CN105602206A - Modified PET (polyethylene terephthalate) composition and preparation method thereof - Google Patents
Modified PET (polyethylene terephthalate) composition and preparation method thereof Download PDFInfo
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- CN105602206A CN105602206A CN201610072639.XA CN201610072639A CN105602206A CN 105602206 A CN105602206 A CN 105602206A CN 201610072639 A CN201610072639 A CN 201610072639A CN 105602206 A CN105602206 A CN 105602206A
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- lactoprene
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- unsaturated polyester
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract 17
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract 7
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 229920006305 unsaturated polyester Polymers 0.000 claims description 41
- 125000001931 aliphatic group Chemical group 0.000 claims description 39
- 238000005987 sulfurization reaction Methods 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 20
- 150000001718 carbodiimides Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002534 radiation-sensitizing agent Substances 0.000 claims description 3
- CDUVPZJMUCMPDM-UHFFFAOYSA-N 2-(2-bromophenyl)-4,5-dihydro-1,3-oxazole Chemical compound BrC1=CC=CC=C1C1=NCCO1 CDUVPZJMUCMPDM-UHFFFAOYSA-N 0.000 claims description 2
- 101000705607 Homo sapiens Protein PET100 homolog, mitochondrial Proteins 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 102100031244 Protein PET100 homolog, mitochondrial Human genes 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 150000002918 oxazolines Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WAMBUHSSUGGLJO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WAMBUHSSUGGLJO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N methyl-p-benzoquinone Chemical group CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention relates to the technical field of high-polymer materials, particularly a PET (polyethylene terephthalate) composition modified by biodegradable bio-based vulcanized polyester rubber particles and a preparation method thereof. The modified PET composition comprises the following components in parts by mass: 100 parts of PET, 0.5-20 parts of bio-based vulcanized polyester rubber particles and 0-0.6 part of hydrolysis-resistant agent. The modified PET composition prepared from the bio-based vulcanized polyester rubber particles has the advantages of higher notch impact strength, higher tensile strength, higher bending strength and certain biodegradability.
Description
Technical field
The present invention relates to technical field of polymer materials, relate to specifically one and vulcanized by biodegradable bio-basedThe PET composition and method of making the same that lactoprene is particle modified.
Background technology
PETG (PET) be with terephthalic acid (TPA) (PTA) or dimethyl terephthalate (DMT) (DMT) andEthylene glycol (EG) makes through esterification or ester exchange and polycondensation reaction for raw material. It has wearability, heat resistance, electrical insulating property, resistance toChemical drugs moral character, is widely used in synthetic polyster fibre and thin film fabrication, civilian blowing, can also serve as engineering plastics for machineTool, electronics, automobile, electrical equipment manufacture and the consumer goods. But because glass transition temperature, the fusing point of PET are higher, conventionally adoptingWith molding temperature under, crystallization rate is compared with slow and reduce with the increase of resin relative molecular mass, crystalline texture is inhomogeneous, chiVery little poor stability, poor toughness (especially notched Izod impact strength is lower), thereby in some domain restrictions the application of PET.
In order to give full play to PET high-performance, advantage cheaply, must carry out toughening modifying and change crystallization row itFor, its toughness is improved and crystallization rate quickening. The modification of PET is had to two kinds of means conventionally, a kind of for adding nucleator and knotBrilliant promoter, thereby the crystalline rate of quickening PET, but this method is difficult to improve the toughness of PET. It is special that Peking University applies forProfit CN102020756B has introduced a kind of crust type macromolecule of ionic that utilizes and has become as PET with cinnamic block copolymerThe method of core agent modified PET, the patent CN104327465A of the beautiful Science and Technology Ltd. of treasure application has introduced one and has utilized carbonic acidCalcium nano particle is as the method for the nucleater modified PET of PET, and these two kinds of methods have changed the crystalline texture of PET, have improved crystallizationSpeed. In addition, Institute of Chemistry, Academia Sinica apply for a patent CN1086404C introduced a kind of with maleic anhydride grafted ethene-The method that octene copolymer elastomer is toughness reinforcing to PET, this method has obviously improved the notched Izod impact strength of PET, but forCrystallization rate and the crystalline texture of PET do not have clear improvement.
