CN107142053A - A kind of environmentally friendly starch-based glue stick and preparation method thereof - Google Patents
A kind of environmentally friendly starch-based glue stick and preparation method thereof Download PDFInfo
- Publication number
- CN107142053A CN107142053A CN201710539295.3A CN201710539295A CN107142053A CN 107142053 A CN107142053 A CN 107142053A CN 201710539295 A CN201710539295 A CN 201710539295A CN 107142053 A CN107142053 A CN 107142053A
- Authority
- CN
- China
- Prior art keywords
- starch
- adhesive
- monomer
- dry basis
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of environmentally friendly starch-based glue stick and preparation method thereof.This adhesive is using starch as primary raw material, using hydrochloric acidolysis, then adds initiator and emulsifying agent blending, then carry out grafting, copolymerization and modification to starch together with the mix monomer of vinylacetate and different types of acrylate.After modified-reaction is finished, a certain amount of plasticizer glycerite and a certain amount of urea are added, a kind of repeatable aqua type starch wood adhesive utilized is finally obtained.Starch adhesive prepared by the present invention overcomes the defect that adhesive property is lost after starch adhesive low temperature gel, possesses the characteristic that thermo-responsive hydro gel solution changes by being grafted different types of acrylate monomer, amylan after gel can recover to recover adhesive property after fluid simultaneously by common heating, or further by secondary grafting copolymerization technique to improve its adhesive property.Starch adhesive reusable edible prepared by the present invention, beneficial to industrialized production and popularization.
Description
Technical field
The present invention relates to a kind of environmentally friendly starch-based glue stick and preparation method thereof, belong to chemical field or high score
Sub- Material Field, is related to the method for adhesive and its preparation.
Background technology
With the reinforcement of increasingly deficient and people's environmental consciousness of petroleum resources, utilize with degradable reproducible biology
The matter raw material such as primary raw material such as starch, soybean protein, lignin prepares wood adhesive and become as inevitable development
Gesture.
Starch is a kind of low biological material of renewable, pollution-free, biodegradable, cost, uses starches as master
Use of the non-renewable resources oil monomer in Wood Adhesive can be effectively reduced by wanting raw material to prepare Wood Adhesive
Amount, economical environment-protective.
A kind of use is proposed in Chinese patent ZL200510040113.5 " a kind of preparation method of Wood Adhesive "
Starch is raw material, carries out acidolysis, oxidation, grafting, copolymerization and modification processing, finally adds the technique that certain auxiliary agent prepares amylan.
The amylan that the technique is prepared has the advantages that with low cost, environmentally friendly.Chinese patent ZL2012 10389343.2 is " a kind of high
Strong water-fast Starch Based Wood Adhesives and preparation method thereof " are carried out also using starch after acid conversion, gelatinization with grafted monomers
Emulsion graft copolymerization, then be blended with plasticizer, preservative and defoamer, obtain the room that stability is good, cementability is high, water resistance is good
Warm cured starch base adhesive, in addition, Chinese patent ZL201010576608.0 " a kind of modified starch base timber adhesive and
Its preparation method and application ", using starch as primary raw material, after acidolysis gelatinization pre-treatment, is existed using Vinyl Acetate Monomer
Graft copolymerization is carried out to starch under seeded emulsion polymerization technique, nano silicon dioxide sol and other auxiliary agents are added after cooling,
Finally give a kind of starch glue for lumber of function admirable.With nontoxic pollution-free, adhesion strength is high, water-tolerant, color breast
White glossy, rate of drying is fast, and the advantages of storage time is long can be widely applied to decoration timber, the bonding of wood-based plate.
At present, the adhesive strength of amylan is up to state standards, but its outward appearance, adhesion strength, water resistance, storage-stable
The indexs such as property need to be improved.The storage stability of especially amylan is relatively poor, and storage holds very much for a long time at low temperature
Easy gel, and the amylan after gel can lose adhesive property substantially, so as to thoroughly lose its application value, can only go out of use
Processing, pollutes environment.Above many disadvantages, limit the process of industrialization of amylan.
