CN113265029A - Long-chain branched polylactic acid with high melt strength and excellent processing fluidity and preparation method thereof - Google Patents
Long-chain branched polylactic acid with high melt strength and excellent processing fluidity and preparation method thereof Download PDFInfo
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- CN113265029A CN113265029A CN202011351873.9A CN202011351873A CN113265029A CN 113265029 A CN113265029 A CN 113265029A CN 202011351873 A CN202011351873 A CN 202011351873A CN 113265029 A CN113265029 A CN 113265029A
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- butyl
- polylactic acid
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- peroxide
- propyl
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 159
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 155
- 238000012545 processing Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 27
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 20
- 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 14
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkyl peroxide Chemical class 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 claims description 6
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 6
- 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 5
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- SYXTYIFRUXOUQP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)C SYXTYIFRUXOUQP-UHFFFAOYSA-N 0.000 claims description 3
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 claims description 3
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 2
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 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
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims 1
- MDTFTYSXAXXQKG-UHFFFAOYSA-N CCCCC(C(CCC)=C(C(C)(C)C)C=C1)=C1C(OO)=O Chemical compound CCCCC(C(CCC)=C(C(C)(C)C)C=C1)=C1C(OO)=O MDTFTYSXAXXQKG-UHFFFAOYSA-N 0.000 claims 1
- JWXUKKHHBQASIW-UHFFFAOYSA-N CCCCC(C)(CCCC)C(C(C)(C)C)OOC(C(C)(C)C)C(C)(CCCC)CCCC Chemical compound CCCCC(C)(CCCC)C(C(C)(C)C)OOC(C(C)(C)C)C(C)(CCCC)CCCC JWXUKKHHBQASIW-UHFFFAOYSA-N 0.000 claims 1
- KZAFXLWXFGOIEZ-UHFFFAOYSA-N CCCCC(C)C(C(C)(C)C)OC(OO)=O Chemical compound CCCCC(C)C(C(C)(C)C)OC(OO)=O KZAFXLWXFGOIEZ-UHFFFAOYSA-N 0.000 claims 1
- RESUXAQRZZEAGD-UHFFFAOYSA-N CCCCC(CCCC)C(C)OC(OO)=O Chemical compound CCCCC(CCCC)C(C)OC(OO)=O RESUXAQRZZEAGD-UHFFFAOYSA-N 0.000 claims 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical compound CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000155 melt Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004970 Chain extender Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- QAPLQMROVGLYLM-UHFFFAOYSA-N 2-butan-2-ylperoxybutane Chemical compound CCC(C)OOC(C)CC QAPLQMROVGLYLM-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 4
- 229920005692 JONCRYL® Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003856 thermoforming Methods 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
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000009987 spinning Methods 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
- 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 1
- 239000002028 Biomass Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 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 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 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 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
Abstract
The invention discloses a long-chain branched polylactic acid with high melt strength and excellent processing fluidity, which is characterized by being prepared from the following raw materials in parts by weight: 93.00 to 99.80 percent of polylactic acid; 0.10 to 2.00 percent of organic peroxide; 0.1 to 5.00 percent of branching regulator. The invention also provides a preparation method of the long-chain branched polylactic acid with high melt strength and excellent processing fluidity. The invention adopts a compound containing one vinyl or allyl and one epoxy bond or isocyanate group as a branching control agent, and adopts a reactive extrusion technology to uniformly introduce a long-chain branching structure into a polylactic acid molecular chain, so that the long-chain branching polylactic acid has excellent melt strength and processing fluidity.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to long-chain branched polylactic acid with high melt strength and excellent processing fluidity and a preparation method thereof.
Background
The polylactic acid (PLA) is completely derived from biomass resources such as corn, cane sugar and the like, and has the characteristics of complete biodegradability, biocompatibility and the like. Compared with other degradable materials, such as Polycaprolactone (PCL), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), polybutylene adipate/terephthalate (PBAT) and the like, polylactic acid has the advantages of being maximum in productivity, lowest in price, best in comprehensive performance, wide in application field and the like, is considered to be a green and environment-friendly new material with the best industrial application prospect, and is expected to gradually replace part of traditional non-degradable plastic products.
