CN111234137A - Method for preparing ionomer type thermoplastic elastomer by grafting polyolefin with maleic acid monoester - Google Patents
Method for preparing ionomer type thermoplastic elastomer by grafting polyolefin with maleic acid monoester Download PDFInfo
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- CN111234137A CN111234137A CN202010178919.5A CN202010178919A CN111234137A CN 111234137 A CN111234137 A CN 111234137A CN 202010178919 A CN202010178919 A CN 202010178919A CN 111234137 A CN111234137 A CN 111234137A
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- thermoplastic elastomer
- maleic acid
- mixing
- acid monoester
- ionomer
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 48
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title claims abstract description 38
- 239000011976 maleic acid Substances 0.000 title claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 18
- 229920000554 ionomer Polymers 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004794 expanded polystyrene Substances 0.000 claims abstract description 24
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 12
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 7
- -1 tert-butyl benzoate peroxide Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims 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 claims description 5
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 claims description 5
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001112 grafted polyolefin Polymers 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 claims description 3
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 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
- VPTNWGPGDXUKCY-KHPPLWFESA-N (z)-4-decoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCOC(=O)\C=C/C(O)=O VPTNWGPGDXUKCY-KHPPLWFESA-N 0.000 claims description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- MHQJUHSHQGQVTM-HNENSFHCSA-N Octadecyl fumarate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C/C(O)=O MHQJUHSHQGQVTM-HNENSFHCSA-N 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010791 domestic waste Substances 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- KGKNBDYZZIBZQL-UHFFFAOYSA-N tert-butyl carboxyoxy carbonate Chemical compound CC(C)(C)OC(=O)OOC(O)=O KGKNBDYZZIBZQL-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- 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
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
Landscapes
- 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)
Abstract
The invention discloses a method for preparing an ionomer-type thermoplastic elastomer by grafting polyolefin with maleic acid monoester, which comprises the following steps: s1, adding the EPS sol and the polyolefin thermoplastic elastomer into a high-speed mixing dryer for mixing to obtain a premix; s2, adding the obtained premix into a mixing roll, then sequentially adding maleic acid monoester, a peroxide initiator and a processing aid, and carrying out grafting reaction mixing to obtain a maleic acid monoester grafted high polymer; s3, adding a metal oxide to the obtained maleic acid monoester graft polymer, and performing ionic neutralization and kneading to obtain an ionomer-type thermoplastic elastomer. The invention replaces maleic anhydride with maleic acid monoester, and introduces ester group into maleic anhydride, thereby not only solving the problem of poor compatibility between carboxylic acid group-containing and polyolefin thermoplastic elastomer, but also preparing ionomer type thermoplastic elastomer with good performance, and simultaneously realizing effective recycling of waste expanded polystyrene and domestic waste grease.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomers, in particular to a method for preparing an ionomer-type thermoplastic elastomer by grafting polyolefin with maleic acid monoester.
Background
Thermoplastic Rubber (Thermoplastic Rubber-TPR), also called Thermoplastic elastomer-TPE, is a material with Rubber and Thermoplastic plastic characteristics, which not only has the excellent properties of high elasticity, aging resistance and oil resistance of the traditional cross-linked vulcanized Rubber, but also has the characteristics of convenient processing and wide processing mode of common plastic, so that the Thermoplastic Rubber is widely used for manufacturing daily products such as Rubber shoes and adhesive tapes and various industrial products such as Rubber tubes, adhesive tapes, adhesive strips, Rubber plates, Rubber parts, adhesives and the like in the Rubber industry. Meanwhile, the thermoplastic elastomer can replace rubber to be widely used for modifying general thermoplastic resins such as PVC, PE, PP, PS and the like, and even engineering plastics such as PU, PA, CA and the like. An ionomer (ionomer), also called ionomer, refers to an ionic polymer formed by neutralizing acid groups on a molecular chain through acid-base neutralization reaction, and because metal ions can be aggregated together through electrostatic interaction or complexation to form a multiple ion pair or ion cluster structure, the special structure can endow a matrix material with new mechanical properties. In recent years, ionomer-type thermoplastic elastomers have been developed rapidly due to the excellent properties of both thermoplastic elastomers and ionomers, but the existing methods have high preparation cost, thereby limiting the further popularization and application of the ionomer-type thermoplastic elastomers.
