CN105838038A - Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition - Google Patents
Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition Download PDFInfo
- Publication number
- CN105838038A CN105838038A CN201610018855.6A CN201610018855A CN105838038A CN 105838038 A CN105838038 A CN 105838038A CN 201610018855 A CN201610018855 A CN 201610018855A CN 105838038 A CN105838038 A CN 105838038A
- Authority
- CN
- China
- Prior art keywords
- pbat
- resin combination
- pbat resin
- iron
- oxolane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title abstract 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims description 56
- 229920005989 resin Polymers 0.000 claims description 56
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004609 Impact Modifier Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 230000003467 diminishing effect Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 3
- 238000003988 headspace gas chromatography Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229920001896 polybutyrate Polymers 0.000 claims 14
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000071 blow moulding Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000035882 stress Effects 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract description 2
- 238000010096 film blowing Methods 0.000 abstract 3
- 239000010408 film Substances 0.000 description 35
- 239000000463 material Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- -1 alcohol ester Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HPTULVAFZQXKIS-UHFFFAOYSA-N NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 Chemical compound NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 HPTULVAFZQXKIS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a poly(butyleneadipate-co-terephthalate) (PBAT) resin composition. The PBAT resin composition comprises a, PBAT, b, iron and c, tetrahydrofuran, wherein the PBAT resin composition contains 1-500ppm of iron and 10-500ppm of tetrahydrofuran. Through use of a trace amount of iron and tetrahydrofuran in the composition, iron content of the PBAT resin composition is controlled in a range of 1-500ppm and tetrahydrofuran content of the PBAT resin composition is controlled in a range of 10-500ppm so that after aging in boiling water for 24h and 48h, a b value is less than 2 and boiling water aging-resistant color stability is obviously improved, and at a film blowing extrusion rate of 178Kg/h, a film thickness range is less than 0.2 microns and film thickness relative deviation is less than 1%. The composition has improved film blowing characteristics. Nonuniform stress distribution-caused hole blowing at vesicle positions in blow molding is prevented and film blowing production continuity is guaranteed.
Description
Technical field
The invention belongs to polymer modification field, be specifically related to a kind of PBAT resin combination.
Background technology
Polyadipate butylene terephthalate (PBAT) is being total to of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester
Polymers, has the characteristic of PBA and PBT concurrently.Containing flexible aliphatic chain and rigidity in polyadipate butylene terephthalate (PBAT)
Fragrant chain thus there is high tenacity and heat-resisting quantity, and due to the existence of ester bond, promote it to have biodegradability simultaneously,
It is the research of current biodegradable plastic to enliven very much apply one of best degradable material with market.
But PBAT resin there is also following defect: as when fair speed blown film, film material thickness extreme difference is relatively big, and
Blow-molding process there will be each position of film bubble due to stress distribution uneven and cause holes situation, affect blown film continuous production.
The present invention after deliberation surprisingly it has been found that, by adding the oxolane of trace in the composition, by PBAT resin combination four
The content of hydrogen furan controls within the specific limits, and PBAT resin combination can be made to have the blown film characteristic being obviously improved, relatively
At high speed during blown film, film material thickness extreme difference is less, and does not haves the situation of holes, it is ensured that the seriality that blown film produces.
It addition, PBAT resin easily turns yellow after soaking in the hot water, resistance to boiling water aging colour stability is poor, affects material
Outward appearance.The present invention has further surprisingly found that, in PBAT resin combination, by adding iron containing compounds, makes the PBAT prepared
Resin combination has the resistance to boiling water aging colour stability being obviously improved.
Summary of the invention
It is an object of the invention to provide a kind of PBAT resin combination, by adding the ferrum element of trace in the composition
And oxolane, the PBAT resin combination prepared can be made to have the resistance to boiling water aging colour stability being obviously improved,
And there is the blown film characteristic substantially covered.
The present invention is achieved by the following technical solutions:
A kind of PBAT resin combination, it is characterised in that include following component:
(a) polyadipate butylene terephthalate；
(b) ferrum element；
(c) oxolane；
Wherein, gross weight based on PBAT resin combination, the weight content of ferrum element is 1ppm-500ppm, the weight of oxolane
Amount content is 10ppm-500ppm.
