CN117757002A - Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof - Google Patents
Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof Download PDFInfo
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- CN117757002A CN117757002A CN202311718418.1A CN202311718418A CN117757002A CN 117757002 A CN117757002 A CN 117757002A CN 202311718418 A CN202311718418 A CN 202311718418A CN 117757002 A CN117757002 A CN 117757002A
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- 229920005989 resin Polymers 0.000 title claims abstract description 187
- 239000011347 resin Substances 0.000 title claims abstract description 187
- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims abstract description 66
- 229920006378 biaxially oriented polypropylene Polymers 0.000 title claims abstract description 63
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 59
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004743 Polypropylene Substances 0.000 claims description 64
- 229920001155 polypropylene Polymers 0.000 claims description 64
- -1 polypropylene Polymers 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000003963 antioxidant agent Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- HKMDCNSGDQBQLI-UHFFFAOYSA-N 2-Hexyl-3-methylenesuccinic acid Chemical compound CCCCCCC(C(O)=O)C(=C)C(O)=O HKMDCNSGDQBQLI-UHFFFAOYSA-N 0.000 claims description 6
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 6
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims description 6
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims description 6
- WSGFXVFLWVXTCJ-VOTSOKGWSA-N Dihydro-3-(2-octenyl)-2,5-furandione Chemical compound CCCCC\C=C\CC1CC(=O)OC1=O WSGFXVFLWVXTCJ-VOTSOKGWSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 6
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 6
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 5
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- NSJAWXMCLJVBPM-UHFFFAOYSA-N 3-butyloxolane-2,5-dione Chemical compound CCCCC1CC(=O)OC1=O NSJAWXMCLJVBPM-UHFFFAOYSA-N 0.000 claims description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 3
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 5
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- 230000006872 improvement Effects 0.000 description 4
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- 150000001875 compounds Chemical class 0.000 description 3
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- 238000010828 elution Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
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- 210000004080 milk Anatomy 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a modified resin and a preparation method thereof, a stiffening master batch, a BOPP film and a preparation method thereof, and relates to the technical field of high polymer materials. The modified resin disclosed by the application is obtained by grafting and modifying hydrogenated petroleum resin through a bio-based carboxylic acid monomer, the softening point of the modified resin is 120-165 ℃, the yellowness index is less than or equal to 15, the content of volatile organic compounds is less than or equal to 500ppm, the acid value is 0.1-25mgKOH/g, the source of raw materials is wide, the content of the volatile organic compounds of the modified resin is low, and the modified resin is suitable for preparing BOPP films with good optical performance, mechanical performance and thermodynamic performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified resin and a preparation method thereof, a stiffening master batch, a BOPP film and a preparation method thereof.
Background
Polypropylene (PP) is a thermoplastic polymer polymerized from propylene monomers. It has excellent heat resistance, chemical corrosion resistance, ultraviolet resistance, high mechanical strength and other excellent performance, and has been used widely in several fields. Wherein, the biaxially oriented polypropylene film (BOPP film) has moisture resistance and certain mechanical property due to light weight, no toxicity and no odor, and is widely applied to the packaging of foods, candies, cigarettes, tea, fruit juice, milk, textiles and the like. However, BOPP films have relatively poor rigidity and thermal stability, which limits their range of applications.
At present, a nucleation modification mode is generally adopted to improve the rigidity of a polypropylene material, for example, researchers find that the addition of a cage-type silsesquioxane supported substituted aryl heterocyclic phosphate or salt nucleating agent in the polypropylene material can play a role in rigidity and permeability improvement, but the permeability improvement effect is limited from the test result.
In addition, the polypropylene material prepared by the existing modification method is often in the condition of too high content of volatile organic compounds, and is not friendly to the environment.
Therefore, it is needed to provide a polypropylene material with good rigidity, thermal stability and transparency and a more environment-friendly preparation method, so as to expand the application field of BOPP films.
Disclosure of Invention
The invention mainly aims to provide a modified resin and a preparation method thereof, a stiffening master batch, a BOPP film and a preparation method thereof, so as to solve the problems of insufficient rigidity, thermal stability and transparency and excessive content of volatile organic compounds in the BOPP film in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a modified resin obtained by graft modification of a hydrogenated petroleum resin with a bio-based carboxylic acid monomer, which has a softening point of 120 to 165 ℃, a yellowness index of 15 or less, a content of volatile organic compounds of 500ppm or less, and an acid value of 0.1 to 25mgKOH/g.
Further, the softening point of the hydrogenated petroleum resin is 125-145 ℃, the yellowness index is less than or equal to 7, and the aromaticity is 0.01-15%; and/or the bio-based carboxylic acid monomer is at least one of 3-hydroxy propionic acid, 2, 5-furan dicarboxylic acid, abietic acid, dehydroabietic acid, 2-dimethyl succinic anhydride, butyl succinic anhydride, 2-octenyl succinic anhydride, ricinoleic acid, dehydrated ricinoleic acid, itaconic acid and hexyl itaconic acid.
