CN114163655A - Method for producing cellulose nanofiber-containing rubber composition - Google Patents
Method for producing cellulose nanofiber-containing rubber composition Download PDFInfo
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- CN114163655A CN114163655A CN202111054017.1A CN202111054017A CN114163655A CN 114163655 A CN114163655 A CN 114163655A CN 202111054017 A CN202111054017 A CN 202111054017A CN 114163655 A CN114163655 A CN 114163655A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 172
- 239000005060 rubber Substances 0.000 title claims abstract description 172
- 229920002678 cellulose Polymers 0.000 title claims abstract description 135
- 239000001913 cellulose Substances 0.000 title claims abstract description 135
- 239000002121 nanofiber Substances 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000003960 organic solvent Substances 0.000 claims abstract description 109
- 239000006185 dispersion Substances 0.000 claims abstract description 74
- 238000009835 boiling Methods 0.000 claims abstract description 60
- 238000004898 kneading Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 41
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 40
- 239000012046 mixed solvent Substances 0.000 claims description 54
- 230000008961 swelling Effects 0.000 claims description 16
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
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- 244000043261 Hevea brasiliensis Species 0.000 description 12
- 229920003052 natural elastomer Polymers 0.000 description 12
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- 239000002904 solvent Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
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- 238000002156 mixing Methods 0.000 description 7
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- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000010068 moulding (rubber) Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000011191 terminal modification Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- WTTXRLXWUGSITL-UHFFFAOYSA-N C(C)(=O)O.C(C)C(COCCO)O Chemical compound C(C)(=O)O.C(C)C(COCCO)O WTTXRLXWUGSITL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000000899 Gutta-Percha Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000000342 Palaquium gutta Species 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 241000245665 Taraxacum Species 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 244000237330 gutta percha tree Species 0.000 description 1
- 229920000588 gutta-percha Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a method for efficiently producing a rubber composition having cellulose nanofibers uniformly dispersed therein and having suitable physical properties. A method for producing a cellulose nanofiber-containing rubber composition comprises a step of kneading a rubber component containing an ethylene-propylene-diene monomer rubber and an unmodified cellulose nanofiber dispersion in the presence of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11.
Description
Technical Field
The present invention relates to a method for producing a rubber composition containing cellulose nanofibers.
Background
It is known that the physical properties of the obtained rubber can be improved by containing cellulose fibers as a filler to be blended in the rubber component in the rubber composition (patent document 1). As such cellulose fibers, microfibrillated cellulose can be cited. However, for the purpose of bleaching or reducing the bonding force between microfibril units to improve the efficiency of defibration into microfibril units, microfibrillated cellulose generally uses wood pulp from which lignin is chemically removed as a raw material, and microfibrillated cellulose produced from wood pulp from which lignin is removed mainly has hydrophilicity derived from cellulose and thus is poor in fusibility to hydrophobic rubber components. Therefore, when microfibrillated cellulose is directly blended in a rubber component to produce a fiber-reinforced rubber, there is a problem that dispersibility of the fiber is deteriorated and improvement of physical properties of the obtained rubber is suppressed.
For example, patent document 1 discloses a rubber/cellulose fiber master batch obtained by stirring and mixing a cellulose fiber having an average fiber diameter of less than 0.5 μm and an oak pulp, and as a method for producing the rubber/cellulose fiber master batch, a rubber/cellulose fiber master batch in which a cellulose fiber is uniformly dispersed in a rubber is produced by mixing a dispersion obtained by fibrillating a cellulose fiber having an average fiber diameter of less than 0.5 μm in water with an oak pulp and drying the mixture.
However, unlike diene rubbers synthesized by emulsion polymerization, ethylene propylene diene rubbers are synthesized in hydrocarbon solvents, and aqueous cement dispersions of ethylene propylene diene rubbers are hardly distributed on the market, and the above-mentioned production methods cannot be used.
Further, patent document 2 discloses that a dispersion in which cellulose microfibers obtained by a mechanical defibration means are dispersed in toluene and a solution in which ethylene-propylene-diene monomer (EPDM) is dissolved in toluene are mixed, toluene is gasified to prepare a cellulose microfiber/EPDM master batch, then EPDM is masticated, and then the master batch is added thereto and kneaded to finally prepare an uncrosslinked rubber composition (example 3-1).
However, when a water-insoluble organic solvent such as toluene is used, if toluene is not used from the time of production of cellulose nanofibers, the cellulose nanofibers are not generally dispersed in the toluene solvent but are aggregated. Mechanical defibration such as disc milling or high-pressure dispersion generates heat when defibering cellulose, and therefore, is very dangerous when using an organic solvent having a low flash point such as toluene.
In addition, cellulose nanofibers are commercially available in the form of an aqueous dispersion, but since cellulose nanofibers form hydrogen bonds and aggregate in a drying step of removing water from the aqueous dispersion, the cellulose nanofibers cannot exist in a highly defibrated state in a process of compounding with a rubber component or a resin component, and the composite material cannot be sufficiently reinforced with the cellulose nanofibers.
Therefore, a method of mixing a cellulose nanofiber aqueous dispersion with rubber paste or a resin emulsion has been proposed (patent documents 3 and 4).
