CN102732186A - Modified starch adhesive and method for preparing same - Google Patents
Modified starch adhesive and method for preparing same Download PDFInfo
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- CN102732186A CN102732186A CN2012102413279A CN201210241327A CN102732186A CN 102732186 A CN102732186 A CN 102732186A CN 2012102413279 A CN2012102413279 A CN 2012102413279A CN 201210241327 A CN201210241327 A CN 201210241327A CN 102732186 A CN102732186 A CN 102732186A
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Abstract
The invention discloses a modified starch adhesive and a method for preparing the same. The modified starch adhesive comprises the following components by weight: 30-50 parts of corn starch, 80-120 parts of deionized water, 25-40 parts of sodium hypochlorite solution, 0.5-2 parts of epichlorohydrin, 30-70 parts of polyvinyl acetate emulsion, 10-30 parts of epoxy resin, 2-7 parts of tertiary amine catalyst, 5-15 parts of filler, 0.2-1 part of surfactant, and 0.2-0.6 part of preservative, wherein the sodium hypochlorite solution serves as the oxidant, the polyvinyl acetate emulsion serves as the high-cohesive-energy reinforcement component, and the epoxy resin servers as the water-tolerant modified component. The method for preparing the modified starch adhesive comprises the following steps: mixing the oxidized starch emulsion prepared in advance, the polyvinyl acetate emulsion and the epoxy resin according to proportion uniformly, adding the catalyst, the filler and the preservative, and stirring quickly and uniformly. The modified starch adhesive disclosed by the invention has the advantages of high shear strength, high water-tolerant shear strength, moderate viscosity, good liquidity, moderate primary drying time, low cost and excellent integrated performance.
Description
Technical field
The present invention relates to starch adhesive of a kind of modification and preparation method thereof.Being specifically related to the Sumstar 190 emulsion is that main glue, PVA are that high cohesion ability enhancement component, epoxy resin are water-fast properties-correcting agent; A kind of new modified starch adhesive that adds stablizer, weighting agent, sanitas and prepare belongs to the wood adhesive preparation field.
Background technology
China is a grain big country, and the W-Gum aboundresources is cheap.Starch is applied as a certain modified component of classical tackiness agent already; Treated starch uses as tackiness agent, also in the production of Corrugated Box, obtains widespread use.Starch is the homopolymer that is formed by D-glucose monomer dehydrating condensation, and molecular weight is 10
6～10
7The order of magnitude.C at each glucose unit
2, C
3And C
6On a hydroxyl is respectively arranged, thereby contain into hundreds of thousands of on each starch molecular chain and arrive up to a million hydroxyls, form a large amount of intramolecularly, intermolecular ydrogen bonding.The existence of a large amount of hydrogen bonds makes it possess the condition that becomes tackiness agent in the starch molecule.But hydrogen bond action power is compared with chemical bonding force and is wanted much weak, and its bond strength does not reach application requiring.So, need through in starch molecular chain, introducing a large amount of equally distributed chemical bonds, it is effectively cooperated with the reduction reactive force of on every side hydrogen bond, just can reach the bond strength requirement.And a large amount of hydroxyl on the starch molecular chain very easily forms hydrogen bond with water, and water tolerance is very poor, and this is the main reason that amylan is used widely at present not yet.
In the starch molecule, intermolecularly contain a large amount of hydrogen bonds, make starch be insoluble to cold water, the heavy property of its aqueous solution anti-freezing is poor, starch very easily is precipitated out from its aqueous solution, can not stable existence.Traditional method generally adopts means such as heating gelatinization, alkaline purification, acid hydrolysis oxidative processing, hydrogen peroxide oxidation processing to improve the stability of amidin.After the heating gelatinization, the viscosity of starch sharply increases, mobile variation, applying glue difficulty.The starch solution that adopts sodium hydroxide solution to handle, modest viscosity, right good fluidity, but the starch color is a tawny, influences the transparency of bonding interface.Hydrochloric acid is done acidolysis agent, ammonium persulphate, and to do the acid hydrolysis oxidative starch solution viscosity of oxidizer treatment less, but excessive hydrolysis and degree of oxidation is not high.Moderate, the good fluidity of hydrogen peroxide oxidation starch viscosity, colour-change is little, but ydrogen peroxide 50 to the oxidation of starch reaction needed under alkaline condition with Fe
2+Be catalyzer, Fe
2+Under alkaline condition, precipitate easily, reaction pair system Ph has relatively high expectations, and is difficult to control.