The content of the invention
Problem to be solved by this invention is that amylan storage stability is poor in the prior art, and adhesive property is bad.
In order to solve the technical problem, the invention provides a kind of environmentally friendly starch-based glue stick and preparation method thereof.The present invention
The adhesive of offer, i.e. amylan, outside preferable adhesive property and storability, also with can reuse
Characteristic；I.e. after amylan lost flowability formation gel, it is only necessary to which heating can recover mobile performance at a certain temperature, realize
Regeneration and adhesive property is not lost substantially；In addition, the gel of the amylan is also used as adhesive seed again through certain
The starch-base timber adhesive that can be regenerated after degree graft copolymerization.
Specifically, the technical scheme is that：
A kind of environmentally friendly starch-based glue stick, wherein, the adhesive includes following raw material components：Starch, polyvinyl alcohol, mistake
Ammonium sulfate, emulsifying agent, mix monomer, sodium hydrogensulfite, glycerine, urea, hydrochloric acid, sodium hydroxide, moisture.
Adhesive of the present invention, wherein, the adhesive is made by following raw material components, by mass, contains starch
100 parts, 6 parts of polyvinyl alcohol, 0.4-1 parts of ammonium persulfate, 1.5-3 parts of emulsifying agent, 70-100 parts of mix monomer, sodium hydrogensulfite
0.3-0.5 parts, 5-8 parts of glycerine, 10-20 parts of urea, water, hydrochloric acid, sodium hydroxide.
Adhesive of the present invention, wherein, the polyvinyl alcohol is one kind or many in PVA1788,2088,2488
Kind, and the polyvinyl alcohol is the mass concentration 10g/100g configured with water solution.
Adhesive of the present invention, wherein, the emulsifying agent is sucrose fatty ester, and methyl glycol fatty acid ester gathers sweet
One or more in oil and fat acid esters.
Adhesive of the present invention, wherein, the mix monomer presses volume by vinylacetate and acrylate monomer
Than for 4-2：1 composition；
Wherein, acrylate monomer is by n-butyl acrylate, isobutyl acrylate, Hexyl 2-propenoate, lauryl ester, third
The composition of the different monooctyl ester of olefin(e) acid, one or two kinds of in hydroxyethyl acrylate.
Adhesive of the present invention, wherein, the starch is tapioca, and sweet potato starch, farina, corn forms sediment
One or more in powder, waxy corn starch, wheaten starch.
A kind of preparation method of environmentally friendly starch-based glue stick, it is characterised in that this method comprises the following steps：
（1）The acidolysis pretreatment of starch：Starch is made into 30 ~ 50% with 0.5 ~ 1 mole every liter of hydrochloric acid（w/w）Suspension,
In reaction vessel, 1 ~ 3h of acidolysis at 60 DEG C is warming up to；With between sodium hydroxide regulation pH to 4 ~ 5, while adding starch on dry basis weight
10% ~ 15% polyvinyl alcohol, 1.5% ~ 3% emulsifying agent of starch on dry basis weight, and starch on dry basis weigh 0.4 ~ 1% ammonium persulfate,
30 ~ 40min is blended.
Wherein, emulsifying agent is sucrose fatty ester, methyl glycol fatty acid ester, one kind or many in polyglyceryl fatty acid ester
Kind；Polyvinyl alcohol is the one or more in PVA1788,2088,2488, and the polyvinyl alcohol is that the quality configured with water is dense
Spend 10g/100g solution.
(2) graft copolymerization：Step（1）Described in after blending reaction terminates, be warming up to 65 ~ 72 DEG C, be gradually added
Starch on dry basis weighs 70 ~ 100%（w/w）Mix monomer；The duration for adding monomer is 2.5h, is 1.5h left in grafting time
The right side is added and ammonium persulfate equivalent molar content after adding the ammonium persulfate that starch on dry basis weighs 0.3% ~ 0.5%, several minutes again
Then sodium hydrogensulfite, whole graft reaction control be warming up to 85 DEG C within 3h, and it is complete to be incubated 30min removal unreacteds
Monomer.