However, the composite materials produced by these methods sometimes have an effect on the properties of the rubber paste or resin emulsion. Further, it cannot be applied to rubber or resin which is not distributed as rubber paste or resin emulsion on the market.
Prior art documents
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-206864
Patent document 2: japanese patent laid-open publication No. 2019-163861
Patent document 3: japanese patent laid-open publication No. 2015-98576
Patent document 4: japanese patent laid-open publication No. 2016-29169
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for efficiently producing a rubber composition having cellulose nanofibers uniformly dispersed therein and having suitable physical properties.
The present inventors have conducted intensive studies to develop a technique for sufficiently dispersing unmodified cellulose nanofibers in a rubber composition using a rubber component containing Ethylene Propylene Diene Monomer (EPDM), and as a result, have found that cellulose nanofibers can be dispersed in a rubber composition very uniformly and efficiently by using a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11 as a solvent, and that the obtained rubber composition has suitable physical properties, and have completed the present invention.
Further, the present inventors have found that cellulose nanofibers can be dispersed in a rubber composition very uniformly and efficiently by using a mixed solvent of a water-soluble organic solvent having an SP value of 10 or more and a water-insoluble organic solvent having an SP value of 9 or less, wherein at least one of the water-soluble organic solvent and the water-insoluble organic solvent has a boiling point of 150 ℃ to 220 ℃ inclusive and the SP value of the mixed solvent is 8.5 to 11, and that the obtained rubber composition has suitable physical properties, thereby completing the present invention.
The first embodiment of the present invention relates to a method for producing a cellulose nanofiber-containing rubber composition, which comprises a step of kneading an EPDM-containing rubber component and an unmodified cellulose nanofiber dispersion in the presence of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
In the first embodiment, the method may further comprise a step of swelling the rubber component containing EPDM with a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11, and a step of kneading the swollen rubber component and the unmodified cellulose nanofiber dispersion.
The first embodiment may include a step of kneading the rubber component containing EPDM, which has been swollen with the water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11, and the unmodified cellulose nanofiber dispersion.
In the first embodiment, the water-soluble organic solvent having a boiling point of 150 to 220 ℃ and an SP value of 8.5 to 11 may be 1 or more selected from an alcohol solvent, an ether solvent and an ester solvent.
In the first embodiment, the unmodified cellulose nanofiber dispersion may be a dispersion of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
In addition, a second embodiment of the present invention relates to a method for producing a cellulose nanofiber-containing rubber composition, comprising a step of kneading a rubber component containing ethylene-propylene-diene rubber and an unmodified cellulose nanofiber dispersion in the presence of a mixed solvent, wherein the mixed solvent is a mixed solvent of a water-soluble organic solvent having an SP value of 10 or more and a water-insoluble organic solvent having an SP value of 9 or less, at least one of the water-soluble organic solvent and the water-insoluble organic solvent has a boiling point of 150 ℃ to 220 ℃ inclusive, and the SP value of the mixed solvent is 8.5 to 11.
In the second embodiment, the step of swelling the rubber component containing ethylene propylene diene monomer with the mixed solvent and the step of kneading the swollen rubber component and the unmodified cellulose nanofiber dispersion may be provided.
In the second embodiment, the step of kneading the rubber component containing ethylene-propylene-diene monomer swollen with the mixed solvent, and the unmodified cellulose nanofiber dispersion may be included.
In the second embodiment, the water-soluble organic solvent may be N-methylpyrrolidone or 1-methoxy-2-propanol, and the water-insoluble organic solvent may be butyl acetate or methoxybutyl acetate.
In the second embodiment, the unmodified cellulose nanofiber dispersion may be a dispersion of the mixed solvent.
In the first or second embodiment, the unmodified cellulose nanofibers may have an average fiber diameter of 20 to 1000 nm.
In the first or second embodiment, the method may further comprise a step of removing the water-soluble organic solvent or the mixed solvent to 1 wt% or less from the rubber component in which the unmodified cellulose nanofibers are dispersed and the rubber component is swollen with the water-soluble organic solvent or the mixed solvent having a boiling point of 150 to 220 ℃ and an SP value of 8.5 to 11.
In the first or second embodiment, the solid content concentration of the unmodified cellulose nanofibers in the cellulose nanofiber-containing rubber composition may be 3 to 30 phr.
Effects of the invention
According to the present invention, in any of the first embodiment or the second embodiment, the unmodified cellulose nanofibers can be dispersed in the rubber composition very uniformly and efficiently. Further, a rubber molded product obtained by crosslinking the obtained rubber composition has high rubber hardness, elasticity, and suitable physical properties.
Detailed Description
An embodiment of a method for producing a cellulose nanofiber-containing rubber composition according to the present invention will be described below.
(first embodiment)
The method for producing a cellulose nanofiber-containing rubber composition according to a first embodiment of the present invention (hereinafter also referred to as the production method according to the first embodiment) includes a step of kneading a rubber component containing EPDM and an unmodified cellulose nanofiber dispersion in the presence of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
In the production method according to the first embodiment, as described above, the solvent is a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11, so that the unmodified cellulose nanofibers can be dispersed in the rubber composition very uniformly and efficiently, and the rubber molded product obtained by crosslinking the obtained rubber composition has high rubber hardness and elasticity, and thus has suitable physical properties.
