CN104893629A - Normal-temperature curable bio-oil starch adhesive for wood and preparation method of adhesive - Google Patents
Normal-temperature curable bio-oil starch adhesive for wood and preparation method of adhesive Download PDFInfo
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- CN104893629A CN104893629A CN201510332706.2A CN201510332706A CN104893629A CN 104893629 A CN104893629 A CN 104893629A CN 201510332706 A CN201510332706 A CN 201510332706A CN 104893629 A CN104893629 A CN 104893629A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 79
- 239000012075 bio-oil Substances 0.000 title claims abstract description 78
- 239000008107 starch Substances 0.000 title claims abstract description 74
- 235000019698 starch Nutrition 0.000 title claims abstract description 74
- 239000000853 adhesive Substances 0.000 title claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002023 wood Substances 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 125000003636 chemical group Chemical group 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000000839 emulsion Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229920000881 Modified starch Polymers 0.000 claims description 28
- 239000004368 Modified starch Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 235000019426 modified starch Nutrition 0.000 claims description 28
- 238000004513 sizing Methods 0.000 claims description 24
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000032050 esterification Effects 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 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 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 5
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 229940100445 wheat starch Drugs 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 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 abstract 1
- 230000002335 preservative effect Effects 0.000 abstract 1
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000010008 shearing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- -1 bark Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a normal-temperature curable bio-oil starch adhesive for wood and a preparation method and belongs to the technical field of adhesive preparation. According to the method, bio-oil has a catalytic esterification reaction under the action of strong-acid cation exchange resin, and a monomer of a starch graft copolymerization reaction is obtained; the starch is modified with an acidolysis oxidation and graft copolymerization composite method, and an adhesive base resin framework is formed; the bio-oil is added to modify chemical groups on the adhesive base resin framework and can be used as aids such as filler, a preservative and the like, and the bio-oil starch adhesive is prepared. The starch adhesive has the advantages of normal-temperature curing, environment-friendliness, low cost, good adhesion property, high water resistance and excellent storage stability.
Description
Technical field
The invention belongs to sizing agent preparing technical field, particularly a kind of preparation method of timber ambient cure bio oil starch adhesive.
Background technology
Today that day by day exhausted and environmental consciousness is constantly strengthened at petroleum resources, with renewable natural polymer child resource cheap and easy to get for main raw material, adopt novel environment-friendly process, develop high-performance environment-friendly sizing agent and become a kind of trend.Starch adhesive raw material sources are extensive, cheap, nontoxic, environmental protection, are considered to one of the most potential sizing agent, are widely used in the non-structural such as indoor, house ornamentation integrated timber field.
But compared with synthetic resin sizing agent, starch adhesive exists the shortcomings such as poor water resistance, poor storage stability, bonding strength be low, limit its range of application in timber industry.For starch adhesive Problems existing, method of modifying main is at present by oxidation, gelatinization, esterification, grafting, the means such as crosslinked, reduce the hydrophilic radical quantity on starch molecule and introduce other active group, thus reduce the wetting ability of starch adhesive, improve its bonding strength and storge quality.As patent (application number: 201010568522.3) take starch as raw material, after carrying out acidolysis gelatinization pre-treatment, under the condition of emulsifying agent, adopt vinyl acetate and butyl acrylate two kinds of monomers to carry out grafting, copolymerization and modification to starch, add auxiliary agent after cooling, prepared that a kind of bonding strength is high, the environment-friendly type starch glue for lumber of water-tolerant sticks agent; Patent (application number: 201410074081.X) utilizes hypochlorite oxidation starch emulsion, and under linking agent effect with acrylamide and acrylate monomer graft copolymerization, add filler and sanitas after cooling to prepare environment-friendly type starch glue for lumber and stick agent, there is good stability in storage, water tolerance and bonding strength.
But numerous starch adhesive method of modifying mainly concentrates on the aspects such as water tolerance, bonding strength and the stability in storage improving starch adhesive, and less to the ambient cure Study on Problems of starch adhesive.Meanwhile, in starch adhesive preparation process, add a large amount of auxiliary agents, cause starch adhesive to there is the higher problem of cost.