According to a second aspect of the present invention, there is provided a method for producing the above modified resin, comprising the steps of:
s1, adding hydrogenated petroleum resin, a bio-based carboxylic acid monomer and an antioxidant into a first solvent to obtain a mixed solution;
s2, adding an initiator into the mixed solution to react to obtain a reaction product;
s3, removing the first solvent in the reaction product, eluting unreacted bio-based carboxylic acid monomer by using a second solvent, and drying to obtain the modified resin.
Further, the first solvent is a mixed solution of xylene and N, N-Dimethylformamide (DMF); and/or
The second solvent is at least one of diethyl ether, phenetole, ethanol, methanol, isopropanol, isobutanol, acetone, methyl acetone, butanone, ethyl acetate and methyl acetate; and/or
The antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; and/or
The initiator is at least one of dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), bis (tert-butyl peroxyisopropyl) benzene, 2-butanone peroxide, azobisisobutyronitrile (AIBN) and azobisisoheptonitrile; and/or
The mass ratio of the hydrogenated petroleum resin to the bio-based carboxylic acid monomer is (49.5-69.5): (0.1-15), the mass ratio of the hydrogenated petroleum resin to the antioxidant is (49.5-69.5): (0.1-0.5), the mass ratio of the hydrogenated petroleum resin to the first solvent is (49.5-69.5): (30-50), the mass ratio of the hydrogenated petroleum resin to the initiator is (49.5-69.5): (0.05-2); and/or
In the step S2, the reaction temperature is 70-200 ℃ and the reaction time is 0.25-3h; and/or
In the step S3, the first solvent is removed under the conditions that the pressure is 5 to 15kPa and the temperature is 70 to 115 ℃; and/or
And in the step S3, drying is carried out in a vacuum environment at 50-90 ℃.
Further, in the first solvent, the mass ratio of the xylene to the N, N-dimethylformamide is 1: (0.3-2); and/or
The addition amount of the second solvent is 0.5-50% of the mass of the reaction product after the first solvent is removed; and/or
The hindered phenol antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 330 and antioxidant 3114; and/or
The phosphite antioxidant is at least one of antioxidant 168 and antioxidant 626.
According to the third aspect of the invention, a stiffening master batch is also disclosed, the stiffening master batch comprises the modified resin and the first polypropylene resin, and the mass ratio of the modified resin to the first polypropylene resin is 1: (0.8-1.2).
According to a fourth aspect of the present invention, there is disclosed a BOPP film comprising a first layer, an intermediate layer and a second layer connected in sequence; wherein, the material of the intermediate layer comprises the stiffening master batch and the second polypropylene resin, and the mass ratio of the second polypropylene resin to the stiffening master batch in the intermediate layer is 1: (0.2-0.4); the mass ratio of the total mass of the first layer and the second layer to the intermediate layer is 1: (0.2-0.6), the mass ratio of the first layer to the second layer being 1: (0.75-1.25); the material of the first and second layers comprises a second polypropylene resin.
Further, the first polypropylene resin and the second polypropylene resin in the stiffening master batch are homo-polypropylene resins, and the melt flow rates of the first polypropylene resin and the second polypropylene resin measured under the conditions of 230 ℃ and 2.16kg are respectively and independently 2-4g/10min; the tensile yield strength of the first polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%; the tensile yield strength of the second polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%; and/or
When the thickness of the BOPP film is 30 mu m, the longitudinal elastic modulus of the BOPP film is more than or equal to 1700MPa, the longitudinal heat shrinkage rate is 3-12%, the transverse heat shrinkage rate is 3-12%, the haze is less than or equal to 2%, and the heat sealing strength measured by heat sealing at 135 ℃ for 0.3s is more than or equal to 2.4N/15mm.
According to a fifth aspect of the present invention, a method for preparing BOPP film is disclosed, comprising the steps of:
s1, adding modified resin and first polypropylene resin into a screw extruder for extrusion granulation to obtain stiffening master batches;
s2, adding the stiffening master batch into a screw extruder, adding the raw materials of the first layer and the second layer into respective auxiliary extruders, converging and flowing out of the dies of the three layers of materials, cooling, and stretching by a film biaxially-oriented polypropylene (BOPP) film.
Further, in the step S1, the temperature of the screw extruder is 160-240 ℃ and the screw rotating speed is 150-300r/min; and/or
In S2, stretching is divided into longitudinal stretching and transverse stretching, and the longitudinal stretching conditions are as follows: the preheating temperature is 220-280 ℃, the stretching temperature is 120-150 ℃, the stretching multiplying power is 4.0-6.0, and the transverse stretching conditions are as follows: preheating temperature 220-280 deg.c, stretching temperature 150-180 deg.c, setting temperature 25-50 deg.c and stretching multiplying power 8.0-10.0.
By applying the technical scheme of the invention, the hydrogenated petroleum resin grafted and modified by the bio-based carboxylic acid monomer is taken as a stiffening raw material, and after being blended with the polypropylene material, the polypropylene material can be induced to nucleate and crystallize in an alpha crystal form, so that smaller and more uniform spherulites are formed, thereby being beneficial to improving the rigidity, the optical performance and the thermodynamic performance of the BOPP film product; in addition, the BOPP film prepared by the modified resin has the advantages of less content of volatile organic compounds and better environmental protection performance.