The water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11 used in the production method according to the first embodiment has a boiling point of 150 ℃ or higher, and therefore is difficult to vaporize even when the rubber component and the unmodified cellulose nanofibers are kneaded, and the unmodified cellulose nanofibers are easily dispersed in the rubber component sufficiently. Further, the organic solvent is water-soluble, so that aggregation of the unmodified cellulose nanofibers is suppressed, the SP value is 8.5 to 11, the EPDM-containing rubber component can be easily swollen, and the unmodified cellulose nanofibers can be easily dispersed in the rubber component.
However, when the organic solvent used is deviated from any of the physical properties of a boiling point of 150 ℃ to 220 ℃, an SP value of 8.5 to 11, and water solubility, the rubber hardness tends to be lowered, the dispersibility of the unmodified cellulose nanofibers in the rubber component tends to be deteriorated, the rubber composition tends to be less likely to be kneaded, and the productivity tends to be deteriorated, as described in comparative examples described later.
Therefore, in the production method according to the first embodiment, in order to obtain a rubber composition having predetermined physical properties (hereinafter referred to as a first rubber composition), it is necessary to use the water-soluble organic solvent having the boiling point and SP value in the above-mentioned specific ranges.
The above SP value is called Solubility Parameter (Solubility Parameter), and the value calculated by HSPiP ver.5.2.06 is used in the present invention.
Examples of the water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11 include alcohol solvents, ether solvents, ester solvents, and the like.
Examples of the alcohol solvent include 3-methoxybutanol, 3-methoxy-3-methyl-1-butanol, and diacetone alcohol.
Examples of the ether solvent include diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol n-propyl ether, and triethylene glycol dimethyl ether.
Examples of the ester solvent include diethylene glycol monoethyl ether acetate and ethyl lactate.
The water-soluble organic solvents can be used alone or in combination of 2 or more.
The type of the water-soluble organic solvent is not particularly limited, and 3-methoxy-3-methyl-1-butanol can be safely used for production because its flash point disappears when the water ratio is 20% or more.
In the production method according to the first embodiment, a water-soluble organic solvent other than the water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11 may be used in combination.
Examples of the other water-soluble organic solvent include N-methylpyrrolidone (boiling point 202 ℃ C., SP value 11.5), 1-methoxy-2-propanol (boiling point 120 ℃ C., SP value 10.2), propylene glycol (boiling point 188 ℃ C., SP value 14.5), pyridine (boiling point 115 ℃ C., SP value 15.1), acetonitrile (boiling point 82 ℃ C., SP value 12.2), isopropanol (boiling point 82 ℃ C., SP value 13.3), ethanol (boiling point 78 ℃ C., SP value 13.3), methanol (boiling point 65 ℃ C., SP value 14.7), and the like.
When the other water-soluble organic solvent is used in combination with the water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11, the ratio of the organic solvents to be mixed is not particularly limited as long as the SP value of the resulting mixed solvent is in the range of 8.5 to 10.1.
In the present invention, the swelling means a state in which the water-soluble organic solvent enters between polymer molecules of the rubber component and the force of intermolecular expansion is balanced with the elasticity of the network formed by crosslinking. The swelling depends on the affinity of the water-soluble organic solvent for the polymer of the rubber component, and the better the affinity is, the larger the swelling is.
The rubber component used in the production method according to the first embodiment is a main component of the first rubber composition, and may be solid EPDM such as diene rubber that cannot be used as a rubber cement.
The rubber component that can be used together with EPDM is not particularly limited as long as it is a solid rubber that can swell in a water-soluble organic solvent having an SP value of 8.5 to 11, and examples thereof include natural rubber, synthetic diene rubber, a mixture of natural rubber and synthetic diene rubber, and non-diene rubbers other than these.
Examples of the natural rubber include natural oak pulp, technical grade rubber (TSR), tabella Rubber (RSS), gutta percha, natural rubber derived from eucommia ulmoides, natural rubber derived from guayule, natural rubber derived from taraxacum, and resin component fermented rubber. The natural rubber of the present invention includes modified natural rubbers such as epoxidized natural rubber, methacrylic acid-modified natural rubber, and styrene-modified natural rubber obtained by modifying these natural rubbers.
Examples of the synthetic diene rubber include styrene-butadiene copolymer rubber (SBR), Butadiene Rubber (BR), Isoprene Rubber (IR), nitrile rubber (NBR), Chloroprene Rubber (CR), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), ethylene- α -olefin copolymer rubber (SPO), ethylene- α -olefin-diene copolymer rubber, and modified synthetic diene rubbers thereof. The modified synthetic diene rubber includes diene rubbers obtained by modification techniques such as main chain modification, single-terminal modification, and both-terminal modification. Examples of the modifying functional group of the modified synthetic diene rubber include various functional groups such as an epoxy group, an amino group, an alkoxy group, a hydroxyl group, an alkoxysilyl group, a polyether group, and a carboxyl group, and the modified synthetic diene rubber may contain 1 or 2 or more of these functional groups.
The method for producing the synthetic diene rubber is not particularly limited, and emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, cationic polymerization, and the like can be mentioned. Also, the glass transition temperature of the synthetic diene rubber is not particularly limited.
The cellulose nanofiber dispersion used in the production method according to the first embodiment is a liquid in which unmodified cellulose nanofibers are dispersed.