However, polylactic acid, a straight-chain aliphatic polyester, has a particularly low melt strength, and therefore, strain hardening is insufficient, and it is difficult to satisfy the requirements of stretch flow field-based processing and molding processes such as film blowing, bottle blowing, thermoforming, foaming, and spinning. For example, polylactic acid has problems of unstable bubble, easy breaking, uneven thickness, low production efficiency, etc. in the film blowing process, products have uneven thickness and easy breaking in the thermoforming process, and problems of uneven bubble size, easy hole opening and hole merging, etc. in the foaming process. In addition, the polylactic acid has a very narrow melt molding temperature window, and when the processing temperature is low, insufficient plasticization is likely to be caused, and melt processing is difficult, and when the processing temperature is high, degradation is likely to occur, and the final performance is reduced. Therefore, the improvement of the melt strength of the polylactic acid has important significance for improving the processability and promoting the industrial popularization of the polylactic acid.
It is reported that the melt strength of polylactic acid can be obviously improved by introducing a long-chain branched structure into the molecular chain of the polylactic acid. At present, the reported preparation methods of long-chain branched polylactic acid mainly comprise copolymerization technology, reactive extrusion technology and radiation induction technology. Wherein, the reactive extrusion technology has the advantages of low cost, simple and convenient operation and high production efficiency, and is most suitable for industrialized application. Specifically, in the melt extrusion process, on one hand, a multifunctional chain extender and a terminal hydroxyl group of polylactic acid or a terminal carboxyl group of polylactic acid perform a terminal group chemical reaction, and on the other hand, an organic peroxide induces polylactic acid or polylactic acid compounded by acrylate/allyl compounds to perform a free radical grafting reaction, so that a long-chain branched structure is introduced into a polylactic acid molecular chain. As shown in FIG. 1, the functional groups in the multifunctional branching promoter are all subjected to a grafting reaction with the middle position of the polylactic acid molecular chain, so that the structure of the generated long-chain branched polylactic acid is a four-arm, six-arm or even more-arm branched structure. Although the melt strength of polylactic acid can be improved by adopting a reaction extrusion technology to endow a long-chain branched structure to the polylactic acid, the shear viscosity of the long-chain branched polylactic acid is increased sharply, so that the processability of the polylactic acid is greatly reduced. On the basis that the shear viscosity of the polylactic acid is not greatly improved, the melt strength of the polylactic acid is greatly improved, and the method has important significance for developing the polylactic acid product formed by processing in a stretching flow field and expanding the application field of the polylactic acid product.
Disclosure of Invention
The invention aims to solve the technical problem of providing long-chain branched polylactic acid with high melt strength and excellent processing flowability. The technical scheme is as follows:
a long-chain branched polylactic acid with high melt strength and excellent processing fluidity is characterized by being prepared from the following raw materials in parts by weight: 93.00 to 99.80 percent of polylactic acid; 0.10 to 2.00 percent of organic peroxide; 0.1 to 5.00 percent of branching regulator.
Preferably, the long-chain branched polylactic acid with high melt strength and excellent processing fluidity is prepared from the following raw materials in parts by weight: 96.00-99.50% of polylactic acid; 0.20 to 1.00 percent of organic peroxide; 0.3 to 3.00 percent of branching regulator.
Preferably, the polylactic acid is one or a combination of more of L-type polylactic acid, D-type polylactic acid and LD-type polylactic acid.
Preferably, the organic peroxide is one or more of alkyl peroxide, aryl peroxide, diarylacyl peroxide, peroxyketal, peroxyester, peroxycarbonate, and cyclic peroxide.