The waste Expanded Polystyrene (EPS) is widely used in the packaging and transportation industries of fast food packaging, household appliances, instruments, artware and other easily damaged valuable products, and the fields of building heat-insulating wall materials and the like due to the advantages of light weight, strong shock resistance, easy molding, good heat-insulating property and the like. However, since the Expanded Polystyrene (EPS) product is disposable, it causes environmental pollution if it is discarded after use, and it is typically "white garbage". Therefore, how to effectively and reasonably recycle the waste Expanded Polystyrene (EPS) to improve the recycling value of the waste Expanded Polystyrene (EPS) is an environmental problem which needs to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing an ionomer-type thermoplastic elastomer by grafting polyolefin with maleic acid monoester.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing an ionomeric thermoplastic elastomer from a maleic acid monoester grafted polyolefin comprising the steps of:
s1, adding the EPS sol and the polyolefin thermoplastic elastomer into a high-speed mixing dryer for mixing to obtain a premix;
s2, adding the premix obtained in the step S1 into a mixing roll, then sequentially adding maleic acid monoester, a peroxide initiator and a processing aid, and carrying out grafting reaction mixing to obtain a maleic acid monoester grafted high polymer;
s3, adding a metal oxide to the maleic acid monoester graft polymer obtained in the step S2, and performing ion neutralization and kneading to obtain an ionomer-type thermoplastic elastomer.
Further, the weight ratio of the EPS sol, the polyolefin thermoplastic elastomer, the maleic acid monoester, the peroxide initiator, the processing aid and the metal oxide is 10-25: 35-55: 15-30: 0.05-2: 2-8: 5 to 20.
Further, in step S1, the mixing temperature is 80-120 ℃, the mixing time is 5-20 min, in step S2, the mixing temperature is 115-150 ℃, the mixing time is 15-25 min, in step S3, the mixing temperature is 120-200 ℃, and the mixing time is 15-30 min.
Further, the polyolefin thermoplastic elastomer is one or a combination of more than two of SBS, SEBS or CPE, and the weight average molecular weight of the polyolefin thermoplastic elastomer is 20000-400000.
Further, the maleic acid monoester is one or a combination of more than two of monoethyl maleate, monopropyl maleate, monobutyl maleate, monodecanyl maleate and monostecanyl maleate, the peroxide initiator is one or a combination of more than two of dibenzoyl peroxide, dicumyl peroxide, benzoyl tert-butyl peroxide, di-tert-butylperoxyisopropyl benzene, tert-butyl hydroperoxide, tert-butyl peroxybenzoate and tert-butyl peroxydicarbonate, and the metal oxide is one or a combination of more than two of sodium oxide, potassium oxide, magnesium oxide, aluminum oxide, barium oxide, iron oxide, calcium oxide and zinc oxide.
Further, the grafting rate of the maleic acid monoester grafted high polymer is 6-15%, the solid content of the EPS sol is 25-35%, and the EPS sol is obtained by completely dissolving waste expanded polystyrene in a compound solvent at normal temperature.
Further, the compound solvent comprises high-grade mixed fatty acid esters, citric acid esters and a cosolvent, wherein the high-grade mixed fatty acid esters are a mixture of two or three of methyl ester, ethyl ester and butyl ester synthesized by mixed fatty acids with the carbon atom number of 16-18, the weight of the high-grade mixed fatty acid esters accounts for 55-60% of the total weight of the compound solvent, the cosolvent is a combination of one or more of alcohols with the carbon atom number of 6, 8 and 12, the weight of the cosolvent accounts for 22-27% of the total weight of the compound solvent, the balance is the citric acid esters, and the citric acid esters are one or more of triethyl citrate, tributyl citrate and tributyl acetylcitrate.
The second object of the present invention is to provide an ionomer-type thermoplastic elastomer obtained by the above method for preparing an ionomer-type thermoplastic elastomer from a polyolefin grafted with a maleic acid monoester.
