CN108641622A - A kind of starch-base adhesive and preparation method thereof - Google Patents
A kind of starch-base adhesive and preparation method thereof Download PDFInfo
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- CN108641622A CN108641622A CN201810381368.5A CN201810381368A CN108641622A CN 108641622 A CN108641622 A CN 108641622A CN 201810381368 A CN201810381368 A CN 201810381368A CN 108641622 A CN108641622 A CN 108641622A
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- Prior art keywords
- starch
- base adhesive
- adhesive preparation
- preparation
- inorganic filler
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of starch-base adhesives and preparation method thereof, it is related to starch-base adhesive technical field, the starch-base adhesive is with starch, polyvinyl alcohol and inorganic filler are raw material, pass through physics respectively, chemistry, which is combined, pre-processes starch, then pretreated starch is subjected to oxidation processes using Fenton reagent, finally by the starch and polyvinyl alcohol after oxidation, inorganic filler, crosslinking agent and surfactant carry out ultrasonic reaction, it is prepared into starch-base adhesive, not only water resistance and bonding quality are good for the starch-base adhesive of preparation, and there is high heat resistance.
Description
Technical field
The invention belongs to adhesive technical fields, are related to starch-base adhesive technical field, and in particular to a kind of starch base
Adhesive and preparation method thereof.
Background technology
As conglomerate general character product and technology, the completely new society of the adhesives performance such as nontoxic, environmental-friendly, degradable
It can demand so that using natural biomass materials as raw material, obtain various environment compatibility height, low manufacture cost, economical and practical
Green adhesive product and technology become current adhesive field research hotspot.
Biomass adhesive mainly has starch adhesive, protein-based adhesive, lignin adhesive, tannins glue
Glutinous agent and their modified product, starch have many advantages, such as to derive from a wealth of sources, are cheap, renewable, degradable, are most to have
One of natural glue of potentiality to be exploited.There are a large amount of glycosidic bonds and hydroxyl with reactivity, and starch on starch molecular chain
Itself has Optical instrument again, therefore, can substitute traditional amino resins gluing agent as Formaldehyde-free adhesive, but simple
There are many deficiencies in use for starch-base adhesive, as wet bonding strength is relatively low, poor water resistance.Starch emulsion exists not
Stabilization, poor fluidity, easy retrogradation, poor storage stability, easy the problems such as going mouldy.Starch adhesive mainly by oxidation, gelatinization,
The means such as esterification, grafting, crosslinking, are modified starch raw material with physics, chemistry or bioanalysis, close hydroxyl and introduce other
Active group makes the hydroxyl quantity in emulsion system be reduced to degree appropriate, while maintaining enough active group numbers,
And change the solubility of starch, viscosity etc., to reach the bonding action that can either ensure starch adhesive by modification, and can be with
Water resistance and mobile performance are improved, the purpose of extending shelf life.As Chinese patent publication No. CN102585726A announces a kind of lead to
The starch-based biomass latex adhesive of chemical crosslinking modified preparation is crossed, the binder of preparation has good adhesive property, can
For replacing the adhesives such as hydroxyl butylbenzene breast and white glue with vinyl, Chinese patent publication No. CN102642222A to disclose a kind of using pre-
Then the bio oil of processing and wild tapioca add oxidant, poly-vinyl alcohol solution, prepared by lye, ethanedioic acid and borax
Bio oil starch is without aldehyde adhesive.
In recent years, although starch adhesive has obtained extensive concern and will just, also many technical bottleneck problems
It is not well solved, the problems such as bonding quality, production efficiency, technique performance need to be continued to explore to grind
Study carefully.
Invention content
According to the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to propose a kind of starch-base adhesive
And preparation method thereof, in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
A kind of starch-base adhesive preparation method, is as follows：
1) pretreatment of starch：Starch is subjected to extrusion at pressure 5-10MPa, 80-90 DEG C of temperature, it then will be puffing
Starch afterwards is added in NaOH solution, and ultrasonic reaction 50-70min obtains starch emulsion；Pretreatment can destroy the crystallization of starch
Structure, improves reaction efficiency, and oxidation process obtains ideal result to optimize the performance of oxidized starch；
2) starch oxidation：Fenton reagent is added into starch emulsion and carries out oxidation reaction, and keeps pH value of solution in 9.5-
10.5, it after reacting 3.5-4.5h, filters, is dried in vacuo, grinding obtains oxidized starch, and carrying out oxidation processes to starch makes starch band
There are carboxyl and aldehyde radical, improves the flowing of its glue；
3) prepared by adhesive：Oxidized starch is dissolved in poly-vinyl alcohol solution, after emulsifying 5-10min, crosslinking is added
Agent, inorganic filler and surfactant, ultrasonic reaction 30-40min obtain no aldehyde biomass adhesive.
