CN1737029A - Shell biolobic material phenolic resin and its preparation method - Google Patents
Shell biolobic material phenolic resin and its preparation method Download PDFInfo
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- CN1737029A CN1737029A CN 200510011006 CN200510011006A CN1737029A CN 1737029 A CN1737029 A CN 1737029A CN 200510011006 CN200510011006 CN 200510011006 CN 200510011006 A CN200510011006 A CN 200510011006A CN 1737029 A CN1737029 A CN 1737029A
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- shell
- biolobic material
- shell biolobic
- phenolic resin
- phenol
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title claims description 81
- 229920001568 phenolic resin Polymers 0.000 title claims description 27
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 26
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 210000002706 plastid Anatomy 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000012434 nucleophilic reagent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000014036 Castanea Nutrition 0.000 claims description 3
- 241001070941 Castanea Species 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 241000353135 Psenopsis anomala Species 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 229920003987 resole Polymers 0.000 description 29
- 239000002028 Biomass Substances 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 11
- 238000004026 adhesive bonding Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000003292 glue Substances 0.000 description 9
- 244000068645 Carya illinoensis Species 0.000 description 8
- 235000009025 Carya illinoensis Nutrition 0.000 description 8
- 241000758789 Juglans Species 0.000 description 7
- 235000009496 Juglans regia Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000020234 walnut Nutrition 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 235000013312 flour Nutrition 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 240000004929 Juglans cinerea Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000014056 Juglans cinerea Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000723418 Carya Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000013757 Juglans Nutrition 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 241000544657 Larix gmelinii Species 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a shell-organism phenol resin and its preparation method. Wherein, using smashed shell-organism active powder to replace some phenol or resorcinol; with formaldehyde and copolymerization reaction, one obtains the said product, which can be used in plastic and other industry, has advantages of no industrial secondary pollution, low cost, etc.
Description
Technical field
The present invention relates to a kind of synthetic resins, more particularly, the present invention relates to use through the active powder of the shell biolobic material of pulverizing and activation treatment obtains, replace or part fortified phenol or Resorcinol, under formaldehyde participates in, by copolyreaction, obtain the suitable shell biolobic material phenolic resin made from pure petrochemical material of resol performance.Simultaneously, the invention still further relates to the preparation method of described shell biolobic material phenolic resin.
Background technology
The employed resol of modern timber tackiness agent is with petrochemical material---phenol or Resorcinol and formaldehyde reaction form, owing to limit by petroleum resources, the price of petrochemicals and the production cost of derived product thereof have been the gesture that one road hurricane rises, especially phenol or Resorcinol, worldwide well sold and in short supply petroleum chemicals have been become, for this reason, people are making great efforts to seek to replace or part replaces the plastid of reproducibility Biological resources of petrochemical material or its chemical composition raw material as the environmentally friendly resol of a new generation.
United States Patent (USP) (United States Patent 4,098,765,1978) to shell or its inner septum of the pecan (Pecan) in the hickory (Caryaillinoensis), obtain the pecan shell extraction liquid through pulverizing, extract, filtering, under acidic conditions, react, obtain resol through dewatering and pulverizing again with formaldehyde, be dissolved in and obtain pure dissolubility resol in the ethanol, as paper, impregnation of timber liquid.United States Patent (USP) (United States patent 4,201,699,1980 and 4,201851,1980) to the inner septum in the pecan shell, water extracts under high temperature, alkaline condition, after the extraction liquid dehydration, filtering, replaces part phenol or Resorcinol (maximum replacement amount is no more than 60%), obtain resol with phenol or Resorcinol and formaldehyde reaction, as the tackiness agent of glued board, fiberboard or shaving board.The deficiency of above-mentioned United States Patent (USP) be to extract the chemical substance in the pecan shell, to filter and dewater after be used again, rather than whole utilizations of pecan shell plastid, therefore certainly existing the industrial production energy consumption big, can produce the problem of waste water, waste residue in producing, thereby increased the industrial production cost.Simultaneously, above-mentioned United States Patent (USP) only relates to the pecan shell utilization, does not relate to the utilization of walnut (Walnut) shell that utilizes in the white walnut (Juglans).