Further, the ionomer-type thermoplastic elastomer has a neutralization degree of 50 to 100%.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses maleic acid monoester to replace maleic anhydride as a grafting modifier, uses a premix obtained by fully mixing EPS sol (which is obtained by adopting a compound solvent (derived from domestic waste grease) to completely dissolve waste EPS) and polyolefin thermoplastic elastomers (SBS, SEBS, CPE and the like) through a high-speed mixing dryer as a macromolecular chain grafting acceptor, uses a peroxide initiator as an open chain agent, performs grafting reaction and mixing in a mixing mill to obtain a series of maleic acid monoester grafted high polymers with the grafting rate of 6-15%, then uses metal oxides (sodium oxide, magnesium oxide, aluminum oxide and the like) to perform ionic neutralization and mixing on the maleic acid monoester grafted high polymers through the mixing mill to obtain a series of ionomer thermoplastic elastomers with the neutralization degree of 506-100%, uses the maleic acid monoester to replace maleic anhydride, introduces an ester group into the maleic anhydride, the method not only can solve the problem of poor compatibility of carboxylic acid group-containing and polyolefin thermoplastic elastomers, but also can prepare ionomer thermoplastic elastomers with good performance, and simultaneously realize effective recycling of waste expanded polystyrene and domestic waste grease.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Adding 10 parts by weight of EPS sol with the solid content of 25% and 40 parts by weight of SBS into a high-speed mixing dryer, mixing for 15min at 100 ℃ to obtain a premix, adding the obtained premix into a mixing roll, sequentially adding 15 parts by weight of maleic acid monoethyl ester, 0.08 part by weight of dicumyl peroxide and 8 parts by weight of processing aids into the premix, mixing for 20min at 115 ℃, mixing through a grafting reaction to obtain a maleic acid monoester grafted polymer with the grafting rate of 12%, adding 15 parts by weight of potassium oxide into the maleic acid monoester grafted polymer, mixing for 20min at 135 ℃, and performing ion neutralization and mixing to obtain a series of ionomer type thermoplastic elastomers with the neutralization degree of 50-75%.
Example 2
Adding 25 parts by weight of EPS sol with the solid content of 25% and 55 parts by weight of CPE into a high-speed mixing dryer, mixing for 20min at 120 ℃ to obtain a premix, adding the obtained premix into a mixing roll, then sequentially adding 25 parts by weight of maleic acid monoethyl ester, 0.08 part by weight of dicumyl peroxide and 8 parts by weight of processing aids into the premix, mixing for 20min at 135 ℃, mixing through a grafting reaction to obtain a maleic acid monoester grafted polymer with the grafting rate of 12%, then adding 15 parts by weight of potassium oxide into the maleic acid monoester grafted polymer, mixing for 20min at 180 ℃, and performing ion neutralization and mixing to obtain a series of ionomer type thermoplastic elastomers with the neutralization degree of 75-100%.
Example 3
Adding 20 parts by weight of EPS sol with the solid content of 25% and 35 parts by weight of SEBS into a high-speed mixing dryer, mixing for 15min at 150 ℃ to obtain a premix, adding the obtained premix into a mixing roll, sequentially adding 30 parts by weight of monopropyl maleate, 2 parts by weight of dicumyl peroxide and 8 parts by weight of a processing aid into the premix, mixing for 25min at 150 ℃, mixing through a grafting reaction to obtain a maleic acid monoester grafted high polymer with the grafting rate of 15%, adding 5 parts by weight of magnesium oxide into the maleic acid monoester grafted high polymer, mixing for 20min at 135 ℃, and performing ion neutralization and mixing to obtain a series of ionomer type thermoplastic elastomers with the neutralization degree of 50-75%.
Example 4
Adding 10 parts by weight of EPS sol with the solid content of 35% and 40 parts by weight of SEBS into a high-speed mixing dryer, mixing for 15min at 100 ℃ to obtain a premix, adding the obtained premix into a mixing roll, then sequentially adding 15 parts by weight of maleic acid monoethyl ester, 0.08 part by weight of dibenzoyl peroxide and 8 parts by weight of processing aids into the premix, mixing for 20min at 115 ℃, mixing through a grafting reaction to obtain a maleic acid monoester grafted polymer with the grafting rate of 6%, then adding 15 parts by weight of magnesium oxide into the maleic acid monoester grafted polymer, mixing for 20min at 135 ℃, and performing ion neutralization and mixing to obtain a series of ionomer type thermoplastic elastomers with the neutralization degree of 60-85%.
