CN105801755A - Modified polyolefins, methods of forming the same, and blends thereof - Google Patents
Modified polyolefins, methods of forming the same, and blends thereof Download PDFInfo
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- CN105801755A CN105801755A CN201410834608.4A CN201410834608A CN105801755A CN 105801755 A CN105801755 A CN 105801755A CN 201410834608 A CN201410834608 A CN 201410834608A CN 105801755 A CN105801755 A CN 105801755A
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- polyolefin
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- -1 fatty acid salt Chemical class 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000004743 Polypropylene Substances 0.000 claims description 37
- 229920001155 polypropylene Polymers 0.000 claims description 37
- 239000000344 soap Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920003245 polyoctenamer Polymers 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical class OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 32
- 230000008025 crystallization Effects 0.000 description 32
- 229920002521 macromolecule Polymers 0.000 description 14
- GAAKLDANOSASAM-UHFFFAOYSA-N undec-10-enoic acid;zinc Chemical compound [Zn].OC(=O)CCCCCCCCC=C GAAKLDANOSASAM-UHFFFAOYSA-N 0.000 description 12
- 229940118257 zinc undecylenate Drugs 0.000 description 12
- 239000004595 color masterbatch Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 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 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GZAROOOHRGKEPC-UHFFFAOYSA-N n-butyl-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)C GZAROOOHRGKEPC-UHFFFAOYSA-N 0.000 description 2
- NPFIXJIFUHTLRP-UHFFFAOYSA-N n-cyclohexyl-2-methylpropanamide Chemical compound CC(C)C(=O)NC1CCCCC1 NPFIXJIFUHTLRP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- CJDPTOSHLLCQCD-UHFFFAOYSA-N 3,6-bis(tert-butylperoxy)-3,6-dimethylcyclohexyne Chemical compound CC(C)(C)OOC1(C)CCC(C)(OOC(C)(C)C)C#C1 CJDPTOSHLLCQCD-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- YRIBCMYGTPNNPO-UHFFFAOYSA-N C(C)C1=CC=2C(C3=CC=CC=C3C(C2C=C1)=O)=O.C(C)C1=CC=2C(C3=CC=CC=C3C(C2C=C1)=O)=O Chemical compound C(C)C1=CC=2C(C3=CC=CC=C3C(C2C=C1)=O)=O.C(C)C1=CC=2C(C3=CC=CC=C3C(C2C=C1)=O)=O YRIBCMYGTPNNPO-UHFFFAOYSA-N 0.000 description 1
- MRULEFICMDJKGS-UHFFFAOYSA-N C(N)(=O)N=NC(C#N)(C)C.C(=O)N Chemical compound C(N)(=O)N=NC(C#N)(C)C.C(=O)N MRULEFICMDJKGS-UHFFFAOYSA-N 0.000 description 1
- PWAXKXFOUNQKJG-UHFFFAOYSA-N CC(CC1=CC=C(C=C1)SC)(C)N1CCOCC1.C1(=CC=CC=C1)CC(C)N1CCOCC1 Chemical compound CC(CC1=CC=C(C=C1)SC)(C)N1CCOCC1.C1(=CC=CC=C1)CC(C)N1CCOCC1 PWAXKXFOUNQKJG-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N methyl mercaptane Natural products SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VIHFRCKJTLYJMW-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1.C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 VIHFRCKJTLYJMW-UHFFFAOYSA-N 0.000 description 1
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 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
- 238000011084 recovery Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a forming method of modified polyolefin, which comprises the following steps: mixing 100 parts by weight of a polyolefin, 1 to 20 parts by weight of a fatty acid salt having a double bond, and 0.1 to 5.0 parts by weight of a radical initiator to form a mixture; energy is provided to the mixture to react the mixture to form the modified polyolefin.
Description
Technical field
The present invention relates to a kind of upgrading polyolefin, more specifically it relates to its method for modifying with use its blend.