Contain a large amount of hydroxyls on the starch molecular chain, very easily form hydrogen bond with water, water tolerance is very poor, and this is the major reason that amylan is difficult to promote in the wood bonding field.Usually adopt small molecules linking agents such as isocyanic ester, formaldehyde, epoxy chloropropane,, improve the water resistance of starch adhesive with hydroxyl generation crosslinking reaction on the starch molecular chain.Isocyanic ester costs an arm and a leg, active isocyanate groups easily with the water reaction, cause waste, finally and the crosslinked amount of isocyanate of starch hydroxyl seldom, water-fast modified effect is not obvious.Formaldehyde is done under catalyzer, the hot conditions at the vitriol oil, and with hydroxyl generation dehydrated crosslinking reaction on the starch molecular chain, the water tolerance and the cohesive strength of starch adhesive are more satisfactory.But formaldehyde has serious threat to direct labor's vision system and respiratory system, and, wood veneer, furniture that the amylan that adopts formaldehyde to make linking agent is produced, the formaldehyde that retains is very big to the pollution of human body and environment.Experiment showed, in a large number epoxy chloropropane can with starch generation crosslinking reaction, between starch molecular chain, introduce equally distributed chemical bond, cooperates the cohesive strength of raising starch adhesive, but can not improve the water tolerance of starch adhesive with a large amount of hydrogen bonds on every side.Through graft reaction, on starch molecular chain, introduce bond strength and the water tolerance that the high hydrophobic grouping of internal cohesive energy improves simultaneously starch adhesive, become the main direction of present modified starch adhesive.Generally, the grafted chain of high cohesion ability mostly is a polar, and water tolerance is bad; And the grafted chain of water-tolerant generally all is nonpolar, and cohesive strength improves not obvious.And graft reaction generally all needs radical initiator under hot conditions, to carry out, starch high temperature gelatinization this moment, and viscosity sharply increases, the mobile variation of system, sterically hindered increase, graft reaction is difficult to carry out smoothly.
So, hope a kind of novel modified starch adhesive of preparation now, require cohesive strength height, water-tolerant, good fluidity, can be widely used in the production of wood veneer; Prepare simple, with low cost; Nuisanceless to human body, environment.
Summary of the invention
To the above defective of starch adhesive, target of the present invention is to prepare a kind of modified starch adhesive.Adopt the chlorine bleach liquor to make oxygenant; The color of not obvious intensification starch when improving the heavy property of starch solution anti-freezing; Add the high cohesion ability component PVA good, strengthen the cohesive strength of starch adhesive, adopt epoxy resin to make linking agent with Sumstar 190 breast consistency; The carboxyl generation crosslinking reaction of epoxy resin and Sumstar 190 obviously improves water resistance.
The present invention realizes through following technical scheme:
A kind of starch adhesive of modification is characterized in that: the component of described modified starch adhesive and mass fraction are:
Described W-Gum is that general industry is used starch, and white or little band pale yellow powder, amylose content are 20%～30%.
Described chlorine bleach liquor self-control feeds 30 ℃, the sodium hydroxide solution of 30% massfraction with chlorine and prepares the chlorine bleach liquor, and available chlorine content is 5%～10%.
Described epoxy chloropropane, CP, density 1.18～1.20g/cm
3, on the molecule chlorine atom and epoxide group can with hydroxyl generation crosslinking reaction on the starch molecular chain, between molecular chain, form all the chemical bond with distribution, improve the shearing resistance of starch adhesive on a small quantity.
Described aqueous polyvinyl acetate emulsion self-control; Initiator is an ammonium persulphate, and protective colloid is that Z 150PH, emulsifying agent are anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent tween-80 paralled system, the reaction product oyster white; Solid content 25%～30%, viscosity 600～700mpas.