Drawings
FIG. 1 is a Fourier infrared spectrum of the modified resin and hydrogenated petroleum resin of example 1;
FIG. 2 shows the modified resin and hydrogenated petroleum resin of example 1 1 H-NMR spectrum;
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background of the invention, the BOPP films in the prior art have the problems of relatively low rigidity, insufficient transparency and insufficient thermal stability. In order to solve the above problems, in an exemplary embodiment of the present invention, there is provided a modified resin obtained by graft modification of a hydrogenated petroleum resin with a bio-based carboxylic acid monomer, which has a softening point of 120 to 165 ℃, a yellowness index of 15 or less, a volatile organic compound content of 500ppm or less, and an acid value of 0.1 to 25mgKOH/g.
The hydrogenated petroleum resin grafted and modified by the bio-based carboxylic acid monomer has relatively low content of volatile organic compounds, and the blending of the modified resin and the polypropylene resin can induce polypropylene to nucleate and crystallize in an alpha crystal form to form finer grains, thereby being beneficial to improving the mechanical property, the optical property and the thermodynamic property of the BOPP film.
As a preferred embodiment of the invention, the hydrogenated petroleum resin has a softening point of 125-145 ℃ and a yellowness index of less than or equal to 7 and an aromaticity of 0.01-15%; and/or the bio-based carboxylic acid monomer is at least one of 3-hydroxy propionic acid, 2, 5-furan dicarboxylic acid, abietic acid, dehydroabietic acid, 2-dimethyl succinic anhydride, butyl succinic anhydride, 2-octenyl succinic anhydride, ricinoleic acid, dehydrated ricinoleic acid, itaconic acid and hexyl itaconic acid.
The above limitation on the properties of hydrogenated petroleum resin is to balance the rigidity and transparency of BOPP film, so that it has good rigidity, transparency and thermal stability, and also has a certain heat seal strength. The modification of hydrogenated petroleum resin with the bio-based carboxylic acid monomer can reduce the softening point of the hydrogenated petroleum resin, is favorable for reducing the content of volatile organic compounds in BOPP films and reduces environmental pollution.
In another exemplary embodiment of the present invention, there is provided a method for preparing a modified resin, comprising the steps of:
s1, adding hydrogenated petroleum resin, a bio-based carboxylic acid monomer and an antioxidant into a first solvent to obtain a mixed solution;
s2, adding an initiator into the mixed solution to react to obtain a reaction product;
s3, removing the first solvent in the reaction product, eluting unreacted bio-based carboxylic acid monomer by using a second solvent, and drying to obtain the modified resin.
The preparation method is simple, carboxylic acid monomers can be rapidly grafted on hydrogenated petroleum resin by preparing the modified resin under the conditions, the color degradation is inhibited, the modified resin with lower yellowness index is prepared, and the optical performance of the prepared BOPP film is improved.
As a preferred embodiment of the present invention, the first solvent is a mixed solution of xylene and N, N-dimethylformamide; and/or
The second solvent is at least one of diethyl ether, phenetole, ethanol, methanol, isopropanol, isobutanol, acetone, methyl acetone, butanone, ethyl acetate and methyl acetate; and/or
The antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; and/or
The initiator is at least one of dicumyl peroxide, dibenzoyl peroxide, bis (tert-butyl peroxyisopropyl) benzene, 2-butanone peroxide, azodiisobutyronitrile and azodiisoheptanenitrile; and/or
The mass ratio of the hydrogenated petroleum resin to the bio-based carboxylic acid monomer is (49.5-69.5): (0.1-15), the mass ratio of the hydrogenated petroleum resin to the antioxidant is (49.5-69.5): (0.1-0.5), the mass ratio of the hydrogenated petroleum resin to the first solvent is (49.5-69.5): (30-50), the mass ratio of the hydrogenated petroleum resin to the initiator is (49.5-69.5): (0.05-2); and/or
In the step S2, the reaction temperature is 70-200 ℃ and the reaction time is 0.25-3h; and/or
In the step S3, the first solvent is removed under the conditions that the pressure is 5 to 15kPa and the temperature is 70 to 115 ℃; and/or
And in the step S3, drying is carried out in a vacuum environment at 50-90 ℃.
The kind of the first solvent can influence the grafting rate of the modified resin, and the selected xylene and N, N-dimethylformamide are compounded to ensure that the grafting rate of the modified resin is relatively high, so that the modified resin is favorable for improving the rigidity of the polypropylene material, and meanwhile, the modified resin also has a lower yellowness index, and is suitable for being applied to a plurality of fields. At least one of the components is selected as a second solvent, so that unreacted bio-based carboxylic acid monomer can be efficiently eluted, the content of volatile organic compounds in the product is reduced, and the mechanical property, optical property and environmental protection property of the BOPP film are improved. The initiation reaction under the above conditions can realize the efficient graft modification of hydrogenated petroleum resin with less initiator, while inhibiting the color deterioration.
As a preferred embodiment of the present invention, the first solvent has a mass ratio of xylene to N, N-dimethylformamide of 1: (0.3-2).
The mass ratio of the two components in the first solvent is limited, so that the modified resin has higher grafting rate, and the yellowness index of the modified resin does not change obviously, thereby being more suitable for improving the comprehensive performance of the BOPP film.