Example 5
Adding 10 parts by weight of EPS sol with the solid content of 30% and 40 parts by weight of SBS into a high-speed mixing dryer, mixing for 15min at 100 ℃ to obtain a premix, adding the obtained premix into a mixing roll, then sequentially adding 15 parts by weight of monobutyl maleate, 0.08 part by weight of dibenzoyl peroxide and 8 parts by weight of processing aid into the premix, mixing for 25min at 150 ℃, mixing through a grafting reaction to obtain a maleic acid monoester grafted polymer with the grafting rate of 12%, then adding 20 parts by weight of alumina into the maleic acid monoester grafted polymer, mixing for 30min at 200 ℃, and performing ion neutralization and mixing to obtain a series of ionomer type thermoplastic elastomers with the neutralization degree of 50-90%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A process for preparing an ionomeric thermoplastic elastomer from a maleic acid monoester grafted polyolefin, comprising the steps of:
s1, adding the EPS sol and the polyolefin thermoplastic elastomer into a high-speed mixing dryer for mixing to obtain a premix;
s2, adding the premix obtained in the step S1 into a mixing roll, then sequentially adding maleic acid monoester, a peroxide initiator and a processing aid, and carrying out grafting reaction mixing to obtain a maleic acid monoester grafted high polymer;
s3, adding a metal oxide to the maleic acid monoester graft polymer obtained in the step S2, and performing ion neutralization and kneading to obtain an ionomer-type thermoplastic elastomer.
2. The method for preparing the ionomer type thermoplastic elastomer from the maleic acid monoester grafted polyolefin according to claim 1, wherein the weight ratio of the EPS sol, the polyolefin thermoplastic elastomer, the maleic acid monoester, the peroxide initiator, the processing aid and the metal oxide is 10-25: 35-55: 15-30: 0.05-2: 2-8: 5 to 20.
3. The method of claim 1, wherein the mixing temperature is 80 to 120 ℃ and the mixing time is 5 to 20min in step S1, the kneading temperature is 115 to 150 ℃ and the kneading time is 15 to 25min in step S2, and the kneading temperature is 120 to 200 ℃ and the kneading time is 15 to 30min in step S3.
4. The method for preparing the ionomer-type thermoplastic elastomer from the maleic monoester-grafted polyolefin according to claim 1, wherein the polyolefin thermoplastic elastomer is one or a combination of two or more of SBS, SEBS or CPE, and the weight average molecular weight of the polyolefin thermoplastic elastomer is 20000 to 400000.
5. The method of claim 1, wherein the maleic acid monoester is one or more of monoethyl maleate, monopropyl maleate, monobutyl maleate, monodecanyl maleate and monostearyl maleate, the peroxide initiator is one or more of dibenzoyl peroxide, dicumyl peroxide, benzoyl tert-butyl peroxide, di-tert-butylperoxyisopropyl benzene, tert-butyl hydroperoxide, tert-butyl benzoate peroxide and tert-butyl dicarbonate peroxide, and the metal oxide is one or more of sodium oxide, potassium oxide, magnesium oxide, aluminum oxide, barium oxide, iron oxide, calcium oxide and zinc oxide.
6. The method for preparing the ionomer-type thermoplastic elastomer from the maleic monoester-grafted polyolefin according to claim 1, wherein the grafting ratio of the maleic monoester-grafted polymer is 6-15%, the solid content of the EPS sol is 25-35%, and the EPS sol is obtained by completely dissolving waste expanded polystyrene in a compound solvent at normal temperature.
7. The method for preparing an ionomeric thermoplastic elastomer of claim 6, it is characterized in that the compound solvent comprises higher mixed fatty acid lipids, citric acid lipids and a cosolvent, wherein the higher mixed fatty acid ester is a mixture of two or three of methyl ester, ethyl ester and butyl ester synthesized by mixed fatty acid with 16-18 carbon atoms, the weight of the high-grade mixed fatty acid ester accounts for 55-60% of the total weight of the compound solvent, the cosolvent is one or a combination of more than two of alcohols with 6, 8 and 12 carbon atoms, the weight of the cosolvent accounts for 22-27% of the total weight of the compound solvent, the balance of citric acid lipid, wherein the citric acid lipid is one or the combination of more than two of triethyl citrate, tributyl citrate and acetyl tributyl citrate.
8. An ionomeric thermoplastic elastomer prepared by the method of any one of claims 1 to 7.
9. The ionomeric thermoplastic elastomer according to claim 8, wherein the ionomeric thermoplastic elastomer has a degree of neutralization of from 50 to 100%.
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