CN103122228A - Bio-oil starch adhesive for wood and preparation method - Google Patents
Bio-oil starch adhesive for wood and preparation method Download PDFInfo
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- CN103122228A CN103122228A CN2013100659334A CN201310065933A CN103122228A CN 103122228 A CN103122228 A CN 103122228A CN 2013100659334 A CN2013100659334 A CN 2013100659334A CN 201310065933 A CN201310065933 A CN 201310065933A CN 103122228 A CN103122228 A CN 103122228A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 95
- 235000019698 starch Nutrition 0.000 title claims abstract description 90
- 239000008107 starch Substances 0.000 title claims abstract description 84
- 239000012075 bio-oil Substances 0.000 title claims abstract description 78
- 239000000853 adhesive Substances 0.000 title claims abstract description 60
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002023 wood Substances 0.000 title abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000001590 oxidative effect Effects 0.000 claims abstract description 30
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- 125000003636 chemical group Chemical group 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 229920000881 Modified starch Polymers 0.000 claims description 32
- 239000004368 Modified starch Substances 0.000 claims description 32
- 235000019426 modified starch Nutrition 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 15
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 235000013312 flour Nutrition 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- -1 oxygenant 2-5 part Substances 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 7
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 2
- 239000003381 stabilizer Substances 0.000 abstract 2
- 238000004925 denaturation Methods 0.000 abstract 1
- 230000036425 denaturation Effects 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- 238000010008 shearing Methods 0.000 description 12
- 150000003926 acrylamides Chemical class 0.000 description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 241000227425 Pieris rapae crucivora Species 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004137 mechanical activation Methods 0.000 description 3
- 239000004836 Glue Stick Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000004026 adhesive bonding 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
- 239000000227 bioadhesive Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a bio-oil starch adhesive for wood, which belongs to the technical field of adhesive preparation. A preparation method comprises the following steps: carrying out acidolysis, oxidation and denaturation on starches by using a hydrochloric acid and an oxidant so as to reduce the molecular weight of the starches and improve the reactivity of the starches; then, adding an emulsifier and a stabilizer into the obtained object, and carrying out graft copolymerization on the obtained mixture and acrylamide under the action of an initiator; adding bio-oil, so that chemical groups on a skeleton structure are modified by using substances such as acid and aldehyde and the like in the bio-oil, thereby obtaining a host adhesive; and finally, adding a crosslinking agent and packing into the host adhesive so as to obtain the bio-oil starch adhesive, wherein the mass part of each raw material component is as follows: 80-120 parts of the starches, 150 parts of the hydrochloric acid, 2-5 parts of the oxidant, 1-3 parts of the emulsifier, 10-20 parts of the stabilizer, 0.3-0.6 part of the initiator, 10-20 parts of the acrylamide, 5-20 parts of the bio-oil, 5-10 parts of the crosslinking agent, and 10-15 parts of the packing. The bio-oil starch adhesive disclosed by the invention can replace a white emulsion and can be widely used in the aspects of wood ornaments, wood processing and artificial boards.
Description
Technical field
The invention belongs to the production of adhesive technical field, particularly a kind of timber preparation method of bio oil starch adhesive.
Background technology
Starch adhesive is a kind of as natural adhesive, has the advantages such as quality is light, pollution-free without burn into, raw material is easy to get, cheap, easy to use, is widely used in the bonding of paper, cotton fabric, trade mark etc.But there are the shortcomings such as bonding strength is lower, the chance tide easily goes mouldy in starch adhesive, and has limited the application aspect the timber-work gummed.The applicant provides a kind of with bio oil, mechanical activation starch, oxalic dialdehyde at patent CN201210135823.6, and oxalic acid, water, oxygenant, solidifying agent polymeric polyisocyanate, weighting agent etc. are raw material, and minute five steps prepare the method for starch-based glue stick.At first be mixed with starch emulsion with mechanical activation starch, again it is carried out acid hydrolysis oxidative and make the acid hydrolysis oxidative starch emulsion, add again bio oil and oxalic dialdehyde with its copolymerization, add afterwards oxalic acid to obtain tackiness agent host to its esterification, add in tackiness agent host at last solidifying agent isocyanic ester and weighting agent make a kind of Sheng Wu You ?Dian Fen ?the glyoxal resin tackiness agent.