Wherein, mix monomer is that vinylacetate and variety classes acrylate are constituted, and its volume ratio is 4:1~2:1；Third
Olefin(e) acid ester monomer by n-butyl acrylate, isobutyl acrylate, Hexyl 2-propenoate, lauryl ester, Isooctyl acrylate monomer,
The composition of one or two kinds of in hydroxyethyl acrylate.
（3）After graft reaction terminates, the 60% glycerite plasticizer that starch on dry basis weighs 5% ~ 8% is added, shallow lake is added
The urea of powder dry basis 10 ~ 20%, and adjusted with sodium acid carbonate after pH to 6, cooling discharge packs the starch-based glue stick produced.
Adhesive of the present invention, wherein, synthesized adhesive has Thermo-sensitive, and adhesive is at temperature≤5 DEG C
Time forms gel, and when temperature is more than 70 DEG C, liquid is reverted to after heating 3-5h.Thermo-sensitive of the present invention, refers to,
The adhesive that this programme is provided has forms gel in low temperature, recovers the characteristic of liquid in high temperature；Especially, in temperature
Degree is less than or equal to that when 5 DEG C gel can be formed, after gel is formed, and temperature is more than after 70 DEG C, heating 3-5h, same solidifying
Glue reverts to liquid.
Adhesive of the present invention, wherein, the adhesive after gel is used as two after heating recovers cementitiousness
Secondary graft copolymerization prepares the seed of adhesive, prepares secondary adhesive.
Application of any adhesive of the present invention in decorative board is glued.
The beneficial effects of the present invention are：
(1) preferably, room temperature condition lower storage period, is more than 250 days starch adhesive storage stability prepared by the present invention, and in pole
Hold and deposited under cryogenic conditions up to 30 days, in addition, thermo-responsive hydro gel-fluid transformation performance is also equipped with, can be extensive by mode of heating
Multiple fluid state, possesses the characteristic that iterative cycles are utilized.
(2) starch adhesive prepared by the present invention loses adhesive property after overcoming starch adhesive low temperature gel
Defect, after possessing the characteristic that thermo-responsive hydro gel-fluid changes, gel by being grafted different types of acrylate monomer
Amylan can pass through common heating and recover to recover adhesive property simultaneously after fluid, it is or further common by secondary grafting
Poly- technology is to improve its adhesive property.Therefore, the starch adhesive reusable edible for preparing of the present invention, beneficial to industrialized production and
Promote.
(3) starch adhesive prepared by the present invention has preferable adhesive property, basically reaches HG/T2727-2010 institutes
The adhesive property of defined venamul.And under extreme conditions after gel, after heating recovery fluid,
It still has the adhesive property of virgin rubber stick more than 90%.
Embodiment
With reference to embodiment, the present invention will be further described.Listed embodiment, which is only demonstrated, to be used, and shows this
The spirit and scope of invention are not limited to details and its modification case in this.
Embodiment 1
This example demonstrates that the behavior pattern of the formula of adhesive, preparation method and adhesive.
（a）Dispensing information：
Contain following component in formula, be formulated (in mass), cornstarch 100g, ammonium persulfate 1.1g, sucrose-fatty
The g of ester 2, the g of vinylacetate 50, n-butyl acrylate 30g, the g of PVA-124 88 1.0, sodium hydrogensulfite 0.5g,
The g of urea 15, the ml of glycerine 6, hydrochloric acid are some, and sodium hydroxide is some, and water is some.Some in this formula are not unrestrictedly to use,
And refer to contain the concrete restriction index to the substance migration in concrete technology step.
