CN107805484A - A kind of preparation method of wood materials starch adhesive - Google Patents

A kind of preparation method of wood materials starch adhesive Download PDF

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Publication number
CN107805484A
CN107805484A CN201711006767.5A CN201711006767A CN107805484A CN 107805484 A CN107805484 A CN 107805484A CN 201711006767 A CN201711006767 A CN 201711006767A CN 107805484 A CN107805484 A CN 107805484A
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China
Prior art keywords
starch
adhesive
prepared
preparation
polyvinyl alcohol
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CN201711006767.5A
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Chinese (zh)
Inventor
杨雅雯
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Chengdu Newland Jingmao Trading Co Ltd
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Chengdu Newland Jingmao Trading Co Ltd
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Priority to CN201711006767.5A priority Critical patent/CN107805484A/en
Publication of CN107805484A publication Critical patent/CN107805484A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021Block or graft polymers containing only sequences of polymers of C08C or C08F
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J187/00Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of preparation method of wood materials starch adhesive, first passes through starch oxidation gelatinization grafted silane coupling agent and modified starch is prepared;Then starch adhesive is prepared in polyvinyl alcohol hot melt adhesive, polycyanate ester and the mixed and modified starch of carboxylic styrene butadiene latex.The polyvinyl alcohol hot melt adhesive is network structure, effectively improves the dry strength and wet strength of adhesive;The preparation method of the present invention is simple, by the water resistance of Grafting-coupling Agent mongolicum Turcz. with Modified Starch Adhesive, while improves the compatibility in starch crosslinking agent between each composition, the homogeneous starch adhesive of performance is prepared.