Background technology
Polypropylene (PP) has the features such as low-gravity, excellent physical mechanical property, the good and easy recovery of chemical stability and is widely used.Along with compatriots' living standard improves, the fast development of the industries such as automobile, household electrical appliances and building, also there is higher requirement for material physical chemistry performance, cause that PP can not meet the market demand gradually.High-performance polypropylene developing material has become industrial development important directions, and wherein one of important method of upgrading PP is for utilizing nucleator to change crystalling propylene characteristic, and then affects or change its physics and chemical characteristic.PP material is crystalline polymer, is easily formed bigger geode in reaction extrusion upgrading cooling procedure, and during deformation, external force causes crackle easily to make PP material produce brittle fracture.On the other hand, heterogeneous nucleation agent can effectively make original homogeneous nucleation process be changed into heterogeneous nucleation process, accelerate crystallization rate, further refined grain structure, promote its initial strength, rigidity, shorten cycle of operation forming period, promote dimensional stability etc., therefore its research is had important practical significance.In addition, because PP structural nature is nonpolarity, not good with xenogenesis macromolecule compatibility.In sum, high-performance polypropylene technological development that is functionalized and that form nuclearity soon is had concurrently particularly important.
Summary of the invention
The upgrading polyolefin that one embodiment of the invention provides, including: the polyolefin of 100 weight portions, the soap with double bond of 1 to 20 weight portion react with the radical initiator of 0.1 to 5.0 weight portion and to form.
The blend that one embodiment of the invention provides, including the upgrading polyolefin that 1 weight portion is above-mentioned；And 2 to 50 other polyolefin of weight portion.
The polyolefinic forming method of upgrading that one embodiment of the invention provides, including: mix the radical initiator of the polyolefin of 100 weight portions, the soap with double bond of 1 to 20 weight portion and 0.1 to 5.0 weight portion, to form mixture；Provide energy to mixture, make mixture reaction form upgrading polyolefin.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in further detail.
One embodiment of the invention mixes the radical initiator of the polyolefin of 100 weight portions, the soap with double bond of 1 to 20 weight portion and 0.1 to 5.0 weight portion, to form mixture.Then provide energy to mixture, make mixture reaction form the upgrading polyolefin of ionic grafting.In an embodiment of the present invention, polyolefin can be polyethylene, polypropylene, polybutene, polyhexene, polyoctenamer, above-mentioned copolymer or combinations of the above.The weight average molecular weight of said polyolefins can between 2 ten thousand to 8 ten thousand.If polyolefinic weight average molecular weight is too high, then macromolecule lamellar crystalline texture is big, it is impossible to flow in macromolecule, it is impossible to lure that microfacies spherocrystal generates into, promotes that crystalline rate promotes.If polyolefinic weight average molecular weight is too low, then easily it is dispersed in high polymer main chain, it is impossible to form heterogeneous nucleation mechanism, promote crystalline growth.
In an embodiment of the present invention, the above-mentioned soap with double bond includes oleate, undecylenate salt, acrylates or combinations of the above.For example, the soap with double bond can be Zinc Undecylenate.If the soap consumption with double bond is too low, then collateralization/polar degree is not enough.If the soap consumption with double bond is too high, then unreacted reactant is easily had to remain in macromolecular chain.
