CN111825802B - Ethylene oxide-octene copolymer composition and preparation method thereof - Google Patents
Ethylene oxide-octene copolymer composition and preparation method thereof Download PDFInfo
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- CN111825802B CN111825802B CN201910330534.3A CN201910330534A CN111825802B CN 111825802 B CN111825802 B CN 111825802B CN 201910330534 A CN201910330534 A CN 201910330534A CN 111825802 B CN111825802 B CN 111825802B
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 10
- 238000002844 melting Methods 0.000 claims abstract description 45
- 230000008018 melting Effects 0.000 claims abstract description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 37
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 21
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 102220042174 rs141655687 Human genes 0.000 claims description 14
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 3
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 2
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- -1 dicumyl hydroperoxide Chemical compound 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 description 21
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-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
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UEQQSYLAFDICAY-UHFFFAOYSA-N C=1(C(=CC=CC1)C)C.ClC(C(=O)O)(Cl)Cl Chemical compound C=1(C(=CC=CC1)C)C.ClC(C(=O)O)(Cl)Cl UEQQSYLAFDICAY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an ethylene oxide-octene copolymer composition, which comprises, by weight, 0.2% -10.0% of styrene monomers, 0.5% -10.0% of glycidyl methacrylate monomers and/or glycidyl methacrylate derivative monomers, 70.0% -99.0% of ethylene-octene copolymers and 0.2% -10.0% of talcum powder. According to the invention, the talcum powder is added, so that the grafting rate of the epoxidized ethylene-octene copolymer is ensured, and the crosslinking degree is reduced; the melting point of the initiator is further preferred, further reducing the degree of crosslinking.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ethylene oxide-octene copolymer composition and a preparation method thereof.
Background
Ethylene-octene copolymer (POE) is a new type of thermoplastic elastomer developed by metallocene, and has plasticity of plastics and elasticity of rubber. The POE mainly comprises a polyethylene crystallization area and a polyoctene amorphous area, and the special structure endows the POE with excellent mechanical property, rheological property and ultraviolet resistance. In addition, POE has good low-temperature toughness, good compatibility with polyolefin and low price, so that the POE is widely applied to toughening modification of plastics.
The method is the simplest and most effective method for carrying out melt grafting modification on POE by taking Glycidyl Methacrylate (GMA) as a monomer and adopting a double screw. However, in the melt grafting process, on one hand, the liquid GMA monomer is unevenly dispersed in the resin and is easily self-polymerized at high temperature, so that the grafting efficiency is low; on the other hand, in the presence of an initiator, a free radical chain segment generated in the POE resin is easy to crosslink, the melt index is greatly reduced, the flowability of the product is poor, and the toughening efficiency is reduced. Therefore, the preparation of GMA grafted POE with high grafting ratio and low crosslinking degree is the focus of research and development.
In order to improve the melt fluidity of POE and reduce the crosslinking degree of the POE, the Chinese patent (CN 101747600B) adds a crosslinking inhibitor triphenyl phosphite or dimethylformamide to capture and quench free radicals generated in a molecular chain of the POE, so that the crosslinking degree of the POE is reduced, but the method hinders the grafting reaction, so that the grafting rate of the obtained product is lower. Chinese patent (CN 102391432B) discloses a high-fluidity ethylene-alpha-octene graft copolymer and a preparation method thereof, which inhibit the POE crosslinking phenomenon in the extrusion process by selecting high-fluidity POE resin and adding various additives such as a lubricant, an antioxidant, a liquid additive and the like into the system, but the added additives are more, the reaction system is more complex and the reaction is difficult to control. In order to improve the dispersion of the monomer and the initiator in the resin, the chinese patent (CN 106674432 a) starts from an extrusion reaction device, and they adopt a sectional feeding manner to feed the reaction monomer and the initiator in the second or fifth section of a twin-screw, so as to reduce the generation of cross-linking by-products in the melt grafting process of the polymer, but the preparation method is cumbersome. Chinese patent (CN 104479078A) also adopts a method of compounding a casting film forming device and a double-screw extrusion device, and reduces the phenomenon of uneven monomer dispersion and the occurrence of cross-linking side reaction in the reaction process by spraying a monomer and an initiator after polymer casting film forming and then carrying out double-screw reactive extrusion, but the operations are more complicated, and need to be carried out for a plurality of times, and special equipment is also needed.