The weight content of ferrum element of the present invention uses the test of micro-wave digestion-ICP-OES method: weigh the sample after 0.1g pulverizes
Product, put in micro-wave diminishing pot, add nitric acid 5mL and make it be totally submerged sample, more slowly instill 1.0mL hydrogen peroxide,
After reaction 2min, close the lid, sealed digestion tank, put in Hyperfrequency waves eliminating stove and clear up, after being cooled to room temperature, will disappear
The solution solved in tank is transferred in volumetric flask after 0.45 μm membrane filtration, with distilled water diluting to 50mL, uses ICP-OES
Test.
Wherein, the content of oxolane uses Headspace Gas Chromatography: a certain amount of sample is placed in liquid nitrogen biological container
After middle 5min, take out and pulverize, sieve, take the product of 30-40 mesh, weigh a certain amount of sample；Use Agilent company
The 7890A type gas chromatograph produced, chromatographic column is that Agilent company produces DB-WAX type gas chromatographic column, uses peace victory
Human relations company produces 7697 type head-space sampler sample introductions；Headspace sampling condition is 100 DEG C, and constant temperature is sample introduction after 4 hours；Work song
Line is demarcated by oxolane/methanol solution.
Polyadipate butylene terephthalate (PBAT) resin of the present invention is tetramethylene adipate and terephthaldehyde
The copolymer of acid butanediol ester, easily turns yellow after soaking in the hot water, and its reason turned yellow exists mainly due to its aromatic structure
React under wet heat condition, generate new conjugated structure.General PBAT resin extruded blown film speed is less than 100Kg/h, this
Time inflation film manufacturing machine production capacity can not be fully utilized, production is uneconomic.When more speed extrusion blown film, film material is thick
Degree extreme difference is relatively big, and there will be in blow-molding process each position of film bubble due to stress distribution uneven and cause holes situation,
Affect blown film continuous production.And the present invention is found by research, by adding iron containing compounds and four in PBAT resin
Hydrogen furan, controls in the range of 1ppm-500ppm by the content of ferrum element in compositions, and the content of oxolane controls
In the range of 10ppm-500ppm, the speed that the aromatic structure in PBAT resin reacts under wet heat condition can be delayed,
So that the PBAT resin combination prepared has the resistance to boiling water aging colour stability being obviously improved, and PBAT can be made
Resin combination has the blown film characteristic being obviously improved, and when fair speed blown film (178Kg/h), film material thickness extreme difference is the most relatively
Little, and oxolane functions similarly to the effect of lubricant in resin, prevents each position of film bubble in blow-molding process
Holes situation is caused, it is ensured that the seriality that blown film produces owing to stress distribution is uneven.
If the too high levels of ferrum element in PBAT resin combination, PBAT resin demonstrates celadon, affects outward appearance, ferrum unit
The content of element is too low, and after boiling water aging was boiling water aging 24 hours and 48 hours, variable color is serious, and b value changes and is more than 2,
Therefore, gross weight based on PBAT resin combination, the weight content of ferrum element is preferably 10ppm-250ppm, more preferably
For 30ppm-80ppm.
If the content of oxolane is too low in PBAT resin combination, during blown film, material is by inflation, PBAT molecular motion
Resistance is relatively big, owing to stretching is uneven, causes thin film became uneven, becomes apparent from especially in the case of thin film is relatively thin；If
The too high levels of oxolane in PBAT resin combination, during blown film, oxolane rich region due to low strength,
Easily cause holes.It is preferred, therefore, that gross weight based on PBAT resin, the weight content of oxolane is
15ppm-200ppm, more preferably 20ppm-60ppm.
Wherein, the weight of mutual-phenenyl two acid bromide two alcohol ester's unit in polyadipate butylene terephthalate (PBAT) resin
Content T% is 35wt%-65wt%.When T% is less than 35wt%, the goods made are too soft, are unfavorable for using.T% is higher than 65wt%
Time, goods are too hard, are unfavorable for using.
Wherein, the melt index of described polyadipate butylene terephthalate (PBAT) resin is with GB/T 3682-2000
Standard, is 190 DEG C in temperature, and load is for 8g/10min-25g/10min under the conditions of 5Kg.Melt index is less than 8g/10min
Time, course of processing energy consumption becomes big, uneconomical.When melt index is higher than 25g/10min, in the course of processing, film bubble is unstable,
Membrane material quantitative change is poor.