（b）The step of preparing adhesive
（1）The acidolysis pretreatment of starch：By cornstarch with 0.5M hydrochloric acid with being made into 35%（w/w）Suspension, load four mouthfuls
Flask, is warming up to acidolysis 1.5h at 60 DEG C, and pH to 4.5 is adjusted with sodium hydroxide, while adding starch on dry basis weighs 10%
PVA2488 solution, starch on dry basis weighs 2% sucrose fatty ester, and tapioca starch dry basis 0.6% ammonium persulfate, blending
30min。
（2）Graft copolymerization：（1）Described in after blending reaction terminates, be warming up to 70 DEG C, starch on dry basis be added dropwise
Weigh 80%（w/w）Mix monomer, the volume ratio of vinylacetate and n-butyl acrylate is 1.67 in mix monomer:1, it is added dropwise
The duration of monomer is 2.5h, and add at 1.5h after the ammonium persulfate that starch on dry basis weighs 0.4% or so, several minutes plus
Enter the sodium hydrogensulfite with ammonium persulfate equivalent molar content, then whole graft reaction control be warming up to 85 DEG C within 3h,
And it is incubated the 30min removal complete monomers of unreacted.
（3）After graft reaction terminates, the % of starch on dry basis 6 plasticizer glycerine is added, starch on dry basis is added and weighs 15%
The urea of left and right, and adjusted with sodium acid carbonate after pH to 6, cooling discharge, packaging produces final starch-base timber adhesive.
(c) the adhesive property test of the adhesive obtained
Tested according to HG/T 2727-2010 venamul wood adhesives methods described, prepared wood-gluing
The compression shear dry strength MPa of agent is 7.8MPa, and wet strength is 3.3MPa, white appearance, storage time（25 DEG C, d >=250
My god, 0 ~ 4 DEG C, 30 days）
(d) the repeatable utility test of the adhesive obtained
Prepared wood adhesive is formed after gel at 4 DEG C, loses cementitiousness, but dried in 60 DEG C of baking ovens
Fluid liquid can be returned to after 240min, its compression shear dry strength is determined according to HG/T 2727-2010 methods describeds
MPa is 7.3MPa, the 93.6% of dry strength before being about, and wet strength is 3.05MPa, the 92.4% of wet strength before being about.
Embodiment 2
This example demonstrates that the behavior pattern of the formula of adhesive, preparation method and adhesive.
（a）Dispensing information：
Contain following component in formula, (in mass), tapioca 100g, the g of ammonium persulfate 1.2, polyglycereol are fatty for formula
The g of acid esters 1.5, vinylacetate 60 g, hydroxy-ethyl acrylate 30g, the 1.5g of PVAC polyvinylalcohol 1788, the g of urea 12, glycerine
8 ml, hydrochloric acid is some, and sodium hydroxide is some, and water is some.Some in this formula are not unrestrictedly to use, and are referred in specific work
Contain the concrete restriction index to the substance migration in skill step.
（b）The step of preparing adhesive
（1）The acidolysis pretreatment of starch：By tapioca with 0.5M hydrochloric acid with being made into 40%（w/w）Suspension, load four mouthfuls
Flask, is warming up to acidolysis 2.5h at 60 DEG C, and adjust pH to 4 with sodium hydroxide adds the PVA1788 that starch on dry basis weighs 15% simultaneously
Solution, starch on dry basis weighs 1.5% polyglyceryl fatty acid ester, and tapioca starch dry basis 0.8% ammonium persulfate, 30min is blended.
（2）Graft copolymerization：（1）Described in after blending reaction terminates, be warming up to 68 DEG C, starch on dry basis be added dropwise
Weigh 90%（w/w）Mix monomer, the volume ratio of vinylacetate and hydroxy-ethyl acrylate is 2 in mix monomer:1, it is added dropwise single
The duration of body is 2h, and add at 1.5h add after the ammonium persulfate that starch on dry basis weighs 0.4% or so, several minutes with
Then the sodium hydrogensulfite of ammonium persulfate equivalent molar content, whole graft reaction control be warming up to 85 DEG C within 2.5h, and
It is incubated 30min and removes the complete monomer of unreacted.
（3）After graft reaction terminates, the % of starch on dry basis 8 plasticizer glycerine is added, starch on dry basis is added and weighs 12%
The urea of left and right, and adjusted with sodium acid carbonate after pH to 6, cooling discharge, packaging produces final starch-base timber adhesive.