Described epoxy resin is bisphenol A-type, and the trade mark is E-44, and softening temperature is 12～20 ℃, and oxirane value is 0.41～0.47, and the water white transparency thick liquid is mobile poor.
Described tertiary amine catalyst is triethylamine, N, a kind of in N-dimethyl amine, the N-methyl-diethyl-amine.
Described weighting agent is a kind of in kaolin, sodium sulfate, talcum powder, the white titanium pigment.
Described tensio-active agent is one or more in sodium lauryl sulphate, tween-80, the sapn.
Described sanitas is a kind of among RH-893, the PREVENTOL D7 F.
The preparation method of above-mentioned modified starch adhesive is:
1), preparation Sumstar 190 solution:
A) 30～50 parts of W-Gums of weighing, 80～120 parts of deionized water configuration solution;
B) chlorine being fed 30 ℃, the sodium hydroxide solution of 30% massfraction, to be prepared into available chlorine content be 5%～10% chlorine bleach liquor, adds 25～40 parts of chlorine bleach liquores to the solution of step a), reacts 4h;
C) with 0.1mol/l hydrochloric acid soln set-up procedure b) system is Ph=9～10, drips linking agent epoxy chloropropane crosslinking reaction 30min; Reduce to 25 ℃ of room temperature dischargings, obtain the Sumstar 190 emulsion, subsequent use;
2), preparation aqueous polyvinyl acetate emulsion: 7～9 parts of Z 150PH of weighing, 100 parts of deionized waters add there-necked flask, about 90 ℃ of constant temperature oil bath heated and stirred 1h, are configured to 7%～9% polyvinyl alcohol solution, are cooled to 70～75 ℃; Add 1 part of sodium lauryl sulphate, 1.5 parts of tween-80s, 25 parts of Vinyl Acetate Monomers, 0.5 part of ammonium persulfate initiator successively, reaction 30min; Add 0.5 part of ammonium persulphate again, and in two hours 0 part of Vinyl Acetate Monomer of Dropwise 5, be added dropwise to complete afterreaction 30min, add 6～8 parts of plasticizer phthalic acid dibutylesters, reduce to 25 ℃ of room temperature dischargings;
3,30～70 parts of steps 2 of weighing) aqueous polyvinyl acetate emulsion of preparation, 10～30 parts of epoxy resin add in the Sumstar 190 emulsion of 100 parts of step 1); Add an amount of tertiary amine catalyst, weighting agent, skimmer, sanitas more in proportion; Stir 20min, promptly obtain uniform and stable, cohesive strength is high, water-fast shearing resistance is high modified starch adhesive of the present invention.
Beneficial effect
The present invention has following beneficial effect:
The low in raw material cost that the present invention adopted is easy to get, and production cost is lower by about 70% than timber " three-aldehyde glue " commonly used, cohesive strength, water-fast shearing resistance satisfy GB/T 9846-2004 require (>=0.7MPa).Adopt hypochlorite oxidation agent Sumstar 190 colour-change not obvious; Aqueous polyvinyl acetate emulsion and Sumstar 190 breast consistency are good, and shearing resistance improves obviously; Epoxy resin is crosslinked fully with the Sumstar 190 carboxyl under the tertiary amine catalyst existence condition, and water-fast shearing resistance improves significantly; On the other hand, the part self-crosslinking reaction can take place in epoxy resin under the tertiary amine catalyst effect, form fine and close epoxy resin film, further improves water tolerance.
Therefore, the prepared modified starch adhesive of the present invention overcomes the defective of traditional modified starch adhesive, has excellent performance, has a wide range of applications, and huge advantage is being arranged aspect plywood production, the timber splicing.
Embodiment
Below in conjunction with instance the present invention is further specified.
Embodiment 1
According to modified starch adhesive preparation method in the patent of the present invention, prepare Sumstar 190 breast and aqueous polyvinyl acetate emulsion in advance.An amount of PVA, epoxy resin are added in the Sumstar 190 emulsion, add an amount of tertiary amine catalyst, weighting agent, skimmer, sanitas etc., stir 20min fast, promptly get sample.