Still more preferably, the organic peroxide is di-t-butyl peroxide, 2-di-t-butylperoxybutane, 2, 5-dimethylhexane-2, 5-di-t-butyl peroxide, 2, 5-dimethyl-3-hexyne-2, 5-di-t-butyl peroxide, dicumyl peroxide, bis (2-t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, 5, 5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxy-2-ethylhexyl carbonate, dibenzoyl peroxide, dicumyl peroxide, bis (2-t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, t-butylperoxy-benzoate, t-butylperoxy-2-ethylhexyl carbonate, t-ethyl hexanoate, di-2, di-t-butyl peroxy-2-ethyl hexanoate, di-butyl peroxy-2-isopropyl carbonate, di-butyl peroxide, dicumyl peroxide, di-2-butyl peroxide, dicumyl peroxide, di-2-butyl peroxide, dicumyl peroxide, di-butyl peroxide, dicumyl peroxide, di-2-butyl peroxide, di-butyl peroxide, dicumyl peroxide, di-butyl peroxide, dicumyl peroxide, di-2-butyl peroxide, di-2-butyl peroxide, di, One or a combination of more of bis (4-methylbenzoyl) peroxide, 1, 3-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, ethyl-3, 3-bis (t-butylperoxy) butyrate, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, and 3,3,6,6,9, 9-hexamethyl-1, 2,4, 5-tetrapentane tetroxide.
Still more 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-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (t-butylperoxy) valerate and ethyl-3, 3-di (t-butylperoxy) butyrate; the peroxycarbonate is one or the combination of more of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy2-ethylhexyl carbonate and tert-amyl peroxy2-ethylhexyl carbonate.
Preferably, the molecular structure general formula of the branching regulator is: r1-R-R2Wherein R is C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl or C7-C20Alkaryl groups, which groups may comprise straight or branched alkyl moieties; r1Is a group containing a carbon-carbon double bond such as a vinyl group, an allyl group, an acrylate group or a methacrylate groupClustering; r2The reactive group is an active group such as an epoxy group or an isocyanate group which can chemically react with a terminal hydroxyl group of the polylactic acid and/or a terminal carboxyl group of the polylactic acid.
More preferably, the molecular structure of the branching control agent contains one vinyl group or allyl group and one epoxy group or isocyanate group at the same time. More preferably, the branching control agent is one or more of 4-vinylbenzyl glycidyl ether, allyl glycidyl ether, isocyanate ethyl acrylate, isocyanoethyl methacrylate, allyl isocyanate, vinyl isocyanate, and 3-isopropenyl- α, α -dimethylbenzyl isocyanate. Still more preferably, the branching control agent is one or a combination of 4-vinylbenzyl glycidyl ether and 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate.
The invention also provides a preparation method of the long-chain branched polylactic acid with high melt strength and excellent processing fluidity, which is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 93.00 to 99.80 percent of polylactic acid; 0.10 to 2.00 percent of organic peroxide; 0.1 to 5.00 percent of branched regulator;
(2) drying polylactic acid at 90-120 deg.C for 60-120min to make the water content of polylactic acid less than 200ppm, and cooling to 10-30 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
Preferably, the screw length-diameter ratio of the twin-screw extruder in the step (4) is 36:1 to 52: 1.
The temperature of the twin-screw extruder in the above step (4) is preferably 180-.
In step (4), the granulation method generally includes the steps of drawing strips, cooling (e.g., air cooling), granulating, and the like.
The long-chain branched polylactic acid with high melt strength and excellent processing fluidity has the following advantages:
(1) the invention adopts the branching regulating and controlling agent to regulate and control the molecular topological structure of the long-chain branching polylactic acid, and in the melt extrusion process, the branching regulating and controlling agent can not only carry out chemical reaction with the terminal hydroxyl group of the polylactic acid or the terminal carboxyl group of the polylactic acid, but also carry out free radical grafting reaction with the polylactic acid under the initiation action of organic peroxide, thereby introducing the long-chain branching structure into the molecular chain of the polylactic acid. As one selected branch regulator molecule can introduce one long-chain branching structure into a polylactic acid molecular chain at most, the long-chain branching structure distribution in the finally prepared long-chain branching polylactic acid can be imagined to be more uniform, so that the melt strength of the polylactic acid is more efficiently improved, and the shear viscosity of the polylactic acid is only improved in a small range. Finally, the long-chain branched polylactic acid not only meets the processing and forming requirements related to a stretching flow field, but also has excellent processing and flowing properties.
As shown in fig. 2, the molecular structure of the branching control agent contains two functional groups at the same time, wherein one functional group is subjected to a grafting reaction with the middle position of the polylactic acid molecular chain, and the other functional group is subjected to a grafting reaction with the head of the polylactic acid molecular chain, so that the structure of the generated long-chain branched polylactic acid is a three-arm branched structure, and the generation of other more-arm branched structures by the long-chain branched polylactic acid is avoided. The three-arm branched structure can greatly reduce the shear viscosity and greatly improve the processing performance.