This preparation method's the first step starch used is mechanical activation starch, needs to drop into special-purpose starch processing device, can cause the tackiness agent cost to improve; This production of adhesive is in third and fourth step, oxalic dialdehyde is with emulsion copolymerization, when oxalic acid carries out esterification to starch, oxalic dialdehyde, oxalic acid, sodium hydroxide etc. add membership and cause that in reaction system, the fluctuation of pH value and temperature raise, if in these situations, the processing parameter regulation and control are untimely, emulsion can be lumpd by PhastGel, and technology stability is not strong; This production of adhesive for guaranteeing tackiness agent water tolerance and wet bonding strength, makes its bonding property and urea-formaldehyde resin suitable in the 5th step, need to add the higher solidifying agent isocyanic ester of price in the impregnation process, makes the tackiness agent high expensive.
Summary of the invention
The objective of the invention is for overcoming the weak point of prior art, provide a kind of timber with bio oil starch adhesive and preparation method thereof, obtain that a kind of preparation technology is simple, excellent property, the relatively low environmental protection wood adhesive of cost.The property indices of this bio oil starch adhesive and venamul (white glue with vinyl) wood adhesive quite, harmful substance contents and cost be all lower than being at present commercially available high quality white latex, and alternative white glue with vinyl is widely used for wood decoration, wood working and antificielle plate aspect.
Timber of the present invention bio oil starch adhesive is characterized in that, with hydrochloric acid and oxygenant, starch is carried out the acid hydrolysis oxidative sex change, reduces the starch molecule amount, improves its reactive behavior; Add again emulsifying agent and stablizer, and under the initiator effect with acrylamide generation graft copolymerization; Add again bio oil, utilize the materials such as acid in bio oil, aldehyde that chemical group on skeleton structure is modified, obtain tackiness agent host; Add at last linking agent and filler to make the bio oil starch adhesive;
Each feed composition mass parts is as follows: starch 80-120 part, 150 parts of hydrochloric acid, oxygenant 2-5 part, emulsifying agent 1-3 part, stablizer 10-20 part, initiator 0.3-0.6 part, acrylamide 10-20 part, bio oil 5-20 part, linking agent 5-10 part, filler 10-15 part;
Described starch is any one of tapioca (flour), W-Gum, yam starch, wheat starch; Hydrochloric acid is the solution of concentration 0.3-0.6mol/L; Oxygenant or initiator are any one in the ammonium persulphate, Potassium Persulphate, Sodium Persulfate of massfraction 10%; Emulsifying agent is any one or a few combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, sodium butylnaphthalenesulfonate; Stablizer is the polyvinyl alcohol of massfraction 10%, its model be in 1750,1788,1799 any one; Bio oil is under the condition of isolated air or anoxic, adopt medium temperature of reaction (500～650 ℃), high heating rate (103～105 ℃/s) and the utmost point lose heart and biomass (being comprised: wood powder under the condition of the body residence time (less than 2s), agricultural crop straw, bark, shell etc.) carry out thermochemistry and transform the liquid product that obtains, water ratio 35% ?40%, the pH value is 3.5 left and right; Linking agent is oxalic dialdehyde or the glutaraldehyde solution of massfraction 40%; Filler is any one in flour, light calcium carbonate, wilkinite, kaolin.