Summary of the invention
The object of the invention is the weak point for overcoming prior art, a kind of timber ambient cure bio oil starch adhesive and preparation method are proposed, product liquid-the bio oil obtained by utilizing Wooden Biomass fast pyrogenation, the novel timber ambient cure starch adhesive prepare a kind of environmental protection, with low cost, cohesiveness good, water tolerance is strong, having excellent storage stability.
The present invention adopts following technical scheme:
The timber ambient cure bio oil starch adhesive that the present invention proposes, is characterized in that, adopts storng-acid cation exchange resin to carry out catalytic esterification to bio oil, obtains the monomer of starch graft copolymer reaction; Adopt the method treated starch of acid hydrolysis oxidative, graft copolymerization compound, form sizing agent host skeleton; By adding bio oil, modifying chemical group on sizing agent host skeleton, simultaneously as the auxiliary agent such as filler, sanitas, being prepared into bio oil starch adhesive.
Above-mentioned bio oil starch adhesive each feed composition mass parts is as follows: bio oil 120 parts, dehydrated alcohol 160-200 part, catalyzer 8-10 part, starch 100 parts, hydrochloric acid 140-160 part, oxygenant 2-4 part, emulsifying agent 1-3 part, stablizer 10-30 part, initiator 0.3-0.7 part, vinyl acetate 10-20 part, butyl acrylate 5-15 part.
Described bio oil is under the condition of anaerobic or anoxic, adopts medium temperature of reaction (500-600 DEG C), high heating rate (10
3-10
5dEG C/s) and extremely short gas residence time (being less than 2s) biomass (comprising: wood powder, agricultural crop straw, bark, shell etc.) are carried out the liquid product that thermochemical study obtains, water ratio is 20%-30%, and pH value is 2.5-3.5;
Catalyzer is storng-acid cation exchange resin, and its model is 732, one in NKC-9, D072; Starch is any one in W-Gum, tapioca (flour) or wheat starch;
The hydrochloric acid soln of hydrochloric acid to be concentration be 0.3-0.5mol/L;
Oxygenant and initiator are ammonium persulphate, Potassium Persulphate, any one in Sodium Persulfate that massfraction is 15%;
Emulsifying agent is any one or combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10;
Stablizer to be massfraction be 8% polyvinyl alcohol, its model is any one in 1750,1788,1799.
The timber preparation method of ambient cure bio oil starch adhesive that the present invention proposes, mainly comprises the following steps:
The first step: after 80-100 part bio oil and 160-200 part dehydrated alcohol being mixed completely, join in bio oil reaction kettle of the esterification, add 8-10 part catalyzer, heat 4-5 hour in the water bath with thermostatic control of 50-60 DEG C, cooling discharge obtains bio oil esterification products; Again with 10-20 part vinyl acetate, 5-15 part butyl acrylate mixes, and obtains grafted monomer mixed solution.
Second step: the hydrochloric acid of 100 parts of starch 140-160 part 0.3-0.5mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and 50-55 DEG C is warming up in 10-15min, and keep this temperature to the 3rd step, add 2-4 part oxygenant, carry out acid hydrolysis oxidative sex change 30-50min, obtain acid hydrolysis oxidative modified starch emulsion; 1-3 part emulsifying agent is added again and 10-30 part massfraction is the stablizer of 8% in acid hydrolysis oxidative modified starch emulsion, in 5-10min, pH to 2-3 is regulated with the sodium hydroxide solution that massfraction is 20%, in 1-2h, divide 2-4 batch add 40-60 part grafted monomer mixed solution, after continuing reaction 0.5-1h, add 0.4-0.6 part initiator for reaction 1-2h and obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 3-5 batch and adds 20-40 part bio oil in 10-20min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 30-50min.