Above-mentioned radical initiator, according to the difference of initial conditions, can be divided into light trigger and thermal initiator.nullSuitable thermal initiator can be azo，Such as 2，2 '-azo double; two (2，4-dimethyl n valeronitrile) (2，2’-azobis(2，4-dimethylvaleronitrile))、Dimethyl-2，Double; two (2-the methyl propionate) (dimethyl2 of 2 '-azo，2’-azobis(2-methylpropionate)、2，2-azobis isobutyronitrile (2，2-azobisisobutyronitrile，It is called for short AIBN)、2，Double; two (the 2-methyliso-butyronitrile) (2 of 2-azo，2-azobis(2-methylisobutyronitrile))、1，Double; two (hexamethylene-1-nitrile) 1 of 1 '-azo，1’-azobis(cyclohexane-1-carbonitrile))、2，Double; two [N-(2-the acrylic)-2-methyl propanamide] (2 of 2 '-azo，2’-azobis[N-(2-propenyl)-2-methylpropionamide])、1-[(cyano group-1-Methylethyl) azo] Methanamide (1-[(cyano-1-methylethyl) azo] formamide)、2，Double; two (the N-butyl-2-methyl propanamide) (2 of 2 '-azo，2’-azobis(N-butyl-2-methylpropionamide))、2，Double; two (the N-cyclohexyl-2-methyl propanamide) (2 of 2 '-azo，2 '-azobis (N-cyclohexyl-2-methylpropionamide) or other suitable azo-initiator；nullPeroxide includes benzoyl peroxide (benzoylperoxide，It is called for short BPO)、1，1-bis(t-butylperoxy) cyclohexane (1，1-bis(tert-butylperoxy)cyclohexane)、2，5-bis-(t-butylperoxy)-2，5-dimethyl cyclohexane (2，5-bis(tert-butylperoxy)-2，5-dimethylcyclohexane)、2，5-bis-(t-butylperoxy)-2，5-dimethyl-3-cyclohexyne (2，5-bis(tert-butylperoxy)-2，5-dimethyl-3-cyclohexyne)、Double; two (1-(t-butylperoxy)-1-Methylethyl) benzene (bis (1-(tert-butylpeorxy)-1-methy-ethyl) benzene)、Tert-butyl hydroperoxide (tert-butylhydroperoxide)、Tert-butyl peroxide (tert-butylperoxide)、Tert-butyl hydroperoxide benzoic acid (tert-butylperoxybenzoate)、Hydrogen phosphide cumene (Cumenehydroperoxide)、Hexamethylene ketone group peroxide (cyclohexanoneperoxide)、Cumyl peroxide (dicumylperoxide)、Lauroyl peroxide (lauroylperoxide) or other suitable peroxide.nullSuitable light trigger includes acetophenones，Such as 2-methyl isophthalic acid-(4-(methyl mercaptan base) phenyl-2-morpholino propane (2-methyl-1-(4-(methylthio) phenyl)-2-morpholino-propane)、1-hydroxycyclohexylphenylketone (1-hydroxycyclohexylphenylketone)、Diethoxy acetophenone (diethoxyacetophenone)、2-hydroxy-2-methyl-1-phenyl-1-propyl group-1-ketone (2-hydroxy-2-methyl-1-phenyl-propane-l-one)、2-tolyl-2-(dimethylamino)-1-[4-(morpholinyl) phenyl]-1-butanone (2-benzyl-2-(dimethylamino)-1-[4-(morpholinyl) phenyl]-1-butanone) and other suitable 1-Phenylethanone.；Benzoinum class, such as Benzoinum (benzoin), benzoin methyl ether (benzoinmethylether), dimethoxybenzoin (benzyldimethylketal) and other suitable Benzoinum；Benzophenone, such as benzophenone (benzophenone), 4-phenyl benzophenone (4-phenylbenzophenone), dihydroxy benaophenonel (hydroxylbenzophenone) or other suitable benzophenone；Thioxanthene ketone, such as isopropyl thioxanthone (isopropylthioxanthone), 2-chloro thiaxanthone (2-chlorothioxanthone) or other suitable thiaxanthone；Anthraquinones such as 2-ethyl-anthraquinone (2-ethylanthraquinone) or other suitable anthraquinone.When radical initiator is thermal initiator, applying is heat energy to the energy of mixture.When radical initiator is light trigger, applying is ultraviolet to the energy of mixture.If the consumption of radical initiator is too high, then easily macromolecule is caused to deteriorate when secondary operations.If the consumption of radical initiator is too low, then functionalized efficiency is not good, easily has unreacted reactant to remain.
After said mixture reaction, the upgrading polyolefin of molecular weight narrow distribution, highly polar upgrading and poor fluidity can be obtained.Above-mentioned upgrading polyolefin because of in molecular structure length segment coexist, and tool polarity phase separation property, its crystallization rate can be substantially improved.
In another embodiment of the invention, the upgrading polyolefin of desirable 1 weight portion and other polyolefin of 2 to 50 weight portions such as polyethylene, polypropylene, polybutene, polyhexene, polyoctenamer, above-mentioned copolymer or combinations of the above are blended, to form blend.Comparing with the not blended polyolefinic polyolefin of upgrading, the crystallization rate of blend is very fast.
In order to above and other objects of the present invention, feature and advantage can be become apparent, several embodiments cited below particularly coordinate appended accompanying drawing, are described in detail below:
Embodiment
Embodiment 1-1
(melt index is 3g/10min to take the random polypropylene Macromolecule color masterbatch 5020 of 1.8 kilograms, 230 DEG C, fusing point 130.9 DEG C, crystallization temperature 88.7 DEG C, and crystalline rate is 0.17 (1/s), mould purchased from platform), the Zinc Undecylenate (zincundecylenate) of the cumyl peroxide (DCP) of 0.2phr and 1phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 133.7 DEG C, and crystallization temperature is 97 DEG C, and crystallization rate is 0.72 (1/s).
Embodiment 1-2
Take the Zinc Undecylenate of the random polypropylene Macromolecule color masterbatch 5020 of 1.8 kilograms, DCP and 2phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 134.7 DEG C, and crystallization temperature is 100 DEG C, and crystallization rate is 1.46 (1/s).