The preparation method of the bio oil starch adhesive that the present invention proposes comprises the following steps:
The first step: it is 40% starch emulsion that 80-120 part starch is mixed with massfraction with the hydrochloric acid of 150 parts of 0.3-0.6mol/L, and keep three steps of this temperature to the be warming up to 45-55 ℃ in 10min after, add 2-5 part oxygenant, carry out acid hydrolysis oxidative sex change 30-60min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 1-3 part emulsifying agent and 10-20 part massfraction in the acid hydrolysis oxidative modified starch emulsion is 10% stablizer, be that 10% sodium hydroxide is regulated the pH value to 4-5 in 10min with massfraction, divide 3-6 batch and add 10-20 part acrylamide in 30-60min, after continuing reaction 30-60min, add 0.3-0.6 part initiator for reaction 30-60min to obtain graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 4-6 batch and add 5-20 part bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 30-60min, obtain bio oil starch adhesive host;
The 4th step: add 5-10 part linking agent and 10-15 part filler to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.
Advantage applies the following aspects of the present invention
1, the present invention can implement on conventional adhesive producing equipment, does not need additionally to drop into processing units; The inventive method preparation technology is simple, and reaction conditions is gentle, and the processing parameter regulation and control are easy, and technology stability is high; Bio oil starch adhesive of the present invention does not need the solidifying agent isocyanic ester that adds price higher, and bonding property is suitable with the common white latex.
2, the main raw material of the inventive method employing is cheap and reproducible starch and bio oil, does not substantially discharge toxic and harmful, has good environment compatibility; This tackiness agent is with respect to the common white latex, and total volatile organism is lower, and environmental-protecting performance is more excellent.
3, the inventive method is by graft acrylamide side chain on starch molecule, form the basic skeleton structure of tackiness agent host, and the effect by the linking agent dialdehyde, forming stable reticulated structure between starch molecule and between grafted branches, make this tackiness agent have good bonding property, its dry compression shearing resistance and wet compression shearing resistance of glueing joint goods is suitable with the common white latex, compares with the common white latex to have higher price-performance ratio.
4, in the bio oil starch adhesive system that obtains of the present invention owing to having polyphenol, acid, the aldehyde material of being introduced by bio oil and having neither part nor lot in a small amount of dialdehyde of crosslinking reaction, these materials have fine fungistatic effect, and be equivalent to add compound preservative in adhesive system, efficiently solve the starch-based glue stick and meet the difficult problem that tide easily goes mouldy.
Embodiment
The timber that the present invention the proposes preparation method of bio oil starch adhesive, each constituent mass part in its raw material is as follows:
Starch 80-120 part, 150 parts of hydrochloric acid, oxygenant 2-5 part, emulsifying agent 1-3 part, stablizer 10-20 part, initiator 0.3-0.6 part, acrylamide 10-20 part, bio oil 5-20 part, linking agent 5-10 part, filler 10-15 part; Described starch is any one of tapioca (flour), W-Gum, yam starch, wheat starch; Hydrochloric acid is the solution of concentration 0.3-0.6mol/L; Oxygenant or initiator are any one in the ammonium persulphate, Potassium Persulphate, Sodium Persulfate solution of massfraction 10%; Emulsifying agent is any one or a few combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, sodium butylnaphthalenesulfonate; Stablizer is the polyvinyl alcohol of massfraction 10%, its model be in 1750,1788,1799 any one; Bio oil is under the condition of isolated air or anoxic, adopt medium temperature of reaction (500～650 ℃), high heating rate (103～105 ℃/s) and the utmost point lose heart and biomass (being comprised: wood powder under the condition of the body residence time (less than 2s), agricultural crop straw, bark, shell etc.) carry out thermochemistry and transform the liquid product that obtains, water ratio 35% ?40%, the pH value is 3.5 left and right; Linking agent is oxalic dialdehyde or the glutaraldehyde solution of massfraction 40%; Filler is any one in flour, light calcium carbonate, wilkinite, kaolin; Acrylamide is the commercially available prod.
