JP2011225712A - Method for producing biomass phenol resin - Google Patents
Method for producing biomass phenol resin Download PDFInfo
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- JP2011225712A JP2011225712A JP2010096555A JP2010096555A JP2011225712A JP 2011225712 A JP2011225712 A JP 2011225712A JP 2010096555 A JP2010096555 A JP 2010096555A JP 2010096555 A JP2010096555 A JP 2010096555A JP 2011225712 A JP2011225712 A JP 2011225712A
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- phenols
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 150000002989 phenols Chemical class 0.000 claims abstract description 39
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 25
- 229920000881 Modified starch Polymers 0.000 claims abstract description 22
- 235000019426 modified starch Nutrition 0.000 claims abstract description 21
- 239000002803 fossil fuel Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 31
- 229920002472 Starch Polymers 0.000 claims description 19
- 235000019698 starch Nutrition 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000006266 etherification reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 9
- -1 unsaturated alkyl phenols Chemical class 0.000 abstract description 4
- 241000196324 Embryophyta Species 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 15
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 15
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 15
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 15
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000001879 gelation Methods 0.000 description 10
- 239000008107 starch Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001254 oxidized starch Substances 0.000 description 4
- 235000013808 oxidized starch Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000013804 distarch phosphate Nutrition 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000001341 hydroxy propyl starch Substances 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical compound CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ATPYWZKDGYKXIM-UHFFFAOYSA-N acetic acid phosphoric acid Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.OP(O)(O)=O ATPYWZKDGYKXIM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、成形材料、鋳造用鋳型、エポキシ樹脂硬化剤、各種バインダー等に用いられるバイオマスフェノール樹脂の製造方法に関する。 The present invention relates to a method for producing a biomass phenol resin used for molding materials, casting molds, epoxy resin curing agents, various binders and the like.
植物は、繰り返し同じ土地で生産でき、石油や鉱物より短時間で再生される資源である。また、石油などの化石燃料由来原料を使用したプラスチックは、製品の焼却時に二酸化炭素を排出し、大気中の二酸化炭素総量を増加させるが、植物由来の原料を使用したプラスチックは、大気中の二酸化炭素総量を増加させない、いわゆるカーボンニュートラル材料である。そのため、環境への配慮から、石油などの化石燃料由来原料の代わりに、植物由来原料を使用した、いわゆるバイオマス樹脂の開発が進められている。
植物由来原料を使用した熱硬化性プラスチックとして、フェノール類と、砂糖類及び澱粉類の混合物とを、酸性触媒の存在下で反応させて得られたフェノール樹脂が開示されている（例えば、特許文献１参照。）。
また、フェノール類とトウモロコシ種皮等の澱粉系物質とを酸性触媒の存在下で反応後、ホルムアルデヒドを加え、反応させて得られたフェノール樹脂が開示されている（例えば、特許文献２参照。）。
さらに、フェノール類と木材からフェノール樹脂を製造する際、融点１００℃以下の反応性物質（ベンジルアルコール等）を添加することで、樹脂の軟化点を下げたフェノール樹脂が開示されている（例えば、特許文献３参照。）。
Plants are resources that can be repeatedly produced on the same land and regenerated in less time than oil and minerals. In addition, plastics that use fossil fuel-derived raw materials such as petroleum emit carbon dioxide during product incineration and increase the total amount of carbon dioxide in the atmosphere. However, plastics that use plant-derived raw materials do not emit carbon dioxide in the atmosphere. This is a so-called carbon neutral material that does not increase the total amount of carbon. Therefore, in consideration of the environment, so-called biomass resins using plant-derived materials instead of fossil fuel-derived materials such as petroleum are being developed.
As thermosetting plastics using plant-derived raw materials, phenol resins obtained by reacting phenols with a mixture of sugars and starches in the presence of an acidic catalyst are disclosed (for example, patent documents). 1).
Further, a phenol resin obtained by reacting phenols with starch-based substances such as corn seed coat in the presence of an acidic catalyst and then adding formaldehyde to react is disclosed (for example, see Patent Document 2).
Furthermore, when producing a phenol resin from phenols and wood, a phenol resin having a lowered softening point of the resin by adding a reactive substance (such as benzyl alcohol) having a melting point of 100 ° C. or lower is disclosed (for example, (See Patent Document 3).