Advantage applies of the present invention is in the following aspects:
1. the main raw material that the inventive method adopts is cheap and reproducible starch and bio oil, and asepsis environment-protecting, has good environment compatibility;
2. the present invention utilizes a large amount of low-molecular-weight organic carboxyl acid in bio oil, as formic acid, acetic acid etc., under storng-acid cation exchange resin condition, catalytic esterification is carried out with dehydrated alcohol, obtain the low molecule ester compound with ambient cure characteristic, can be used as the main component of starch ambient cure grafted monomer; , mix with vinyl acetate, butyl acrylate, the grafted monomer mixed solution obtaining starch has higher percentage of grafting and good ambient cure effect meanwhile;
3. there is the material such as phenols, acids, aldehydes introduced by bio oil in the bio oil starch adhesive system that the present invention obtains, aldehyde radical, carboxyl polymerization reaction take place wherein in aldehydes matter and starch molecule, the tack of increase sizing agent; Acid can with starch generation esterification, reduce hydroxyl quantity, improve water tolerance; Aldehydes mass-energy and starch generation crosslinking reaction, can improve the bonding property of sizing agent;
4. the material such as phenols, acids, aldehydes contained in bio oil used in the present invention has good fungistatic effect, can be used as sanitas and uses; Meanwhile, bio oil add the solidification value that can reduce sizing agent, improve curing speed, increase sizing agent perviousness, make sizing agent have good use properties, can be used as solidifying agent and thinner uses; Other materials contained in bio oil can be used as the auxiliary agents such as filler and use.Adding of bio oil, decrease the use of chemical feedstocks, reduce the cost of starch adhesive.
Embodiment
A kind of timber ambient cure bio oil starch adhesive that the present invention proposes and preparation method, its raw material is composed as follows:
Bio oil 120 parts, dehydrated alcohol 160-200 part, catalyzer 8-10 part, starch 100 parts, hydrochloric acid 140-160 part, oxygenant 2-4 part, emulsifying agent 1-3 part, stablizer 10-30 part, initiator 0.3-0.7 part, vinyl acetate 10-20 part, butyl acrylate 5-15 part.
Described bio oil is under the condition of anaerobic or anoxic, adopts medium temperature of reaction (500-600 DEG C), high heating rate (10
3-10
5dEG C/s) and extremely short gas residence time (being less than 2s) biomass (comprising: wood powder, agricultural crop straw, bark, shell etc.) are carried out the liquid product that thermochemical study obtains, water ratio is 20%-30%, and pH value is 2.5-3.5; Catalyzer is storng-acid cation exchange resin, and its model is 732, one in NKC-9, D072; Starch is any one in W-Gum, tapioca (flour) or wheat starch; The hydrochloric acid soln of hydrochloric acid to be concentration be 0.3-0.5mol/L; Oxygenant and initiator are ammonium persulphate, Potassium Persulphate, any one in Sodium Persulfate that massfraction is 15%; Emulsifying agent is any one or combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10; Stablizer to be massfraction be 8% polyvinyl alcohol, its model is any one in 1750,1788,1799.
The preparation method of a kind of timber ambient cure bio oil starch adhesive that the present invention proposes, comprises the following steps:
The first step: after 80-100 part bio oil and 160-200 part dehydrated alcohol being mixed completely, join in bio oil reaction kettle of the esterification, add 8-10 part catalyzer, heat 4-5 hour in the water bath with thermostatic control of 50-60 DEG C, cooling discharge obtains bio oil esterification products; Again with 10-20 part vinyl acetate, 5-15 part butyl acrylate mixes, and obtains grafted monomer mixed solution.
Second step: the hydrochloric acid of 100 parts of starch 140-160 part 0.3-0.5mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and 50-55 DEG C is warming up in 10-15min, and keep this temperature to the 3rd step, add 2-4 part oxygenant, carry out acid hydrolysis oxidative sex change 30-50min, obtain acid hydrolysis oxidative modified starch emulsion; 1-3 part emulsifying agent is added again and 10-30 part massfraction is the stablizer of 8% in acid hydrolysis oxidative modified starch emulsion, in 5-10min, pH to 2-3 is regulated with the sodium hydroxide solution that massfraction is 20%, in 1-2h, divide 2-4 batch add 40-60 part grafted monomer mixed solution, after continuing reaction 0.5-1h, add 0.4-0.6 part initiator for reaction 1-2h and obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 3-5 batch and adds 20-40 part bio oil in 10-20min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 30-50min.
Describe the present invention below in conjunction with specific embodiment.
Embodiment 1
The present embodiment each feed composition mass parts is as follows: bio oil 120 parts, dehydrated alcohol 160 parts, 732 strong acid cation exchange resin catalysts 8 parts, W-Gum 100 parts, hydrochloric acid 140 parts, ammonium persulfate oxidizing agent 2 parts, sodium laurylsulfonate emulsifying agent 1 part, the polyvinyl alcohol stablizer of 1,750 10 parts, ammonium persulfate initiator 0.3 part, vinyl acetate 10 parts, butyl acrylate 15 parts.