The preparation method of the bio oil starch adhesive that the present invention proposes comprises the following steps:
The first step: it is 40% starch emulsion that 80-120 part starch is mixed with massfraction with the hydrochloric acid of 150 parts of 0.3-0.6mol/L, and keep three steps of this temperature to the be warming up to 45-55 ℃ in 10min after, add 2-5 part oxygenant, carry out acid hydrolysis oxidative sex change 30-60min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 1-3 part emulsifying agent and 10-20 part massfraction in the acid hydrolysis oxidative modified starch emulsion is 10% stablizer, be that 10% sodium hydroxide is regulated the pH value to 4-5 in 10min with massfraction, divide 3-6 batch and add 10-20 part acrylamide in 30-60min, after continuing reaction 30-60min, add 0.3-0.6 part initiator for reaction 30-60min to obtain graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 4-6 batch and add 5-20 part bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 30-60min, obtain bio oil starch adhesive host;
The 4th step: add 5-10 part linking agent and 10-15 part filler to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.
Embodiment 1
Each feed composition mass parts of the present embodiment is as follows: 80 parts of tapioca (flour)s, 150 parts of hydrochloric acid, 2 parts, ammonium persulphate oxygenant, 1 part of sodium lauryl sulphate emulsifying agent, 10 parts of polyvinyl alcohol stablizers, 0.3 part of ammonium persulfate initiator, 10 parts of acrylamides, 5 parts of bio oil, 5 parts of oxalic dialdehyde linking agents, 10 parts of flour fillers;
The preparation method of the bio oil starch adhesive of the present embodiment comprises the following steps:
The first step: it is 40% starch emulsion that 80 portions of tapioca (flour)s are mixed with massfraction with the hydrochloric acid of 150 parts of 0.3mol/L, and be warming up to 45 ℃ and keep three steps of this temperature to the in 10min, adding 2 parts of massfractions is 10% ammonium persulfate solution, carry out acid hydrolysis oxidative sex change 30min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 1 part of sodium lauryl sulphate and 10 parts of massfractions in the acid hydrolysis oxidative modified starch emulsion is 10% 1750 type polyvinyl alcohol solutions, be that 10% sodium hydroxide is regulated pH value to 4 in 10min with massfraction, divide 3 batches and add 10 parts of acrylamides in 30min, after continuing reaction 30min, adding 0.3 part of massfraction is that 10% ammonium persulfate solution reaction 30min obtains graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 4 batches and add 5 parts of bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 30min, obtain bio oil starch adhesive host;
The 4th step: add 5 parts of oxalic dialdehydes and 10 parts of flour to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.The gained tackiness agent is light yellow, good fluidity, and dry compression shearing resistance is 8.12MPa, the wet compression shearing resistance is 3.27MPa.
Embodiment 2
Each feed composition mass parts of the present embodiment is as follows: 100 parts of W-Gums, 150 parts of hydrochloric acid, 3 parts of potassium persulfate oxidation agent, 2 parts of Sodium dodecylbenzene sulfonate emulsifying agents, 15 parts of polyvinyl alcohol stablizers, 0.4 part of Potassium Persulphate initiator, 15 parts of acrylamides, 10 parts of bio oil, 7.5 parts of glutaraldehyde cross-linking agent, 15 parts of light calcium carbonate fillers;
The preparation method of bio oil starch adhesive comprises the following steps:
The first step: it is 40% starch emulsion that 100 parts of W-Gums are mixed with massfraction with the hydrochloric acid of 150 parts of 0.4mol/L, and be warming up to 50 ℃ and keep three steps of this temperature to the in 10min, adding 3 parts of massfractions is 10% potassium persulfate solution, carry out acid hydrolysis oxidative sex change 45min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 2 parts of Sodium dodecylbenzene sulfonatees and 15 parts of massfractions in the acid hydrolysis oxidative modified starch emulsion is 10% 1788 type polyvinyl alcohol solutions, be that 10% sodium hydroxide is regulated pH value to 4.5 in 10min with massfraction, divide 4 batches and add 15 parts of acrylamides in 45min, after continuing reaction 45min, adding 0.4 part of massfraction is that 10% potassium persulfate solution reaction 45min obtains graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 5 batches and add 10 parts of bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 45min, obtain bio oil starch adhesive host;
The 4th step: add 7.5 parts of glutaraldehyde and 15 parts of light calcium carbonates to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.The gained tackiness agent is light yellow, good fluidity, and dry compression shearing resistance is 8.42MPa, the wet compression shearing resistance is 3.57MPa.