The access approaches of ferrum element of the present invention, can be by the polyadipate butylene terephthalate (PBAT) in synthesis
Resin directly adds iron containing compounds.
Described iron containing compounds is selected from iron sesquioxide, ferroso-ferric oxide, ferrous oxide, ferrous sulfate, iron sulfate, sulphuric acid
In ferrum ammonium, Ferrous ammonium sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, iron chloride, iron sesquioxide or ferroso-ferric oxide
One or more.
The access approaches of oxolane of the present invention, can be by by polyadipate butylene terephthalate (PBAT)
Resin obtains through extruder pelletize after mixing with oxolane.
According to different purposes needs, the PBAT resin combination of the present invention can further include other auxiliary agent, the most anti-
Oxidant, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer, antistatic additive, de-
Mould agent, pigment etc..Based on PBAT resin 100 weight portion, the addition of other auxiliary agent can add 0-10 weight as required
Amount part.
Described antioxidant one in suffocated amine antioxidant, Hinered phenols antioxidant or phosphite ester kind antioxidant or
Several, specifically can list the one or two kinds of in 1010,168,1076,445,1098 and above mixture；
Described light stabilizer is hindered amine light stabilizer, specifically can list UV-944, UV-234,770DF, 328,
One or two kinds of in 531 and above mixture；
Described impact modifier is the one in PTW, styrene-ethylene/butylene-styrene block copolymer SEBS or two
The mixture planted；
Described fire retardant is the one or two kinds of in red phosphorus, OP1240, OP1230 and above mixture；
Described fluorescent whitening agent is a kind of in double triazine amino-stilbene, titanium dioxide or the mixture of the two；
Described lubricant be the one in Pulvis Talci, ethylene bis stearamide EBS, erucyl amide, zinc stearate, silicone oil or
Person two kinds and above mixture；
Described plasticizer is the one or two kinds of in glycerol, citric acid, butyl citrate, epoxy soybean oil etc. and above
Mixture；
Described antistatic additive is permanent antistatic agent, specifically can list PELESTAT-230, PELESTAT-6500,
One or two kinds of in SUNNICO ASA-2500 and above mixture；
Described releasing agent is the one or two kinds of in silicone oil, paraffin, white mineral oil, vaseline and above mixture；
Described pigment be the one or two kinds of in white carbon black, black race, titanium dioxide, zinc sulfide, phthalocyanine blue, fluorescent orange and more than
Mixture.
The present invention compared with prior art, has the advantages that
The present invention is by adding iron containing compounds and the oxolane of trace in the composition, by the content of ferrum element in compositions
Controlling in the range of 1ppm-500ppm, the content of oxolane controls in the range of 10ppm-500ppm, can delay PBAT
The speed that aromatic structure in resin reacts under wet heat condition, makes the PBAT resin combination prepared at boiling water
Aging 24 hours and after 48 hours, the change of b value, less than 2, had the resistance to boiling water aging colour stability being obviously improved, and
When blown film extruded velocity is 178Kg/h, thickness extreme difference < 0.2 μm, and thickness relative deviation < 1%, there is blowing of being obviously improved
Membrane property, and oxolane functions similarly to the effect of lubricant in resin, prevents film bubble each in blow-molding process
Position causes holes situation owing to stress distribution is uneven, it is ensured that the seriality that blown film produces.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment,
But embodiments of the present invention are not limited by following embodiment.
Iron containing compounds of the present invention and oxolane derive from commercial.
PBAT resin syntheses processes:
P-phthalic acid and the BDO of metering are put in reactor, is warming up to 220～240 DEG C of reactions to benzene two
Formic acid reacts completely, puts in reactor by the adipic acid of metering, continues reaction to adipic acid in 180～220 DEG C and reacts completely,
Put into proper catalyst and stabilizer, in 30～60 minutes, reacting kettle inner pressure is reduced to below 50Pa, in 220～260 DEG C
React to the viscosity specified, stop stirring, in reactor, be filled with high pure nitrogen, resin is extruded from reactor pelletize,
I.e. obtain PBAT resin.Change p-phthalic acid and the inventory of adipic acid, i.e. available different p-phthalic acid butanediols
The PBAT resin of ester units content.