Each component and mass fraction thereof are following:
Embodiment 2
Raw materials pretreatment and modified starch adhesive preparation method are with embodiment 1.
Each component and mass fraction thereof are following:
Embodiment 3
Raw materials pretreatment and modified starch adhesive preparation method are with embodiment 1.
Each component and mass fraction thereof are following:
Embodiment 4
Raw materials pretreatment and modified starch adhesive preparation method are with embodiment 1.
Each component and mass fraction thereof are following:
Embodiment 5
Raw materials pretreatment and modified starch adhesive preparation method are with embodiment 1.
Each component and mass fraction thereof are following:
Embodiment 6
Raw materials pretreatment and modified starch adhesive preparation method are with embodiment 1.
Each component and mass fraction thereof are following:
According to the formulation modified starch adhesive of the foregoing description 1～6, by GB/T 9846-2004 requirement preparation shearing resistance test bars, water-fast shearing resistance is according to 4.15 parts among the GB/T 17657-1999, and II class wood veneer is stipulated.Adopt SANS universal testing machine test shearing resistance and water-fast shearing resistance, rate of extension is 1mm/min.With reference to GB/T 2794-1995, with NDJ-79 type rotational viscosimeter, the stable viscosity of test modified starch adhesive sample.Amylan is just done the mensuration of time and is as the criterion with tack-free.
The modified starch adhesive performance test data is seen table 1
The performance test of table 1 modified starch adhesive
The modified starch adhesive visible by table 1, that the present invention produces, high, the water-fast shearing resistance of shearing resistance improves obviously, modest viscosity, good fluidity, the time of just doing is moderate, and cost is low, and over-all properties is superior, has very high using value in the plywood production field.
Claims (2)
1. the starch adhesive of a modification, it is characterized in that: the component of described modified starch adhesive and mass fraction are:
Described W-Gum is the industrial starch of amylose content 20%～30%,
Described chlorine bleach liquor's available chlorine content is 5%～10%,
Described epoxy chloropropane is a CP, density 1.18～1.20g/cm
3,
Described aqueous polyvinyl acetate emulsion is a solid content 25%～30%, the solution of viscosity 600～700mpas,
Described epoxy resin is bisphenol A-type, and softening temperature is 12～20 ℃, and oxirane value is 0.41～0.47,
Described tertiary amine catalyst is triethylamine, N, a kind of in N-dimethyl amine, the N-methyl-diethyl-amine,
Described weighting agent is a kind of in kaolin, sodium sulfate, talcum powder, the white titanium pigment,
Described tensio-active agent is one or more in sodium lauryl sulphate, tween-80, the sapn,
Described sanitas is a kind of among RH-893, the PREVENTOL D7F.
2. the preparation method of the starch adhesive of a modification as claimed in claim 1, said method comprises the steps:
1), preparation Sumstar 190 solution:
A) 30～50 parts of W-Gums of weighing, 80～120 parts of deionized water configuration solution;
B) chlorine being fed 30 ℃, the sodium hydroxide solution of 30% massfraction, to be prepared into available chlorine content be 5%～10% chlorine bleach liquor, adds 25～40 parts of chlorine bleach liquores to the solution of step a), reacts 4h, obtains the Sumstar 190 emulsion;
C) with 0.1mol/l hydrochloric acid soln set-up procedure b) the Sumstar 190 emulsion of preparation is Ph=9～10, drips linking agent epoxy chloropropane crosslinking reaction 30min; Reduce to 25 ℃ of room temperature dischargings, obtain Sumstar 190 solution, subsequent use;
2), preparation aqueous polyvinyl acetate emulsion: 7～9 parts of Z 150PH of weighing, 100 parts of deionized waters add there-necked flask, about 90 ℃ of constant temperature oil bath heated and stirred 1h, are configured to 7%～9% polyvinyl alcohol solution, are cooled to 70～75 ℃; Add 1 part of sodium lauryl sulphate, 1.5 parts of tween-80s, 25 parts of Vinyl Acetate Monomers, 0.5 part of ammonium persulfate initiator successively, reaction 30min; Add 0.5 part of ammonium persulphate again, and in two hours 0 part of Vinyl Acetate Monomer of Dropwise 5, be added dropwise to complete afterreaction 30min, add 6～8 parts of plasticizer phthalic acid dibutylesters, reduce to 25 ℃ of room temperature dischargings, obtain aqueous polyvinyl acetate emulsion;
3), 30～70 parts of steps 2 of weighing) aqueous polyvinyl acetate emulsion of preparation, 10～30 parts of epoxy resin add in the Sumstar 190 solution of 100 parts of step 1) preparations; Add tertiary amine catalyst, weighting agent, skimmer, sanitas in the described ratio of claim 1 again; Stir 20min, promptly obtain the starch adhesive of described modification.