Embodiment 3
Each feed composition mass parts of the present embodiment is as follows: 120 parts of yam starchs, 150 parts of hydrochloric acid, 4 parts, Sodium Persulfate oxygenant, 3 parts of petroleum sodium sulfonate emulsifying agents, 20 parts of polyvinyl alcohol stablizers, 0.5 part of Sodium Persulfate initiator, 20 parts of acrylamides, 15 parts of bio oil, 10 parts of oxalic dialdehyde linking agents, 10 parts of wilkinite fillers;
The preparation method of bio oil starch adhesive comprises the following steps:
The first step: it is 40% starch emulsion that 120 parts of yam starchs are mixed with massfraction with the hydrochloric acid of 150 parts of 0.5mol/L, and be warming up to 55 ℃ and keep three steps of this temperature to the in 10min, adding 4 parts of massfractions is 10% Sodium Persulfate solution, carry out acid hydrolysis oxidative sex change 60min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 3 parts of petroleum sodium sulfonates and 20 parts of massfractions in the acid hydrolysis oxidative modified starch emulsion is 10% 1799 type polyvinyl alcohol solutions, be that 10% sodium hydroxide is regulated pH value to 5 in 10min with massfraction, divide 6 batches and add 20 parts of acrylamides in 60min, after continuing reaction 60min, adding 0.5 part of massfraction is that 10% Sodium Persulfate solution reaction 60min obtains graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 6 batches and add 15 parts of bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 60min, obtain bio oil starch adhesive host;
The 4th step: add 10 parts of oxalic dialdehydes and 10 parts of wilkinites to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.The gained tackiness agent is light yellow, good fluidity, and dry compression shearing resistance is 8.62MPa, the wet compression shearing resistance is 3.69MPa.
Embodiment 4
Each feed composition mass parts of the present embodiment is as follows: 100 parts of wheat starches, 150 parts of hydrochloric acid, 5 parts, ammonium persulphate oxygenant, 2 parts of sodium butylnaphthalenesulfonate emulsifying agents, 15 parts of polyvinyl alcohol stablizers, 0.6 part of ammonium persulfate initiator, 15 parts of acrylamides, 20 parts of bio oil, 10 parts of oxalic dialdehyde linking agents, 15 parts of kaolin fillers;
The preparation method of bio oil starch adhesive comprises the following steps:
The first step: it is 40% starch emulsion that 100 portions of wheat starches are mixed with massfraction with the hydrochloric acid of 150 parts of 0.6mol/L, and be warming up to 50 ℃ and keep three steps of this temperature to the in 10min, adding 5 parts of massfractions is 10% ammonium persulfate solution, carry out acid hydrolysis oxidative sex change 45min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 2 parts of sodium butylnaphthalenesulfonates and 15 parts of massfractions in the acid hydrolysis oxidative modified starch emulsion is 10% 1750 type polyvinyl alcohol solutions, be that 10% sodium hydroxide is regulated pH value to 4.5 in 10min with massfraction, divide 5 batches and add 15 parts of acrylamides in 45min, after continuing reaction 45min, adding 0.4 part of massfraction is that 10% ammonium persulfate solution reaction 45min obtains graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 5 batches and add 10 parts of bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 45min, obtain bio oil starch adhesive host;
The 4th step: add 10 parts of oxalic dialdehydes and 15 parts of kaolin to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.The gained tackiness agent is light yellow, good fluidity, and dry compression shearing resistance is 8.79MPa, the wet compression shearing resistance is 3.77MPa.