The unmodified cellulose nanofibers mean materials obtained by modifying cellulose nanofibers obtained from a raw material plant without modification treatment for modification.
Cellulose nanofibers are cellulose-derived fibrous materials composed of a skeletal component of plant cell walls obtained by finely unraveling plant fibers. Examples of the plant as a raw material of the cellulose nanofibers include wood, bamboo, rice, potato, sugarcane, aquatic weeds, and seaweeds.
The cellulose nanofibers may be composed of only cellulose, or may be lignocellulose nanofibers containing lignin.
These unmodified cellulose nanofibers may be used by mixing 2 or more kinds.
The average fiber diameter of the unmodified cellulose nanofibers is not more than 1000nm, and is preferably 50 to 500nm from the viewpoint of easy dispersion in the first rubber composition and easy acquisition of appropriate strength and elasticity.
The unmodified cellulose nanofibers preferably have a fiber length of 1 to 1000 μm, from the viewpoint of easy dispersion in the first rubber composition and easy acquisition of suitable strength and elasticity.
The average fiber diameter and the fiber length in the present invention can be measured by a scanning electron microscope or an atomic force microscope.
In the production method according to the first embodiment, the cellulose nanofiber dispersion may be a dispersion of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
The content of the unmodified cellulose nanofibers in the cellulose nanofiber dispersion is not particularly limited, and may be adjusted to 1 to 30% by weight.
The method for dispersing the cellulose nanofibers in a water-soluble organic solvent having a boiling point of 150 to 220 ℃ and an SP value of 8.5 to 11 is not particularly limited as long as it is a known method.
The cellulose nanofiber dispersion can also be prepared by dispersing cellulose nanofibers in water and then replacing the water with a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
In the production method according to the first embodiment, as a method of kneading the rubber component of EPDM swollen with the water-soluble organic solvent and the cellulose nanofiber dispersion to disperse the unmodified cellulose nanofibers, for example, there can be mentioned:
method 1-1) comprising a step of kneading a rubber component comprising EPDM and a cellulose nanofiber dispersion dispersed in a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11;
method 2-1), comprising: a step of swelling a rubber component containing EPDM with a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11, and
and a step of kneading the swollen rubber component and the cellulose nanofiber dispersion.
Specifically, as method 1-1), there is a method in which a cellulose nanofiber dispersion dispersed in a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11 is put into a rubber component containing EPDM that is being masticated in a kneader, and the water-soluble organic solvent is gasified while kneading the above components.
Further, as the method 2-1), there is a method in which a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11 is added to a rubber component containing EPDM being masticated in a kneader, the rubber component is swollen while kneading the same, and then a cellulose nanofiber dispersion dispersed in a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11 is added, and the water-soluble organic solvent is gasified while kneading the same.
In method 2-1), the step of adding a water-soluble organic solvent having a boiling point of 150 to 220 ℃ and an SP value of 8.5 to 11 and swelling the rubber component while kneading them can be omitted depending on the type of the kneading apparatus and the type of the water-soluble organic solvent.
The water-soluble organic solvent to be kneaded with the rubber component may be the same as or different from the water-soluble organic solvent used for the cellulose nanofiber dispersion.
Examples of the kneading machine include internal mixers (e.g., Banbury mixer, pin mixer (ショーミキサー), and kneading mixer), rolls, and extruders (e.g., GORDON kneader, transfer mixer, cavity transfer mixer, pin mixer, and twin-screw extruder).
The temperature condition for swelling the rubber component is not particularly limited as long as it is a temperature at which the rubber component is not crosslinked, and may be appropriately adjusted depending on the type of the rubber component, and is preferably 80 to 130 ℃.
The kneading time for swelling the rubber component is not particularly limited.
The temperature condition for vaporizing the water-soluble organic solvent while carrying out the above kneading is not particularly limited as long as it is a temperature at which the rubber component is not crosslinked, and is preferably 100 to 150 ℃.
The kneading may be continued until the water-soluble organic solvent is not observed around the first rubber composition, and the specific time is not particularly limited, and may be 1 to 3 hours.
Further, by using the kneader and the organic solvent recovery apparatus in combination, the water-soluble organic solvent can be recovered and regenerated, which makes it more environmentally friendly and reduces the cost.
(second embodiment)
A method for producing a cellulose nanofiber-containing rubber composition according to a second embodiment of the present invention (hereinafter also referred to as a production method according to a second embodiment) includes a step of kneading a rubber component containing ethylene-propylene-diene rubber and an unmodified cellulose nanofiber dispersion in the presence of a mixed solvent of a water-soluble organic solvent having an SP value of 10 or more and a water-insoluble organic solvent having an SP value of 9 or less (hereinafter also referred to as a mixed solvent according to a second embodiment), wherein at least one of the water-soluble organic solvent and the water-insoluble organic solvent has a boiling point of 150 ℃ to 220 ℃ inclusive, and the SP value of the mixed solvent is 8.5 to 11.