Disclosure of Invention
The present invention has been made to overcome the above technical problems, and an object of the present invention is to provide an epoxidized ethylene-octene copolymer composition in which the degree of crosslinking is improved while the graft ratio is ensured.
Another object of the present invention is to provide a process for producing an epoxidized ethylene-octene copolymer composition, which is simple in process, can suppress the self-polymerization of GMA and the progress of POE crosslinking reaction during grafting, and can further produce an epoxidized ethylene-octene copolymer having a low degree of crosslinking.
The invention is realized by the following technical scheme:
an ethylene oxide-octene copolymer composition comprises, by weight, 0.2% -10.0% of styrene monomers, 0.5% -10.0% of glycidyl methacrylate monomers and/or glycidyl methacrylate derivative monomers, 70.0% -99.0% of ethylene-octene copolymers, and 0.2% -10.0% of talcum powder.
Before and after the grafting reaction, the talcum powder plays a role in promoting the reaction and reducing crosslinking, and the talcum powder is not consumed. Other monomers, and ethylene-octene copolymers, are consumed during the reaction, but are generally not completely reacted, leaving some unreacted monomer or ethylene-octene copolymer in the final product.
The epoxidized ethylene-octene copolymer composition also comprises an initiator.
During the reaction, most of the initiator is decomposed, most of the initiator exists in other compound forms in the product, and the initiator used can be deduced according to the reaction mechanism by detecting the corresponding compound.
Customary initiators, such as dicumyl peroxide, having a melting point of 42 ℃ (abbreviated to DCP in English); cumene hydroperoxide, melting point 53 ℃; dibenzoyl peroxide, melting point 103-; n-butyl 4, 4-di (t-butylperoxy) valerate, mp 146 ℃; diacetyl peroxide, melting point 30 ℃; succinic peroxide, melting point 125 ℃; dicumyl peroxide, melting point 40 ℃.
Preferably, said initiator is selected from initiators having a melting point below 10 ℃;
the initiator with the melting point lower than 10 ℃ is at least one selected from tert-amyl peroxyacetate, tert-amyl peroxybenzoate, 2-di (tert-butylperoxy) butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, 2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide and 1,1,3, 3-tetramethylbutyl hydroperoxide.
It has been found that initiators having a melting point below 10 ℃ reduce the occurrence of local excessive crosslinking reactions and also promote grafting compared to initiators having a melting point above 10 ℃.
The density of the ethylene-octene copolymer is 0.860-0.880 g/cm -3 And a melt index of 0.5 to 18g/10min (190 ℃, 2.16 kg).
The glycidyl methacrylate derivative monomer is selected from allyl glycidyl ether or at least one of derivatives thereof.
The styrene monomer is at least one selected from styrene, alpha-methyl styrene, alpha-ethyl styrene and derivatives thereof.
Preferably, the particle size of the talcum powder is D90=2-15 microns.
The preparation method of the epoxidized ethylene-octene copolymer composition comprises the following steps: uniformly mixing a styrene monomer, a glycidyl methacrylate monomer and/or a glycidyl methacrylate derivative monomer, an ethylene-octene copolymer, talcum powder and an initiator, and then putting the mixture into a screw extruder for melting plasticization, extrusion, drying and grain cutting to obtain an epoxidized ethylene-octene copolymer composition; wherein the length-diameter ratio L/D of the screw extruder is = 30-60, the rotating speed is 150-500 rpm, and the temperature of each section of screw is 60-215 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of an epoxidized ethylene-octene copolymer composition, and surprisingly discovers that the talcum powder can effectively inhibit the self-polymerization of GMA and the POE crosslinking reaction in the grafting process in the reactive extrusion process of a screw extruder, so that the epoxidized ethylene-octene copolymer has good fluidity. Furthermore, the invention finds that the melting point of the initiator is lower than 10 ℃, and the degree of crosslinking can be further reduced to improve the grafting rate. On the one hand, the phenomenon that the product grafting rate is lower due to the fact that a cross-inhibiting agent is introduced to capture free radicals is avoided, on the other hand, raw materials can be subjected to reactive extrusion after being uniformly mixed at one time, and the method is simple and convenient and does not need to use special equipment.
Detailed Description
The present invention will be further illustrated by the following specific embodiments, and the following examples are illustrative of the present invention and are not intended to limit the present invention.