(2) The invention adopts the double-screw reactive extrusion technology to prepare the long-chain branched polylactic acid with high melt strength and excellent processing fluidity, has the advantages of simple and convenient operation, high production efficiency, low processing cost and strong controllability, and can meet the requirement of large-scale production;
(3) the long-chain branched polylactic acid with high melt strength and excellent processing fluidity can be suitable for processing and forming modes involving a melt stretching field, such as kettle pressure foaming, mould pressing foaming, extrusion foaming, thermoforming, film blowing, blow molding, spinning and the like, and has the advantages of high production efficiency and low processing energy consumption due to the excellent processing fluidity.
Drawings
FIG. 1 is a general chemical reaction diagram of a four-arm or six-arm branched structure of a long-chain branched polylactic acid in the background of the invention;
FIG. 2 is a general chemical reaction diagram of the three-arm branched structure of long-chain branched polylactic acid in the context of the present invention.
Detailed Description
Example 1
In this embodiment, the preparation method of the long-chain branched polylactic acid with both high melt strength and excellent processing fluidity sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 98.30 percent of polylactic acid, 0.50 percent of organic peroxide (tert-amyl peroxy-2-ethylhexyl carbonate) and 1.20 percent of branching regulator (4-ethylene benzyl glycidyl ether);
(2) drying polylactic acid at 100 deg.C for 120min to make the water content of polylactic acid less than 200ppm, and cooling to 20 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
The length-diameter ratio of the screw of the double-screw extruder in the step (4) is 48: 1.
The temperature of the twin-screw extruder in the above step (4) was 180 ℃.
In step (4), the granulation method generally comprises the steps of drawing strips, air cooling, granulating and the like.
Example 2
In this embodiment, the preparation method of the long-chain branched polylactic acid with both high melt strength and excellent processing fluidity sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.70% of polylactic acid, 1.50% of organic peroxide (tert-amyl peroxy-2-ethylhexyl carbonate) and 1.80% of branching regulator (4-vinylbenzyl glycidyl ether);
(2) drying polylactic acid at 115 deg.C for 60min to make the water content of polylactic acid less than 200ppm, and cooling to 20 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
The length-diameter ratio of the screw of the twin-screw extruder in the step (4) is 52: 1.
The temperature of the twin-screw extruder in the above step (4) was 200 ℃.
In step (4), the granulation method generally comprises the steps of drawing strips, air cooling, granulating and the like.
Example 3
In this embodiment, the preparation method of the long-chain branched polylactic acid with both high melt strength and excellent processing fluidity sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 95.80% of polylactic acid, 1.20% of organic peroxide (tert-amyl peroxy-2-ethylhexyl carbonate) and 2.50% of branching regulator (4-vinylbenzyl glycidyl ether);
(2) drying polylactic acid at 120 deg.C for 80min to make the water content of polylactic acid less than 200ppm, and cooling to 25 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
The length-diameter ratio of the screw of the double-screw extruder in the step (4) is 48: 1.
The temperature of the twin-screw extruder in the above step (4) was 220 ℃.
In step (4), the granulation method generally comprises the steps of drawing strips, air cooling, granulating and the like.
Example 4
In this embodiment, the preparation method of the long-chain branched polylactic acid with both high melt strength and excellent processing fluidity sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 97.70% of polylactic acid, 1.00% of organic peroxide (wherein, 0.50% of n-butyl-4, 4-di (tert-butylperoxy) valerate and 0.50% of tert-amyl peroxy-2-ethyl hexyl carbonate), 1.30% of branched regulator (3-isopropenyl-alpha, alpha-dimethyl benzyl isocyanate);
(2) drying the polylactic acid at 100 ℃ for 90min to ensure that the moisture content of the polylactic acid is less than 200ppm, and cooling to 25 ℃;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
The length-diameter ratio of the screw of the double-screw extruder in the step (4) is 48: 1.
The temperature of the twin-screw extruder in the above step (4) was 200 ℃.
In step (4), the granulation method generally comprises the steps of drawing strips, air cooling, granulating and the like.