Description

A kind of preparation method of wood materials starch adhesive
Technical field
The invention belongs to the technical field of wood materials crosslinking agent, and in particular to a kind of wood materials starch adhesive Preparation method.
Background technology
In recent years, environmental problem receives much concern, and green, health also turn into hot topic, national to dissociate first for adhesive The content of aldehyde has done strict regulations.At present, the wide variety of adhesive of wood processing field be phenolic resin, formaldehyde resin and Melamine resin, but these adhesives can discharge formaldehyde in the production and use process, cause environmental pollution and Public harm.
As Environmental Protection in China regulation is gradually improved, develops pollution-free, nonhazardous, meet " environmental protection, health, safety " requirement Green adhesive is imperative.Based Wood Adhesives kind will accelerate to update, hydrotropismization, solidification, solvent free, low toxicity Change direction to develop.And starch is as a kind of wide material sources, excellent honest and clean, the environment-friendly natural polymer of price, have it is nontoxic, be no different Taste, free of contamination feature, there is good cementability and film forming, be excellent natural resources adhesive.But its poor water resistance And less stable, it is imperative to develop a kind of preferable starch-base adhesive of water resistance.Meanwhile global pollution is serious, China Adhere to walking the road of sustainable development, it is therefore desirable to develop green nontoxic adhesive.
The content of the invention
It is an object of the invention to provide a kind of preparation method of wood materials starch adhesive, starch oxidation is first passed through Modified starch is prepared in gelatinization grafted silane coupling agent;Then by polyvinyl alcohol hot melt adhesive, polycyanate ester and carboxy styrene-butadiene rubber Starch adhesive is prepared in the mixed and modified starch of breast;The preparation method of the present invention is simple, passes through Grafting-coupling Agent modified starch The water resistance of adhesive, while improve the compatibility in starch crosslinking agent between each composition, the homogeneous starch of performance is prepared Adhesive.
The present invention is achieved through the following technical solutions:A kind of preparation method of wood materials starch adhesive, it is main Comprise the following steps:
Step A:Starch oxidation gelatinization is handled, silane coupler is added and carries out graft reaction, modified starch is prepared;
Step B, polyvinyl alcohol hot melt adhesive is prepared, polyvinyl alcohol hot melt adhesive, glycerine, polyethylene glycol and crosslinking agent are passed through into machinery Power chemical grinding is modified and is prepared;Polyvinyl alcohol hot melt adhesive is dissolved in the hot water, then adds in step A what is be prepared Modified starch, continue graft reaction;
Step C, add carboxylic styrene butadiene latex, starch adhesive is prepared in isocyanates.
The starch adhesive is often used as the bonding of timber and paper.There are a large amount of hydroxyls on the surface of timber and paper Base, structure is similar, so the adhesive of both base materials is the same.Due to the improvement of people's living standards, people require glue The content of formaldehyde is more and more lower in glutinous agent, and three-aldehyde glue before just can not slowly meet the needs of people, based Wood Adhesives face Face and challenge.Starch adhesive using natural polymer as raw material meets requirement and the Green Chemistry of the sustainable development in China Concept.
Starch is compound of polysaccharide, belongs to natural polymer, and it is photosynthetic to be that plant is passed through by light and carbon dioxide The natural organic matter of synthesis is acted on, is white powder.Starch is made up of ɑ-D-Glucose as elementary cell, after dehydration Glucose has been grouped together into starch molecule with glycosidic bond, and the formula of starch is (C6H10O5)n, wherein n is unknown.Form sediment Powder is not soluble in water at normal temperatures, and the suspension of starch is heated to certain temperature, and starch can be swelled, and then disintegrates and obtains gelatinization shallow lake Powder.However, contain substantial amounts of hydroxyl in gelatinized starch, and it is intermolecular to form substantial amounts of hydrogen bond, cause emulsion viscosity very big, flow Dynamic property is very poor, and this solid content for also resulting in gelatinized starch will not be very high, and adhesion strength is very poor.
The carboxylic styrene butadiene latex is to add the copolymer that a small amount of carboxylic acid generated by emulsion polymerization with butadiene, styrene, It is a kind of milky aqueous dispersion with bluish violet gloss.The carboxylic styrene butadiene latex has higher cohesive force and conjunctiva strong Degree, machinery and chemical stability are good, the advantages that mobility, bin stability are good, and loading is big.In the carboxylic styrene butadiene latex Residual benzene class monomer is seldom, belongs to environmentally friendly machine.The carboxylic styrene butadiene latex is a kind of adhesive in itself, is by butadiene, benzene Ethene and the copolymerization of a small amount of Carboxylation emulsion form, and price is relatively low, there is preferable water resistance, and-COOH and-NCO forms cross-linked network in addition Network, water resistance effectively improve.
In order to preferably realize the present invention, further, the silane coupler is vinyltrimethoxy silane, ethene Any one in ethyl triethoxy silicane alkane, vinyl three ('beta '-methoxy ethyoxyl) silane.
Organo-silicon compound in the molecule of the silane coupler simultaneously containing two kinds of different chemical property groups, it is passed through Allusion quotation product can use formula YSiX3Represent, wherein Y is non-hydrolytic group, including alkenyl and end carry Cl, NH2, SH, ring Oxygen, N3、(Methyl)The alkyl of the functional groups such as acryloxy, NCO, i.e. carbon functional group;Wherein X is hydrolyzable groups, Including Cl, OMe, OEt, OC2H4OCH3, OSiMe3And OAc etc..Due to this special construction, in the molecule of silane coupler simultaneously With energy and the chemically combined reactive group of inanimate matter material and the reactive group combined with organic matter materials chemistry.The silane Coupling agent can improve the compatibility of adhesive, improve the stability of adhesive.
In order to preferably realize the present invention, further, starch is in H in the step A2O2In solution after oxidation gelatinization, adjust PH value of solution=5-9 is saved, silane coupler graft reaction is added and modified starch is prepared.
In order to preferably realize the present invention, further, in the step B, the polyvinyl alcohol hot melt adhesive is poly- by 85 parts Vinyl alcohol PUR, 8 parts of glycerine, 5 parts of polyethylene glycol and 2 parts of crosslinking agent compositions;The crosslinking agent be adipic acid, succinic acid, Any one in maleic anhydride, borax.
In order to preferably realize the present invention, further, after polyethylene hot-melt adhesive dissolves in water in the step B, Modified starch is added under the conditions of 50 DEG C, rise temperature is incubated 0.5-1.5h to 70-80 DEG C.