Example 1
94.0% POE resin (density 0.870 g/cm) -3 The melt index is 5g/10 min), 3.0% GMA, 1.5% styrene, 0.3%2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane (melting point is lower than 8 ℃) and 1.2% talcum powder (particle size is D90=5 microns) are mixed uniformly in a high-speed mixer, and then the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-1 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃ and 170 ℃ and at the screw rotating speed of 250 revolutions per minute.
Example 2
94.0% POE resin (density 0.870 g/cm) -3 After the melt index is 5g/10 min), 3.0% GMA, 1.5% styrene, 0.3% dicumyl peroxide (DCP, melting point 42 ℃) and 1.2% talcum powder (particle size is D90=5 microns) are uniformly mixed in a high-speed mixer, the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-2 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 250 revolutions per minute.
Example 3
94.0% POE resin (density 0.870 g/cm) -3 Melt index of 5g/10 min), 3.0% GMA, 1.5% styrene, 0.3%2, 5-di-tert-butylperoxy-2, 5Dimethylhexane (melting point lower than 8 ℃) and 1.2% talc (particle size D90=20 μm) were mixed homogeneously in a high-speed mixer and then fed via a hopper into a twin-screw extruder for reactive extrusion, the twin-screw extruder having a length-to-diameter ratio L/D =36, the extrusion temperatures in the first to ninth stages were: the E-POE-3 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 250 revolutions per minute.
Example 4
90.0% POE resin (density 0.863 g/cm) -3 The melt index is 13g/10 min), 4.0% GMA, 3.0% styrene, 0.5% tert-amyl peroxyacetate (melting point is lower than 0 ℃) and 2.5% talcum powder (particle size is D90=2 microns) are mixed uniformly in a high-speed mixer, and then added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =48 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-4 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 120 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 350 r/min.
Example 5
68.0% of POE resin (density of 0.880 g/cm) -3 The melt index is 18g/10 min), 10.0% GMA, 10.0% alpha-ethyl styrene, 2.0% ditert amyl peroxide (melting point is lower than 0 ℃) and 10.0% talcum powder (particle size is D90=10 microns) are mixed uniformly in a high-speed mixer, and then the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =60 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-5 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 120 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃ and 170 ℃ at a screw rotating speed of 200 revolutions per minute.
Example 6
99.0% POE resin (density 0.868 g/cm) -3 Melt index 0.5g/10 min), 0.5% allyl glycidyl ether, 0.2% styrene, 0.1%1,1,3, 3-tetramethylbutylhydroperoxide (melting point below 0 ℃ C.) and 0.2% of talcum powder (the particle size is D90=12 microns) is uniformly mixed in a high-speed mixer, and then is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =60 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-6 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 210 ℃, 210 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 500 revolutions per minute.
Example 7
78.0% POE resin (density 0.873 g/cm) -3 The melt index is 11g/10 min), 8.0% GMA, 6.0% alpha-methyl styrene, 1.2% tert-butyl peroxybenzoate (melting point is lower than 0 ℃) and 6.8% talcum powder (particle size is D90=8 microns) are mixed uniformly in a high-speed mixer, and then the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =48 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-7 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 400 r/min.
Example 8
88.0% POE resin (density 0.875 g/cm) -3 After the melt index is 3g/10 min), 6.0% GMA, 2.0% styrene, 0.4% tert-butyl cumyl peroxide (melting point is lower than 0 ℃) and 3.6% talcum powder (particle size is D90=15 microns) are uniformly mixed in a high-speed mixer, the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =30 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-8 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 150 revolutions per minute.
Example 9
90.0 percent of POE resin (the density is 0.875 g/cm) -3 Melt index 6g/10 min), 4.0% allyl glycidyl ether, 1.0% styrene, 1.5% diisopropylbenzene hydroperoxide (melting point below 0 ℃) and 3.5% talc (particle size D90=9 μm) were mixed in a high-speed mixerAfter uniform mixing, adding the mixture into a double-screw extruder through a feeding hopper for reactive extrusion, wherein the length-diameter ratio L/D =48 of the double-screw extruder, and the extrusion temperatures of the first section to the ninth section are respectively as follows: the E-POE-9 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 210 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 360 revolutions per minute.
