CN102558468B - Bamboo/wood tar-furfural thermosetting resin and preparation method thereof - Google Patents
Bamboo/wood tar-furfural thermosetting resin and preparation method thereof Download PDFInfo
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- CN102558468B CN102558468B CN 201110451131 CN201110451131A CN102558468B CN 102558468 B CN102558468 B CN 102558468B CN 201110451131 CN201110451131 CN 201110451131 CN 201110451131 A CN201110451131 A CN 201110451131A CN 102558468 B CN102558468 B CN 102558468B
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 49
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 49
- 241001330002 Bambuseae Species 0.000 title claims abstract description 49
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 49
- 239000011425 bamboo Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002023 wood Substances 0.000 title abstract description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011276 wood tar Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000011269 tar Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000006837 decompression Effects 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 8
- 239000003610 charcoal Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 2
- 239000005011 phenolic resin Substances 0.000 abstract 2
- 229920001568 phenolic resin Polymers 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 7
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 6
- 229920003987 resole Polymers 0.000 description 5
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- -1 aldehyde compound Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 230000009325 pulmonary function Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The invention provides bamboo/wood tar-furfural thermosetting resin, which is prepared by the following method: adding tar/wood tar and furfural to a reactor at a mass ratio of tar to furfural being 1:(1.0-1.2), uniformly stirring, and pre-heating to 68-72 DEG C; adding a basic catalyst to pH being 8-11, and reacting at 85-110 DEG C for 2-5h, wherein the amount of the basic catalyst is 7-9% the mass of the bamboo/wood tar; and naturally cooling the reaction liquid, and dewatering under reduced pressure to obtain the bamboo/wood tar-furfural thermosetting resin. According to the invention, bamboo/wood processing byproduct namely bamboo/wood tar is used for completely replacing phenol to synthesize the thermosetting resin together with furfural, not only are the problems of high raw material toxicity, environmental pollution and the like in the traditional phenolic resin preparing process solved, but also the bamboo/wood charcoal byproduct namely bamboo/wood tar is changed into valuables, and the resources are sufficiently utilized. Therefore, the preparation method is a green and environment-friendly new way for preparing phenolic resin.
Description
(1) technical field
The present invention relates to a kind of bamboo/wood tar oil-furfural thermosetting resin and preparation method thereof.
(2) background technology
Resol is the resin that is formed by phenols and aldehyde compound polycondensation, wherein with phenol and formaldehyde condensation polymer and resol the most important, it has advantages such as cheap, heat-resisting, corrosion-resistant, fire-retardant, that burning fuming is few, is widely used as moulding compound, sizing agent, coating etc.But its shortcoming is synthesis material phenol is prototype matter poisonous substance, and toxicity is big, and it can make protein degradation, and people's nerve, liver, kidney are suffered damage; Raw material formaldehyde has strong carcinogenic and short cancer effect, can cause pulmonary function, liver function and immunologic dysfunction etc., and healthy and environment are had harm.Therefore, the raw material of seeking environmental protection substitutes phenol and formaldehyde is very necessary.
Bamboo/wood tar oil is the main by product in bamboo/charcoal production process, at present to the development and use of bamboo/wood tar oil also seldom, many times as waste treatment, causes the wasting of resources.Contain nearly hundred kinds of organic compound based on phenols in bamboo/wood tar oil, these phenolic compounds have a lot of adjacency pairs position not have substituting group (as 4-ethylphenol, 2,6-syringol etc.), all might with aldehydes generation crosslinking reaction; Furfural has active aldehyde radical, can be that raw material makes by starch.Therefore utilizing bamboo/wood tar oil and furfural to substitute the method for phenol and formaldehyde novolak resin, help to solve the shortcoming that existing resol raw material exists, is a kind of practicable resins approach than environmental protection.
(3) summary of the invention
The objective of the invention is to utilize bamboo (wood) the charcoal main by product bamboo of production (wood) tar replacing whole phenol and furfural to synthesize thermosetting resin.
The technical solution used in the present invention is:
A kind of bamboo/wood tar oil-furfural thermosetting resin is prepared by following method:
(1) by tar and furfural mass ratio 1: 1.0～1.2 bamboo/wood tar oil and furfural are placed reactor, stir, be preheated to 65 ℃～75 ℃;
(2) adding basic catalyst, to make pH be 8～11, in 85 ℃～110 ℃ reaction 2～5h down; Described basic catalyst quality consumption is 7～9% of bamboo/wood tar oil quality;
(3) reaction end afterreaction liquid naturally cools to 45～55 ℃, and decompression dehydration gets described bamboo/wood tar oil-furfural thermosetting resin.