China PetroChemical Corporations etc. have announced the ultra-fine fully vulcanized powder rubber that a kind of particle diameter is 20-2000nmGrain (CN1152082C), and utilize above-mentioned ultra-fine fully vulcanized powder rubber particulate reinforcement PET (CN1513912A), obviously improveThe toughness of PET. Regrettably, the synthesis material of the above-mentioned micro-nano rubber grain relating to all derives from non-renewable fossil moneySource, and there is not biodegradable, after use, can produce a large amount of discarded objects, environment is caused to pollution to a certain degree.
Visible, above-mentioned PET modifier scarcely has biological degradability, and is difficult to improve toughness, the crystallization speed of PET simultaneouslyRate has also been brought some problems in application, after use, can produce a large amount of discarded objects, and environment is caused to dirt to a certain degreeDye.
Summary of the invention
For the above-mentioned defect of the prior art of mentioning, the invention provides a kind of biodegradable bio-based sulphur that adoptsChange the particle modified PET composition and method of making the same of lactoprene, prepared modified PET composition not only has higher lackingMouth impact strength, and there is higher crystallization rate and uniform crystalline texture, also there is certain biological degradability simultaneouslyEnergy.
The present invention is achieved through the following technical solutions:
A kind of modified PET composition, it comprises each component with following mass fraction:
PET100 part
Bio-based sulfuration lactoprene particle 0.5-20 part
Hydrolysis-resisting agent 0-0.6 part.
Described PET is PETG, and its intrinsic viscosity is 0.4-1.0dl/g.
Described bio-based sulfuration lactoprene particle is to adopt institute in applicant's patent of invention in early stage (CN103012818B)Preparation, taking bio-based monomer dihydroxylic alcohols and binary acid as raw material, the bio-based fat that contains two keys in design, synthetic molecules chainFat family unsaturated polyester (UP); By regulating and controlling emulsifying process etc., prepare the controlled unsaturated polyester emulsion of micella particle diameter; Finally, pass throughRadiation vulanization and spray drying technology are prepared the controlled bio-based sulfuration lactoprene particle of gel content, and it has can be completely rawThing degradation characteristic and can give the good toughness of PET, high crystallization rate, uniformly crystalline texture.
The preparation method of described bio-based sulfuration lactoprene particle, specifically comprises the following steps:
A. synthesising biological base aliphatic unsaturated polyester (UP)
(1) by component A and B component 0.95～1.2:1.0 mixing in molar ratio, stir and be warming up to 160～200 DEG C, esterificationReact 0.5～1 hour, obtain polyester prepolyer, described component A is bio-based aliphatic dihydroxy alcohol; B component is bio-based fatOne or both in family's binary acid or bio-based binary aliphatic acid anhydrides, described bio-based aliphatic dibasic acid and bio-based fatFat family dibasic acid anhydride comprises bio-based aliphatic unsaturated dibasic acid, bio-based aliphatic unsaturated dicarboxylic acid anhydride and bio-based fatFat family monounsaturated dicarboxylic acid, bio-based aliphatic dicarboxylic acid acid anhydride, wherein bio-based aliphatic unsaturated dibasic acid or bio-basedAliphatic unsaturated dicarboxylic acid anhydride account for 5 of bio-based aliphatic dibasic acid or bio-based binary aliphatic acid anhydrides integral molar quantity～50％；
(2) the above-mentioned catalyst that adds said components A and B component gross mass 0.01～1% in making polyester prepolyer,0.02～0.4% polymerization inhibitor is warming up to 200～220 DEG C at 1 atmospheric normal pressure to the pressure range of 1000Pa, anti-Answer 2～4 hours, make bio-based aliphatic unsaturated polyester (UP);