In the production method according to the second embodiment, since the water-soluble organic solvent having specific physical properties and the water-insoluble organic solvent having specific physical properties as described above are mixed and the SP value of the obtained mixed solvent is adjusted to 8.5 to 11, the solvent is less likely to be vaporized even when the rubber component and the unmodified cellulose nanofibers are kneaded, and the unmodified cellulose nanofibers are likely to be sufficiently dispersed in the rubber component. Further, aggregation of the unmodified cellulose nanofibers is suppressed, the rubber component containing EPDM is easily swollen, and the unmodified cellulose nanofibers are easily dispersed in the rubber component. Therefore, similarly to the first embodiment, the rubber molded product obtained by crosslinking the rubber composition obtained by the production method according to the second embodiment (hereinafter referred to as the second rubber composition) has high rubber hardness and also has elasticity, and thus has suitable physical properties.
In the production method according to the second embodiment, the upper limit value of the SP value of the water-soluble organic solvent and the lower limit value of the SP value of the water-insoluble organic solvent are not particularly limited as long as the SP of the mixed solvent of the second embodiment can be adjusted to a specific range.
Examples of the water-soluble organic solvent having an SP value of 10 or more include N-methylpyrrolidone (boiling point: 202 ℃ C.), 1-methoxy-2-propanol (boiling point: 120 ℃ C.), propylene glycol (boiling point: 188 ℃ C.), pyridine (boiling point: 115 ℃ C.), acetonitrile (boiling point: 82 ℃ C.), isopropanol (boiling point: 82 ℃ C.), ethanol (boiling point: 78 ℃ C.), and methanol (boiling point: 65 ℃ C.).
Examples of the water-insoluble organic solvent having an SP value of 9 or less include butyl acetate (boiling point 126 ℃ C.), methoxybutyl acetate (boiling point 172 ℃ C.), xylene (boiling point 140 ℃ C.), toluene (boiling point 110 ℃ C.), and mineral spirits (boiling point 130 to 230 ℃ C.).
In the production method according to the second embodiment, the water-soluble organic solvent and the water-insoluble organic solvent may be selected so that at least one of the water-soluble organic solvent having an SP value of 10 or more and the water-insoluble organic solvent having an SP value of 9 or less has a boiling point of 150 ℃ to 220 ℃ inclusive and the SP value of the mixed solvent of the second embodiment is 8.5 to 11.
Among them, from the viewpoint of excellent dispersibility of the mixed solvent of the second embodiment, it is preferable to use N-methylpyrrolidone or 1-methoxy-2-propanol as the water-soluble organic solvent; as the water-insoluble organic solvent, butyl acetate or methoxybutyl acetate is preferably used.
The mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent in the mixed solvent of the second embodiment is not particularly limited as long as the SP value of the obtained mixed solvent of the second embodiment can be adjusted to a range of 8.5 to 11.
The rubber component used in the production method according to the second embodiment is a main component of the second rubber composition. Specifically, any rubber component may be used in the production method according to the first embodiment. Detailed description about the rubber component is omitted.
The cellulose nanofiber dispersion used in the production method according to the second embodiment is a liquid in which unmodified cellulose nanofibers are dispersed. Specifically, any cellulose nanofibers may be used in the production method according to the first embodiment. Detailed description about the cellulose nanofibers is omitted.
In the production method according to the second embodiment, the cellulose nanofiber dispersion may be a dispersion of a mixed solvent of the water-soluble organic solvent and the water-insoluble organic solvent (mixed solvent of the second embodiment).
The content of the unmodified cellulose nanofibers in the cellulose nanofiber dispersion is not particularly limited, and may be adjusted to 1 to 30% by weight.
The method for dispersing the cellulose nanofibers in the mixed solvent of the second embodiment may be a known method, and is not particularly limited.
Alternatively, the cellulose nanofiber dispersion may be prepared by dispersing cellulose nanofibers in water, mixing the mixed solvent of the second embodiment, and replacing water with the mixed solvent.
In the production method according to the second embodiment, as a method of kneading the rubber component of EPDM swollen by the mixed solvent of the second embodiment and the cellulose nanofiber dispersion to disperse unmodified cellulose nanofibers, for example, there can be mentioned:
method 1-2): the method includes a step of kneading a rubber component containing EPDM and a cellulose nanofiber dispersion dispersed in the mixed solvent of the second embodiment.
Method 2-2): comprising the step of swelling a rubber component containing EPDM with the mixed solvent of the second embodiment; and a step of kneading the swollen rubber component and the cellulose nanofiber dispersion.
Specifically, as the method 1-2), there is a method in which the cellulose nanofiber dispersion dispersed in the mixed solvent of the second embodiment is put into a rubber component containing EPDM that is being masticated in a kneader, and the mixed solvent of the second embodiment is gasified while kneading them.
Further, as the method 2-2), there can be mentioned a method in which the mixed solvent of the second embodiment is charged into the rubber component containing EPDM that is being masticated in a kneader, the rubber component is swollen while kneading them, and then the water-soluble organic solvent is vaporized while kneading them by charging the cellulose nanofiber dispersion dispersed in the mixed solvent of the second embodiment.
In the method 2-2), depending on the type of the kneading apparatus and the type of the organic solvent, the step of charging the mixed solvent of the second embodiment and kneading the mixed solvent while swelling the rubber component may be omitted.
The water-soluble organic solvent kneaded with the rubber component and the water-soluble organic solvent and the water-insoluble organic solvent used for the cellulose nanofiber dispersion may be the same or different.