The timber preparation method of ambient cure bio oil starch adhesive of the present embodiment, comprises the following steps:
The first step: after 80 parts of bio oil and 160 parts of dehydrated alcohols are mixed completely, join in bio oil reaction kettle of the esterification, add 8 parts of catalyzer, heat 4 hours in the water bath with thermostatic control of 60 DEG C, cooling discharge obtains bio oil esterification products; Again with 10 parts of vinyl acetates, 15 parts of butyl acrylate mixing, obtain grafted monomer mixed solution.
Second step: 100 parts of W-Gums hydrochloric acid of 140 parts of 0.5mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and in 15min, be warming up to 55 DEG C, and keep this temperature to the 3rd step, adding 2 parts of massfractions is the ammonium persulphate of 15%, carry out acid hydrolysis oxidative sex change 30min, obtain acid hydrolysis oxidative modified starch emulsion; Add in acid hydrolysis oxidative modified starch emulsion again 1 part of sodium laurylsulfonate and 10 parts of massfractions be 8% model be the polyvinyl alcohol of 1750, in 5min, pH to 2 is regulated with the sodium hydroxide that massfraction is 20%, in 1h, divide 2 batches add 40 portions of grafted monomer mixed solutions, continue reaction 0.5h after, add 0.4 part of massfraction be 15% ammonium persulphate reaction 1h obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 5 batches and adds 40 parts of bio oil in 20min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 50min.
Gained sizing agent is light yellow, good fluidity, dry compression shearing resistance 9.43MPa, and wet compression shearing resistance 3.66MPa reaches 61 days storage period.
Embodiment 2
The present embodiment each feed composition mass parts is as follows: bio oil 120 parts, dehydrated alcohol 180 parts, NKC-9 strong acid cation exchange resin catalyst 9 parts, tapioca (flour) 100 parts, hydrochloric acid 150 parts, 3 parts, oxygenant, emulsifying agent 2 parts, stablizer 20 parts, initiator 0.5 part, vinyl acetate 15 parts, butyl acrylate 10 parts.
The timber preparation method of ambient cure bio oil starch adhesive of the present embodiment, comprises the following steps:
The first step: after 90 parts of bio oil and 180 parts of dehydrated alcohols are mixed completely, join in bio oil reaction kettle of the esterification, add 9 parts of NKC-9 storng-acid cation exchange resins, heat 5 hours in the water bath with thermostatic control of 55 DEG C, cooling discharge obtains bio oil esterification products; Again with 15 parts of vinyl acetates, 10 parts of butyl acrylate mixing, obtain grafted monomer mixed solution.
Second step: 100 portions of tapioca (flour)s hydrochloric acid of 150 parts of 0.4mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and in 10min, be warming up to 50 DEG C, and keep this temperature to the 3rd step, adding 3 parts of massfractions is the Potassium Persulphate of 15%, carry out acid hydrolysis oxidative sex change 40min, obtain acid hydrolysis oxidative modified starch emulsion; Add in acid hydrolysis oxidative modified starch emulsion again 2 parts of Sodium dodecylbenzene sulfonatees and 20 parts of massfractions be 8% model be the polyvinyl alcohol of 1788, in 10min, pH to 2.5 is regulated with the sodium hydroxide solution that massfraction is 20%, in 1.5h, divide 3 batches add 50 portions of grafted monomer mixed solutions, continue reaction 1h after, add 0.5 part of massfraction be 15% Potassium Persulphate reaction 1h obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 4 batches and adds 30 parts of bio oil in 15min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 40min.
Gained sizing agent is light yellow, good fluidity, dry compression shearing resistance 9.28MPa, and wet compression shearing resistance 3.45MPa reaches 56 days storage period.
Embodiment 3
The present embodiment each feed composition mass parts is as follows: bio oil 120 parts, dehydrated alcohol 200 parts, D072 strong acid cation exchange resin catalyst 10 parts, wheat starch 100 parts, hydrochloric acid 160 parts, 4 parts, Sodium Persulfate oxygenant, OP-10 emulsifying agent 3 parts, model is the polyvinyl alcohol stablizer 30 parts of 1799, Sodium Persulfate initiator 0.7 part, vinyl acetate 20 parts, butyl acrylate 5 parts.