(3) be cooled to 150 DEG C, in the above-mentioned bio-based aliphatic unsaturated polyester (UP) making, add said components A and groupThe radiosensitizer of point B gross mass 0～8% and 5～10% emulsifying agent A, stir, cooling after, make the biology of pasteBase aliphatic unsaturated polyester ester admixture;
B. prepare bio-based aliphatic unsaturated polyester emulsion
Take the bio-based aliphatic unsaturated polyester ester admixture of the paste making in the steps A of certain mass, putIn 20～40 DEG C of water bath containers, then add emulsifying agent B and deionized water, dispersed with stirring 0.5～1 hour, makes bio-basedThe emulsion that aliphatic unsaturated polyester (UP) mass fraction is 5～30%, the bio-based aliphatic that emulsifying agent B consumption is taken pasteIn unsaturated polyester ester admixture 5～20% of contained bio-based aliphatic unsaturated polyester (UP) quality;
C. the radiation vulcanization of bio-based aliphatic unsaturated polyester emulsion
The bio-based aliphatic unsaturated polyester emulsion that above-mentioned steps B is made is through gamma-rays or high-energy electron beam irradiation sulphurChange, dose of radiation scope is 5～100kGy, is prepared into bio-based sulfuration lactoprene emulsion;
D. the spraying of bio-based sulfuration lactoprene emulsion is dry
The bio-based sulfuration lactoprene emulsion making through step C is sprayed dry, can be made into bio-based sulfuration poly-Ester rubber particles.
Wherein, the aliphatic dihydroxy alcohol of bio-based described in steps A is selected from 1,3-PD, BDO, 2,3-fourth twoThe mixture of one or more in alcohol or 1,10-decanediol; Described bio-based aliphatic unsaturated dibasic acid and bio-based fatFat family unsaturated dicarboxylic acid anhydride is selected from one or more the mixture in itaconic acid, fumaric acid, itaconic anhydride or fumaric acid anhydride,Bio-based aliphatic dicarboxylic acid and bio-based aliphatic dicarboxylic acid acid anhydride are selected from succinic acid, decanedioic acid, adipic acid, fourth twoThe mixture of one or more in acid anhydrides or adipic anhydride.
Catalyst described in steps A is selected from one or both in butyl titanate or p-methyl benzenesulfonic acid.
Polymerization inhibitor described in steps A is selected from hydroquinones, adjacent methyl hydroquinone, 1,4-benzoquinone or MEHQOne or more mixture.
Radiosensitizer described in steps A is selected from BDO two (methyl) acrylate, diethylene glycol two (firstBase) a kind of in acrylate, trimethylolpropane tris (methyl) acrylate or pentaerythrite four (methyl) acrylate orMultiple mixture.
Emulsifying agent A described in steps A is nonionic emulsifier, is selected from APES, anhydrous sorbitolMonostearate, polyoxyethylene anhydrate sorbitol monostearate, polyoxyethylene oleic acid ester, PEG400 monoleate orThe mixture of one or more in APG.
Emulsifying agent B described in step B is anion emulsifier, is selected from neopelex, dodecyl sulphateThe mixture of one or more in sodium, potassium oleate or enuatrol.
The average grain diameter of described bio-based sulfuration lactoprene particle is 10～1000nm, and gel content is 70～90%.
Described hydrolysis-resisting agent is the one in Carbodiimides, oxazoline compounds and epoxide hydrolysis-resisting agentOr multiple, preferably, described hydrolysis-resisting agent is polycarbodiimide UN-03, carbodiimides UN-150,2-alkyl-2-oxazoleOne or more in quinoline, o-bromophenyl-2-oxazoline, phenyl glycidyl ether and bisphenol-A bisglycidyl ether.
A kind of preparation method of described modified PET composition: in proportion by dry PET, bio-based sulfuration lactopreneParticle and hydrolysis-resisting agent make modified PET composition by the mode of high-temperature fusion blend in blender.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention adopts the particle modified PET of bio-based sulfuration lactoprene, significantly improves the toughness of PET, preparedModified PET has higher notched Izod impact strength.