As a preferred embodiment of the present invention, the second solvent is added in an amount of 0.5% to 50% by mass of the reaction product after removal of the first solvent.
The amount of the second solvent is limited as described above in order to effectively remove the unreacted bio-based carboxylic acid monomer.
Typically, but not by way of limitation, the hindered phenolic antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 330, antioxidant 3114; the phosphite antioxidant is at least one of antioxidant 168 and antioxidant 626.
In a typical embodiment of the present invention, a stiffening masterbatch is also disclosed, the stiffening masterbatch comprising the modified resin and the first polypropylene resin, the mass ratio of the modified resin to the first polypropylene resin being 1: (0.8-1.2).
The components in the proportion are used as stiffening master batches, so that polypropylene can be induced to form an excellent nucleation crystal form, the rigidity and toughness of the polypropylene can be synchronously improved under the condition that the impact strength of the polypropylene is not reduced, the heat-resistant deformation of the polypropylene is improved, the heat shrinkage rate of the polypropylene is reduced, the transparency of the BOPP film is higher, and the content of volatile organic compounds is lower.
In one exemplary embodiment of the present invention, a BOPP film is disclosed, comprising a first layer, an intermediate layer, and a second layer connected in sequence; wherein, the material of the intermediate layer comprises the stiffening master batch and the second polypropylene resin, and the mass ratio of the second polypropylene resin to the stiffening master batch in the intermediate layer is 1: (0.2-0.4); the mass ratio of the total mass of the first layer and the second layer to the intermediate layer is 1: (0.2-0.6), the mass ratio of the first layer to the second layer being 1: (0.75-1.25); the material of the first and second layers comprises a second polypropylene resin.
The structure and the components of the BOPP film are limited to effectively improve the rigidity of the BOPP film without affecting the ductility of the BOPP film, and expand the application range of the BOPP film.
As a preferred embodiment of the present invention, the first polypropylene resin and the second polypropylene resin are homopolypropylene resins, and each independently has a melt flow rate of 2 to 4g/10min measured at 230 ℃ under 2.16 kg; the tensile yield strength of the first polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%; the tensile yield strength of the second polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%.
The BOPP film is prepared by the first polypropylene resin and the second polypropylene resin, when the thickness of the BOPP film is 30 mu m, the longitudinal elastic modulus is more than or equal to 1700MPa, the longitudinal heat shrinkage is 3-12%, the transverse heat shrinkage is 3-12%, the haze is less than or equal to 2%, and the heat sealing strength measured by heat sealing at 135 ℃ for 0.3s is more than or equal to 2.4N/15mm. The BOPP film has good comprehensive performance and wide application field.
In an exemplary embodiment of the present invention, there is provided a method for preparing a BOPP film, comprising the steps of:
s1, adding modified resin and first polypropylene resin into a screw extruder for extrusion granulation to obtain stiffening master batches;
s2, adding the stiffening master batch into a screw extruder, adding the raw materials of the first layer and the second layer into respective auxiliary extruders, converging and flowing out of the dies of the three layers of materials, cooling, and stretching by a film biaxially-oriented polypropylene (BOPP) film.
As a preferred embodiment of the present invention, in the above S1, the temperature of the screw extruder is 160-240℃and the screw rotation speed is 150-300r/min; and/or
In S2, stretching is divided into longitudinal stretching and transverse stretching, and the longitudinal stretching conditions are as follows: the preheating temperature is 220-280 ℃, the stretching temperature is 120-150 ℃, the stretching multiplying power is 4.0-6.0, and the transverse stretching conditions are as follows: preheating temperature 220-280 deg.c, stretching temperature 150-180 deg.c, setting temperature 25-50 deg.c and stretching multiplying power 8.0-10.0.
The BOPP film prepared under the conditions can have good physical and mechanical properties, and the content of volatile organic compounds is low.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
The main test method of the resin and film products in the invention is as follows:
softening point: GB/T2294-2019 method for measuring softening point of coking solid products;
yellowness index: HG/T3862-2006 test method for Plastic yellow index;
aromaticity (hydrogen spectrum): JY/T0578-2020 general rule of superconducting pulse Fourier transform nuclear magnetic resonance spectroscopy test method;
acid value: ASTM D974-21 Standard test method for determining acid-base number by color indicator titration;
volatile organic compounds: US EPA 5021A-2014, analysis was performed using HS-GC-MS;
modulus of elasticity: DIN 53457-Z "determination of modulus of elasticity in plastics test";
heat shrinkage (vertical/horizontal): BMSTT02 measures the dimensional stability of the film, i.e., machine/transverse heat shrinkage;
haze: ASTM D1003-13 Standard test method for haze and light transmittance of transparent plastics;
heat seal strength: QB/T2358-1998 test method for heat seal Strength of Plastic film packaging bag.