Embodiment 1-3
Take the Zinc Undecylenate (zincundecylenate) of the random polypropylene Macromolecule color masterbatch 5020 of 1.8 kilograms, DCP and 5phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 134.8 DEG C, and crystallization temperature is 101.0 DEG C, and crystallization rate is 1.59 (1/s).
5020 is as shown in table 1 with the fusing point (Tm) of upgrading PP of embodiment 1-1 to 1-3, crystallization temperature (Tc) and both differences (△ T=Tm-Tc).It is said that in general, the more little then crystallization rate of △ T is more fast.
Table 1
| 5020 | Embodiment 1-1 | Embodiment 1-2 | Embodiment 1-3 | |
| Tm | 130.9 | 133.7 | 134.7 | 134.8 |
| Tc | 88.7 | 97.0 | 100.4 | 101.0 |
| △T | 42.2 | 36.7 | 34.3 | 33.8 |
Embodiment 2-1
(melt index is 1.8g/10min to take the single gauge polypropylene Macromolecule color masterbatch 612 of 1.8 kilograms, 230 DEG C, fusing point 145.0 DEG C, crystallization temperature 105.1 DEG C, and crystalline rate are 0.13 (1/s), purchased from Li Changrong), the Zinc Undecylenate of DCP and 1phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 143.2 DEG C, and crystallization temperature is 105.6 DEG C, and crystallization rate is 0.17 (1/s).
Embodiment 2-2
Take the Zinc Undecylenate of the single gauge polypropylene Macromolecule color masterbatch 612 of 1.8 kilograms, DCP and 2phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 143.6 DEG C, and crystallization temperature is 107.4 DEG C, and crystallization rate is 0.24 (1/s).
Embodiment 2-3
Take the Zinc Undecylenate of the single gauge polypropylene Macromolecule color masterbatch 612 of 1.8 kilograms, DCP and 5phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 145.0 DEG C, and crystallization temperature is 111.4 DEG C, and crystallization rate is 0.64 (1/s).
612 is as shown in table 2 with the fusing point (Tm) of upgrading PP of embodiment 2-1 to 2-3, crystallization temperature (Tc) and both differences (△ T=Tm-Tc).
Table 2
| 612 | Embodiment 2-1 | Embodiment 2-2 | Embodiment 2-3 | |
| Tm | 145.0 | 143.2 | 143.6 | 145.0 |
| Tc | 105.1 | 105.6 | 107.4 | 111.4 |
| △T | 39.9 | 37.6 | 36.2 | 33.6 |
Embodiment 3-1
(melt index is 1500g/10min to take the single gauge polypropylene Macromolecule color masterbatch 6936 of 1.8 kilograms, 230 DEG C, fusing point 153.3 DEG C, crystallization temperature 111.9 DEG C, purchased from Mobil), the Zinc Undecylenate of DCP and 1phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 153.8 DEG C, and crystallization temperature is 115.4 DEG C.
Embodiment 3-2
Take the Zinc Undecylenate of the single gauge polypropylene Macromolecule color masterbatch 6936 of 1.8 kilograms, DCP and 2phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 153.2 DEG C, and crystallization temperature is 114.6 DEG C.
Embodiment 3-3
Take the Zinc Undecylenate of the single gauge polypropylene Macromolecule color masterbatch 6936 of 1.8 kilograms, DCP and 5phr of 0.2phr, with feeding manner of twin screw, reacted by expressing technique, screw feed mouth temperature 160 DEG C, screw speed 200rpm, about 60 seconds response time.The upgrading PP of gained after above-mentioned reaction, its fusing point is 153.3 DEG C, and crystallization temperature is 114.3 DEG C.
6936 is as shown in table 3 with the fusing point (Tm) of upgrading PP of embodiment 3-1 to 3-3, crystallization temperature (Tc) and both differences (△ T=Tm-Tc).
Table 3
| 6936 | Embodiment 3-1 | Embodiment 3-2 | Embodiment 3-3 | |
| Tm | 153.3 | 153.8 | 153.2 | 153.3 |
| Tc | 111.9 | 115.4 | 114.6 | 114.3 |
| △T | 41.4 | 38.4 | 38.6 | 39.0 |
Embodiment 4-1
Take the 5020 of 1.8 kilograms and the 6936 of 2phr insert in extruder blended, the blend fusing point of gained is 134.0 DEG C, and crystallization temperature is 95.2 DEG C.Take the 5020 of 1.8 kilograms and the 6936 of 10phr insert in extruder blended, the blend fusing point of gained is 138.3 DEG C, and crystallization temperature is 99.4 DEG C.