Example 5
In this embodiment, the preparation method of the long-chain branched polylactic acid with both high melt strength and excellent processing fluidity sequentially comprises the following steps:
(1) the following raw materials are prepared by weight: 96.40% of polylactic acid, 2.00% of organic peroxide (wherein the n-butyl-4, 4-di (tert-butylperoxy) valerate is 0.10%, the tert-amyl peroxy-2-ethylhexyl carbonate is 0.10%), 1.60% of branched regulator (wherein the 4-ethylene benzyl glycidyl ether is 0.80%, and the 3-isopropenyl-alpha, alpha-dimethyl benzyl isocyanate is 0.80%);
(2) drying polylactic acid at 95 deg.C for 110min to make the water content of polylactic acid less than 200ppm, and cooling to 15 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
The length-diameter ratio of the screw of the twin-screw extruder in the step (4) is 52: 1.
The temperature of the twin-screw extruder in the above step (4) was 210 ℃.
In step (4), the granulation method generally comprises the steps of drawing strips, air cooling, granulating and the like.
Comparative example 1
In this comparative example, pure polylactic acid was used.
Comparative example 2
The preparation method of polylactic acid in this comparative example is different from that of example 1 in that:
the polylactic acid is prepared from the following raw materials in parts by weight: 98.30% of polylactic acid, 0.50% of tert-amyl peroxy-2-ethylhexyl carbonate and 1.20% of triallyl benzenetricarboxylate.
The preparation process is as follows:
(1) drying polylactic acid at 120 deg.C for 60min to make the water content of polylactic acid less than 250ppm, and cooling to 20 deg.C;
(2) adding tert-amyl peroxy-2-ethylhexyl carbonate and triallyl benzenetricarboxylate into polylactic acid, and uniformly mixing to obtain a mixed material;
(3) and melting and extruding the mixed material through a double-screw extruder, and bracing, air cooling and granulating the material extruded by the double-screw extruder to obtain granular polylactic acid.
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 200 ℃.
Comparative example 3
The preparation method of polylactic acid in this comparative example is different from that of example 1 in that:
the polylactic acid is prepared from the following raw materials in parts by weight: 96.50 percent of polylactic acid, 1.50 percent of tert-amyl peroxy-2-ethylhexyl carbonate and 0.80 percent of chain extender (Bass Joncryl ADR-4368).
The preparation process is as follows:
(1) drying polylactic acid at 100 deg.C for 70min to make the water content of polylactic acid less than 250ppm, and cooling to 20 deg.C;
(2) adding tert-amyl peroxy-2-ethylhexyl carbonate and a Basff chain extender into polylactic acid, and uniformly mixing to obtain a mixed material;
(3) and melting and extruding the mixed material through a double-screw extruder, and bracing, air cooling and granulating the material extruded by the double-screw extruder to obtain granular polylactic acid.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 52: 1.
The temperature of the twin-screw extruder in the above step (3) was 200 ℃.
Comparative example 4
The preparation method of polylactic acid in this comparative example is different from that of example 1 in that:
the polylactic acid is prepared from the following raw materials in parts by weight: 96.30 percent of polylactic acid, 1.50 percent of tert-amyl peroxy-2-ethylhexyl carbonate, 1.20 percent of triallyl phthalate and 0.50 percent of chain extender (Bassfer Joncryl ADR-4368).
The preparation process is as follows:
(1) drying polylactic acid at 100 deg.C for 70min to make the water content of polylactic acid less than 250ppm, and cooling to 20 deg.C;
(2) adding tert-amyl peroxy-2-ethylhexyl carbonate, triallyl phthalate and a Basff chain extender into polylactic acid, and uniformly mixing to obtain a mixed material;
(3) and melting and extruding the mixed material through a double-screw extruder, and bracing, air cooling and granulating the material extruded by the double-screw extruder to obtain granular polylactic acid.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 42: 1.
The temperature of the twin-screw extruder in the above step (3) was 200 ℃.
The properties of the polylactic acids obtained in the above examples 1 to 5 and comparative examples 1 to 4 were measured, wherein:
the polylactic acid particles obtained in examples 1 to 5 and comparative examples 1 to 4 were mixed at 80oC, drying in a vacuum oven for 12 hours, and then measuring the melt index (MFI) and the Melt Strength (MS) of the long-chain branched polylactic acid. The test results are shown in table 1 below.