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| CN 201210241327 CN102732186B (en) | 2012-07-12 | 2012-07-12 | Modified starch adhesive and method for preparing same |
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|---|---|---|---|
| CN 201210241327 CN102732186B (en) | 2012-07-12 | 2012-07-12 | Modified starch adhesive and method for preparing same |
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| CN102732186A true CN102732186A (en) | 2012-10-17 |
| CN102732186B CN102732186B (en) | 2013-12-25 |
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| CN 201210241327 Expired - Fee Related CN102732186B (en) | 2012-07-12 | 2012-07-12 | Modified starch adhesive and method for preparing same |
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| CN104804678A (en) * | 2014-01-24 | 2015-07-29 | 金东纸业（江苏）股份有限公司 | Composite rubber solution, its application in card, and card made by using rubber solution |
| CN104817975A (en) * | 2015-04-20 | 2015-08-05 | 许金兰 | Starch adhesive used at low temperature and preparation method thereof |
| CN104946135A (en) * | 2015-07-06 | 2015-09-30 | 中材高新成都能源技术有限公司 | Polymeric adhesive |
| CN105153998A (en) * | 2015-08-28 | 2015-12-16 | 北京林业大学 | Adhesive for artificial board and preparation method of adhesive |
| CN106085286A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of Environment-friendlyadhesive adhesive |
| CN106085284A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of novel timber adhesive |
| CN106085285A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of based Wood Adhesives |
| CN106147650A (en) * | 2016-08-10 | 2016-11-23 | 南宁市邦得力木业有限责任公司 | A kind of environment-friendly type based Wood Adhesives |
| CN106221610A (en) * | 2016-08-10 | 2016-12-14 | 南宁市邦得力木业有限责任公司 | A kind of timber environment-protective adhesive |
| CN106634738A (en) * | 2016-12-17 | 2017-05-10 | 浦北县建业胶合板有限责任公司 | Starch-based wood adhesive and preparation method thereof |
| CN106675437A (en) * | 2016-12-11 | 2017-05-17 | 钦州学院 | Oxidized starch modifier and preparation method thereof |
| CN106700985A (en) * | 2016-12-05 | 2017-05-24 | 唐肖近 | Binding agent |
| CN107936869A (en) * | 2017-12-04 | 2018-04-20 | 徐州得铸生物科技有限公司 | A kind of preparation method of composite type modified starch adhesive |
| CN108410385A (en) * | 2018-03-16 | 2018-08-17 | 佛山市利丰日用品有限公司 | A kind of environment-friendly type decoration surface lining and preparation method thereof |
| JP2018203821A (en) * | 2017-05-31 | 2018-12-27 | 王子ホールディングス株式会社 | Woody board adhesive, woody board and method for producing the same |
| CN109988529A (en) * | 2019-02-25 | 2019-07-09 | 潘荣强 | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum |
| CN110437765A (en) * | 2019-08-22 | 2019-11-12 | 温州包鹿新材料有限公司 | A kind of environmental protection amylum adhesive and preparation method thereof |
| CN110437764A (en) * | 2019-08-16 | 2019-11-12 | 严佳飞 | A kind of resin modified amylum adhesive and preparation method thereof |
| CN112143436A (en) * | 2020-09-28 | 2020-12-29 | 钟雨玲 | Preparation method of high-temperature and high-humidity resistant polyurethane adhesive |
| JP2021011580A (en) * | 2017-05-31 | 2021-02-04 | 王子ホールディングス株式会社 | Woody board adhesive |
| CN113462337A (en) * | 2021-07-09 | 2021-10-01 | 武汉梓强生态科技有限公司 | Grouting type high-molecular binder crack repairing adhesive |