Embodiment 5
Each feed composition mass parts of the present embodiment is as follows: 100 parts of tapioca (flour)s, 150 parts of hydrochloric acid, 4 parts, ammonium persulphate oxygenant, 3 parts of emulsifying agents (1 part of sodium lauryl sulphate, 2 parts of petroleum sodium sulfonates), 10 parts of polyvinyl alcohol, 0.4 part of ammonium persulfate initiator, 10 parts of acrylamides, 10 parts of bio oil, 5 parts of oxalic dialdehyde linking agents, 15 parts of flour fillers;
The preparation method of bio oil starch adhesive comprises the following steps:
The first step: it is 40% starch emulsion that 100 portions of tapioca (flour)s are mixed with massfraction with the hydrochloric acid of 150 parts of 0.5mol/L, and be warming up to 50 ℃ and keep three steps of this temperature to the in 10min, adding 4 parts of massfractions is 10% ammonium persulfate solution, carry out acid hydrolysis oxidative sex change 45min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: add 3 parts of emulsifying agents (1 part of sodium lauryl sulphate in acid hydrolysis oxidative modified starch emulsion, 2 parts of petroleum sodium sulfonates) and 10 parts of massfractions be 10% 1750 type polyvinyl alcohol solutions, be that 10% sodium hydroxide is regulated pH value to 4.5 in 10min with massfraction, divide 5 batches and add 10 parts of acrylamides in 45min, after continuing reaction 45min, adding 0.4 part of massfraction is that 10% ammonium persulfate solution reaction 45min obtains graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 5 batches and add 10 parts of bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 45min, obtain bio oil starch adhesive host;
The 4th step: add 10 parts of oxalic dialdehydes and 15 parts of flour to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.The gained tackiness agent is light yellow, good fluidity, and dry compression shearing resistance is 8.82MPa, the wet compression shearing resistance is 3.75MPa.
Claims (3)
1. a timber bio oil starch adhesive, is characterized in that, with hydrochloric acid and oxygenant, starch carried out the acid hydrolysis oxidative sex change, reduces the starch molecule amount, improves its reactive behavior; Add again emulsifying agent and stablizer, and under the initiator effect with acrylamide generation graft copolymerization; Add again bio oil, utilize the materials such as acid in bio oil, aldehyde that chemical group on skeleton structure is modified, obtain tackiness agent host; Add at last linking agent and filler to make the bio oil starch adhesive;
Each feed composition mass parts is as follows: starch 80-120 part, 150 parts of hydrochloric acid, oxygenant 2-5 part, emulsifying agent 1-3 part, stablizer 10-20 part, initiator 0.3-0.6 part, acrylamide 10-20 part, bio oil 5-20 part, linking agent 5-10 part, filler 10-15 part.
2. bio oil starch adhesive as claimed in claim 1, is characterized in that, described starch is any one of tapioca (flour), W-Gum, yam starch, wheat starch; Oxygenant or initiator are any one in the ammonium persulphate, Potassium Persulphate, Sodium Persulfate of massfraction 10%; Emulsifying agent is any one or a few combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, sodium butylnaphthalenesulfonate; Stablizer is the polyvinyl alcohol of massfraction 10%, its model be in 1750,1788,1799 any one; Bio oil is under the condition of isolated air or anoxic, adopt the high heating rate () of 500～650 ℃ of medium temperature of reaction, 103～105 ℃/s and lose heart less than the 2s utmost point and biomass are carried out thermochemistry under the condition of the body residence time and transform the liquid product that obtains, water ratio 35% ?40%, the pH value is 3.5 left and right; Linking agent is oxalic dialdehyde or the glutaraldehyde solution of massfraction 40%.