ところが、特許文献１に記載のフェノール樹脂は高軟化点で成形時の流動性が低く、硬化物を得るための成形の際の加工性が不十分であった。
また、特許文献２に記載のフェノール樹脂は、化石燃料由来のフェノール類を使用した市販のノボラック樹脂に比べて成形物の曲げ強度が約３５％も低く、それを改善するため、ホルマリンによる架橋反応を施しているが、それでも約２０％も強度が低かった。
更に、特許文献３記載のフェノール樹脂は、ベンジルアルコールの添加によりベンジルフェノールを反応系で誘導し、低軟化点化を実現しているが、ベンジルアルコール自体が高価であることや植物由来率が低下するなどの課題があった。
本発明は、低軟化点で成形時の流動性が高く、成形加工性に優れ、植物由来率が高く、且つベンジルアルコールのような高価な石油系原料をしない、低コストなバイオマスフェノール樹脂を提供することを目的とする。
However, the phenol resin described in Patent Document 1 has a high softening point and low fluidity at the time of molding, and the workability at the time of molding to obtain a cured product was insufficient.
In addition, the phenol resin described in Patent Document 2 has a bending strength of about 35% lower than that of a commercially available novolak resin using a phenol derived from fossil fuel. However, the strength was still about 20% low.
Furthermore, although the phenol resin described in Patent Document 3 induces benzylphenol in the reaction system by adding benzyl alcohol and realizes a low softening point, benzyl alcohol itself is expensive and the plant-derived rate decreases. There were issues such as.
The present invention provides a low-cost biomass phenol resin with a low softening point, high fluidity during molding, excellent moldability, high plant-derived rate, and no expensive petroleum-based raw materials such as benzyl alcohol. The purpose is to do.
［１］糖質類として澱粉誘導体と、植物由来不飽和アルキルフェノール類及び化石燃料由来フェノール類を含有するフェノール類とを、酸性触媒存在下で反応させることを特徴とするバイオマスフェノール樹脂の製造方法。 [1] A method for producing a biomass phenol resin, comprising reacting a starch derivative as a saccharide with a phenol containing a plant-derived unsaturated alkylphenol and a fossil fuel-derived phenol in the presence of an acidic catalyst.
［２］澱粉誘導体１００質量部に対して、フェノール類が２００〜８００質量部である［１］記載のバイオマスフェノール樹脂の製造方法。 [2] The method for producing a biomass phenol resin according to [1], wherein phenols are 200 to 800 parts by mass with respect to 100 parts by mass of the starch derivative.
［３］澱粉誘導体が、各種澱粉のエステル化及び／またはエーテル化及び／または酸化及び／または架橋した澱粉誘導体の単独または混合物である［１］または［２］記載のバイオマスフェノール樹脂の製造方法。 [3] The method for producing a biomass phenol resin according to [1] or [2], wherein the starch derivative is a single or mixture of starch derivatives obtained by esterification and / or etherification and / or oxidation and / or crosslinking of various starches.
［４］フェノール類中の植物原料由来不飽和アルキルフェノール類と化石燃料由来フェノール類の質量比率が、植物原料由来不飽和アルキルフェノール類：化石燃料由来フェノール類＝１：９９〜５０：５０である［１］〜［３］のいずれかに記載のバイオマスフェノール樹脂の製造方法。 [4] The mass ratio of unsaturated alkylphenols derived from plant raw materials to phenols derived from fossil fuels in phenols is plant raw material derived unsaturated alkylphenols: fossil fuel derived phenols = 1: 99 to 50:50. ] The manufacturing method of the biomass phenol resin in any one of [3].
本発明のバイオマスフェノール樹脂の製造方法によれば、高い植物由来率を有する上に、低軟化点で成形時の流動性が高く、成形加工性に優れるバイオマスフェノール樹脂を低コストで製造できる。 According to the method for producing a biomass phenol resin of the present invention, it is possible to produce a biomass phenol resin having a high plant-derived rate, a low softening point, high fluidity during molding, and excellent molding processability at low cost.
本発明のバイオマスフェノール樹脂の製造方法は、糖質類として澱粉誘導体と、植物由来不飽和アルキルフェノール類及び化石燃料由来フェノール類を含有するフェノール類とを、酸性触媒存在下で反応させる方法である。
この反応では、酸性触媒によって、澱粉誘導体からヒドロキシメチルフルフラールが生成し、そのヒドロキシメチルフルフラールとフェノール類とが酸性触媒によって反応することによって、バイオマスフェノール樹脂を形成する。
The method for producing a biomass phenol resin of the present invention is a method in which a starch derivative as a saccharide and a phenol containing a plant-derived unsaturated alkylphenol and a fossil fuel-derived phenol are reacted in the presence of an acidic catalyst.