Wherein mutual-phenenyl two acid bromide two alcohol ester's unit content passes through1H NMR tests, and with deuterochloroform as solvent, TMS is internal standard,
Result calculates according to the following formula:
Wherein: T% is mutual-phenenyl two acid bromide two alcohol ester's unit content；
S8.1For1Absworption peak area at 8.1ppm in H NMR spectra；
S2.3For1Absworption peak area at 2.3ppm in H NMR spectra；
Embodiment 1-20 and comparative example 1-2:
Formula as shown in table 1, by PBAT resin, iron containing compounds, oxolane, antioxidant 1010, erucyl amide etc.
Put in single screw extrusion machine after the mixing of other auxiliary agents, in 170 DEG C-210 DEG C extrusions, pelletizes, obtain compositions.Will combination
Thing puts in inflation film manufacturing machine after drying, and extruded, blown film obtains PBAT thin film.Performance test data is shown in Table 1.
Method of evaluating performance:
(1) color: use the spherical shape particle after pelletize, the DC-P3 that uses Beijing Xing Guang colour examining instrument company to produce complete from
Dynamic colour examining colour-difference-metre is directly tested.
(2) weight content of ferrum element adopts test with the following method: weighs the sample after 0.1g pulverizes, puts in micro-wave diminishing pot,
Adding nitric acid 5mL makes it be totally submerged sample, more slowly instills 1.0mL hydrogen peroxide, after reaction 2min, closes the lid,
Sealed digestion tank, puts in Hyperfrequency waves eliminating stove and clears up.After being cooled to room temperature, by 0.45 μm of the solution in counteracting tank
It is transferred to after membrane filtration in volumetric flask, with distilled water diluting to 50mL.Use Agilent Technologies 700
Series ICP-OES tests.
(3) film thickness fialar micrometer is tested: uniformly takes 10 measurement points on the thin film of 1m*1m and measures.
Thickness extreme difference is 10 and measures maximum gauge value and the difference of minimum thickness value in point.
Thickness relative deviation is calculated as follows:
Wherein average film thickness uniformly takes 10 on the thin film of 1m*1m and measures point, takes arithmetic mean respectively after test thickness
Value.
Holes situation is that continuous blown film produces 8 hours, film bubble holes number of times occurs.
(4) content of oxolane uses Headspace Gas Chromatography: a certain amount of sample is placed in 5min in liquid nitrogen biological container
After, take out and pulverize, sieve, take the product of 30-40 mesh, weigh a certain amount of sample；Use the 7890A that Agilent company produces
Type gas chromatograph, chromatographic column is that Agilent company produces DB-WAX type gas chromatographic column, uses Agilent company to produce 7697
Type head-space sampler sample introduction；Headspace sampling condition is 100 DEG C, and constant temperature is sample introduction after 4 hours；Working curve by oxolane/
Methanol solution is demarcated.
Table 1 embodiment 1-20 and the proportioning of each component of comparative example 1-2 and the performance test results
Continued 1
Wherein, b0 is b value before boiling water aging, and b24 is boiling water aging b value after 24 hours, and b48 is that boiling water aging 48 is little
B value time after, b0-b24 is b value before boiling water aging and boiling water aging difference of b value after 24 hours, and b0-b48 is boiling water
B value before aging and the boiling water aging difference of b value after 48 hours, the absolute value of difference is the least, shows the resistance to boiling of compositions
The aging colour stability of water is the best；THF content is content of tetrahydrofuran.
From table 1 it follows that iron content is 1-500ppm in PBAT compositions, content of tetrahydrofuran is
During 10ppm-500ppm, after boiling water aging 24 hours and 48 hours, the change of b value, less than 2, shows that compositions has good
Good resistance to boiling water aging colour stability, and under the conditions of blown film extruded velocity is 178Kg/h, thickness extreme difference < 0.2 μm,
< 1%, holes number is 0 to thickness relative deviation, shows that PBAT resin combination has good blown film characteristic.And comparative example 1
Iron content is less than 1ppm, content of tetrahydrofuran less than during 10ppm and comparative example 2 iron content is beyond 500ppm,
When content of tetrahydrofuran is beyond 500ppm, the change of b value is more than 2, thickness extreme difference ＞ 0.2, thickness relative deviation ＞ 1%, broken
Hole count ＞ 0, shows that compositions resistance to boiling water aging colour stability and blown film characteristic are poor.