The materials used in the examples and comparative examples are as follows:
hydrogenated petroleum resin a: the softening point is 135.0 ℃, the yellowness index YI is 3.0, the aromaticity is 3.5%, and the hydrogenated petroleum resin HM-1300 is manufactured by the Hene Material science and technology Co., ltd;
hydrogenated petroleum resin B: the softening point is 140.0 ℃, the yellowness index YI is 1.0, the aromaticity is 1%, the carbon five hydrogenated petroleum resin H5-1400W is obtained from the Hene materials science and technology Co., ltd;
hydrogenated petroleum resin C: the softening point is 140.0 ℃, the yellowness index YI is 1.0, the aromaticity is 5%, the hydrogenated petroleum resin HM-1400 is manufactured by the Hene Material science and technology Co., ltd;
hydrogenated petroleum resin D: the softening point is 140.0 ℃, the yellowness index YI is 1.0, the aromaticity is 10%, the high aromatic hydrocarbon hydrogenated resin HA-140 is obtained from the company of Hene Material science and technology Co., ltd;
hydrogenated petroleum resin E: the softening point is 140.0 ℃, the yellowness index YI is 1.0, the aromaticity is 15%, and the high aromatic hydrocarbon hydrogenation resin HR-140 is manufactured by the Hene materials science and technology Co., ltd;
hydrogenated petroleum resin F: the softening point is 140.0 ℃, the yellowness index YI is 1.0, the aromaticity is 0.01%, and the total hydrogenated petroleum resin HP-140 is manufactured by the Hene Material technologies Co., ltd;
rosin acid: industrial grade, purity is more than or equal to 75%;
dehydroabietic acid: industrial grade, purity is more than or equal to 98.0%;
2-octenyl succinic anhydride: medical grade, purity is more than or equal to 99.0%;
itaconic acid: industrial grade, purity is more than or equal to 98.0%.
First polypropylene resin and second polypropylene resin a: the melt flow rate measured at 230℃under 2.16kg was 3g/10min, the tensile yield strength was 32MPa, the tensile breaking stress was 16MPa, the isotactic index was 95%, the Vicat softening point was 150℃and the ash content was 0.030%, shanghai petrochemical Sanren F280.
Second polypropylene resin B: the melt flow rate measured at 230℃and 2.16kg was 3.2g/10min, the tensile yield strength was 35MPa, the tensile breaking stress was 22MPa, the isotactic index was 97%, the Vicat softening point was 156℃and the ash content was 0.016%, PPH-03T, china petrochemical and sea refining division.
Second polypropylene resin C: the melt flow rate measured at 230℃under 2.16kg was 2.8g/10min, the tensile yield strength was 47MPa, the tensile breaking stress was 18MPa, the isotactic index was 93%, the Vicat softening point was 165℃and the ash content was 0.010%, singapore polyolefin Co., ltd. FS3011E3.
Example 1
In an embodiment of the modified resin of the present invention, the preparation method of the modified resin is as follows:
s1, adding 40 parts of a first solvent into a stirred high-pressure reaction kettle in advance, and then adding 55 parts of hydrogenated petroleum resin A, 4.5 parts of abietic acid and 0.5 part of an antioxidant to obtain a mixed solution;
s2, adding 0.5 part of initiator dibenzoyl peroxide into the mixed solution, heating to 125 ℃, and reacting for 0.75h to obtain a reaction product;
s3, removing the first solvent in the reaction product at 110 ℃ and 15kPa, then adding a second solvent accounting for 5% of the mass of the reaction product after removing the first solvent, eluting unreacted bio-based carboxylic acid monomer for 15min, and then drying in a vacuum oven at 68 ℃ for 30min to obtain the modified resin.
The first solvent is a compound with the mass ratio of dimethylbenzene to DMF being 1:0.5;
the antioxidant is a compound with the mass ratio of the antioxidant 1010 to the antioxidant 168 being 1:1;
the second solvent is acetone.
Fig. 1 is a fourier infrared spectrum of the modified resin and hydrogenated petroleum resin in example 1, and the characteristic peak comparison shows that the molecular end group of the modified resin has a structure of-c=o-, and the result shows that the grafting of the bio-based carboxylic acid monomer is successful. FIG. 2 shows the modified resin and hydrogenated petroleum resin of example 1 1 The H-NMR spectrum shows that the modified resin molecule has introduced olefinic bond group, and this further shows that the grafting of the bio-based carboxylic acid monomer is successful.
Examples 2 to 6
Examples 2 to 6 are modified resins, examples 2 to 6 differ from example 1 only in the types of hydrogenated petroleum resins, and the hydrogenated petroleum resins used in examples 2 to 6 are hydrogenated petroleum resin B, hydrogenated petroleum resin C, hydrogenated petroleum resin D, hydrogenated petroleum resin E, and hydrogenated petroleum resin F, respectively.
Effect examples 1 to 6
Effect examples 1-6 are BOPP films prepared from examples 1-6, wherein the preparation method of effect example 1 is as follows:
s1, adding modified resin and first polypropylene resin into a screw extruder in a mass ratio of 1:1, and extruding and granulating at 220 ℃ under the condition of 200r/min to obtain stiffening master batches;
s2, mixing the second polypropylene resin A and the stiffening master batch according to the mass ratio of 1:0.4, adding the mixture into a screw extruder as a raw material of the middle layer, adding the second polypropylene resin A as a raw material of the first layer and a raw material of the second layer into respective auxiliary extruders, and flowing out after converging at a die head. The temperature of the extruder was 240℃and the screw speed was 200r/min. The longitudinal stretching preheating temperature is 220 ℃, the stretching temperature is 120 ℃, and the stretching multiplying power is 5.0; the transverse stretching preheating temperature is 220 ℃, the stretching temperature is 150 ℃, the shaping temperature is 40 ℃, and the stretching multiplying power is 9.0. Biaxially stretched to obtain BOPP film with film thickness of 30 μm. Wherein the mass ratio of the first layer to the second layer to the intermediate layer is 1:1:0.8.