Preferably, the pH of the NaOH solution is 9-11, and temperature is 40-60 DEG C, and the solid-liquid ratio with expanded starch is 1:3-
8。
Preferably, the power of the ultrasound is 100-200w, frequency 15-25Hz, 40-70 DEG C of temperature.
Preferably, the Fenton reagent is the FeSO by 0.1-0.15g4With the concentration 15-25%H of 30-40mL2O2Solution
It constitutes, the environment friendly and pollution-free oxidant of Fenton reagent, and oxidation rate is fast.
Preferably, the vacuum drying temperature is 50-65 DEG C.
Preferably, the grain size of the oxidized starch is 150-250 mesh.
Preferably, it is 1 that the inorganic filler, which is mass ratio,:The bentonite and graphene oxide of 0.3-0.8 has to improve and form sediment
Powder adhesive shear thinning behavior and thermal stability.
Preferably, the crosslinking agent is 6- methoxymethylene melamines, makes methoxyl group and starch and polyvinyl alcohol point
Hydroxyl in subchain carries out etherificate and forms cross-linked structure, improves adhesive water resistance.
Preferably, the starch-base adhesive includes following mass percent ingredient：Oxidized starch 20-30%, polyethylene
Alcohol 8-13%, inorganic filler 4-10%, surfactant 1.5-3%, crosslinking agent 0.4-1.2% and excess water.
Preferably, the starch-base adhesive includes following mass percent ingredient：Oxidized starch 25%, polyvinyl alcohol
10%, inorganic filler 8%, surfactant 2%, crosslinking agent 1% and water 54%.
Compared with prior art, beneficial effects of the present invention：
1. the method pretreated starch that the present invention is combined using the puffing and chemical alkaline hydrolysis of physical impact, physical impact are puffing
Strengthen starch from inside, improve the oxidation activity of starch, improve the oxidation effectiveness of starch, chemical alkaline hydrolysis destroys starch
Plot structure is crystallized, oxidation modification reaction efficiency is improved, pretreatment can destroy the crystalline texture of starch, improve reaction efficiency, by force
Change oxidation course and obtains ideal result to optimize the performance of oxidized starch.
2. the present invention, as oxidant, has the advantages that environment friendly and pollution-free and oxidation rate is fast using Fenton reagent, it is crosslinked
Agent is 6- methoxymethylene melamines, and methoxyl group is made to carry out etherificate formation with the hydroxyl on starch and polyvinyl alcohol molecule chain
Cross-linked structure improves adhesive water resistance.
3. the present invention adds bentonite and graphene oxide inorganic filler, bentonitic lamellar structure into starch adhesive
It is interspersed between starch adhesive polymer, being rich in for graphene oxide has a large amount of oxygen-containing functional group and oxidized starch and crosslinking agent
Reaction forms solid reticular structure, has and improves the behavior of starch adhesive shear thinning and thermal stability.
Specific implementation mode
It below by the description to embodiment, is described in further detail, to help those skilled in the art to this hair
Bright inventive concept, technical solution have more complete, accurate and deep understanding.
Embodiment 1
Starch-base adhesive includes following mass percent ingredient in the present embodiment：Oxidized starch 25%, polyvinyl alcohol
10%, inorganic filler 8%, surfactant 2%, crosslinking agent 1% and water 54%, wherein inorganic filler is that mass ratio is 1:0.5
Bentonite and graphene oxide, surfactant is dodecyl sodium sulfate.