Tar is a kind of thick liquid of black, is the product of organism process heating destructive distillation, and bamboo/wood tar oil of the present invention is the product of bamboo or wood distillation process, and wherein the mol ratio of phenols and furfural is less than 1.
Bamboo/wood tar oil of the present invention-furfural thermosetting resin, solids content are 64～72%, and viscosity is 4700～7000mPas (25 ℃), and the pH value is 8～11, and furfural content is 0.9～1.20% (mass percent), and solidification value is 150～160 ℃.
The invention still further relates to the preparation method of described bamboo/wood tar oil-furfural thermosetting resin, described method is as follows:
(1) by tar and furfural mass ratio 1: 1.0～1.2 bamboo/wood tar oil and furfural are placed reactor, stir, be preheated to 65 ℃～75 ℃;
(2) adding basic catalyst, to make pH be 8～11, in 85 ℃～110 ℃ reaction 2～5h down; Described basic catalyst quality consumption is 7～9% of bamboo/wood tar oil quality; Described basic catalyst can be alkali metal hydroxide, as sodium hydroxide, potassium hydroxide etc., can aqueous solution form add in the reactor, and aqueous solution mass concentration is 30～50%;
(3) reaction end afterreaction liquid naturally cools to 45～55 ℃, and decompression dehydration gets described bamboo/wood tar oil-furfural thermosetting resin.
Preferably, described basic catalyst is the aqueous sodium hydroxide solution of mass concentration 40%, and the sodium hydroxide quality is 7～9% of bamboo/wood tar oil quality in the aqueous solution.
Preferably, described aqueous sodium hydroxide solution adds in the reactor in batches: at first add 70～80% of catalyzer total mass, be heated to 85 ℃～110 ℃ reaction 0.5h after, add remaining catalyzer again, in 85 ℃～110 ℃ reaction 1.5～4h.
Preferably, described step (3) decompression dehydration carries out dewatering time 2～3h under vacuum tightness 0.08～0.09MPa.
Chief value of the present invention is mainly reflected in: the present invention utilizes the whole fortified phenols of by product bamboo/wood tar oil and the synthetic thermosetting resin of furfural of bamboo/wood working, not only help to solve existing resol and prepare problems such as the material toxicity that process exists is big, environmental pollution, and bamboo/charcoal by product bamboo/wood tar oil turned waste into wealth, having taken full advantage of resource, is a new way than environmental protection of preparation phenolic resinoid.
(4) description of drawings
The bamboo tar that Fig. 1 makes for embodiment-furfural resol IR collection of illustrative plates.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Take by weighing 66.58g bamboo tar (from certain bamboo charcoal source mill by product, analyze through FTIR, mainly contain phenolic compounds such as phenol, 4-ethylphenol, 2-ethylphenol, 6-syringol) place the 250mL there-necked flask, take by weighing the 66.57g furfural again and mix with above-mentioned bamboo tar, taking by weighing 4.663g NaOH then, to be made into massfraction be 40% the aqueous solution.Above-mentioned there-necked flask is put into magnetic stir bar, put into 70 ℃ the pre-heat agitated 30min of oil bath, be warming up to 85 ℃ then, add for the first time 9.32g NaOH solution, add remaining NaOH solution behind the 30min, reaction 4h stops heating, naturally cooling under 85 ℃ of temperature afterwards.
When the reaction product temperature is down to 50 ℃, be decompression dehydration under the 0.09MPa in vacuum tightness, decompression dehydration 2h gets product.Its product solids content is 67.7%, and viscosity is 6099mPas, and the pH value is 9.7, and furfural content is 1.17%.
Embodiment 2:
Take by weighing 66.60g bamboo tar (with embodiment 1) and place the 250mL there-necked flask, take by weighing the 79.00g furfural again and mix with above-mentioned bamboo tar, taking by weighing 5.322g NaOH then, to be made into massfraction be 40% the aqueous solution.Above-mentioned there-necked flask is put into magnetic stir bar, put into 70 ℃ the pre-heat agitated 30min of oil bath, be warming up to 95 ℃ then, add for the first time 10.64g NaOH solution, add remaining NaOH solution behind the 30min again, reaction 2h stops heating, naturally cooling under 95 ℃ of temperature afterwards.
After the reaction product temperature is down to 50 ℃, be decompression dehydration under the 0.09MPa in vacuum tightness, decompression dehydration 2h gets product.Its product solids content is 64.3%, and viscosity is 4766mPas, and the pH value is 9.7, and furfural content is 1.14%, and its IR collection of illustrative plates is referring to Fig. 1.