United States Patent (USP) (United States Patent 4,200,723,1980 and 4,201,700,1980) the Pericarppium arachidis hypogaeae water is extracted under high temperature, alkaline condition, after the extraction liquid dehydration, filtering, replace part phenol or Resorcinol, obtain resol with phenol or Resorcinol and formaldehyde reaction, as wood adhesive.The deficiency of above-mentioned United States Patent (USP) also be to extract the chemical substance in the Pericarppium arachidis hypogaeae, to filter and dewater after be used again, rather than, also exist the problem and the high problem of production cost that produce waste water, waste residue in the industrial production to whole utilizations of Pericarppium arachidis hypogaeae plastid.
China Shen Rui clear (1982) attempts the extender of white walnut walnut shell flour as glued board usefulness urea-formaldehyde resin, but does not relate to the copolymerization process of shell biolobic material phenolic resin.(1994) such as China Liu Qiming attempt to utilize Pericarppium arachidis hypogaeae or black liquid, Huang Ruzhu etc. (1995) to attempt to utilize the Pinus massoniana Lamb bark, Lin Jin etc. (1996) attempt to utilize the bark of dahurian larch extract to come the part fortified phenol to produce resol, but all exist need the chemical composition in the above-mentioned biomass be extracted, filtration and processed, the production cost height is difficult to realize the problem of suitability for industrialized production.
Attempt with the nut-shell of white walnut (2002) such as China Zhang Hongjian is the part surrogate (Chinese invention patent 02113646.3 " a kind of powdered wood adhesive and preparation method thereof ") of phenol, produce nut-shell-phenol-formaldehyde resin with the formaldehyde copolymerization, but exist the deficiency of nut-shell activation treatment overlong time (5～80 hours), this has just limited it and has further applied.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, provide a kind of with the shell biolobic material that is rich in lignin or tannin whole plastid part fortified phenol or Resorcinol synthetic resol.Another object of the present invention is to provide a kind of need not all utilize the method for preparing biomass resol through extraction, filtration and processed, technology shell biolobic material plastid simple and direct, time-saving energy-saving.
Purpose of the present invention is achieved by following technical proposals.
The invention provides a kind of shell biolobic material phenolic resin, this shell biolobic material phenolic resin adopts following method to prepare: the shell biolobic material plastid is crushed to fine powder below 40 orders, add the activity protecting agent that accounts for shell biolobic material weight 2%～8%, under normal pressure, handled 0.5～2 hour, and obtained the active powder of shell biolobic material; Adding accounts for the water of 1～5 times of shell biolobic material weight and 2～5 times nucleophilic reagent, adds to account for the basic catalyst of shell biolobic material weight 60%～100% or 3%～10% an acidic catalyst, stirs; Under the pressure condition of normal pressure or 1～2Mpa, heat treated 2～100 minutes is made the shell biolobic material activation solution; Add the phenol account for 1～5 times of shell biolobic material weight or Resorcinol then, 3～6 times formaldehyde carries out copolyreaction, makes required shell biolobic material phenolic resin.
Wherein, described shell biolobic material plastid is selected from a kind of in nut-shell, acorn cup shell, Exocarpium cocois (Cocos nucifera L), chestnut shell, Pericarppium Armeniacae Amarum, Pericarppium arachidis hypogaeae or the melon seed cases or their mixture.Described activity protecting agent is selected from a kind of in furfural, trimeric cyanamide, polyvinyl alcohol, the glycerol or their mixture.Described nucleophilic reagent is selected from a kind of in sodium hydroxide, S-WAT, Phenylsulfonic acid and salt thereof, phenol, Resorcinol, the trimeric cyanamide or their mixture; Described basic catalyst is selected from a kind of in sodium hydroxide, ammonium hydroxide, sodium sulphite, the S-WAT or their mixture; Described an acidic catalyst is selected from a kind of in phosphoric acid, Phenylsulfonic acid, acetic acid, hydrochloric acid, sulfuric acid, the anthraquinone or their mixture.
The invention provides a kind of preparation method of shell biolobic material phenolic resin, this method adopts the step of following order:
(1) shell biolobic material is crushed to fine powder below 40 orders, adds the activity protecting agent that accounts for shell biolobic material weight 2%～8%, heat treated is 0.5～2 hour under normal pressure, obtains the active powder of shell biolobic material;
(2) adding accounts for the water of 1～5 times of shell biolobic material weight and 2～5 times nucleophilic reagent, adds to account for the basic catalyst of shell biolobic material weight 60%～100% or 3%～10% an acidic catalyst, stirs;
(3) heat treated 2～100 minutes under the pressure condition of normal pressure or 1～2Mpa is made the shell biolobic material activation solution;
(4) add the phenol account for 1～5 times of shell biolobic material powder weight or Resorcinol, 3～6 times formaldehyde carries out copolyreaction, makes required shell biolobic material phenolic resin.