Comparative example 1
94.0% POE resin (density 0.870 g/cm) -3 The melt index is 5g/10 min), 3.0% GMA, 1.5% styrene, 0.3%2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane (melting point is lower than 8 ℃) and 1.2% calcium carbonate (particle size is D90=5 microns) are mixed uniformly in a high-speed mixer, and then the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-10 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃ and 170 ℃ and at the screw rotating speed of 250 revolutions per minute.
Comparative example 2
94.0% POE resin (density 0.870 g/cm) -3 After the melt index is 5g/10 min), 3.0% GMA, 1.5% styrene, 0.3%2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane (melting point is lower than 8 ℃) and 1.2% titanium dioxide (particle size is D90=5 microns) are mixed uniformly in a high-speed mixer, the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively: the E-POE-11 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 250 revolutions per minute.
Comparative example 3
95.2% POE resin (density 0.870 g/cm) -3 Melt index of 5g/10 min), 3.0 percent of GMA, 1.5 percent of styrene and 0.3 percent of 2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane (melting point is lower than 8 ℃) are mixed evenly in a high-speed mixer and added into a double-screw extruder through a feeding hopper for reactionSexual extrusion, the length-diameter ratio L/D of a double-screw extruder is =36, and the extrusion temperatures of the first section to the ninth section are respectively as follows: the E-POE-12 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 250 revolutions per minute.
Comparative example 4
95.0% POE resin (density 0.870 g/cm) -3 The melt index is 5g/10 min), 3.0 percent of GMA, 1.5 percent of styrene, 0.3 percent of 2, 5-di-tert-butyl peroxy-2, 5-dimethyl hexane (the melting point is lower than 8 ℃) and 0.2 percent of cross-linking inhibiting agent triphenyl phosphite are uniformly mixed in a high-speed mixer, and then added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures from the first section to the ninth section are respectively: the E-POE-13 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃ and 170 ℃ and at the screw rotating speed of 250 revolutions per minute.
Comparative example 5
95.2% POE resin (density 0.870 g/cm) -3 After the melt index is 5g/10 min), 3.0% GMA, 1.5% styrene and 0.3% dicumyl peroxide (DCP, the melting point is 42 ℃) are uniformly mixed in a high-speed mixer, the mixture is added into a double-screw extruder through a feeding hopper for reactive extrusion, the length-diameter ratio L/D =36 of the double-screw extruder is used, and the extrusion temperatures of the first section to the ninth section are respectively as follows: the E-POE-14 can be obtained by melting, plasticizing, extruding, drying and granulating the materials at 60 ℃, 100 ℃, 190 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 170 ℃ and the screw rotating speed of 250 revolutions per minute.
Method for testing various performances
(1) Test of graft ratio
Adding the obtained epoxidized ethylene-octene copolymer composition (hereinafter referred to as E-POE) into toluene, dissolving, heating and refluxing for 30min, then precipitating and washing with acetone, repeating the operation for 3 times, and finally drying to obtain the purified E-POE.
Weighing purified E-POE, adding the E-POE into dimethylbenzene, dropwise adding 1.00G of trichloroacetic acid-dimethylbenzene solution, heating to 120-130 ℃, refluxing for 30min until the polymer is completely dissolved, adding two drops of 10G/L phenolphthalein ethanol solution, maintaining the system at 80-100 ℃, titrating to the phenolphthalein end point by using potassium hydroxide/ethanol solution with certain concentration, simultaneously carrying out blank test, and calculating the grafting rate G (%):
in the formula, V 0 Titration of the volume of potassium hydroxide/ethanol solution consumed without grafting of POE, mL;
v-volume of potassium hydroxide/ethanol solution consumed in E-POE titration, mL;
c-the quantity concentration of potassium hydroxide substance, mol/L;
m-mass of graft, g;
relative molecular mass of the M-epoxy group-containing graft monomer, g/mol.
(2) Mechanical Property test
The notched impact strength of the cantilever beam is tested according to ISO 180-93;
the flexural properties were tested according to ISO 178-93.
(3) Melt index test
Epoxidized ethylene-octene copolymer: melt index was measured according to ASTM D1238 at 190 ℃ and a weight of 2.16 kg.
PBT flame-retardant reinforced material: melt index was measured according to ASTM D1238 at 250 ℃ and a weight of 2.16 kg.