Claims (9)
1. a PBAT resin combination, it is characterised in that include following component:
(a) polyadipate butylene terephthalate；
(b) ferrum element；
(c) oxolane；
Wherein, gross weight based on PBAT resin combination, the weight content of ferrum element is 1ppm-500ppm, and the weight content of oxolane is 10ppm-500ppm.
A kind of PBAT resin combination the most according to claim 1, it is characterized in that, the weight content of described ferrum element uses the test of micro-wave digestion-ICP-OES method: weigh the sample after 0.1g pulverizes, put in micro-wave diminishing pot, adding nitric acid 5mL makes it be totally submerged sample, the most slowly instill 1.0mL hydrogen peroxide, after reaction 2min, close the lid, sealed digestion tank, put in Hyperfrequency waves eliminating stove and clear up, after being cooled to room temperature, solution in counteracting tank is transferred in volumetric flask after 0.45 μm membrane filtration, with distilled water diluting to 50mL, use ICP-OES test；
The weight content of described oxolane uses Headspace Gas Chromatography: be placed in liquid nitrogen biological container after 5min by a certain amount of sample, takes out and pulverizes, sieves, take the product of 30-40 mesh, weigh a certain amount of sample；Using the 7890A type gas chromatograph that Agilent company produces, chromatographic column is that Agilent company produces DB-WAX type gas chromatographic column, uses Agilent company to produce 7697 type head-space sampler sample introductions；Headspace sampling condition is 100 DEG C, and constant temperature is sample introduction after 4 hours；Working curve is demarcated by oxolane/methanol solution.
A kind of PBAT resin combination the most according to claim 1, it is characterised in that gross weight based on PBAT resin combination, the weight content of ferrum element is 10ppm-250ppm, being preferably 30ppm-80ppm, the weight content of oxolane is 15ppm-200ppm, preferably 20ppm-60ppm.
A kind of PBAT resin combination the most according to claim 1, it is characterised in that in described polyadipate butylene terephthalate resin, the weight content T% of mutual-phenenyl two acid bromide two alcohol ester's unit is 35wt%-65wt%.
A kind of PBAT resin combination the most according to claim 1, it is characterised in that the melt index of described polyadipate butylene terephthalate resin, with GB/T 3682-2000 standard, is 190 in temperatureoC, load is for 8g/10min-25g/10min under the conditions of 5Kg.
A kind of PBAT resin combination the most according to claim 1, it is characterized in that, described ferrum element derives from iron containing compounds, one or more in iron sesquioxide, ferroso-ferric oxide, ferrous oxide, ferrous sulfate, iron sulfate, ammonium ferric sulfate, Ferrous ammonium sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, iron chloride, iron sesquioxide or ferroso-ferric oxide of described iron containing compounds.
A kind of PBAT resin combination the most according to claim 1, it is characterized in that, described PBAT resin combination also includes the one or more than one in other auxiliary agent, specially antioxidant, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer, antistatic additive, releasing agent, pigment.
8. according to a kind of PBAT resin combination described in any one of claim 1-7, it is characterised in that described PBAT resin combination is after boiling water aging 24 hours and 48 hours, and the change of b value is less than 2.