The timber preparation method of ambient cure bio oil starch adhesive of the present embodiment, comprises the following steps:
The first step: after 100 parts of bio oil and 200 parts of dehydrated alcohols are mixed completely, join in bio oil reaction kettle of the esterification, add 10 parts of D072 storng-acid cation exchange resins, heat 5 hours in the water bath with thermostatic control of 50 DEG C, cooling discharge obtains bio oil esterification products; Again with 20 parts of vinyl acetates, 5 parts of butyl acrylate mixing, obtain grafted monomer mixed solution.
Second step: 100 portions of wheat starches hydrochloric acid of 160 parts of 0.3mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and in 10min, be warming up to 50 DEG C, and keep this temperature to the 3rd step, add 4 parts of oxygenants, carry out acid hydrolysis oxidative sex change 50min, obtain acid hydrolysis oxidative modified starch emulsion; Add in acid hydrolysis oxidative modified starch emulsion again 3 parts of OP-10 and 30 part massfractions be 8% model be the polyvinyl alcohol of 1799, in 5min, pH to 3 is regulated with the sodium hydroxide solution that massfraction is 20%, in 2h, divide 4 batches add 60 portions of grafted monomer mixed solutions, continue reaction 1h after, add 0.6 part of massfraction be 15% Sodium Persulfate reaction 2h obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 3 batches and adds 20 parts of bio oil in 10min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 30min.
Gained sizing agent is light yellow, good fluidity, dry compression shearing resistance 9.37MPa, and wet compression shearing resistance 3.56MPa reaches 59 days storage period.
Embodiment 4
The present embodiment each feed composition mass parts is as follows: bio oil 120 parts, dehydrated alcohol 160 parts, 732 strong acid cation exchange resin catalysts 8 parts, starch 100 parts, hydrochloric acid 150 parts, ammonium persulfate oxidizing agent 3 parts, the mixed solution emulsifying agent of sodium lauryl sulphate and OP-10 2 parts, the polyvinyl alcohol stablizer of 1,750 20 parts, ammonium persulfate initiator 0.5 part, vinyl acetate 15 parts, butyl acrylate 10 parts.
The timber preparation method of ambient cure bio oil starch adhesive of the present embodiment, comprises the following steps:
The first step: after 80 parts of bio oil and 160 parts of dehydrated alcohols are mixed completely, join in bio oil reaction kettle of the esterification, add 8 parts of catalyzer, heat 5 hours in the water bath with thermostatic control of 55 DEG C, cooling discharge obtains bio oil esterification products; Again with 15 parts of vinyl acetates, 10 parts of butyl acrylate mixing, obtain grafted monomer mixed solution.
Second step: 100 parts of starch hydrochloric acid of 150 parts of 0.5mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and in 15min, be warming up to 55 DEG C, and keep this temperature to the 3rd step, adding 3 parts of massfractions is the ammonium persulphate of 15%, carry out acid hydrolysis oxidative sex change 40min, obtain acid hydrolysis oxidative modified starch emulsion; Add in acid hydrolysis oxidative modified starch emulsion again the mixed solution of 2 parts of sodium lauryl sulphate and OP-10 and 20 parts of massfractions be 8% model be the polyvinyl alcohol of 1750, in 10min, pH to 2.5 is regulated with the sodium hydroxide solution that massfraction is 20%, in 2h, divide 4 batches add 60 portions of grafted monomer mixed solutions, continue reaction 1h after, add 0.5 part of massfraction be 15% ammonium persulphate reaction 2h obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 4 batches and adds 40 parts of bio oil in 20min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 50min.
Gained sizing agent is light yellow, good fluidity, dry compression shearing resistance 9.56MPa, and wet compression shearing resistance 3.72MPa reaches 65 days storage period.
Claims (9)
1. a timber ambient cure bio oil starch adhesive, is characterized in that, adopts storng-acid cation exchange resin to carry out catalytic esterification to bio oil, obtains the monomer of starch graft copolymer reaction; Adopt the method treated starch of acid hydrolysis oxidative, graft copolymerization compound, form sizing agent host skeleton; By adding bio oil, modifying chemical group on sizing agent host skeleton, simultaneously as the auxiliary agent such as filler, sanitas, being prepared into bio oil starch adhesive.