2, the present invention adopts the particle modified PET of bio-based sulfuration lactoprene, obviously improves PET crystalline rate, changes knotCrystal structure, optimizes crystal property.
3, the present invention adopts the particle modified PET of bio-based sulfuration lactoprene, and bio-based sulfuration lactoprene particle is at PETIn be separated into controlled dispersion and be uniformly dispersed.
The synthetic raw material of the bio-based sulfuration lactoprene particle that 4, the present invention adopts is bio-based materials, has hadComplete biodegradable, has reduced the dependence to fossil resource to a certain extent, and has alleviated white pollution problems.
The preparation technology of the modified PET composition that 5, the present invention proposes is simple, needn't, by other special installations, operateCheng Rongyi implements.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, material therefor is as follows:
PET56151: du pont company produces;
Bio-based sulfuration lactoprene particle: Qingdao University of Science and Technology produces;
Hydrolysis-resisting agent: carbodiimides hydrolysis-resisting agent UN-150, TUV chemical company produces.
Embodiment 1
By dry 100 parts (mass fraction, lower with) PET56151,0.5 part of bio-based sulfuration lactoprene particle,0.015 part of carbodiimides hydrolysis-resisting agent UN-150 makes modification by the mode of high-temperature fusion blend in double screw extruderPET composition.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Wherein, preparation method's following (seeing CN103012818B embodiment 2) of described bio-based sulfuration lactoprene particle:
To being equipped with in the reaction unit of magnetic agitation, nitrogen gateway, heater, thermometer, add 12.56g(0.165mol) 1,3-PD, 14.87g (0.165mol) BDO and 4.61g (0.039mol) succinic acid, 31.55g(0.156mol) decanedioic acid, 12.19g (0.105mol) fumaric acid are warming up to 180 DEG C under the condition of nitrogen protection and stirring,Esterification 1 hour, obtains polyester prepolyer. Above-mentioned add in making polyester prepolyer 75.8mg p-methyl benzenesulfonic acid and151.6mg 1,4-benzoquinone, is warming up to 220 DEG C, and in reaction unit, pressure is decompressed to 1500Pa gradually by 1 atmospheric normal pressure, anti-Answer 2.5 hours, making number-average molecular weight is 4132, and weight average molecular weight is 7478, the bio-based fat that polydispersity coefficient is 1.81Family's unsaturated polyester (UP). Be cooled to after 150 DEG C, add 3.7890g pentaerythrite four (methyl) acrylate and 6.0624g to gather second twoAlcohol 400 monoleates, stir, cooling after, make the bio-based aliphatic unsaturated polyester ester admixture of paste.
The bio-based aliphatic unsaturated polyester ester admixture that takes the above-mentioned paste of 11.3g (comprises 10g bio-based aliphatic notSaturated polyester, 0.5g pentaerythrite four (methyl) acrylate and 0.8g PEG400 monoleate), be placed on 30 DEG CIn water bath containers, then add 0.77g enuatrol, 0.52g neopelex and 37.41g deionized water, mechanical agitation0.5 hour, make the emulsion that bio-based aliphatic unsaturated polyester (UP) mass fraction is 20%, the micella particle diameter of this emulsion is95nm。
The bio-based aliphatic unsaturated polyester emulsion that above-mentioned steps is made vulcanizes through high-energy electron beam irradiation, radiation agentAmount is 20kGy, is prepared into the crosslinked bio-based sulfuration lactoprene emulsion of polyester molecule chain.
Above-mentioned bio-based sulfuration lactoprene emulsion is sprayed dry, making gel content is 89%, and particle diameter isThe bio-based sulfuration lactoprene particle of 95nm. Spray-dired technological parameter is: spray dryer inlet temperature is 145 DEG C,Outlet temperature is 50 DEG C; Atomisation pressure is 0.3MPa.
In following embodiment 2-10, the preparation method of bio-based sulfuration lactoprene particle is identical therewith, therefore repeat no more.