In order to preferably realize the present invention, further, carboxylic styrene butadiene latex is mixed at ambient temperature in the step C Starch adhesive is prepared with polycyanate ester.
In order to preferably realize the present invention, further, the polyvinyl alcohol hot melt adhesive is reacted by mechanical lapping to be prepared Obtain.
Beneficial effects of the present invention:
(1)The modified starch is prepared by starch-grafted silane coupler, contains silicon oxygen bond in the modified starch, has Preferable water resistance;
(2)Contain isocyanates and carboxylic styrene butadiene latex in the starch adhesive, the isocyanates is cross-linked to form with hydroxyl The firm chemical bond such as ammonia ester bond and urea bond;Simultaneously on carboxylic styrene butadiene latex carboxyl can be reacted with NCO to be formed it is insoluble In the cross-linked network of water, the isocyanates and carboxylic styrene butadiene latex generate synergy, effectively increase amylan The water resistance of glutinous agent;
(3)The polyvinyl alcohol hot melt adhesive is by 85 parts of polyvinyl alcohol hot melt adhesives, 8 parts of glycerine, 5 parts of polyethylene glycol and 2 parts of crosslinkings Agent forms;It is network structure in the polyvinyl alcohol hot melt adhesive, effectively improves the adhesion strength of adhesive;
(4)The preparation method of the starch adhesive is simple, and the water resistance for the starch adhesive being prepared is preferable.
Embodiment
Embodiment 1:
A kind of preparation method of wood materials starch adhesive, according to mass parts calculate mainly by 100 parts of modified corn starch, 30 parts of polyvinyl alcohol hot melt adhesives, 35 parts of polycyanate esters and 20 parts of carboxylic styrene butadiene latex compositions;The modified corn starch is by 100 parts Cornstarch and 8 parts of vinyltrimethoxy silane graft reactions are prepared;
A kind of preparation method of wood materials starch adhesive, is mainly included the following steps that:
Step A:Starch oxidation gelatinization is handled, in H2O2In solution after oxidation gelatinization, pH value of solution=5 are adjusted, are added silane coupled Agent KH550 graft reactions, are prepared modified starch;
Step B, polyvinyl alcohol hot melt adhesive is prepared, polyvinyl alcohol hot melt adhesive, glycerine, polyethylene glycol and crosslinking agent are passed through into machinery Power chemical grinding is modified and is prepared;After polyethylene hot-melt adhesive dissolves in water, modified starch is added under the conditions of 50 DEG C, is risen High-temperature to 70 DEG C insulation 1h;
Step C, add carboxylic styrene butadiene latex at ambient temperature, starch adhesive is prepared in isocyanates.
The polyvinyl alcohol hot melt adhesive is by 85 parts of polyvinyl alcohol hot melt adhesives, 8 parts of glycerine, 5 parts of polyethylene glycol and 2 parts of crosslinkings Agent forms;The crosslinking agent is adipic acid;Polyvinyl alcohol hot melt adhesive is prepared by mechanical lapping reaction.
Grafted silane coupling agent in the starch adhesive, on the one hand introduces silicon oxygen bond in starch, on the other hand can be with It is compatibility to improve composition in starch adhesive;The addition of polyvinyl alcohol hot melt adhesive can effectively improve in the starch crosslinking agent The stability of starch adhesive, improve compatibility of the polycyanate ester in adhesive.
Found after test, it is respectively 6.95MPa and 3.91MPa to test the dry strength of water-based adhesive and wet strength; The polyvinyl alcohol hot melt adhesive is network structure, effectively improves the dry strength and wet strength of adhesive;The water-based adhesive Outward appearance is milky and gloss is preferable;Analysis data above obtains, adhesion strength, the water resistance of the water-based adhesive being prepared Preferably, the water resistance of the water-based adhesive meets national standard.
The present invention is prepared for a kind of preferable starch adhesive of water resistance, and amylan is improved by introducing carboxylic styrene butadiene latex The adhesion strength of glutinous agent, while starch is biodegradable, organic solvent-free in starch adhesive, is a kind of green nontoxic Adhesive.
Embodiment 2:
A kind of preparation method of wood materials starch adhesive, according to mass parts calculate mainly by 100 parts of modified corn starch, 32 parts of polyvinyl alcohol hot melt adhesives, 36 parts of polycyanate esters and 23 parts of carboxylic styrene butadiene latex compositions;The modified corn starch is by 100 parts Cornstarch and the graft reaction of 5 silane coupling A -172 are prepared;
A kind of preparation method of wood materials starch adhesive, is mainly included the following steps that:
Step A:Starch oxidation gelatinization is handled, in H2O2In solution after oxidation gelatinization, pH value of solution=5 are adjusted, are added silane coupled Agent KH550 graft reactions, are prepared modified starch;
Step B, polyvinyl alcohol hot melt adhesive is prepared, polyvinyl alcohol hot melt adhesive, glycerine, polyethylene glycol and crosslinking agent are passed through into machinery Power chemical grinding is modified and is prepared;After polyethylene hot-melt adhesive dissolves in water, modified starch is added under the conditions of 50 DEG C, is risen High-temperature to 80 DEG C insulation 1h;
Step C, add carboxylic styrene butadiene latex at ambient temperature, starch adhesive is prepared in isocyanates.
The polyvinyl alcohol hot melt adhesive is by 85 parts of polyvinyl alcohol hot melt adhesives, 8 parts of glycerine, 5 parts of polyethylene glycol and 2 parts of crosslinkings Agent forms.Grafted silane coupling agent in the starch adhesive, on the one hand introduces silicon oxygen bond in starch, on the other hand can carry Composition is compatibility in high starch adhesive;The addition of polyvinyl alcohol hot melt adhesive can effectively improve shallow lake in the starch crosslinking agent The stability of powder adhesive, improve compatibility of the polycyanate ester in adhesive.
Found after test, it is respectively 6.75MPa and 4.13MPa to test the dry strength of water-based adhesive and wet strength; The polyvinyl alcohol hot melt adhesive is network structure, effectively improves the dry strength and wet strength of adhesive;The water-based adhesive Outward appearance is milky and gloss is preferable;Analysis data above obtains, adhesion strength, the water resistance of the water-based adhesive being prepared Preferably, the water resistance of the water-based adhesive meets national standard.
The present invention is prepared for a kind of preferable starch adhesive of water resistance, and amylan is improved by introducing carboxylic styrene butadiene latex The adhesion strength of glutinous agent, while starch is biodegradable, organic solvent-free in starch adhesive, is a kind of green nontoxic Adhesive.
It is described above, be only presently preferred embodiments of the present invention, any formal limitation not done to the present invention, it is every according to Any simply modification, the equivalent variations made according to the technical spirit of the present invention to above example, each fall within the protection of the present invention Within the scope of.