In this reaction, hydroxymethylfurfural is produced from a starch derivative by an acidic catalyst, and the hydroxymethylfurfural and phenols react with the acidic catalyst to form a biomass phenol resin.
まずは、本発明のバイオマスフェノール樹脂に使用する澱粉誘導体について説明する。一般的に澱粉誘導体は、その糊化温度やその時の粘度が低くなっているため、特に澱粉を原料とした時に見られる樹脂製造時の急激な増粘に伴う、攪拌停止を回避できる。急激な増粘による攪拌停止は、局所的に熱がかかり糖質類の炭化を引き起こし、目的のバイオマスフェノール樹脂が製造出来なくなってしまう。
澱粉誘導体としては、各種澱粉のエステル化及び／またはエーテル化及び／または酸化及び／または架橋した澱粉誘導体の単独または混合物が好ましい。各種澱粉のエステル化した澱粉誘導体としては、酢酸澱粉、リン酸化澱粉、オクテニルコハク酸澱粉が挙げられ、各種澱粉をエーテル化した澱粉誘導体としては、ヒドロキシプロピル澱粉、ヒドロキシエチル澱粉が挙げられ、各種澱粉を酸化した澱粉誘導体としては酸化澱粉が挙げられ、各種澱粉を架橋した澱粉誘導体としては、リン酸架橋澱粉が挙げられる。また各種澱粉について、エステル化、エーテル化、酸化、架橋反応のいずれかを２種以上行った澱粉誘導体である複合澱粉としては、酢酸アジピン酸架橋澱粉、酢酸リン酸化架橋澱粉、酢酸酸化澱粉、ヒドロキシプロピルリン酸架橋澱粉、リン酸モノエステル化リン酸架橋澱粉が挙げられる。これら各種澱粉誘導体は１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
First, the starch derivative used for the biomass phenol resin of this invention is demonstrated. In general, starch derivatives have a low gelatinization temperature and a low viscosity at that time, so that it is possible to avoid stirring stoppage accompanying a rapid increase in viscosity during resin production, particularly when starch is used as a raw material. Stopping stirring due to sudden thickening causes localized heat and carbonization of saccharides, making it impossible to produce the target biomass phenol resin.
As the starch derivative, a starch derivative alone or a mixture obtained by esterification and / or etherification and / or oxidation and / or crosslinking of various starches is preferable. Examples of esterified starch derivatives of various starches include starch acetate, phosphorylated starch, and octenyl succinate starch. Examples of starch derivatives obtained by etherifying various starches include hydroxypropyl starch and hydroxyethyl starch. The oxidized starch derivative includes oxidized starch, and the starch derivative obtained by crosslinking various starches includes phosphoric acid crosslinked starch. As for various starches, composite starches that are starch derivatives obtained by performing esterification, etherification, oxidation, or crosslinking reaction at least two kinds include starch adipic acid crosslinked starch, acetate phosphorylated crosslinked starch, acetate oxidized starch, hydroxy Examples thereof include propyl phosphate cross-linked starch and phosphate monoesterified phosphate cross-linked starch. These various starch derivatives may be used individually by 1 type, and may be used in combination of 2 or more type.
フェノール類に含まれる植物原料由来不飽和アルキルフェノール類としては、例えば、カルダノール、カシューナッツシェルリキッドなどが挙げられるが、反応性が高く、入手が容易な点からカルダノールが好ましい。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the plant material-derived unsaturated alkylphenols contained in the phenols include cardanol and cashew nut shell liquid, but cardanol is preferred because of its high reactivity and easy availability. These may be used individually by 1 type and may be used in combination of 2 or more type.
フェノール類中に含まれる化石燃料由来フェノール類としては特に限定されないが、フェノール、クレゾール、キシレノール、プロピルフェノール、ブチルフェノール、ブチルクレゾール、フェニルフェノール、クミルフェノール、メトキシフェノール、ブロモフェノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳなどが挙げられる。これらの中でも、反応性が高く、しかも入手容易な点で、フェノール、クレゾール、キシレノール、ビスフェノールＡが好ましい。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 The fossil fuel-derived phenols contained in the phenols are not particularly limited, but phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, bisphenol A, bisphenol F , Bisphenol S and the like. Among these, phenol, cresol, xylenol, and bisphenol A are preferable because they are highly reactive and easily available. These may be used individually by 1 type and may be used in combination of 2 or more type.