Compared with prior art, the present invention has following outstanding advantage:
1. up to now, the plastid that all utilizes shell biolobic material is not arranged all both at home and abroad, replacement or part fortified phenol or Resorcinol prepare the report of shell biolobic material phenolic resin.The present invention proposes all preparation methods of the shell biolobic material phenolic resin of utilization of shell biolobic material plastid first: obtain the shell biolobic material active body through pulverizing and active protection processing; with water, nucleophilic reagent, alkalescence or an acidic catalyst is treatment solution; heat treated is made the shell biolobic material activation solution under normal pressure or pressurized conditions; make shell biolobic material phenolic resin with phenol or Resorcinol and formaldehyde copolyreaction; the resol that replaces pure petrochemical material preparation is as wood adhesive.
2. the preparation method of the resol that all utilize of the shell biolobic material plastid that proposes of the present invention, whole shell biolobic materials are fully used, simultaneously, avoided the industrial production secondary pollution because of extracting, filter shell biolobic material and complex process such as dehydration having been simplified technological process.Especially the present invention can shorten the technological operation time effectively, and the heat treated time shortened to 2～100 minutes by original 5～80 hours, had saved energy consumption, had reduced production cost significantly, helped realizing large-scale industrial production.
3. the shell biolobic material phenolic resin that proposes of the present invention, because wherein shell biolobic material has absorptions, in conjunction with the natural function of free phenol and free aldehyde, so the wood gluing goods made from shell biolobic material phenolic resin have objectionable impurities burst sizes such as free phenol and free aldehyde than the low advantage more than 30% of pure petrochemical material phenol resin timber laminated product.
4. nut-shell, acorn cup shell, Exocarpium cocois (Cocos nucifera L), chestnut shell, Pericarppium Armeniacae Amarum, Pericarppium arachidis hypogaeae and various melon seed cases all are the reproducibility Biological resources that are rich in lignin or tannin, wherein the overwhelming majority all is a little wastes, is not used as industrial chemicals so far and realizes the scale industrialized utilization.The present invention proposes to utilize housing biomass such as nut-shell partly to replace petrochemicals in short supply day by day first---phenol or Resorcinol, preparation and the suitable shell biolobic material phenolic resin of pure petrochemical material resol performance, be society, economy and ecological environment benefit not only to transforming the disposability resource, and to saving petroleum resources, improve the security of China's petrochemical industry resource, all have great importance.
Embodiment
By specific embodiments of the invention given below, can further be well understood to the present invention, but they not limitation of the invention.
Embodiment 1
Get 100 kilograms of nut-shells, it is ground into walnut shell flour below 40 orders, add 5 kilograms of furfurals, obtain the active powder of nut-shell with pulverizer; Add 210 kg of water, 120 kg phenol and 40 kilograms of S-WATs successively, under 150 ℃ temperature, handled 1 hour, obtain the active liquid of nut-shell; Add 160 kilograms of phenol and 480 kilograms of formaldehyde, reaction is 3 hours under 100 ℃ of temperature, obtain nut-shell biomass resol, its free phenol content is 0.089%, content of free aldehyde is 0.096%, gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 2.23Mpa.
Embodiment 2
Get 100 kilograms on acorn cup shell, other condition obtains acorn cup shell biomass resol with embodiment 1, its free phenol content is 0.103%, content of free aldehyde is 0.114%, and its gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 1.81Mpa.
Embodiment 3
Get 100 kilograms of Pericarppium arachidis hypogaeaes, other condition obtains peanut hull biologic matter resol with embodiment 1, its free phenol content is 0.077%, content of free aldehyde is 0.082%, and its gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 1.92Mpa.
Embodiment 4
Get 100 kilograms of Exocarpium cocois (Cocos nucifera L)s, other condition obtains Exocarpium cocois (Cocos nucifera L) biomass resol with embodiment 1, its free phenol content is 0.099%, content of free aldehyde is 0.094%, and its gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 1.76Mpa.