Starch-base adhesive preparation method in the present embodiment, is as follows：
1) pretreatment of starch：Tapioca is placed in extruder accumulator, the pressure of extruder is set as
7MPa, temperature are set as 85 DEG C, and tapioca is carried out extrusion, then will be puffing after tapioca be added to pH and be
10, temperature is 1 in 50 DEG C of NaOH solution, to keep solid-liquid ratio:6, then starch mixed liquor is placed in ultrasound emission instrument,
Ultrasonic power 150w, frequency 25Hz, under temperature 60 C, ultrasonic reaction 60min obtains starch emulsion；
2) starch oxidation：The FeSO by 0.13g is added into starch emulsion4With the concentration 20%H of 35mL2O2Solution is constituted
Fenton reagent carry out oxidation reaction, be used in combination NaOH solution in step (2) to adjust pH value of solution, keeps pH value of solution 10, aoxidize
After anti-4h, reaction solution is filtered, and is dried in vacuo at 60 DEG C, by the starch ground after drying, and 200 mesh sieve is crossed, obtains
Oxidized starch；
3) prepared by adhesive：Take quality accounting be 25% oxidized starch, 10% polyvinyl alcohol, 8% by mass ratio
It is 1:The inorganic filler of 0.5 bentonite and graphene oxide mixing, 2% dodecyl sodium sulfate surfactant, 1%
Polyvinyl alcohol is dissolved in deionized water, heating stirring by 6- methoxymethylene melamine crosslinkers, 54% deionized water
It is cold to go that poly-vinyl alcohol solution is made to complete melt, then oxidized starch is dissolved in poly-vinyl alcohol solution, in pressure 5Mpa
After lower emulsifying 7min, crosslinking agent, inorganic filler and surface active agent is added, mixed liquor is placed in ultrasonic wave
In power 150w in transmitter, frequency 20Hz, ultrasonic reaction 30min under temperature 60 C, natural cooling obtain no aldehyde biomass gluing
Agent.
Embodiment 2
The present embodiment with embodiment 1, unlike in the present embodiment starch-base adhesive include following mass percent at
Point：Oxidized starch 20%, polyvinyl alcohol 8%, inorganic filler 4%, surfactant 1.5%, crosslinking agent 0.5% and water 66%.
Embodiment 3
The present embodiment with embodiment 1, unlike in the present embodiment starch-base adhesive include following mass percent at
Point：Oxidized starch 30%, polyvinyl alcohol 13%, inorganic filler 10%, surfactant 3%, crosslinking agent 1.2% and water
42.8%.
Embodiment 4
The present embodiment is with embodiment 1, the difference is that the pressure of starch extrusion is 5MPa, temperature 80 in the present embodiment
DEG C, Fenton reagent is the FeSO by 0.1g4With the concentration 25%H of 30mL2O2Solution is constituted.
Embodiment 5
The present embodiment is with embodiment 1, the difference is that the pressure of starch extrusion is 10MPa in the present embodiment, temperature is
90 DEG C, Fenton reagent is the FeSO by 0.5g4With the concentration 15%H of 40mL2O2Solution is constituted.
The present invention is exemplarily described above in conjunction with specific embodiment, it is clear that the present invention implements not by upper
The limitation of mode is stated, if the improvement of the various unsubstantialities of inventive concept and technical scheme of the present invention progress is used, or
It is not improved by the present invention design and technical solution directly apply to other occasions, protection scope of the present invention it
It is interior.Protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (10)
1. a kind of starch-base adhesive preparation method, which is characterized in that be as follows：
1) pretreatment of starch：Starch is subjected to extrusion at pressure 5-10MPa, 80-90 DEG C of temperature, then will be puffing after
Starch is added in NaOH solution, and ultrasonic reaction 50-70min obtains starch emulsion；
2) starch oxidation：Fenton reagent is added into starch emulsion and carries out oxidation reaction, and keeps pH value of solution in 9.5-10.5, instead
It after answering 3.5-4.5h, filters, is dried in vacuo, grinding obtains oxidized starch；
3) prepared by adhesive：Oxidized starch is dissolved in poly-vinyl alcohol solution, after emulsifying 5-10min, crosslinking agent, nothing is added
Machine filler and surfactant, ultrasonic reaction 30-40min obtain no aldehyde biomass adhesive.
2. starch-base adhesive preparation method according to claim 1, which is characterized in that the pH of the NaOH solution is 9-
11, temperature is 40-60 DEG C, and the solid-liquid ratio with expanded starch is 1:3-8.
3. starch-base adhesive preparation method according to claim 1, which is characterized in that the power of the ultrasound is 100-
200w, frequency 15-25Hz, 40-70 DEG C of temperature.
4. starch-base adhesive preparation method according to claim 1, which is characterized in that the Fenton reagent is by 0.1-
The FeSO of 0.15g4With the concentration 15-25%H of 30-40mL2O2Solution is constituted.