Embodiment 2
By 100 parts of dry PET56151,1 part of bio-based sulfuration lactoprene particle, 0.03 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 3
By 100 parts of dry PET56151,2 parts of bio-based sulfuration lactoprene particles, 0.06 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 4
By 100 parts of dry PET56151,4 parts of bio-based sulfuration lactoprene particles, 0.12 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 5
By 100 parts of dry PET56151,8 parts of bio-based sulfuration lactoprene particles, 0.24 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 6
By 100 parts of dry PET56151,12 parts of bio-based sulfuration lactoprene particles, 0.36 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 7
By 100 parts of dry PET56151,16 parts of bio-based sulfuration lactoprene particles, 0.48 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 8
By 100 parts of dry PET56151,20 parts of bio-based sulfuration lactoprene particles, 0.6 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in double screw extruder.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 9
100 parts of dry PET56151,8 parts of bio-based sulfuration lactoprene particles are passed through high in double screw extruderThe mode of temperature melt blending makes modified PET composition.
The temperature that double screw extruder is each section is respectively 160-250 DEG C, and screw speed is 100-300rpm.
Embodiment 10
By 100 parts of dry PET56151,8 parts of bio-based sulfuration lactoprene particles, 0.24 part of carbodiimides water resistantSeparate agent UN-150 and make modified PET composition by the mode of high-temperature fusion blend in banbury.
The operating temperature of banbury is 250 DEG C, and 80rpm mixes 10 minutes to batch mixing balance.
Comparative example 1
Get PET56151 one-component and add in double screw extruder, through the same processing technology of above-described embodiment and granulationProcess is made contrast material.
Performance test:
The preparation of test bars: by above-mentioned modified PET composition on vulcanizing press in 250 DEG C, 10MPa depresses toThe sheet material that 4mm is thick, is cooled to room temperature.
Cantilever beam notched Izod impact strength is tested by ISO180/1A standard, and specimen types is I type, specimen size(mm): 80 × 10 × 4; Breach type is A: the wide 2mm of breach, dark 2mm.
Hot strength test detects by ASTMD638 standard, and specimen types is I type, specimen size (mm): 150 ×10 × 4, draw speed is 50mm/min.
Bending strength and bending modulus test detect by ISO178 standard, specimen size (mm): 80 × 10 × 4, acrossDistance is 50mm, rate of bending 2mm/min.
Embodiment 1～10 and the made material property of comparative example 1 are in table 1:
Table 1 material properties test result
As seen from the above table, the test performance of the embodiment batten of application technical solution of the present invention has with respect to comparative exampleHigh notched Izod impact strength, and in hot strength and bending strength, all there is the mechanical property that meets general application requirements.When the toughness of the PET of modification composition increases substantially, its intensity level still normally uses feelings higher than material far awayPerformance number under condition, thus its range of application greatly increased, there is high innovative value.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-described embodimentRestriction, other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplification,All should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (7)
1. a modified PET composition, is characterized in that, comprises each component with following mass fraction:
PET100 part
Bio-based sulfuration lactoprene particle 0.5-20 part
Hydrolysis-resisting agent 0-0.6 part.
2. modified PET composition according to claim 1, is characterized in that, described PET is polyethylene terephthalateEster, its intrinsic viscosity is 0.4-1.0dl/g.