The upgrading PP of the embodiment 3-3 formation taking 5020 and the 2phr of 1.8 kilograms inserts in extruder blended, and the blend fusing point of gained is 134.0 DEG C, and crystallization temperature is 96.1 DEG C.The upgrading PP of the embodiment 3-3 formation taking 5020 and the 10phr of 1.8 kilograms inserts in extruder blended, and the blend fusing point of gained is 139.1 DEG C, and crystallization temperature is 103.8 DEG C.
The fusing point (Tm) of blends described above, crystallization temperature (Tc) and both differences (△ T=Tm-Tc) are as shown in table 4.
Table 4
From the foregoing, upgrading PP can effectively reduce the △ T of blend, and then accelerate crystallization rate.
The present invention utilizes ionic grafting thing out-phase fast nucleation concept on same surface, the manipulation of length segment and the manipulation that is separated in binding molecule structure, make polyolefin macromolecule possess polarity with can rapid crystallization behavior manipulation ability, do not need to import the nucleus additive of common organic system, inorganic system, its technique is simple, is suitable for continuous way and produces.
Although the present invention is with several embodiments openly as above; so it is not limited to the present invention; any have usually intellectual in the art; without departing from the spirit and scope of the present invention; when making arbitrary change and retouching, therefore protection scope of the present invention is when being as the criterion depending on the defined person of appended claims.
Claims (10)
1. a upgrading polyolefin, including:
The polyolefin of 100 weight portions, the soap with double bond of 1 to 20 weight portion react with the radical initiator of 0.1 to 5.0 weight portion and form.
2. upgrading polyolefin as claimed in claim 1, wherein this polyolefin includes polyethylene, polypropylene, polybutene, polyhexene, polyoctenamer, above-mentioned copolymer or combinations of the above.
3. upgrading polyolefin as claimed in claim 1, wherein this polyolefinic weight average molecular weight is between 2 ten thousand to 8 ten thousand.
4. upgrading polyolefin as claimed in claim 1, wherein this soap with double bond includes oleate, undecylenate salt, acrylates or combinations of the above.
5. upgrading polyolefin as claimed in claim 1, wherein this radical initiator includes thermal initiator or light trigger.
6. a blend, including:
The upgrading polyolefin as claimed in claim 1 of 1 weight portion；And
Other polyolefin of 2 to 50 weight portions.
7. blend as claimed in claim 6, wherein this other polyolefin includes polyethylene, polypropylene, polybutene, polyhexene, polyoctenamer, above-mentioned copolymer or combinations of the above.
8. the polyolefinic forming method of upgrading, including:
Mix the radical initiator of the polyolefin of 100 weight portions, the soap with double bond of 1 to 20 weight portion and 0.1 to 5.0 weight portion, to form a mixture；
There is provided an energy to this mixture, make this mixture reaction form a upgrading polyolefin.
9. the polyolefinic forming method of upgrading as claimed in claim 8, wherein this radical initiator is light trigger, and this energy is ultraviolet.
10. the polyolefinic forming method of upgrading as claimed in claim 8, wherein this radical initiator is thermal initiator, and this energy is heat energy.
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| TW103142105A TWI538928B (en) | 2014-12-04 | 2014-12-04 | Modified polyolefin and method for manufacturing the same and blend including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101696254A (en) * | 2009-10-23 | 2010-04-21 | 中国科学院长春应用化学研究所 | Method for improving melt strength of polypropylene by using fullerene |
| CN103992609A (en) * | 2014-05-20 | 2014-08-20 | 泉州三盛橡塑发泡鞋材有限公司 | Olefin block copolymer foam material and preparation method thereof |
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2014
- 2014-12-04 TW TW103142105A patent/TWI538928B/en active
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| CN101696254A (en) * | 2009-10-23 | 2010-04-21 | 中国科学院长春应用化学研究所 | Method for improving melt strength of polypropylene by using fullerene |
| CN103992609A (en) * | 2014-05-20 | 2014-08-20 | 泉州三盛橡塑发泡鞋材有限公司 | Olefin block copolymer foam material and preparation method thereof |
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| 代少俊等: ""丙烯酸镧对聚丙烯塑料改性作用的研究"", 《稀土》 * |
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