Embodiment 5
Press embodiment 1 and obtain the active powder of 100kg nut-shell; Add 190 kg of water, 110 kilograms of Resorcinols and 45 kilograms of Phenylsulfonic acids successively, under the temperature of 150 ℃ of normal pressures, handled 1 hour, obtain the active liquid of nut-shell; Add 160 kilograms of phenol and 520 kilograms of formaldehyde, reaction is 3 hours under 100 ℃ of temperature, obtain nut-shell biomass resorcinol resin, its free phenol content is 0.071%, content of free aldehyde is 0.085%, its gluing technique and glue performance are suitable with pure petrochemical material resorcinol resin, and bonding strength is more than the 2.67Mpa.
Embodiment 6
Press embodiment 1 and obtain the active powder of 100kg nut-shell; Add 4 kilograms of trimeric cyanamides and 2 kilograms of polyvinyl alcohol, obtain the active powder of nut-shell; Other condition is identical with example 1, obtains nut-shell biomass resol, and its free phenol content is 0.110%, and content of free aldehyde is 0.113%, and gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 1.76Mpa.
Embodiment 7
Get 100 kilograms of nut-shells, it is ground into walnut shell flour below 40 orders, add 5 kilograms of furfurals, obtain the active powder of nut-shell with pulverizer; Add 220 kg of water, 130 kilograms of phenol and 7 kilograms of hydrochloric acid successively, under 150 ℃ temperature, handled 1 hour, obtain the active liquid of nut-shell; Other condition is identical with example 1, obtains nut-shell biomass resol, and its free phenol content is 0.091%, and content of free aldehyde is 0.107%, and gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 2.10Mpa.
Embodiment 8
Get 100 kilograms of nut-shells, it is ground into walnut shell flour below 40 orders, add 5 kilograms of furfurals, obtain the active powder of nut-shell with pulverizer; Add 220 kg of water, 130 kilograms of phenol and 7 kilograms of hydrochloric acid successively, under 120 ℃ temperature, handled 2 hours, obtain the active liquid of nut-shell; Other condition is identical with example 1, obtains nut-shell biomass resol, and its free phenol content is 0.064%, and content of free aldehyde is 0.071%, and gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 2.12Mpa.
Embodiment 9
Get 100 kilograms of nut-shells, it is ground into walnut shell flour below 40 orders, add 5 kilograms of furfurals, obtain the active powder of nut-shell with pulverizer; Add 220 kg of water, 130 kilograms of phenol and 7 kilograms of hydrochloric acid successively, under 120 ℃ temperature, handled 2 hours, obtain the active liquid of nut-shell; Add 160 kilograms of phenol and 480 kilograms of formaldehyde, reaction is 2 hours under 100 ℃ of temperature, obtain nut-shell biomass resol, its free phenol content is 0.124%, content of free aldehyde is 0.127%, gluing technique and glue performance are suitable with pure petrochemical material resol, and bonding strength is more than the 2.31Mpa.
Claims (7)
1. shell biolobic material phenolic resin, this shell biolobic material phenolic resin adopts following method to prepare: the shell biolobic material plastid is crushed to fine powder below 40 orders, add the activity protecting agent that accounts for shell biolobic material weight 2%～8%, under normal pressure, handled 0.5～2 hour, and obtained the active powder of shell biolobic material; Adding accounts for the water of 1～5 times of shell biolobic material weight and 2～5 times nucleophilic reagent, adds to account for the basic catalyst of shell biolobic material weight 60%～100% or 3%～10% an acidic catalyst, stirs; Under the pressure condition of normal pressure or 1～2Mpa, heat treated 2～100 minutes is made the shell biolobic material activation solution; Add the phenol account for 1～5 times of shell biolobic material weight or Resorcinol then, 3～6 times formaldehyde carries out copolyreaction, promptly obtains required shell biolobic material phenolic resin.
2. shell biolobic material phenolic resin according to claim 1, wherein said shell biolobic material plastid are selected from a kind of in nut-shell, acorn cup shell, Exocarpium cocois (Cocos nucifera L), chestnut shell, Pericarppium Armeniacae Amarum, Pericarppium arachidis hypogaeae or the melon seed cases or their mixture.