(c) the adhesive property test of the adhesive obtained
The compression shear dry strength MPa of prepared wood adhesive is 9.49MPa, and wet strength is 4.12MPa, white appearance,
Storage time（25 DEG C, d >=250 day, 0 ~ 4 DEG C, 50 days）
(d) the repeatable adhesive property test of the adhesive obtained
Prepared wood adhesive is formed after gel at 4 DEG C, and being dried in 70 DEG C of baking ovens can return to after 180 min
Fluid liquid, determines its compression shear dry strength MPa for 9.16 MPa, before being about according to HG/T 2727-2010 methods describeds
The 96.5% of dry strength, wet strength is 4.05 MPa, the 98.3% of wet strength before being about.
（e）The performance test of the adhesive of recycling
Prepared wood adhesive is formed after gel at 4 DEG C, is taken 200g to add in 500ml four-hole boiling flask, is heated to
70 DEG C start stirring, after treating that gel melts completely, add 0.3g ammonium persulfates, after stirring 10min is well mixed, then drip
Plus 30ml Vinyl Acetate Monomers, dripped off in 1.5h, be incubated 30min, be then warming up to 85 DEG C, and be incubated 30min removals not
Complete monomer is reacted, after cooling, starch wood adhesive is similarly obtained., according to side described in HG/T 2727-2010
The compression shear dry strength MPa of the prepared green lumber adhesive of method actual measurement is 10.79MPa, and wet strength is 5.02 MPa, outside
See pure white, storage time（25 DEG C, d >=250 day, 0 ~ 4 DEG C, 60 days）.
Embodiment 3
This example demonstrates that the behavior pattern of the formula of adhesive, preparation method and adhesive.
（a）Dispensing information：
Contain following component in formula, be formulated (in mass), wheaten starch 100g, the g of ammonium persulfate 1.5, propylene glycol fatty
Acid esters 3g, vinylacetate 45 g, Hexyl 2-propenoate 10g, Isooctyl acrylate monomer 10g, PVAC polyvinylalcohol 2088
1.25g, the g of urea 15, the ml of glycerine 8, hydrochloric acid is some, and sodium hydroxide is some, and water is some.Some in this formula are not unlimited
System is used, and refers to contain the concrete restriction index to the substance migration in concrete technology step.
（b）The step of preparing adhesive
（1）The acidolysis pretreatment of starch：By wheaten starch with 0.8M hydrochloric acid with being made into 30%（w/w）Suspension, load four mouthfuls
Flask, is warming up to the h of acidolysis 2 at 60 DEG C, and adjusting pH to 4.3 with sodium hydroxide, addition starch on dry basis weighs 12.5% simultaneously
PVA2088 solution, starch on dry basis weighs 1.5% polyglyceryl fatty acid ester, and the % of tapioca starch dry basis 1 ammonium persulfate, blending
30min。
（2）Graft copolymerization：（1）Described in after blending reaction terminates, be warming up to 68 DEG C, starch on dry basis be added dropwise
Weigh 85%（w/w）Mix monomer, the volume ratio of vinylacetate and Hexyl 2-propenoate/different monooctyl ester mixture is in mix monomer
1.8:1, the duration that monomer is added dropwise is 2h, and adds the ammonium persulfate that starch on dry basis weighs 0.5 % or so at 1.5h, number
The sodium hydrogensulfite with ammonium persulfate equivalent molar content is added after minute, whole graft reaction control is within 2.5h, so
After be warming up to 85 DEG C, and be incubated 30min and remove the complete monomer of unreacted.
（3）After graft reaction terminates, the % of starch on dry basis 8 plasticizer glycerine is added, starch on dry basis is added and weighs 15%
The urea of left and right, and adjusted with sodium acid carbonate after pH to 6, cooling discharge, packaging produces final starch-base timber adhesive.
(c) the adhesive property test of the adhesive obtained
The compression shear dry strength MPa of prepared wood adhesive is 8.77MPa, and wet strength is 3.22MPa, white appearance,
Storage time（25 DEG C, d >=200 day, 0 ~ 4 DEG C, 40 days）
(d) the repeatable adhesive property test of the adhesive obtained
Prepared wood adhesive is formed after gel at 4 DEG C, and stream can be returned to after baking 30min in 70 DEG C of baking ovens
Dynamic state, its compression shear dry strength MPa is 8.42MPa, and wet strength is 2.94MPa.