The production methods of effect examples 2 to 6 differ from effect example 1 in that the second polypropylene resin was different in kind and the second polypropylene resin B was used instead of the second polypropylene resin a.
The performance of examples 1-6 and effect examples 1-6 were tested and the test results are shown in tables 1-2.
TABLE 1
TABLE 2
As can be seen from table 1, under the same reaction conditions, as the aromaticity of the hydrogenated petroleum resin increases, the softening point and acid value of the product modified resin will greatly increase, indicating that the aromatic groups in the molecular structure of the raw material resin contribute to the grafting reaction of rosin acid, but the color number of the modified resin will deteriorate; meanwhile, the volatile organic compounds of the modified resin are obviously reduced along with the increase of the softening point, which shows that the high-softening-point modified resin is more suitable for the application field of BOPP films with requirements on small molecular precipitation performance compared with the low softening point in a certain performance range.
As can be seen from the above Table 2, the BOPP films have good mechanical properties, optical properties and thermodynamic properties, and the elastic modulus and heat seal strength of the BOPP films are remarkably improved along with the increase of the softening point and acid value of the modified resin, which indicates the enhancement of the overall rigidity of the films; however, when the acid value of the modified resin is not less than 8.0mgKOH/g, the increase in heat seal strength tends to be slowed down. The proper improvement of the softening point of the modified resin is helpful for reducing the heat shrinkage rate of BOPP film products and improving the stability of biaxial stretching processing. The high acid value modified resin can obviously increase the haze of the BOPP film, so that the control of the softening point and the acid value of the stiffening modified resin in a proper range is a key for obtaining a better implementation effect. The modified resin can meet the requirements by controlling the softening point of the hydrogenated petroleum resin to be 125-145 ℃ and the yellowness index to be less than or equal to 7 and the aromaticity to be 0.01-15%, so that the BOPP film with good rigidity, thermodynamic stability and optical performance is prepared. Further, when the softening point of the hydrogenated petroleum resin is 125-145 ℃, the yellowness index is less than or equal to 7, and the aromaticity is 1-15%, the hydrogenated petroleum resin has better comprehensive performance.
Examples 7 to 9
Examples 7 to 9 are examples of the modified resin of the present invention, examples 7 to 9 differ from example 1 in the kind of biobased carboxylic acid monomer, dehydroabietic acid is used as biobased carboxylic acid monomer in example 7, 2-octenyl succinic anhydride is used as biobased carboxylic acid monomer in example 8, and itaconic acid is used as biobased carboxylic acid monomer in example 9.
Effect examples 7 to 9
Effect examples 7 to 9 are BOPP films prepared from examples 7 to 9, and the preparation method thereof is the same as that of effect example 1.
Performance tests were performed on examples 7 to 9 and effect examples 7 to 9, and the test results are shown in tables 3 to 4.
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from tables 3-4, the BOPP film prepared by modifying the hydrogenated petroleum resin with the bio-based carboxylic acid monomer has good comprehensive properties. When the types of the bio-based carboxylic acid monomers are itaconic acid and 2-octenyl succinic anhydride, the BOPP film has smaller haze and better transparency, but at the same time, the heat shrinkage rate is also slightly improved; in addition, the mechanical properties of the structure are reduced due to the influence of aliphatic branches; the dehydroabietic acid and the abietic acid are introduced into the modified resin through the rigid condensed ring structure, so that the mechanical property of the BOPP film can be obviously improved, the haze is within 1%, and the comprehensive property is better.
Examples 10 to 14
Examples 10 to 14 are examples of the modified resin of the present invention, and examples 10 to 14 differ from example 1 only in the kind and amount of the initiator, as shown in Table 5.
TABLE 5
Note that: the molar concentration of initiator was calculated as the average density of the first solvent (DMF: xylene=1:1) at 0.904 g/cm.
Effect examples 10 to 14
Effect examples 10 to 14 are BOPP films prepared in examples 10 to 14, and the preparation method thereof is different from effect example 1 in that the second polypropylene resin a is replaced with the second polypropylene resin C.
The results of the performance tests of examples 10 to 14 and effect examples 10 to 14 are shown in tables 6 to 7.
TABLE 6
TABLE 7
As can be seen from Table 6, the above conventional initiators can produce carboxylic acid modified resins under the operating conditions of the present invention; under the condition of the same concentration, the modified resin initiated by DCP has higher softening point and acid value, has higher grafting efficiency on the bio-based carboxylic acid monomer, and is more beneficial to preparing the high-rigidity BOPP film; furthermore, high concentrations of DCP and AIBN are more pronounced to color degradation of the modified resin than high concentrations of BPO; the volatile organic compound content of the modified resin is positively correlated to the amount of initiator used.