Table 1: evaluation results (melt index (MFI) and Melt Strength (MS))
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| MFI(g/10min，210oC,2.16kg) | 12.6 | 9.8 | 8.3 | 10.4 | 8.9 | 18.3 | 3.8 | 4.7 | 2.1 |
| MS（cN） | 33.2 | 38.9 | 42.9 | 31.4 | 35.6 | 0.3 | 18.5 | 15.7 | 23.9 |
Table 1 shows the melt index and melt strength of the polylactic acid obtained in each of the examples and comparative examples. Melt index is a key measure of the flow properties of polymers. Generally, the higher the melt index, the better the processing flow of the polymer; the lower the melt index, the poorer the processing flowability of the polymer.
In the present invention, the melt strength of the long-chain branched polylactic acids prepared in examples 1 to 5 was much higher than that of the pure polylactic acid of comparative example 1, relative to the pure polylactic acid of comparative example 1, indicating that the long-chain branched polylactic acid has excellent melt strength.
The long-chain branched polylactic acids prepared in examples 1 to 5 have a higher melt index and a higher melt strength relative to the conventional branching accelerator (triallyl benzoate) in comparative example 2, indicating that the long-chain branched polylactic acids have both excellent melt strength and processing flowability.
Compared with the conventional chain extender (Bastf Joncryl ADR-4368) in comparative example 3, the long-chain branched polylactic acid prepared in examples 1 to 5 has higher melt index and higher melt strength, which indicates that the long-chain branched polylactic acid has excellent melt strength and processing flowability.
Compared with the conventional branching accelerator (triallyl benzenetricarboxylate) and the chain extender (BASF Joncryl ADR-4368) in the comparative example 4, the long-chain branched polylactic acid prepared in the examples 1 to 5 has higher melt index and higher melt strength, which indicates that the long-chain branched polylactic acid has excellent melt strength and processing flowability.
Generally, the lower the melt index, the higher the melt strength of the polymer, and the higher the melt index, the lower the melt strength of the polymer, while the long-chain branched polylactic acids in examples 1 to 5 of the present invention can achieve both high melt index and high melt strength.
The technology disclosed by the patent is not only limited to the preparation of long-chain branched polylactic acid with high melt strength and excellent processing fluidity, 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 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 long-chain branched polylactic acid with high melt strength and excellent processing fluidity is characterized by being prepared from the following raw materials in parts by weight: 93.00 to 99.80 percent of polylactic acid; 0.10 to 2.00 percent of organic peroxide; 0.1 to 5.00 percent of branching regulator.
2. The long-chain branched polylactic acid with high melt strength and excellent processing fluidity according to claim 1, which is prepared from the following raw materials in parts by weight: 96.00-99.50% of polylactic acid; 0.20 to 1.00 percent of organic peroxide; 0.3 to 3.00 percent of branching regulator.
3. The long-chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 1 or 2, wherein: the polylactic acid is one or the combination of more of L-type polylactic acid, D-type polylactic acid and LD-type polylactic acid.
4. The long-chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 1 or 2, wherein: the organic peroxide is one or more of alkyl peroxide, aryl peroxide, diaryl acyl peroxide, peroxyketal, peroxyester, peroxycarbonate and cyclic peroxide.
