% of organic peroxide, 0.01-3.00% of silane coupling agent, 0.10-5.00% of silicon dioxide particles and 0.01-3.00% of lubricant;
(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 CoDrying for 60-120min to make the water content of the silicon dioxide particles less than 200ppm, and cooling to 10-30oC；
(5) Spraying the rest silane coupling agent on the surface of the silicon dioxide particles, and mixing for 10-30 min;
(6) adding a lubricant and 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 foaming-level biodegradable polyester.
10. The preparation method of the foaming-grade biodegradable polyester material according to claim 9, wherein the foaming-grade biodegradable polyester material comprises the following steps:
the length-diameter ratio of the screw 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 DEGoC。
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| CN114045015B (en) * | 2021-12-22 | 2022-12-27 | 江苏斯尔邦石化有限公司 | Full-biodegradable foaming net and preparation method thereof |
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