| CN115895505A (en) * | 2022-11-30 | 2023-04-04 | 汇胜包装科技有限公司 | Special starch glue for high-temperature-resistant drying paper tube and preparation method thereof |
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| CN104804678A (en) * | 2014-01-24 | 2015-07-29 | 金东纸业（江苏）股份有限公司 | Composite rubber solution, its application in card, and card made by using rubber solution |
| CN104804678B (en) * | 2014-01-24 | 2017-10-17 | 金东纸业（江苏）股份有限公司 | Playing cards made from composite glue solution and its application in playing cards and the application glue |
| CN104817975A (en) * | 2015-04-20 | 2015-08-05 | 许金兰 | Starch adhesive used at low temperature and preparation method thereof |
| CN104946135A (en) * | 2015-07-06 | 2015-09-30 | 中材高新成都能源技术有限公司 | Polymeric adhesive |
| CN105153998A (en) * | 2015-08-28 | 2015-12-16 | 北京林业大学 | Adhesive for artificial board and preparation method of adhesive |
| CN106085285A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of based Wood Adhesives |
| CN106147650A (en) * | 2016-08-10 | 2016-11-23 | 南宁市邦得力木业有限责任公司 | A kind of environment-friendly type based Wood Adhesives |
| CN106221610A (en) * | 2016-08-10 | 2016-12-14 | 南宁市邦得力木业有限责任公司 | A kind of timber environment-protective adhesive |
| CN106085286A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of Environment-friendlyadhesive adhesive |
| CN106085284A (en) * | 2016-08-10 | 2016-11-09 | 南宁市邦得力木业有限责任公司 | A kind of novel timber adhesive |
| CN106700985A (en) * | 2016-12-05 | 2017-05-24 | 唐肖近 | Binding agent |
| CN106675437A (en) * | 2016-12-11 | 2017-05-17 | 钦州学院 | Oxidized starch modifier and preparation method thereof |
| CN106634738A (en) * | 2016-12-17 | 2017-05-10 | 浦北县建业胶合板有限责任公司 | Starch-based wood adhesive and preparation method thereof |
| JP2021011580A (en) * | 2017-05-31 | 2021-02-04 | 王子ホールディングス株式会社 | Woody board adhesive |
| JP2018203821A (en) * | 2017-05-31 | 2018-12-27 | 王子ホールディングス株式会社 | Woody board adhesive, woody board and method for producing the same |
| CN107936869A (en) * | 2017-12-04 | 2018-04-20 | 徐州得铸生物科技有限公司 | A kind of preparation method of composite type modified starch adhesive |
| CN108410385A (en) * | 2018-03-16 | 2018-08-17 | 佛山市利丰日用品有限公司 | A kind of environment-friendly type decoration surface lining and preparation method thereof |
| CN109988529A (en) * | 2019-02-25 | 2019-07-09 | 潘荣强 | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum |
| CN110437764A (en) * | 2019-08-16 | 2019-11-12 | 严佳飞 | A kind of resin modified amylum adhesive and preparation method thereof |
| CN110437765A (en) * | 2019-08-22 | 2019-11-12 | 温州包鹿新材料有限公司 | A kind of environmental protection amylum adhesive and preparation method thereof |
| CN110437765B (en) * | 2019-08-22 | 2020-09-25 | 宁夏吉宏环保包装科技有限公司 | Environment-friendly starch adhesive and preparation method thereof |
| CN112143436A (en) * | 2020-09-28 | 2020-12-29 | 钟雨玲 | Preparation method of high-temperature and high-humidity resistant polyurethane adhesive |
| CN113462337A (en) * | 2021-07-09 | 2021-10-01 | 武汉梓强生态科技有限公司 | Grouting type high-molecular binder crack repairing adhesive |
| CN115895505A (en) * | 2022-11-30 | 2023-04-04 | 汇胜包装科技有限公司 | Special starch glue for high-temperature-resistant drying paper tube and preparation method thereof |
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