5. The long chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 4, wherein: the organic peroxide is di-tert-butyl peroxide, 2-di-tert-butyl peroxybutane, 2, 5-dimethylhexane-2, 5-di-tert-butyl peroxide, 2, 5-dimethyl-3-hexyne-2, 5-di-tert-butyl peroxide, dicumyl peroxide, bis (2-tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3, 5, 5-trimethylhexanoate, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amylperoxy-2-ethylhexyl carbonate, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, di (tert-butyl-2, 5-di-tert-butylperoxy-isopropyl) benzene, di (tert-butylperoxyisopropyl) benzene, tert-butylperoxy-isopropyl carbonate, tert-butyl-propyl-2-butyl-peroxybenzoate, tert-2-ethylhexylcarbonate, di (4-methylbenzoyl) peroxide, di (tert-butyl-2-peroxybenzoate), di (tert-butyl-peroxybenzoate) peroxide, di (tert-butyl-2-isopropylcarbonate, di (tert-butyl-peroxybenzoate) peroxide, di (tert-butyl-2-peroxybenzoate) peroxide, di (tert-butyl-2-butyl-2-peroxybenzoate) peroxide, di (tert-butyl-2-butyl-2-butyl-propyl peroxide, di-butyl-2-propyl peroxycarbonate, di (tert-butyl-2-butyl-propyl peroxycarbonate, di (tert-butyl-propyl-butyl-2-butyl-propyl-butyl-propyl-butyl-propyl-2-butyl-2-propyl-butyl-propyl-butyl-propyl-butyl-propyl-2-propyl-carbonate, tert-2-butyl-propyl-butyl-propyl-carbonate, tert-2-propyl-butyl-propyl-2-propyl-butyl-2-butyl-propyl-butyl-2-butyl-carbonate, tert-2-butyl-2-propyl-butyl-carbonate, tert-butyl-carbonate, 1, 3-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, ethyl-3, 3-bis (t-butylperoxy) butyrate, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane and 3,3,6,6,9, 9-hexamethyl-1, 2,4, 5-tetrapentane or a combination of more thereof.
6. The long chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 4, 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-butyl peroxy) valerate and ethyl-3, 3-di (tert-butyl peroxy) butyrate; the peroxycarbonate is one or the combination of more of tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy2-ethylhexyl carbonate and tert-amyl peroxy2-ethylhexyl carbonate.
7. The long chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 1, wherein: the molecular structure general formula of the branching regulator is as follows: r1-R-R2Wherein R is C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl or C7-C20Alkaryl groups, which groups may comprise straight or branched alkyl moieties; r1Is a group containing a carbon-carbon double bond such as vinyl, allyl, acrylate or methacrylate; r2The reactive group is an active group such as an epoxy group or an isocyanate group which can chemically react with a terminal hydroxyl group of the polylactic acid and/or a terminal carboxyl group of the polylactic acid.
8. The long chain branched polylactic acid having both high melt strength and excellent processing fluidity according to claim 7, wherein: the molecular structure of the branching regulator simultaneously contains a vinyl group or allyl group and an epoxy group or isocyanate group;
the branching regulator is one or the combination of more of 4-vinylbenzyl glycidyl ether, allyl glycidyl ether, isocyanate ethyl acrylate, isocyanoethyl methacrylate, allyl isocyanate, vinyl isocyanate and 3-isopropenyl-alpha, alpha-dimethyl benzyl isocyanate;
the branching regulator is one or the combination of 4-ethylene benzyl glycidyl ether and 3-isopropenyl-alpha, alpha-dimethyl benzyl isocyanate.
9. A preparation method of long-chain branched polylactic acid with high melt strength and excellent processing fluidity is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 93.00 to 99.80 percent of polylactic acid; 0.10 to 2.00 percent of organic peroxide; 0.1 to 5.00 percent of branched regulator;
(2) drying polylactic acid at 90-120 deg.C for 60-120min to make the water content of polylactic acid less than 200ppm, and cooling to 10-30 deg.C;
(3) adding organic peroxide and a branching regulating agent into polylactic acid, and uniformly mixing to obtain a mixed material;
(4) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the material extruded by the double-screw extruder to obtain the granular long-chain branched polylactic acid with high melt strength and excellent processing fluidity.
10. The method of claim 9 for producing a long-chain branched polylactic acid having both high melt strength and excellent processing fluidity, wherein:
the length-diameter ratio of the screw of the double-screw extruder in the step (4) is 36:1-52: 1;
the temperature of the twin-screw extruder in the step (4) is 180-220 ℃.
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| CN115073890B (en) * | 2022-05-05 | 2024-01-26 | 苏州卓聚新材料科技有限公司 | PBAT composite material and preparation method thereof |
| CN115340759A (en) * | 2022-09-16 | 2022-11-15 | 江南大学 | Method for improving strength of polymer melt |
| CN117362958A (en) * | 2023-10-27 | 2024-01-09 | 诺为新材料(杭州)有限责任公司 | High-fluidity polylactic acid composition and preparation method thereof |
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