As is clear from Table 7, effect examples 10 to 14 all have good rigidity, heat stability, transparency and a certain heat seal strength; among them, BOPP films prepared with AIBN as an initiator have low haze and better transparency, but have slightly inferior mechanical properties. And the BOPP film prepared by taking DCP as an initiator has higher mechanical property and heat sealing strength.
Examples 15 to 21
Examples 15 to 21 of the modified resin of the present invention differ from example 1 only in the kind of the first solvent, and are shown in Table 8.
TABLE 8
| Project | First solvent |
| Example 15 | Mixed solution with mass ratio of dimethylbenzene to DMF being 1:0.3 |
| Example 16 | Mixed solution with mass ratio of dimethylbenzene to DMF being 1:1 |
| Example 17 | Mixed solution with mass ratio of dimethylbenzene to DMF being 1:2 |
| Example 18 | Mixed solution with mass ratio of dimethylbenzene to DMF being 1:0.2 |
| Example 19 | Mixed solution with mass ratio of dimethylbenzene to DMF being 1:2.5 |
| Example 20 | Containing only xylenes |
| Example 21 | Containing DMF only |
Effect examples 15 to 21
Effect examples 15 to 21 are BOPP films prepared from the modified resins of examples 15 to 21, and the preparation method thereof is the same as that of effect example 1.
Performance tests were conducted on examples 15 to 21 and effect examples 15 to 21, and the test results are shown in tables 9 to 10.
TABLE 9
Table 10
As shown in tables 9-10 above, as the DMF ratio in the compound solvent increases, the softening point, yellowness index and acid value are reduced to a certain extent, which is helpful for improving the mechanical properties of the modified BOPP film; however, at the same time, the higher DMF content in the solvent increases VOC of the modified resin, thereby further affecting the anti-precipitation performance of the BOPP film and deteriorating the optical performance of the BOPP film; therefore, the ratio of xylene to DMF is preferably 1:0.3-2.0.
Examples 22 to 23
The modified resin of the present invention was prepared in the same manner as in example 1 except that the second solvent was diethyl ether in example 22 and ethyl acetate in example 23.
Comparative example 1
A modified resin was different from the production method of example 1 in that elution was not performed with the second solvent.
Effect examples 22 to 23 and effect comparative example 1
Effect examples 22 to 23 and effect comparative example 1 were prepared in the same manner as in effect example 1.
Performance tests were conducted on examples 22 to 23, comparative example 1 and effect comparative examples 22 to 23 and effect comparative example 1, and the test results are shown in tables 11 to 12.
TABLE 11
Table 12
As is clear from tables 11 to 12, the modified resin had poor color effect, the content of the volatile organic compound was significantly increased, and the performance was deteriorated when the elution treatment was not performed; the haze of BOPP films prepared by the resin is obviously increased, so that the opacity of the films is increased, and the application performance of the films is seriously affected. In addition, the comparison shows that the ethyl acetate has better effect of removing volatile organic compounds and the elution effect is optimal.
Effect comparative example 2
The BOPP film prepared from the hydrogenated petroleum resin in example 1 was prepared in the same manner as in effect example 1 without graft modification of the hydrogenated petroleum resin with a bio-based carboxylic acid monomer.
The effect of comparative example 2 was measured by performing a performance test, and it was found that the longitudinal elastic modulus was 1450MPa, the heat shrinkage (longitudinal/transverse) was 7.9%/7.0%, the haze was 1%, and the heat seal strength was 1.8N/15mm. From the above test results, it is clear that the rigidity and thermodynamic properties of the polypropylene material cannot be greatly improved without modifying the hydrogenated petroleum resin.
As shown by the test results, the BOPP film prepared from the modified resin has good mechanical property, optical property and thermodynamic property, and is suitable for being applied to a plurality of fields.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A modified resin is characterized in that the modified resin is obtained by grafting and modifying hydrogenated petroleum resin through a bio-based carboxylic acid monomer, the softening point of the modified resin is 120-165 ℃, the yellowness index is less than or equal to 15, the content of volatile organic compounds is less than or equal to 500ppm, and the acid value is 0.1-25mgKOH/g.
2. The modified resin of claim 1, wherein the hydrogenated petroleum resin has a softening point of 125-145 ℃, a yellowness index of 7 or less, and an aromaticity of 0.01% -15%; and/or the bio-based carboxylic acid monomer is at least one of 3-hydroxy propionic acid, 2, 5-furan dicarboxylic acid, abietic acid, dehydroabietic acid, 2-dimethyl succinic anhydride, butyl succinic anhydride, 2-octenyl succinic anhydride, ricinoleic acid, dehydrated ricinoleic acid, itaconic acid and hexyl itaconic acid.
3. A method for producing the modified resin according to claim 1 or 2, comprising the steps of:
s1, adding hydrogenated petroleum resin, a bio-based carboxylic acid monomer and an antioxidant into a first solvent to obtain a mixed solution;
s2, adding an initiator into the mixed solution to react to obtain a reaction product;
s3, removing the first solvent in the reaction product, eluting unreacted bio-based carboxylic acid monomer by using a second solvent, and drying to obtain the modified resin.