Claims (6)

1. a kind of preparation method of wood materials starch adhesive, it is characterised in that mainly include the following steps that:
Step A:Starch oxidation gelatinization is handled, silane coupler is added and carries out graft reaction, modified starch is prepared;
Step B, polyvinyl alcohol hot melt adhesive is prepared, polyvinyl alcohol hot melt adhesive, glycerine, polyethylene glycol and crosslinking agent are passed through into machinery Power chemical grinding is modified and is prepared;Polyvinyl alcohol hot melt adhesive is dissolved in the hot water, then adds in step A what is be prepared Modified starch, continue graft reaction;
Step C, add carboxylic styrene butadiene latex, starch adhesive is prepared in isocyanates.
A kind of 2. preparation method of wood materials starch adhesive according to claim 1, it is characterised in that the step Starch is in H in rapid A2O2In solution after oxidation gelatinization, pH value of solution=5-9 is adjusted, silane coupler graft reaction is added and is prepared Modified starch.
A kind of 3. preparation method of wood materials starch adhesive according to claim 2, it is characterised in that the step After polyethylene hot-melt adhesive dissolves in water in rapid B, modified starch is added under the conditions of 50 DEG C, rise temperature is protected to 70-80 DEG C Warm 0.5-1.5h.
A kind of 4. preparation method of wood materials starch adhesive according to claim 1, it is characterised in that the step Carboxylic styrene butadiene latex is mixed at ambient temperature in rapid C and starch adhesive is prepared in polycyanate ester.
5. a kind of preparation method of wood materials starch adhesive according to claim any one of 1-4, its feature exist In polyvinyl alcohol hot melt adhesive is by 85 parts of polyvinyl alcohol hot melt adhesives, 8 parts of glycerine, 5 parts of polyethylene glycol and 2 parts in the step B Crosslinking agent forms;The crosslinking agent is any one in adipic acid, succinic acid, maleic anhydride, borax.
6. the preparation method of a kind of wood materials starch adhesive according to claim 5, it is characterised in that described poly- Vinyl alcohol PUR is prepared by mechanical lapping reaction.
CN201711006767.5A 2017-10-25 2017-10-25 A kind of preparation method of wood materials starch adhesive Pending CN107805484A (en)

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Application Number Priority Date Filing Date Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108867167A (en) * 2018-08-01 2018-11-23 山东金泰然环保科技有限公司 A kind of environment-friendly type coating adhesive and preparation method
CN109233685A (en) * 2018-07-27 2019-01-18 天峨县平昌生态农业有限公司 A kind of environmental protection type veneer board adhesive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233685A (en) * 2018-07-27 2019-01-18 天峨县平昌生态农业有限公司 A kind of environmental protection type veneer board adhesive
CN108867167A (en) * 2018-08-01 2018-11-23 山东金泰然环保科技有限公司 A kind of environment-friendly type coating adhesive and preparation method
CN108867167B (en) * 2018-08-01 2021-03-19 曲阜师范大学 Environment-friendly coating adhesive and preparation method thereof

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Application publication date: 20180316