5. starch-base adhesive preparation method according to claim 1, which is characterized in that the vacuum drying temperature is
50-65℃。
6. starch-base adhesive preparation method according to claim 1, which is characterized in that the grain size of the oxidized starch is
150-250 mesh.
7. starch-base adhesive preparation method according to claim 1, which is characterized in that the inorganic filler is mass ratio
It is 1:The bentonite and graphene oxide of 0.3-0.8.
8. starch-base adhesive preparation method according to claim 1, which is characterized in that the crosslinking agent is 6- methoxyl groups
Methylene tri poly cyanamid.
9. starch-base adhesive preparation method according to claim 1, which is characterized in that the starch-base adhesive includes
Following mass percent ingredient：Oxidized starch 20-30%, polyvinyl alcohol 8-13%, inorganic filler 4-10%, surfactant
1.5-3%, crosslinking agent 0.4-1.2% and excess water.
10. starch-base adhesive preparation method according to claim 1, which is characterized in that institute's starch-base adhesive includes
Following mass percent ingredient：Oxidized starch 25%, polyvinyl alcohol 10%, inorganic filler 8%, surfactant 2%, crosslinking agent
1% and water 54%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810381368.5A CN108641622A (en) | 2018-04-25 | 2018-04-25 | A kind of starch-base adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810381368.5A CN108641622A (en) | 2018-04-25 | 2018-04-25 | A kind of starch-base adhesive and preparation method thereof |
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| CN108641622A true CN108641622A (en) | 2018-10-12 |
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| CN201810381368.5A Pending CN108641622A (en) | 2018-04-25 | 2018-04-25 | A kind of starch-base adhesive and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087945A (en) * | 2019-12-20 | 2020-05-01 | 株洲工大彩色印刷有限公司 | Starch adhesive with antibacterial function and preparation method thereof |
| CN112376318A (en) * | 2020-11-18 | 2021-02-19 | 无锡海博源包装科技有限公司 | Anti-counterfeiting coating, anti-counterfeiting label printing process and anti-counterfeiting label |
| CN112625649A (en) * | 2019-09-24 | 2021-04-09 | 天津大学 | Gelatin-based hydrogel adhesive initiated by Fenton reagent and preparation method and application thereof |
| CN114262603A (en) * | 2022-01-20 | 2022-04-01 | 佛山市卓仕高新型材料有限公司 | Environment-friendly waterproof adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149069A (en) * | 1996-09-21 | 1997-05-07 | 翟广玉 | Preparation and application of expanded corn starch binder |
| CN104974686A (en) * | 2015-06-12 | 2015-10-14 | 广西大学 | Preparation method of cassava starch-based binder |
| CN106009707A (en) * | 2016-06-24 | 2016-10-12 | 佛山市合璟节能环保科技股份有限公司 | Biomass additive for board adhesive as well as preparation method and application thereof |
-
2018
- 2018-04-25 CN CN201810381368.5A patent/CN108641622A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149069A (en) * | 1996-09-21 | 1997-05-07 | 翟广玉 | Preparation and application of expanded corn starch binder |
| CN104974686A (en) * | 2015-06-12 | 2015-10-14 | 广西大学 | Preparation method of cassava starch-based binder |
| CN106009707A (en) * | 2016-06-24 | 2016-10-12 | 佛山市合璟节能环保科技股份有限公司 | Biomass additive for board adhesive as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625649A (en) * | 2019-09-24 | 2021-04-09 | 天津大学 | Gelatin-based hydrogel adhesive initiated by Fenton reagent and preparation method and application thereof |
| CN112625649B (en) * | 2019-09-24 | 2021-09-07 | 天津大学 | Gelatin-based hydrogel adhesive initiated by Fenton reagent and preparation method and application thereof |
| CN111087945A (en) * | 2019-12-20 | 2020-05-01 | 株洲工大彩色印刷有限公司 | Starch adhesive with antibacterial function and preparation method thereof |
| CN112376318A (en) * | 2020-11-18 | 2021-02-19 | 无锡海博源包装科技有限公司 | Anti-counterfeiting coating, anti-counterfeiting label printing process and anti-counterfeiting label |
| CN114262603A (en) * | 2022-01-20 | 2022-04-01 | 佛山市卓仕高新型材料有限公司 | Environment-friendly waterproof adhesive and preparation method thereof |
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Application publication date: 20181012 |