CN100348635C - 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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- CN100348635C CN100348635C CNB200510011006XA CN200510011006A CN100348635C CN 100348635 C CN100348635 C CN 100348635C CN B200510011006X A CNB200510011006X A CN B200510011006XA CN 200510011006 A CN200510011006 A CN 200510011006A CN 100348635 C CN100348635 C CN 100348635C
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Abstract
The present invention discloses shellfish biomass phenolic resin and a preparation method thereof. The method comprises: active powder of shellfish biomass, which is obtained through pulverizing treatment and activating treatment, substitutes part of phenol or resorcinol to obtain the shellfish biomass phenolic resin through a copolymerization reaction under the participation of formaldehyde, and the shellfish biomass phenolic resin prepared from a purely petrified raw material has the performance equivalent to that of phenolic resin. The product used for industries, such as adhesive industries, plastics industries, etc., has the advantages of no secondary pollution of industrial production, simple process, time saving, energy saving, low production cost and small release quantity of harmful substances of the final product.
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 (6)
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; Activity protecting agent wherein is selected from a kind of in furfural, trimeric cyanamide, polyvinyl alcohol and the glycerol or their mixture; 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 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.
4. 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.
5. 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.
6. 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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|---|---|---|---|---|
| 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 |
| JPH05279496A (en) * | 1992-04-03 | 1993-10-26 | Sumitomo Bakelite Co Ltd | Production of phenolic resin laminated board |
| RU2005065C1 (en) * | 1992-01-16 | 1993-12-30 | Станислав Дмитриевич Котов | Method of manufacturing wood flat articles |
| CN1381536A (en) * | 2002-04-17 | 2002-11-27 | 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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- 2005-09-07 CN CNB200510011006XA patent/CN100348635C/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| CN1381536A (en) * | 2002-04-17 | 2002-11-27 | 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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