Embodiment 4
This example demonstrates that the behavior pattern of the formula of adhesive, preparation method and adhesive.
（a）Dispensing information：
Contain following component in formula, be formulated (in mass), farina 100g, the g of ammonium persulfate 1.3, polyglycerol ester
The g of fat acid esters 0.8, the g of sucrose fatty ester 1, the g of vinylacetate 70, lauryl ester 20g, polyvinyl alcohol
PVA1788 1.0g, the g of urea 15, the ml of glycerine 7, hydrochloric acid is some, and sodium hydroxide is some, and water is some.In this formula it is some not
It is unrestrictedly to use, and refers to contain the concrete restriction index to the substance migration in concrete technology step.
（b）The step of preparing adhesive
（1）The acidolysis pretreatment of starch：By farina with 1M hydrochloric acid with being made into 50%（w/w）Suspension, load four mouthfuls
Flask, is warming up to the h of acidolysis 1.5 at 60 DEG C, and adjust pH to 4 with sodium hydroxide adds the PVA1788 that starch on dry basis weighs 10% simultaneously
Solution, starch on dry basis weighs 0.8% polyglyceryl fatty acid ester and 1% sucrose fatty ester, and tapioca starch dry basis 0.9%
Ammonium persulfate, is blended 35min.
（2）Graft copolymerization：Step（1）Described in after blending reaction terminates, be warming up to 72 DEG C, starch be added dropwise
Dry basis 90%（w/w）Mix monomer, the volume ratio of vinylacetate and lauryl ester is 3.5 in mix monomer:1,
The duration that monomer is added dropwise is 2.5h, and adds at 1.5h the ammonium persulfate that starch on dry basis weighs 0.4% or so, several minutes it
The sodium hydrogensulfite with ammonium persulfate equivalent molar content is added afterwards, and then whole graft reaction control be warming up within 3h
85 DEG C, and it is incubated the 30min removal complete monomers of unreacted.
（3）After graft reaction terminates, the plasticizer glycerine of starch on dry basis 7% is added, starch on dry basis is added and weighs 15% left side
Right urea, and adjusted with sodium acid carbonate after pH to 6, cooling discharge, packaging produces final starch-base timber adhesive.
(c) the adhesive property test of the adhesive obtained
The compression shear dry strength MPa of prepared wood adhesive is 7.37MPa, and wet strength is 4.26MPa, white appearance,
Storage time（25 DEG C, d >=250 day, 0 ~ 4 DEG C, 60 days）
(d) the repeatable adhesive property test of the adhesive obtained
Prepared wood adhesive is formed after gel at 4 DEG C, and stream can be returned to after baking 60min in 60 DEG C of baking ovens
Dynamic state, its compression shear dry strength MPa is 6.81MPa, and wet strength is 3.85MPa.
（e）The performance test of the adhesive of recycling
Prepared wood adhesive is formed after gel at 4 DEG C, is taken 200g to add in 500ml four-hole boiling flask, is heated to
70 DEG C start stirring, after treating that gel melts completely, add 0.2g ammonium persulfates, after stirring 10min is well mixed, then drip
Plus 20ml Vinyl Acetate Monomers, dripped off in 1h, be incubated 30min, be then warming up to 85 DEG C, and it is not anti-to be incubated 30min removals
Complete monomer is answered, after cooling, the starch wood adhesive of regeneration is similarly obtained.The prepared new timber glue of actual measurement
The compression shear dry strength of stick is 7. 95MPa, and wet strength is 4.17 MPa, white appearance, storage time（25 DEG C, d >=
250 days, 0 ~ 4 DEG C, 60 days）.
Embodiment 5
This example demonstrates that the behavior pattern of the formula of adhesive, preparation method and adhesive.