Embodiment 3:
Take by weighing the 64.73g wood tar oil (from certain charcoal source mill by product, analyze through FTIR, mainly contain phenolic compounds such as phenol, 4-ethylphenol, 2-ethylphenol, 6-syringol) place the 250mL there-necked flask, take by weighing the 71.20g furfural again and mix with above-mentioned wood tar oil, taking by weighing 5.176g NaOH then, to be made into massfraction be 40% the aqueous solution.Above-mentioned there-necked flask is put into magnetic stir bar, put into 70 ℃ the pre-heat agitated 30min of oil bath, be warming up to 105 ℃ then, add for the first time 10.35g NaOH solution, add remaining NaOH catalyzer behind the 30min, reaction 3h stops heating, naturally cooling under 105 ℃ of temperature afterwards.
Beginning in vacuum tightness when the reaction product temperature drops to 50 ℃ is decompression dehydration under the 0.09MPa, and decompression dehydration 2h gets product.Its product solids content is 71.4%, and viscosity is 6987mPas, and the pH value is 10.1, and furfural content is 0.94%.
Embodiment 4:
Take by weighing 40.00g embodiment 1 prepared bamboo tar-furfuryl resin and be uniformly coated on the plank of three layers of (on four sides) 25cm * 25cm, adopt pressure sintering glue plywood.Hot pressing condition: gluing precompressed 0.5h, pressure are 2.7MPa, and temperature is 140～150 ℃, and hot pressing time is 4min (1min/mm).The gained glued board detects the bonding strength of test specimen according to the requirement of GB/T 17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels ", and gained glued board gummed is functional.
Claims (5)
1. bamboo/wood tar oil-furfural thermosetting resin is prepared by following method:
(1) by tar and furfural mass ratio 1:1.0～1.2 bamboo/wood tar oil and furfural are placed reactor, stir, be preheated to 65 ℃～75 ℃;
(2) adding basic catalyst, to make pH be 8～11, in 85 ℃～110 ℃ reaction 2～5h down; Described basic catalyst quality consumption is 7～9% of bamboo/wood tar oil quality;
(3) reaction solution naturally cools to 45～55 ℃, and decompression dehydration gets described bamboo/wood tar oil-furfural thermosetting resin.
2. the preparation method of bamboo/wood tar oil as claimed in claim 1-furfural thermosetting resin, described method is as follows:
(1) by tar and furfural mass ratio 1:1.0～1.2 bamboo/wood tar oil and furfural are placed reactor, stir, be preheated to 65 ℃～75 ℃;
(2) adding basic catalyst, to make pH be 8～11, in 85 ℃～110 ℃ reaction 2～5h down; Described basic catalyst quality consumption is 7～9% of bamboo/wood tar oil quality;
(3) reaction solution naturally cools to 45～55 ℃, and decompression dehydration gets described bamboo/wood tar oil-furfural thermosetting resin.
3. method as claimed in claim 2 is characterized in that described basic catalyst from the aqueous sodium hydroxide solution of mass concentration 40%, and the sodium hydroxide quality is 7～9% of bamboo/wood tar oil quality in the aqueous solution.
4. method as claimed in claim 3, it is characterized in that described aqueous sodium hydroxide solution adds in the reactor in batches: at first add 70～80% of catalyzer total mass, after being heated to 85 ℃～110 ℃ reaction 0.5h, add remaining catalyzer again, in 85 ℃～110 ℃ reaction 1.5～4h.
5. method as claimed in claim 2 is characterized in that described step (3) decompression dehydration carries out dewatering time 2～3h under vacuum tightness 0.08～0.09MPa.
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| CN103289718B (en) * | 2013-07-02 | 2015-09-09 | 西北大学 | A kind of middle coalite tar prepares the method for dephenolize oil and resol |
| CN109609111B (en) * | 2018-12-27 | 2021-04-06 | 长江大学 | Wood tar resin sand consolidation agent and preparation method and application thereof |
| CN111793488B (en) * | 2019-04-08 | 2022-12-13 | 中国石油化工股份有限公司 | Chemical sand prevention agent for wood tar, preparation method and application thereof |
| CN111852362A (en) * | 2019-04-28 | 2020-10-30 | 中国石油化工股份有限公司 | Chemical sand prevention method for heavy oil thermal recovery |
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| CN100497422C (en) * | 2007-05-25 | 2009-06-10 | 中国林业科学研究院林产化学工业研究所 | Lignin modified phenol furfural resin for moulding material and preparation method thereof |
| CN101717491B (en) * | 2009-11-20 | 2011-09-14 | 北京化工大学 | Method for preparing and condensing polyaromatic hydrocarbon resin by using bamboo tar |
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