The kneading machine is not particularly limited as long as it is an apparatus that can be used in the production method of the first embodiment.
The temperature condition for swelling the rubber component is not particularly limited as long as it is a temperature at which the rubber component is not crosslinked, and is appropriately adjusted depending on the type of the rubber component, and is preferably 80 to 130 ℃.
The kneading time for swelling the rubber component is not particularly limited.
The temperature condition for vaporizing the mixed solvent of the second embodiment while the kneading is performed is not particularly limited as long as it is a temperature at which the rubber component is not crosslinked, and is preferably 100 to 150 ℃.
The kneading may be continued until the mixed solvent of the second embodiment is not observed around the second rubber composition, and the specific time is not particularly limited, and may be 1 to 3 hours.
Further, by using a kneader and an organic solvent recovery apparatus in combination, the mixed solvent of the second embodiment can be recovered and regenerated, which is more environmentally friendly and can reduce the cost.
In the production method of the first or second embodiment, any component such as carbon black, a colorant, a filler, an oil, a plasticizer, a surfactant, a processing aid, or the like may be added to the obtained first or second rubber composition.
The timing of adding these optional components is not particularly limited, and when the method of 1-1) or 1-2) is employed, they may be added in the step of kneading the swollen rubber component and the cellulose nanofiber dispersion; when the method of 2-1) or 2-2) is employed, the method may be added in the step of kneading the rubber component and the water-soluble organic solvent or the mixed solvent of the second embodiment and the cellulose nanofiber dispersion.
In the production method of the first or second embodiment, the water-soluble organic solvent or the mixed solvent of the second embodiment may be removed from the rubber component in which the unmodified cellulose nanofibers are dispersed to 1 wt% or less while swelling with the water-soluble organic solvent or the mixed solvent of the second embodiment.
Examples of the method for removing the water-soluble organic solvent or the mixed solvent of the second embodiment from the rubber component include a method of continuously kneading the rubber component with the temperature of the kneading machine being increased, and vacuum reduced pressure drying.
By removing the water-soluble organic solvent or the mixed solvent of the second embodiment in this manner, a so-called master batch can be produced.
According to the production method of the present invention, since the unmodified cellulose nanofibers are excellent in dispersibility in the first or second rubber composition, a rubber molded product obtained by crosslinking the obtained first or second rubber composition by adjusting the solid content concentration of the unmodified cellulose nanofibers to 3 to 30phr (per rounded rubber) has high rubber hardness and elasticity, and thus has suitable physical properties.
The first or second rubber composition obtained by the production method of the present invention can be used in applications such as conveyor belts, weather strips, vibration-proof rubbers, hoses, wire coatings, and gaskets.
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[ examples ]
[ production example of cellulose nanofiber Dispersion ]
To 30 parts by weight of kraft pulp, 970 parts by weight of purified water was added and stirred. A6-inch ultrafine particle mill (stone mortar mill manufactured by Ganhui Industrial Co., Ltd.) dispersed while gradually decreasing the gap from the disc contact gap, and filtered and concentrated using a Buchner funnel with the end point at which the contact gap decreased to 120 μm so that the cellulose nanofiber dispersion became 7.5 wt% was prepared as an aqueous cellulose nanofiber dispersion (solid content concentration 7.5 wt%, average fiber diameter 80 to 200nm, fiber length 100 μm).
To 400 parts by weight of the aqueous cellulose nanofiber dispersion having a solid content of 7.5% by weight obtained in the above-described manner, 900 parts by weight of diethylene glycol dimethyl ether (water-soluble organic solvent having a boiling point of 162 ℃ C. and an SP value of 9.0, manufactured by Toho chemical Co., Ltd.) was added and stirred.
The cellulose nanofiber dispersion was concentrated by filtration using a buchner funnel until 400 parts by weight of the cellulose nanofiber dispersion was obtained, then 900 parts by weight of diethylene glycol dimethyl ether was added, and the mixture was stirred and concentrated by filtration using a buchner funnel until 400 parts by weight of the cellulose nanofiber dispersion was obtained. The moisture content of the obtained cellulose nanofiber dispersion is 10% or less. The cellulose nanofiber dispersion was used in the examples that follow.
[ example 1]
To 300 parts by weight of EPDM "EPT-4021H" (manufactured by Mitsui chemical Co., Ltd.) plasticated in a kneader (S-type twin-arm kneader (mixing volume 1L) manufactured by Sford, Japan) were added 60 parts by weight of diethylene glycol dimethyl ether (boiling point 162 ℃ C., SP value 9.0) and the rubber component was swollen while kneading at 100 ℃.
Subsequently, 500 parts by weight of a previously prepared diethylene glycol dimethyl ether dispersion containing 6% by weight of unmodified Cellulose Nanofibers (CNF) was added in portions while continuously kneading.
Subsequently, the kneading was continued while heating at 100 to 120 ℃ to remove diethylene glycol dimethyl ether so that the content of diethylene glycol dimethyl ether became 1 wt% or less, thereby obtaining a rubber composition (the solid content concentration of unmodified cellulose nanofibers: 10 phr).
[ examples 2 to 6 ]
A rubber composition was obtained in the same manner as in example 1, except that the organic solvent kneaded with EPDM and the organic solvent of the cellulose nanofiber dispersion were replaced with those described in table 1 below.