2. the preparation method of bio oil starch adhesive as claimed in claim 1, it is characterized in that, preparation method comprises the steps:
The first step: after 80-100 part bio oil and 160-200 part dehydrated alcohol being mixed completely, join in bio oil reaction kettle of the esterification, add 8-10 part catalyzer, heat 4-5 hour in the water bath with thermostatic control of 50-60 DEG C, cooling discharge obtains bio oil esterification products; Again with 10-20 part vinyl acetate, 5-15 part butyl acrylate mixes, and obtains grafted monomer mixed solution;
Second step: the hydrochloric acid of 100 parts of starch 140-160 part 0.3-0.5mol/L is configured to the starch emulsion that massfraction is 40%, pour in sizing agent reactor, and 50-55 DEG C is warming up in 10-15min, and keep this temperature to the 3rd step, add 2-4 part oxygenant, carry out acid hydrolysis oxidative sex change 30-50min, obtain acid hydrolysis oxidative modified starch emulsion; 1-3 part emulsifying agent is added again and 10-30 part massfraction is the stablizer of 8% in acid hydrolysis oxidative modified starch emulsion, in 5-10min, pH to 2-3 is regulated with the sodium hydroxide solution that massfraction is 20%, in 1-2h, divide 2-4 batch add 40-60 part grafted monomer mixed solution, after continuing reaction 0.5-1h, add 0.4-0.6 part initiator for reaction 1-2h and obtain graft copolymerization modified starch emulsion;
3rd step: in graft copolymerization modified starch emulsion, divides 3-5 batch and adds 20-40 part bio oil in 10-20min, is cooled to 40 DEG C with bottom discharge, obtains timber ambient cure bio oil starch adhesive after reaction 30-50min.
3. preparation method as claimed in claim 2, is characterized in that, described bio oil is under the condition of anaerobic or anoxic, adopts medium temperature of reaction 500-600 DEG C, high heating rate 10
3-10
5dEG C/biomass are carried out the liquid product that thermochemical study obtains by s and the short gas residence time that is less than 2s, and water ratio is 20%-30%, and pH value is 2.5-3.5.
4. preparation method as claimed in claim 2, it is characterized in that, described catalyzer is storng-acid cation exchange resin, and its model is 732, one in NKC-9, D072.
5. preparation method as claimed in claim 2, is characterized in that, described starch is any one in W-Gum, tapioca (flour) or wheat starch.
6. preparation method as claimed in claim 2, is characterized in that, the hydrochloric acid soln of described hydrochloric acid to be concentration be 0.3-0.5mol/L.
7. preparation method as claimed in claim 2, is characterized in that, described oxygenant and initiator are ammonium persulphate, Potassium Persulphate, any one in Sodium Persulfate that massfraction is 15%.
8. preparation method as claimed in claim 2, is characterized in that, described emulsifying agent is any one or combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10.
9. preparation method as claimed in claim 2, is characterized in that, described stablizer to be massfraction be 8% polyvinyl alcohol.
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| CN108165216A (en) * | 2017-12-07 | 2018-06-15 | 明光市永德包装有限公司 | A kind of high stability carton starch adhesive |
| US11365330B2 (en) | 2020-04-09 | 2022-06-21 | The University Of Western Ontario | Process for the production of bio-based formaldehyde-free wood adhesives from lignocellulosic biomass |
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| CN105062390A (en) * | 2015-09-23 | 2015-11-18 | 句容市兴武包装有限公司 | Preparation method of adhesive for metal material packaging |
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| CN106634733A (en) * | 2016-10-29 | 2017-05-10 | 常州亚环环保科技有限公司 | Method for preparing plate alignment adhesive free of residual gel |
| CN108165216A (en) * | 2017-12-07 | 2018-06-15 | 明光市永德包装有限公司 | A kind of high stability carton starch adhesive |
| US11365330B2 (en) | 2020-04-09 | 2022-06-21 | The University Of Western Ontario | Process for the production of bio-based formaldehyde-free wood adhesives from lignocellulosic biomass |
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