9. according to a kind of PBAT resin combination described in any one of claim 1-7, it is characterised in that described PBAT resin combination when blown film extruded velocity is 178Kg/h, thickness extreme difference < 0.2 μm, thickness relative deviation < 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610018855.6A CN105838038A (en) | 2016-01-11 | 2016-01-11 | Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610018855.6A CN105838038A (en) | 2016-01-11 | 2016-01-11 | Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105838038A true CN105838038A (en) | 2016-08-10 |
Family
ID=56580539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610018855.6A Pending CN105838038A (en) | 2016-01-11 | 2016-01-11 | Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105838038A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109297900A (en) * | 2017-07-25 | 2019-02-01 | 中国石油天然气股份有限公司 | Method for judging bonding condition of epoxy resin layer in epoxy sleeve repairing pipeline |
| CN112898546A (en) * | 2021-03-24 | 2021-06-04 | 山东道恩高分子材料股份有限公司 | Preparation method of PBAT material with high thermal stability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030069339A1 (en) * | 2001-04-24 | 2003-04-10 | Mitsubishi Engineering-Plastics Corporation | Polybutylene terephthalate resin and compositions and molded articles comprising the resin |
| CN104312106A (en) * | 2014-09-19 | 2015-01-28 | 金发科技股份有限公司 | Completely biodegradable anti-counterfeiting plastic bag and preparation method thereof |
-
2016
- 2016-01-11 CN CN201610018855.6A patent/CN105838038A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030069339A1 (en) * | 2001-04-24 | 2003-04-10 | Mitsubishi Engineering-Plastics Corporation | Polybutylene terephthalate resin and compositions and molded articles comprising the resin |
| CN104312106A (en) * | 2014-09-19 | 2015-01-28 | 金发科技股份有限公司 | Completely biodegradable anti-counterfeiting plastic bag and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109297900A (en) * | 2017-07-25 | 2019-02-01 | 中国石油天然气股份有限公司 | Method for judging bonding condition of epoxy resin layer in epoxy sleeve repairing pipeline |
| CN109297900B (en) * | 2017-07-25 | 2021-07-02 | 中国石油天然气股份有限公司 | Method for judging bonding condition of epoxy resin layer in epoxy sleeve repairing pipeline |
| CN112898546A (en) * | 2021-03-24 | 2021-06-04 | 山东道恩高分子材料股份有限公司 | Preparation method of PBAT material with high thermal stability |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3260493B2 (en) | Pbat resin composition | |
| CN105602209B (en) | PBAT resin composition | |
| CN109021380B (en) | Polypropylene composite material with low odor, scratch resistance and low gloss and preparation method thereof | |
| JP6469930B2 (en) | Biodegradable polyester composition | |
| US20180142060A1 (en) | Biodegradable polyester composition | |
| CN107446336A (en) | A kind of low smell exempts to spray PC/ABS materials and preparation method thereof | |
| CN107793754A (en) | A kind of environmentally friendly low smell exempts to spray daiamid composition and preparation method thereof | |
| CN105838038A (en) | Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition | |
| CN110256844A (en) | A kind of 3D printing color inhibition nylon composite materials and preparation method thereof | |
| CN104725763B (en) | A kind of illumination aging resisting ABS plastic and preparation method thereof | |
| DE10305609B4 (en) | Polypropylene resin composition and molded articles produced therefrom | |
| CN112662114A (en) | Low-odor low-VOC scratch-resistant polypropylene interior material for vehicles and preparation method thereof | |
| CN105838037A (en) | Poly(butyleneadipate-co-terephthalate) (PBAT) resin composition | |
| CN114426747A (en) | Deformation-resistant PVC elastomer automotive interior material | |
| CN107459783B (en) | A kind of polyester terephthalate -co- sebacate resin combination | |
| CN108059804B (en) | PBAT degradation color master batch and preparation method thereof | |
| CN113549269A (en) | Application of nickel cobaltate as flame-retardant synergist | |
| CN105542407A (en) | Glass fiber reinforced PBT composition and preparation method and application thereof | |
| CN106633840B (en) | A kind of automotive upholstery nylon composite materials of low irritant smell and preparation method thereof | |
| CN116535806B (en) | ABS material with low acrylonitrile content and preparation method and application thereof | |
| CN111849115A (en) | Novel high polymer material and display mask of cabinet air conditioner prepared from same | |
| CN108976692A (en) | Low smell ABS composition and preparation method thereof | |
| CN107778848A (en) | A kind of low smell, it is low distribute, antibacterial PA6/ABS alloys and preparation method thereof | |
| CN117645761A (en) | Chlorinated polyethylene powder material for slush molding process and preparation method thereof | |
| CN101831113A (en) | Polypropylene composition and polypropylene material for automotive upholstery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160810 |
|
| RJ01 | Rejection of invention patent application after publication |