フェノール類中の植物原料由来不飽和アルキルフェノール類と化石燃料由来フェノール類の質量比率は、植物原料由来不飽和アルキルフェノール類：化石燃料由来フェノール類が１：９９〜５０：５０であることが好ましく、５：９５〜４０：６０であることがより好ましい。植物原料由来不飽和アルキルフェノール類の質量比率が１：９９以上であれば、得られるバイオマスフェノール樹脂の軟化点を下げることが可能で、成形時の流動性が高く、成形加工性に優れ、５０：５０以下であれば、成形物に要求される実用特性を満足することができる。 The mass ratio of the plant material-derived unsaturated alkylphenols to the fossil fuel-derived phenols in the phenols is preferably 1:99 to 50:50 in terms of the plant material-derived unsaturated alkylphenols: fossil fuel-derived phenols. : 95 to 40:60 is more preferable. If the mass ratio of the unsaturated alkylphenol derived from plant raw materials is 1:99 or more, the softening point of the obtained biomass phenol resin can be lowered, the fluidity during molding is high, and the molding processability is excellent. If it is 50 or less, the practical characteristics required for the molded product can be satisfied.
バイオマスフェノール樹脂を得る際の糖質類とフェノール類との質量比率は、糖質類固形分を１としたときに、フェノール類が１〜２０倍であることが好ましく、２〜８倍であることがより好ましい。フェノール類が糖質類の１倍以上であれば、反応性、収率も高く、非常に高い植物由来率のバイオマスフェノール樹脂が得られ、２０倍以下であれば、経済的にも安価にバイオマスフェノール樹脂が得られる。 The mass ratio of saccharides and phenols when obtaining a biomass phenol resin is preferably 1 to 20 times, preferably 2 to 8 times, when the saccharide solid content is 1. It is more preferable. If phenols are 1 time or more of carbohydrates, the reactivity and yield are high, and a biomass phenol resin with a very high plant-derived rate is obtained. If it is 20 times or less, biomass is economically inexpensive. A phenolic resin is obtained.
糖質類とフェノール類とを反応させる際には、酸性触媒が用いられる。酸性触媒としては、例えば、鉱酸類（例えば、塩酸、硫酸等）、有機酸類（例えば、パラトルエンスルホン酸、シュウ酸等）などが使用される。酸性触媒の使用量は、糖質類固形分とフェノール類との合計を１００質量％とした際に０．１〜５０質量％であることが好ましく、０．２から１０質量％であることがより好ましい。酸性触媒の使用量が０．１質量％以上であれば、十分な糖質類の液状化が可能で、５０質量％以下であれば、酸分解やゲル化を抑制できる。 An acidic catalyst is used when reacting carbohydrates and phenols. As the acidic catalyst, for example, mineral acids (for example, hydrochloric acid, sulfuric acid, etc.), organic acids (for example, paratoluenesulfonic acid, oxalic acid, etc.) are used. The amount of the acidic catalyst used is preferably 0.1 to 50% by mass and preferably 0.2 to 10% by mass when the total of the saccharide solids and phenols is 100% by mass. More preferred. If the usage-amount of an acidic catalyst is 0.1 mass% or more, sufficient liquefaction of carbohydrates is possible, and if it is 50 mass% or less, acid decomposition and gelation can be suppressed.
反応温度は２０〜２００℃であることが好ましく、１２０〜１６０℃であることがより好ましい。反応温度が２０℃以上であれば、充分に反応させることができ、２００℃以下であれば過分解を抑制できる。 The reaction temperature is preferably 20 to 200 ° C, more preferably 120 to 160 ° C. If reaction temperature is 20 degreeC or more, it can be made to react sufficiently, and if it is 200 degrees C or less, overdecomposition can be suppressed.
反応時間は０．５〜２０時間であることが好ましく、１〜３時間であることがより好ましい。反応時間が０．５時間以上であれば、高い収率で樹脂を得ることができ、２０時間以下であれば、生産性の低下を抑制できる。 The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 3 hours. If the reaction time is 0.5 hours or more, the resin can be obtained in a high yield, and if it is 20 hours or less, a decrease in productivity can be suppressed.