（a）Dispensing information：
Contain following component in formula, be formulated (in mass), sweet potato starch 70g, waxy corn starch 30g, ammonium persulfate
1.5 g, the g of sucrose fatty ester 3, vinylacetate 80 g, Hexyl 2-propenoate 20g, the 0.6g of PVAC polyvinylalcohol 1788 gather
The g of vinyl alcohol PVA2488 0.6, the g of urea 10, the ml of glycerine 8, hydrochloric acid is some, and sodium hydroxide is some, and water is some.In this formula
It is some be not unrestrictedly to use, and refer to contain to the concrete restriction index of the substance migration in concrete technology step.
（b）The step of preparing adhesive
（1）The acidolysis pretreatment of starch：Sweet potato starch is made into 35% with 0.9M hydrochloric acid（w/w）Suspension, load four mouthfuls burning
Bottle, is warming up to the h of acidolysis 2.5 at 60 DEG C, and pH to 5 is adjusted with sodium hydroxide, while adding the PVA1788 that starch on dry basis weighs 12%
With PVA2488 solution mixtures（Both amount ratios are 1:1）, starch on dry basis weighs 3% sucrose fatty ester, and cassava dried bean noodles
Base weighs 1% ammonium persulfate, and 40min is blended.
（2）Graft copolymerization：（1）Described in after blending reaction terminates, be warming up to 71 DEG C, starch on dry basis be added dropwise
Weigh 100%（w/w）Mix monomer, the volume ratio of vinylacetate and Hexyl 2-propenoate is 4 in mix monomer:1, monomer is added dropwise
Duration be 3h, and add at 1.5h and to add and mistake after the ammonium persulfate that starch on dry basis weighs 0.5% or so, several minutes
Then the sodium hydrogensulfite of ammonium sulfate equivalent molar content, whole graft reaction control be warming up to 85 DEG C, and protect within 3.5h
Warm 30min removes the complete monomer of unreacted.
（3）After graft reaction terminates, the plasticizer glycerine of starch on dry basis 8% is added, starch on dry basis is added and weighs 10% left side
Right urea, and adjusted with sodium acid carbonate after pH to 6, cooling discharge, packaging produces final starch-base timber adhesive.
(c) the adhesive property test of the adhesive obtained
The compression shear dry strength MPa of prepared wood adhesive is 7.99MPa, and wet strength is 4.37MPa, white appearance,
Storage time（25 DEG C, d >=250 day, 0 ~ 4 DEG C, 50 days）
(d) the repeatable adhesive property test of the adhesive obtained
Prepared wood adhesive is formed after gel at 4 DEG C, and stream can be returned to after baking 60min in 60 DEG C of baking ovens
Dynamic state, its compression shear dry strength MPa is 6.4MPa, and wet strength is 3.52MPa.
Claims (10)
1. a kind of environmentally friendly starch-based glue stick, it is characterised in that the adhesive includes following raw material components：Starch, gathers
Vinyl alcohol, ammonium persulfate, emulsifying agent, mix monomer, ammonium persulfate, glycerine, urea, hydrochloric acid, sodium hydroxide, moisture.
2. a kind of environmentally friendly starch-based glue stick, it is characterised in that the adhesive is made by following raw material components, by quality
Meter, containing 100 parts of starch, 6 parts of polyvinyl alcohol, 0.4-1 parts of ammonium persulfate, 1.5-3 parts of emulsifying agent, 70-100 parts of mix monomer,
0.3-0.5 parts of sodium hydrogensulfite, 5-8 parts of glycerine, 10-20 parts of urea, water, hydrochloric acid, sodium hydroxide.
3. adhesive according to claim 1, it is characterised in that during the polyvinyl alcohol is PVA1788,2088,2488
One or more, and the polyvinyl alcohol is the mass concentration 10g/100g solution configured with water.
4. adhesive according to claim 1, it is characterised in that the emulsifying agent is sucrose fatty ester, propane diols fat
One or more in fat acid esters, polyglyceryl fatty acid ester.