3. modified PET composition according to claim 1, is characterized in that, described bio-based sulfuration lactoprene particlePreparation method, specifically comprise the following steps:
A. synthesising biological base aliphatic unsaturated polyester (UP)
(1) by component A and B component 0.95～1.2:1.0 mixing in molar ratio, stir and be warming up to 160～200 DEG C, esterification0.5～1 hour, obtain polyester prepolyer, described component A is bio-based aliphatic dihydroxy alcohol; B component is bio-based aliphatic twoOne or both in unit's acid or bio-based binary aliphatic acid anhydrides, described bio-based aliphatic dibasic acid and bio-based aliphaticDibasic acid anhydride comprises bio-based aliphatic unsaturated dibasic acid, bio-based aliphatic unsaturated dicarboxylic acid anhydride and bio-based aliphaticMonounsaturated dicarboxylic acid, bio-based aliphatic dicarboxylic acid acid anhydride, wherein bio-based aliphatic unsaturated dibasic acid or bio-based fatFamily's unsaturated dicarboxylic acid anhydride accounts for 5～50% of bio-based aliphatic dibasic acid or bio-based binary aliphatic acid anhydrides integral molar quantity;
(2) at the above-mentioned catalyst, 0.02 that adds said components A and B component gross mass 0.01～1% in making polyester prepolyer～0.4% polymerization inhibitor is warming up to 200～220 DEG C at 1 atmospheric normal pressure to the pressure range of 1000Pa, reaction 2～4 hours, make bio-based aliphatic unsaturated polyester (UP);
(3) be cooled to 150 DEG C, in the above-mentioned bio-based aliphatic unsaturated polyester (UP) making, add said components A and B component totalThe radiosensitizer of quality 0～8% and 5～10% emulsifying agent A, stir, cooling after, make the bio-based fat of pasteFamily's unsaturated polyester ester admixture;
B. prepare bio-based aliphatic unsaturated polyester emulsion
The bio-based aliphatic unsaturated polyester ester admixture that takes the paste making in the steps A of certain mass, is placed on 20In～40 DEG C of water bath containers, then add emulsifying agent B and deionized water, dispersed with stirring 0.5～1 hour, makes bio-based fatThe emulsion that family's unsaturated polyester (UP) mass fraction is 5～30%, the bio-based aliphatic insatiable hunger that emulsifying agent B consumption is taken pasteWith 5～20% of contained bio-based aliphatic unsaturated polyester (UP) quality in polyester mixture;
C. the radiation vulcanization of bio-based aliphatic unsaturated polyester emulsion
The bio-based aliphatic unsaturated polyester emulsion that above-mentioned steps B is made vulcanizes through gamma-rays or high-energy electron beam irradiation,Dose of radiation scope is 5～100kGy, is prepared into bio-based sulfuration lactoprene emulsion;
D. the spraying of bio-based sulfuration lactoprene emulsion is dry
The bio-based sulfuration lactoprene emulsion making through step C is sprayed dry, can be made into bio-based sulfuration polyester rubberMicelle.
4. according to the modified PET composition described in claim 1 or 3, it is characterized in that described bio-based sulfuration lactoprene grainThe average grain diameter of son is 10～1000nm, and gel content is 70～90%.
5. modified PET composition according to claim 1, is characterized in that, described hydrolysis-resisting agent be Carbodiimides,One or more in oxazoline compounds and epoxide hydrolysis-resisting agent.
6. modified PET composition according to claim 1 or 5, is characterized in that, described hydrolysis-resisting agent is poly-carbonization two AsiasAmine UN-03, carbodiimides UN-150,2-alkyl-2-oxazoline, o-bromophenyl-2-oxazoline, phenyl glycidyl ether and twoOne or more in phenol A bisglycidyl ether.
7. a preparation method for modified PET composition as described in claim 1-6 any one, is characterized in that, in proportionDry PET, bio-based sulfuration lactoprene particle and hydrolysis-resisting agent are passed through to the mode of high-temperature fusion blend in blenderMake modified PET composition.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513912A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Polyethanediol terephthalate composition and its preparation method |
| CN102344654A (en) * | 2011-06-17 | 2012-02-08 | 深圳市科聚新材料有限公司 | Hydrolysis resistant PET composite material and preparation method thereof |
| CN103012818A (en) * | 2012-12-21 | 2013-04-03 | 青岛科技大学 | Bio-based vulcanization polyester rubber particle and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513912A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Polyethanediol terephthalate composition and its preparation method |
| CN102344654A (en) * | 2011-06-17 | 2012-02-08 | 深圳市科聚新材料有限公司 | Hydrolysis resistant PET composite material and preparation method thereof |
| CN103012818A (en) * | 2012-12-21 | 2013-04-03 | 青岛科技大学 | Bio-based vulcanization polyester rubber particle and preparation method thereof |
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