Wherein the organic solvent is represented by "∞" when it is water-soluble.
[ comparative examples 1 to 13]
A rubber composition was obtained in the same manner as in example 1, except that the organic solvent kneaded with EPDM and the organic solvent of the cellulose nanofiber dispersion were replaced with those described in tables 2 and 3 below.
(test example 1)
The rubber compositions obtained in examples 1 to 6 and comparative examples 1 to 13 were evaluated for rubber hardness and dispersibility of unmodified cellulose nanofibers according to the following procedures.
[ rubber hardness ]
1) 110 parts by weight of each rubber composition, 7.5 parts by weight of a peroxide crosslinking agent (DCP-40 (manufactured by Nichikoku Co., Ltd.)), 5 parts by weight of zinc oxide and 1 part by weight of stearic acid were mixed in a two-roll mill and kneaded at 70 to 80 ℃ for 10 minutes.
Then, the above-mentioned twin-roll mill is operated to produce a sheet having a thickness of 2.2 to 2.6 mm.
Next, a metal frame having a thickness of 2mm was hot-pressed at 170 ℃ for 20 minutes to carry out a crosslinking treatment, thereby obtaining a test piece having a thickness of 2 mm.
2) The obtained test pieces 3 were stacked to have a thickness of 6mm, and measured randomly at 5 points using a digital durometer "GSD-719J-R (type A)" manufactured by Delile corporation, and the intermediate value was defined as the rubber hardness.
[ dispersibility ]
The presence or absence of coarse particles on the surface of the rubber after molding was visually confirmed, and the rubber was evaluated according to the following criteria.
Good for: almost without coarse grains
". DELTA": coarse grains can be confirmed
"×": can confirm a large amount of coarse grains
[ comprehensive evaluation ]
The evaluation of the production efficiency was carried out by the following overall judgment standards except for the kneading time.
Good for: good dispersibility, rubber hardness of 75 or more and kneading time of less than 3 hours.
". DELTA": 1 or 2 conditions that the dispersibility is good, the rubber hardness is 75 or more, or the kneading time is less than 3 hours are satisfied.
"×": the dispersibility was "X".
The obtained results are shown in table 4.
According to the results shown in Table 4, the rubber-molded articles of examples 1 to 6 had high rubber hardness and coarse particles of unmodified cellulose nanofibers could not be observed in the rubber-molded articles, while the rubber-molded articles of comparative examples 1 to 13 had lower rubber hardness than those of examples 1 to 6 and had almost "Δ" or "x" as an evaluation of dispersibility.
Further, it was confirmed that the rubber moldings of examples 1 to 6 were less likely to deform and had a significantly higher elastic modulus than comparative examples 1 to 4, 7 and 13 in which the dispersibility was evaluated as "x".
From the above, it is understood that the rubber compositions obtained in examples 1 to 6 are suitably used for applications such as conveyor belts, weather strips, vibration-proof rubbers, hoses, wire coatings, and gaskets.
The types of solvents shown in table 4 are as follows.
"Diglyme": diethylene glycol dimethyl ether
"EDM": diethylene glycol ethyl methyl ether
"EDGAC": ethyl diethylene glycol acetate
"butyl cellosolve": ethylene glycol n-butyl ether
"Methobuta": 3-methoxybutanol
"Solfit": 3-methoxy-3-methyl-1-butanol
"method": methoxybutyl acetate
"PMA": propylene glycol monomethyl ether acetate
"cellosolve acetate": ethylene glycol monoethyl ether acetate
"BDG": diethylene glycol monobutyl ether
"PM": propylene glycol monomethyl ether
"NMP": n-methyl-2-pyrrolidone
"DMF": dimethyl formamide
"PG": propylene glycol
"EG": ethylene glycol
[ Table 1]
[ Table 2]
| Name of raw materials | Solid content (%) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| EPT－4021H | 100 | 300 | 300 | 300 | 300 | 300 | 300 |
| Methoxybutyl acetate | 0 | 60 | |||||
| Xylene | 0 | 60 | |||||
| Propylene glycol monomethyl ether acetate | 0 | 60 | |||||
| Ethylene glycol monoethyl ether acetate | 0 | 60 | |||||
| Diethylene glycol monobutyl ether | 0 | 60 | |||||
| Propylene glycol monomethyl ether | 0 | 60 | |||||
| CNF methoxybutyl acetate dispersion | 6 | 500 | |||||
| CNF xylene dispersion | 6 | 500 | |||||
| CNF propylene glycol monomethyl ether acetate dispersion | 6 | 500 | |||||
| CNF ethylene glycol monoethyl ether acetate dispersion | 6 | 500 | |||||
| CNF diethylene glycol monobutyl ether dispersion | 6 | 500 | |||||
| CNF propylene glycol monomethyl ether dispersion | 6 | 500 |
[ Table 3]
[ Table 4]
[ example 7 ]
Butyl acetate and N-methyl-2-pyrrolidone were mixed at a volume ratio of 1: 1, and it was confirmed that the SP value of the resulting mixed solvent was 10.1.
A rubber composition (unmodified cellulose nanofibers having a solid content of 10phr) was obtained in the same manner as in example 1, except that the mixed solvent was used as the solvent.