本発明の製造方法によれば、低軟化点で流動性が高く、成形加工性に優れるバイオマスフェノール樹脂が得られる。また、植物由来率が高いことから、いわゆるカーボンニュートラルの概念により、二酸化炭素量増加を抑制できる。
上記のようなバイオマスフェノール樹脂は、成形材料、鋳造用鋳型、エポキシ樹脂硬化剤、各種バインダー等に用いることができる。
According to the production method of the present invention, a biomass phenol resin having a low softening point and high fluidity and excellent moldability can be obtained. Moreover, since the plant-derived rate is high, an increase in the amount of carbon dioxide can be suppressed by the so-called carbon neutral concept.
The biomass phenol resin as described above can be used for molding materials, casting molds, epoxy resin curing agents, various binders, and the like.
以下の実施例および比較例では、得られたバイオマスフェノール樹脂について、軟化点、ゲル化時間、流動性、植物由来率を以下の方法で調べた。 In the following Examples and Comparative Examples, the obtained biomass phenol resin was examined for softening point, gelation time, fluidity, and plant-derived rate by the following methods.
［軟化点］
ＪＩＳ Ｋ ６９１０に準じて軟化点を測定した。
［ゲル化時間］
ＪＩＳ Ｋ ６９１２に準じてゲル化時間を測定した。（ヘキサメチレンテトラミン添加量１０質量％）
［流動性］
ＪＩＳ Ｋ ６９１０に準じて流動性を測定した。
［植物由来率］
１００−｛［（フェノール仕込み量）−（留去した未反応フェノール量）＋（中和塩の量（理論値））］／（樹脂収量）｝×１００
[Softening point]
The softening point was measured according to JIS K 6910.
[Gelification time]
Gelation time was measured according to JIS K6912. (Hexamethylenetetramine addition amount 10% by mass)
[Liquidity]
The fluidity was measured according to JIS K 6910.
[Plant-derived rate]
100-{[(Phenol charge amount)-(Distilled unreacted phenol amount) + (Amount of neutralized salt (theoretical value))] / (Resin yield)} × 100
［実施例１］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、カルダノール６０ｇ、酢酸澱粉３９６ｇ、濃硫酸７．９ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：３、カルダノールとフェノールの質量比率は５：９５、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム６．０ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール４０１ｇを留去し１０１７ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Example 1]
1128 g of phenol, 60 g of cardanol, 396 g of starch acetate and 7.9 g of concentrated sulfuric acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a condenser. The mass ratio of saccharides and phenols is 1: 3, the mass ratio of cardanol and phenol is 5:95, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of saccharides and phenols. It was 0.5 mass%.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 6.0 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 401 g of unreacted phenol was distilled off at 180 ° C. under a reduced pressure of 11 kPa to obtain 1017 g of a phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［実施例２］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、カルダノール１２５ｇ、酸化澱粉４１８ｇ、濃硫酸８．４ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：３、カルダノールとフェノールの質量比率は１０：９０、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム６．４ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール４００ｇを留去し１０７０ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Example 2]
1128 g of phenol, 125 g of cardanol, 418 g of oxidized starch and 8.4 g of concentrated sulfuric acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a condenser. The mass ratio of saccharides and phenols is 1: 3, the mass ratio of cardanol and phenol is 10:90, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of saccharides and phenols. It was 0.5 mass%.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 6.4 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 400 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 1070 g of a phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［実施例３］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール９４０ｇ、カルダノール２３５ｇ、酢酸澱粉２９４ｇ、濃硫酸７．３ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：４、カルダノールとフェノールの質量比率は２０：８０、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム５．６ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール４４１ｇを留去し９３６ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Example 3]
940 g of phenol, 235 g of cardanol, 294 g of acetic acid starch, and 7.3 g of concentrated sulfuric acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. In addition, the mass ratio of carbohydrates and phenols is 1: 4, the mass ratio of cardanol and phenol is 20:80, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of carbohydrates and phenols. It was 0.5 mass%.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 5.6 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 441 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 936 g of phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［実施例４］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール：７５２ｇ、カルダノール：５０１ｇ、ヒドロキシプロピル澱粉：５０１ｇ、濃硫酸８．８ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：２．５、カルダノールとフェノールの質量比率は４０：６０、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム６．６ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール２８２ｇを留去し１３２８ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Example 4]