(4) Degree of crosslinking test
The melt index of POE and E-POE before and after grafting were measured, respectively, and the degree of crosslinking C (%) was calculated using the formula (1-2):
wherein w is the melt index of the ungrafted POE, and g/10 min;
and q is the melt index of the grafted E-POE, g/10 min.
The preparation method of the flame-retardant reinforced material comprises the following steps:
the E-POE obtained in comparative examples 1-5 and examples 1-9 was used as a toughening agent in the preparation of PBT flame-retardant reinforced material containing 30% glass fiber and 15% aluminum diethylhypophosphite flame retardant. The PBT flame-retardant reinforced material comprises 30 parts of glass fiber, 50 parts of PBT (grade 1100-211M), 15 parts of diethyl aluminum hypophosphite flame retardant and 5 parts of toughening agent. And drying the PBT in an oven at 120 ℃ for 4 hours for later use. Uniformly mixing all materials, adding the materials into a feeding port of a double-screw extruder, extruding and granulating, feeding glass fibers in a side feeding mode, feeding extruded strips into a granulator for granulation after water cooling and blow drying through a water tank to obtain a PBT flame-retardant reinforced material, drying the obtained plastic particles for 4 hours at 120 ℃, adding the plastic particles into a hopper of an injection molding machine, setting a corresponding injection molding process, and performing injection molding and film pressing to obtain a standard sample strip for testing.
Table 1: results of various performance tests of examples and comparative examples
Table 2 results of performance tests of examples and comparative examples
From the example 1 and the example 2, it can be seen that the initiator with the melting point lower than 10 ℃ can improve the grafting ratio and reduce the crosslinking degree, and the prepared epoxidized ethylene-octene copolymer composition has good toughening effect.
As can be seen from example 1/2 and comparative examples 1 to 5, the degree of crosslinking/grafting was lower when a certain amount of talc was added during the reaction. The crosslinking degree/grafting ratio of the obtained product is high by using other inorganic fillers or crosslinking inhibiting agents.
It can be seen from examples 3 and 1 that the particle size of talc affects the progress of the grafting reaction and the crosslinking reaction, and the effect of increasing the grafting ratio and decreasing the degree of crosslinking is reduced when the particle size exceeds D90=15 μm.
Claims (6)
1. An ethylene oxide-octene copolymer composition is characterized by comprising, by weight, 0.2% -10.0% of styrene monomers, 0.5% -10.0% of glycidyl methacrylate monomers and/or glycidyl methacrylate derivative monomers, 70.0% -99.0% of ethylene-octene copolymers and 0.2% -10.0% of talcum powder;
the epoxidized ethylene-octene copolymer composition further comprises an initiator having a melting point of less than 10 ℃;
the particle size of the talcum powder is D90=2-15 microns.
2. The epoxidized ethylene-octene copolymer composition according to claim 1, wherein said initiator having a melting point lower than 10 ℃ is selected from at least one of the group consisting of tert-amyl peroxyacetate, tert-amyl peroxybenzoate, 2-di (tert-butylperoxy) butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide.
3. The epoxidized ethylene-octene copolymer composition according to claim 1, wherein said ethylene-octene copolymer has a density of 0.860 to 0.880 g/cm -3 And a melt index of 0.5 to 18g/10min (190 ℃, 2.16 kg).
4. The epoxidized ethylene-octene copolymer composition according to claim 1, wherein said glycidyl methacrylate derivative monomer is selected from at least one of allyl glycidyl ether or its derivatives.
5. The epoxidized ethylene-octene copolymer composition according to claim 1, wherein said styrenic monomer is selected from at least one of styrene, α -methylstyrene, α -ethylstyrene and derivatives thereof.
6. The method for producing an epoxidized ethylene-octene copolymer composition according to claim 1, characterized by comprising the steps of: uniformly mixing a styrene monomer, a glycidyl methacrylate monomer and/or a glycidyl methacrylate derivative monomer, an ethylene-octene copolymer, talcum powder and an initiator, and then putting the mixture into a screw extruder for melting plasticization, extrusion, drying and grain cutting to obtain an epoxidized ethylene-octene copolymer composition; wherein the length-diameter ratio L/D of the screw extruder is = 30-60, the rotating speed is 150-500 rpm, and the temperature of each section of screw is 60-215 ℃.
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