3. the preparation method of bio oil starch adhesive as claimed in claim 1, is characterized in that, comprises the following steps:
The first step: it is 40% starch emulsion that 80-120 part starch is mixed with massfraction with the hydrochloric acid of 150 parts of 0.3-0.6mol/L, and keep three steps of this temperature to the be warming up to 45-55 ℃ in 10min after, add 2-5 part oxygenant, carry out acid hydrolysis oxidative sex change 30-60min, obtain acid hydrolysis oxidative modified starch emulsion;
Second step: adding 1-3 part emulsifying agent and 10-20 part massfraction in the acid hydrolysis oxidative modified starch emulsion is 10% stablizer, be that 10% sodium hydroxide is regulated the pH value to 4-5 in 10min with massfraction, divide 3-6 batch and add 10-20 part acrylamide in 30-60min, after continuing reaction 30-60min, add 0.3-0.6 part initiator for reaction 30-60min to obtain graft copolymerization modified starch emulsion;
The 3rd step: in graft copolymerization modified starch emulsion, divide 4-6 batch and add 5-20 part bio oil in 20min, be cooled to 40 ℃ with bottom discharge after reaction 30-60min, obtain bio oil starch adhesive host;
The 4th step: add 5-10 part linking agent and 10-15 part filler to carry out impregnation in bio oil starch adhesive host, make timber bio oil starch adhesive.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421454A (en) * | 2013-08-22 | 2013-12-04 | 四川魔力科技有限公司 | Konjac adhesive and preparation method thereof |
| CN104893629A (en) * | 2015-06-16 | 2015-09-09 | 北京林业大学 | Normal-temperature curable bio-oil starch adhesive for wood and preparation method of adhesive |
| CN104910839A (en) * | 2015-06-16 | 2015-09-16 | 北京林业大学 | Regulation and control method for preparation process for bio-oil starch adhesive for wood |
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| CN108641640A (en) * | 2018-04-18 | 2018-10-12 | 海宁玖洲家具有限公司 | The preparation method of furniture environment-friendly adhesive |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845152A (en) * | 1986-05-12 | 1989-07-04 | National Starch And Chemical Corporation | Tape joint compounds utilizing starch stabilized emulsions as binders |
| US5026746A (en) * | 1989-06-26 | 1991-06-25 | Sequa Chemicals, Inc. | Starch based binder composition for non-woven fibers or fabrics |
| CN101805568A (en) * | 2010-03-08 | 2010-08-18 | 北京林业大学 | Bio oil-starch adhesive and preparation method thereof |
| CN102585741A (en) * | 2012-02-16 | 2012-07-18 | 江南大学 | Method for preparing starch adhesive for timber through emulsion polymerization |
| CN102642222A (en) * | 2012-05-03 | 2012-08-22 | 北京林业大学 | Method for preparing aldehyde-free veneer boards by biological oil starch adhesives |
| CN102863933A (en) * | 2012-10-15 | 2013-01-09 | 中南林业科技大学 | High-strength waterproof starch-based wood adhesive and preparation method thereof |
-
2013
- 2013-03-01 CN CN201310065933.4A patent/CN103122228B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845152A (en) * | 1986-05-12 | 1989-07-04 | National Starch And Chemical Corporation | Tape joint compounds utilizing starch stabilized emulsions as binders |
| US5026746A (en) * | 1989-06-26 | 1991-06-25 | Sequa Chemicals, Inc. | Starch based binder composition for non-woven fibers or fabrics |
| CN101805568A (en) * | 2010-03-08 | 2010-08-18 | 北京林业大学 | Bio oil-starch adhesive and preparation method thereof |
| CN102585741A (en) * | 2012-02-16 | 2012-07-18 | 江南大学 | Method for preparing starch adhesive for timber through emulsion polymerization |
| CN102642222A (en) * | 2012-05-03 | 2012-08-22 | 北京林业大学 | Method for preparing aldehyde-free veneer boards by biological oil starch adhesives |
| CN102863933A (en) * | 2012-10-15 | 2013-01-09 | 中南林业科技大学 | High-strength waterproof starch-based wood adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 时君友等: ""木材乳液胶黏剂用复合变性玉米淀粉乳液"", 《林业科学》, vol. 45, no. 6, 30 June 2009 (2009-06-30), pages 121 - 126 * |
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| CN108641640A (en) * | 2018-04-18 | 2018-10-12 | 海宁玖洲家具有限公司 | The preparation method of furniture environment-friendly adhesive |
| WO2020052116A1 (en) * | 2018-09-14 | 2020-03-19 | 江南大学 | Thermosetting starch adhesive for man-made board, and manufacturing method therefor |
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