A 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser tube was charged with 752 g of phenol, 501 g of cardanol, 501 g of hydroxypropyl starch, and 8.8 g of concentrated sulfuric acid. The mass ratio of saccharides and phenols is 1: 2.5, the mass ratio of cardanol and phenol is 40:60, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of saccharides and phenols. It was 0.5 mass% with respect to.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 6.6 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 282 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 1328 g of a phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［実施例５］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール：１３６８ｇ、カルダノール：７２ｇ、酢酸リン酸架橋澱粉：１８０ｇ、濃硫酸８．１ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：８、カルダノールとフェノールの質量比率は５：９５、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム６．１ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール９８７ｇを留去し５３０ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Example 5]
A 2 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 1368 g of phenol, 72 g of cardanol, 180 g of acetic acid phosphoric acid crosslinked starch, and 8.1 g of concentrated sulfuric acid. The mass ratio of saccharides and phenols is 1: 8, the mass ratio of cardanol and phenol is 5:95, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of saccharides and phenols. It was 0.5 mass%.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 6.1 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 987 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 530 g of a phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［比較例１］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール１１２８ｇ、酢酸澱粉３７６ｇ、濃硫酸７．５ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：３、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して０．５質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム５．７ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール３７２ｇを留去し１０２５ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Comparative Example 1]
1128 g of phenol, 376 g of starch acetate and 7.5 g of concentrated sulfuric acid were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a condenser. The mass ratio of saccharides to phenols was 1: 3, and the amount of concentrated sulfuric acid added was 0.5% by mass with respect to the total of 100% by mass of the saccharides solids and phenols.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. 5.7 g of calcium hydroxide dissolved in a small amount of water was added for neutralization. Thereafter, 372 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 1025 g of a phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
［比較例２］
温度計、攪拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、フェノール９４０ｇ、カルダノール２３５ｇ、木粉２９４ｇ、濃硫酸４３．８ｇを仕込んだ。なお、糖質類とフェノール類の質量比率は１：４、カルダノールとフェノールの質量比率は２０：８０、濃硫酸添加量は、糖質類の固形分とフェノール類の合計１００質量％に対して２．９質量％であった。
次いで、昇温途中で生成する水を除きながら１５５℃まで加熱し、１５５℃を保ったまま、１時間攪拌した。少量の水に溶解させた水酸化カルシウム３３．１ｇを添加して中和した。その後、１８０℃、１１ｋＰａの減圧下で未反応のフェノール４７９ｇを留去し８８２ｇのフェノール樹脂を得た。得られた樹脂の軟化点、ゲル化時間、流動性、植物由来率を表１に示す。
[Comparative Example 2]
Phenol 940 g, cardanol 235 g, wood flour 294 g and concentrated sulfuric acid 43.8 g were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a condenser. In addition, the mass ratio of carbohydrates and phenols is 1: 4, the mass ratio of cardanol and phenol is 20:80, and the amount of concentrated sulfuric acid added is 100% by mass in total of the solid content of carbohydrates and phenols. It was 2.9% by mass.
Subsequently, it heated to 155 degreeC, removing the water produced | generated in the middle of temperature rising, and stirred for 1 hour, keeping 155 degreeC. The mixture was neutralized by adding 33.1 g of calcium hydroxide dissolved in a small amount of water. Thereafter, 479 g of unreacted phenol was distilled off under reduced pressure at 180 ° C. and 11 kPa to obtain 882 g of phenol resin. Table 1 shows the softening point, gelation time, fluidity, and plant-derived rate of the obtained resin.
実施例１〜５のフェノール樹脂は、軟化点が低く、流動性が高く、植物由来率が高かった。これに対し、カルダノールを含まない比較例１や、木粉を適用した比較例２は軟化点が高く、流動性が低かった。 The phenol resins of Examples 1 to 5 had a low softening point, high fluidity, and a high plant-derived rate. On the other hand, the comparative example 1 which does not contain cardanol and the comparative example 2 which applied wood flour had a high softening point, and its fluidity | liquidity was low.
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| CN103570901A (en) * | 2013-10-08 | 2014-02-12 | 上海应用技术学院 | Preparation method of environment-friendly phenol aldehyde resin |
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