[ examples 8 and 9, comparative examples 14 to 17 ]
A rubber composition (unmodified cellulose nanofibers having a solid content of 10phr) was obtained in the same manner as in example 7, except that a mixed solvent containing the organic solvent shown in table 5 was used.
The rubber compositions obtained in examples 7 to 9 and comparative examples 14 to 17 were evaluated for rubber hardness and dispersibility of unmodified cellulose nanofibers according to the following procedures.
The obtained results are shown in table 5.
According to the results shown in Table 5, the rubber hardness of the rubber moldings of examples 7 to 9 was higher and coarse particles of unmodified cellulose nanofibers could not be seen in the rubber moldings, while the rubber hardness of the rubber moldings of comparative examples 14 to 17 was lower than those of examples 1 to 6 and the dispersibility was evaluated as "Δ".
Further, it was confirmed that the rubber moldings of examples 7 to 9 were not easily deformed and had high elastic modulus as in the rubber moldings of example 1.
From the above, it is understood that the rubber compositions obtained in examples 7 to 9 are suitably used for applications such as conveyor belts, weather strips, vibration-proof rubbers, hoses, wire coatings, and gaskets.
[ Table 5]
Claims (13)
1. A method for producing a rubber composition containing cellulose nanofibers, characterized in that,
the method comprises a step of kneading a rubber component containing ethylene-propylene-diene monomer rubber and an unmodified cellulose nanofiber dispersion in the presence of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
2. The manufacturing method according to claim 1, comprising:
swelling a rubber component containing ethylene propylene diene monomer with a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11; and
and a step of kneading the swollen rubber component and the unmodified cellulose nanofiber dispersion.
3. The manufacturing method according to claim 1, comprising:
a step of kneading a rubber component containing an ethylene-propylene-diene monomer rubber that has been swollen with a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11, and an unmodified cellulose nanofiber dispersion.
4. The production method according to any one of claims 1 to 3,
the water-soluble organic solvent having a boiling point of 150 to 220 ℃ and an SP value of 8.5 to 11 is at least 1 selected from the group consisting of alcohol solvents, ether solvents and ester solvents.
5. The production method according to any one of claims 1 to 4,
the unmodified cellulose nanofiber dispersion is a dispersion of a water-soluble organic solvent having a boiling point of 150 ℃ to 220 ℃ and an SP value of 8.5 to 11.
6. A method for producing a rubber composition containing cellulose nanofibers, characterized in that,
comprising a step of kneading a rubber component containing ethylene-propylene-diene rubber and an unmodified cellulose nanofiber dispersion in the presence of a solvent mixture,
the mixed solvent is a mixed solvent of a water-soluble organic solvent having an SP value of 10 or more and a water-insoluble organic solvent having an SP value of 9 or less, at least one of the water-soluble organic solvent and the water-insoluble organic solvent has a boiling point of 150 ℃ to 220 ℃ inclusive, and the mixed solvent has an SP value of 8.5 to 11.
7. The manufacturing method according to claim 6, comprising:
swelling a rubber component containing ethylene propylene diene monomer with the mixed solvent; and
and a step of kneading the swollen rubber component and the unmodified cellulose nanofiber dispersion.
8. The manufacturing method according to claim 6,
the method comprises a step of kneading a rubber component containing ethylene-propylene-diene monomer swollen with the mixed solvent, and an unmodified cellulose nanofiber dispersion.
9. The production method according to any one of claims 6 to 8,
the water-soluble organic solvent is N-methyl pyrrolidone or 1-methoxy-2-propanol, and the water-insoluble organic solvent is butyl acetate or methoxybutyl acetate.
10. The production method according to any one of claims 6 to 9,
the unmodified cellulose nanofiber dispersion is a dispersion of the mixed solvent.
11. The production method according to any one of claims 1 to 10,
the average fiber diameter of the unmodified cellulose nanofiber is 20-1000 nm.
12. The production method according to any one of claims 1 to 11,
the method comprises a step of removing the water-soluble organic solvent or the mixed solvent from the rubber component, which is swollen with the water-soluble organic solvent or the mixed solvent having a boiling point of 150 ℃ to 220 ℃ inclusive and an SP value of 8.5 to 11 and in which the unmodified cellulose nanofibers are dispersed, to a level of 1 wt% or less.
13. The production method according to any one of claims 1 to 12,
the concentration of the solid content of the unmodified cellulose nanofibers in the cellulose nanofiber-containing rubber composition is 3 to 30 phr.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020152934 | 2020-09-11 | ||
| JP2020-152934 | 2020-09-11 | ||
| JP2021-139971 | 2021-08-30 | ||
| JP2021139971A JP2022047509A (en) | 2020-09-11 | 2021-08-30 | Method for Producing Cellulose Nanofiber-Containing Rubber Composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114163655A true CN114163655A (en) | 2022-03-11 |
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|---|---|---|---|
| CN202111054017.1A Pending CN114163655A (en) | 2020-09-11 | 2021-09-09 | Method for producing cellulose nanofiber-containing rubber composition |
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| Country | Link |
|---|---|
| CN (1) | CN114163655A (en) |
| TW (1) | TW202222929A (en) |
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2021
- 2021-09-01 TW TW110132414A patent/TW202222929A/en unknown
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| TW202222929A (en) | 2022-06-16 |
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