4. A process according to claim 3, wherein,
the first solvent is a mixed solution of dimethylbenzene and N, N-dimethylformamide; and/or
The second solvent is at least one of diethyl ether, phenetole, ethanol, methanol, isopropanol, isobutanol, acetone, methyl acetone, butanone, ethyl acetate and methyl acetate; and/or
The antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; and/or
The initiator is at least one of dicumyl peroxide, dibenzoyl peroxide, bis (tert-butyl peroxyisopropyl) benzene, 2-butanone peroxide, azodiisobutyronitrile and azodiisoheptanenitrile; and/or
The mass ratio of the hydrogenated petroleum resin to the bio-based carboxylic acid monomer is (49.5-69.5): (0.1-15), the mass ratio of the hydrogenated petroleum resin to the antioxidant is (49.5-69.5): (0.1-0.5), the mass ratio of the hydrogenated petroleum resin to the first solvent is (49.5-69.5): (30-50), the mass ratio of the hydrogenated petroleum resin to the initiator is (49.5-69.5): (0.05-2); and/or
In the step S2, the reaction temperature is 70-200 ℃ and the reaction time is 0.25-3h; and/or
In the step S3, the first solvent is removed under the conditions that the pressure is 5-15kPa and the temperature is 70-115 ℃; and/or
And in the step S3, drying is carried out in a vacuum environment at 50-90 ℃.
5. The method according to claim 4, wherein,
in the first solvent, the mass ratio of the dimethylbenzene to the N, N-dimethylformamide is 1: (0.3-2); and/or
The addition amount of the second solvent is 0.5-50% of the mass of the reaction product after the first solvent is removed; and/or
The hindered phenol antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 330 and antioxidant 3114; and/or
The phosphite antioxidant is at least one of an antioxidant 168 and an antioxidant 626.
6. A stiffening masterbatch comprising a modified resin of claim 1 or 2 or a modified resin produced by the production process of any one of claims 3 to 5 and a first polypropylene resin in a mass ratio of 1: (0.8-1.2).
7. The BOPP film is characterized by comprising a first layer, an intermediate layer and a second layer which are sequentially connected; the material of the middle layer comprises the stiffening master batch and the second polypropylene resin, wherein the mass ratio of the second polypropylene resin to the stiffening master batch in the middle layer is 1: (0.2-0.4); the mass ratio of the total mass of the first layer and the second layer to the intermediate layer is 1: (0.2-0.6), the mass ratio of the first layer to the second layer being 1: (0.75-1.25); the materials of the first layer and the second layer comprise a second polypropylene resin.
8. The BOPP film of claim 7, wherein the first polypropylene resin and the second polypropylene resin in the stiffening masterbatch are homopolypropylene resins, and the melt flow rates of the first polypropylene resin and the second polypropylene resin measured at 230 ℃ and 2.16kg are each independently 2-4g/10min; the tensile yield strength of the first polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%; the tensile yield strength of the second polypropylene resin is more than or equal to 25MPa, the tensile breaking stress is more than or equal to 15MPa, the isotactic index is more than or equal to 90%, the Vicat softening point is more than or equal to 150 ℃ and the ash content is less than or equal to 0.03%; and/or
When the thickness of the BOPP film is 30 mu m, the longitudinal elastic modulus of the BOPP film is more than or equal to 1700MPa, the longitudinal heat shrinkage rate is 3% -12%, the transverse heat shrinkage rate is 3% -12%, the haze is less than or equal to 2%, and the heat sealing strength measured by heat sealing at 135 ℃ for 0.3s is more than or equal to 2.4N/15mm.
9. A process for the preparation of BOPP films according to claim 7 or 8, comprising the steps of:
s1, adding modified resin and first polypropylene resin into a screw extruder for extrusion granulation to obtain stiffening master batches;
s2, adding the stiffening master batch into a screw extruder, adding the raw materials of the first layer and the second layer into respective auxiliary extruders, converging and flowing out of the dies of the three layers of materials, cooling, and stretching by a film biaxially-oriented polypropylene (BOPP) film.
10. The method according to claim 9, wherein,
in the step S1, the temperature of the screw extruder is 160-240 ℃ and the screw rotating speed is 150-300r/min; and/or
In the step S2, the stretching is divided into longitudinal stretching and transverse stretching, and the longitudinal stretching conditions are as follows: the preheating temperature is 220-280 ℃, the stretching temperature is 120-150 ℃, the stretching multiplying power is 4.0-6.0, and the transverse stretching conditions are as follows: preheating temperature 220-280 deg.c, stretching temperature 150-180 deg.c, setting temperature 25-50 deg.c and stretching multiplying power 8.0-10.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311718418.1A CN117757002A (en) | 2023-12-13 | 2023-12-13 | Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311718418.1A CN117757002A (en) | 2023-12-13 | 2023-12-13 | Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof |
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| CN117757002A true CN117757002A (en) | 2024-03-26 |
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| CN202311718418.1A Pending CN117757002A (en) | 2023-12-13 | 2023-12-13 | Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof |
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| CN (1) | CN117757002A (en) |
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