3. shell biolobic material phenolic resin according to claim 1, wherein said activity protecting agent are selected from a kind of in furfural, trimeric cyanamide, polyvinyl alcohol, the glycerol or their mixture.
4. shell biolobic material phenolic resin according to claim 1, wherein said nucleophilic reagent are selected from a kind of in sodium hydroxide, S-WAT, Phenylsulfonic acid and salt thereof, phenol, Resorcinol, the trimeric cyanamide or their mixture.
5. shell biolobic material phenolic resin according to claim 1, wherein said basic catalyst are selected from a kind of in sodium hydroxide, ammonium hydroxide, sodium sulphite, the S-WAT or their mixture.
6. shell biolobic material phenolic resin according to claim 1, wherein said an acidic catalyst are selected from a kind of in phosphoric acid, Phenylsulfonic acid, acetic acid, hydrochloric acid, sulfuric acid, the anthraquinone or their mixture.
7. the preparation method of a shell biolobic material phenolic resin, this method adopts the step of following order:
(1) shell biolobic material is crushed to fine powder below 40 orders, adds the activity protecting agent that accounts for shell biolobic material weight 2%～8%, heat treated is 0.5～2 hour under normal pressure, obtains the active powder of shell biolobic material;
(2) adding accounts for the water of 1～5 times of shell biolobic material weight and 2～5 times nucleophilic reagent, adds to account for the basic catalyst of shell biolobic material weight 60%～100% or 3%～10% an acidic catalyst, stirs;
(3) heat treated 2～100 minutes under the pressure condition of normal pressure or 1～2Mpa is made the shell biolobic material activation solution;
(4) add the phenol account for 1～5 times of shell biolobic material powder weight or Resorcinol, 3～6 times formaldehyde carries out copolyreaction, promptly obtains required shell biolobic material phenolic resin.
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| CNB200510011006XA CN100348635C (en) | 2005-09-07 | 2005-09-07 | Shell biolobic material phenolic resin and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510011006XA CN100348635C (en) | 2005-09-07 | 2005-09-07 | Shell biolobic material phenolic resin and its preparation method |
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| Publication Number | Publication Date |
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| CN1737029A true CN1737029A (en) | 2006-02-22 |
| CN100348635C CN100348635C (en) | 2007-11-14 |
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| US8481642B2 (en) | 2008-06-23 | 2013-07-09 | Csl Carbon Solutions Ltd. | Process for the preparation of hydrothermal hybrid material from biomass, and hydrothermal hybrid material obtainable by the process |
| CN106517137A (en) * | 2016-11-09 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of super-hydrophilic biomimetic material |
| CN108774446A (en) * | 2018-06-01 | 2018-11-09 | 湖南国盛石墨科技有限公司 | A kind of light color graphene conductive coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608408A (en) * | 1985-04-24 | 1986-08-26 | Koppers Company, Inc. | Phenol-HCHO-resorcinol resins for use in forming fast curing wood laminating adhesives |
| US5250588A (en) * | 1990-01-16 | 1993-10-05 | Ceram Sna Inc. | Organic friction material composition for use to produce friction linings |
| RU2005065C1 (en) * | 1992-01-16 | 1993-12-30 | Станислав Дмитриевич Котов | Method of manufacturing wood flat articles |
| JPH05279496A (en) * | 1992-04-03 | 1993-10-26 | Sumitomo Bakelite Co Ltd | Production of phenolic resin laminated board |
| CN1140601C (en) * | 2002-04-17 | 2004-03-03 | 昆明西木木材工业研究开发有限公司 | Powdered wood adhesive and its preparing process |
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2005
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| CN108774446A (en) * | 2018-06-01 | 2018-11-09 | 湖南国盛石墨科技有限公司 | A kind of light color graphene conductive coating |
| CN108912785A (en) * | 2018-06-01 | 2018-11-30 | 湖南国盛石墨科技有限公司 | A kind of graphene conductive coating that storage stability is excellent |
| CN108912786A (en) * | 2018-06-01 | 2018-11-30 | 湖南国盛石墨科技有限公司 | A kind of uniform graphene conductive coating of color |
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| CN109135497A (en) * | 2018-06-01 | 2019-01-04 | 湖南国盛石墨科技有限公司 | A kind of kermesinus graphene conductive coating that storage stability is excellent |
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