5. adhesive according to claim 1, it is characterised in that the mix monomer is by vinylacetate and acrylate
Monomer is 4-2 by volume：1 composition；
Wherein, acrylate monomer is by n-butyl acrylate, isobutyl acrylate, Hexyl 2-propenoate, lauryl ester, third
The composition of the different monooctyl ester of olefin(e) acid, one or two kinds of in hydroxyethyl acrylate.
6. adhesive according to claim 1, it is characterised in that the starch is tapioca, sweet potato starch, potato
One or more in starch, cornstarch, waxy corn starch, wheaten starch.
7. a kind of preparation method of environmentally friendly starch-based glue stick, it is characterised in that this method comprises the following steps：
（1）The acidolysis pretreatment of starch：Starch is made into 30 ~ 50% with 0.5 ~ 1 mole every liter of hydrochloric acid（w/w）Suspension,
In reaction vessel, 1 ~ 3h of acidolysis at 60 DEG C is warming up to；With between sodium hydroxide regulation pH to 4 ~ 5, while adding starch on dry basis weight
10% ~ 15% polyvinyl alcohol, 1.5% ~ 3% emulsifying agent of starch on dry basis weight, and starch on dry basis weigh 0.4 ~ 1% ammonium persulfate,
30 ~ 40min is blended.
Wherein, emulsifying agent is sucrose fatty ester, methyl glycol fatty acid ester, the one or more in polyglyceryl fatty acid ester；It is poly-
Vinyl alcohol is the one or more in PVA1788,2088,2488, and the polyvinyl alcohol is the mass concentration configured with water
10g/100g solution.
(2) graft copolymerization：Step（1）Described in after blending reaction terminates, be warming up to 65 ~ 72 DEG C, be gradually added starch
Dry basis 70 ~ 100%（w/w）Mix monomer；The duration for adding monomer is 2.5h, grafting time be 1.5h or so again
The ammonium persulfate that starch on dry basis weighs 0.3% ~ 0.5% is added, the sodium hydrogensulfite with ammonium persulfate equivalent molar content is then added,
Then whole graft reaction control be warming up to 85 DEG C, and be incubated the 30min removal complete monomers of unreacted within 3h.
Wherein, mix monomer is that vinylacetate and variety classes acrylate are constituted, and its volume ratio is 4:1~2:1；Acrylic acid
Ester monomer is by n-butyl acrylate, isobutyl acrylate, Hexyl 2-propenoate, lauryl ester, Isooctyl acrylate monomer, propylene
The composition of one or two kinds of in sour hydroxyethyl ester.
（3）After graft reaction terminates, the 60% glycerite plasticizer that starch on dry basis weighs 5% ~ 8% is added, starch is added and does
Base weighs 10 ~ 20% urea, and is adjusted with sodium acid carbonate after pH to 6, and cooling discharge packs the starch-based glue stick produced.
8. adhesive according to claim 7, it is characterised in that synthesized adhesive has Thermo-sensitive, adhesive exists
Gel is formed when temperature≤5 DEG C, and when temperature is more than 70 DEG C, liquid is reverted to after heating 3-5h.
9. the adhesive described in above-mentioned any claim, it is characterised in that the adhesive after gel recovers viscous in heating
After knot ability, the seed of adhesive is prepared as secondary grafting copolyreaction, secondary adhesive is prepared.
10. application of the adhesive in decorative board is glued described in above-mentioned any claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710539295.3A CN107142053A (en) | 2017-07-04 | 2017-07-04 | A kind of environmentally friendly starch-based glue stick and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710539295.3A CN107142053A (en) | 2017-07-04 | 2017-07-04 | A kind of environmentally friendly starch-based glue stick and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107142053A true CN107142053A (en) | 2017-09-08 |
Family
ID=59785958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710539295.3A Pending CN107142053A (en) | 2017-07-04 | 2017-07-04 | A kind of environmentally friendly starch-based glue stick and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107142053A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110583299A (en) * | 2019-09-24 | 2019-12-20 | 吉林大学 | Acidic degradable biomass seedling raising tray with controllable water resistance and preparation method thereof |
| CN110964467A (en) * | 2019-12-24 | 2020-04-07 | 彭敏 | High-strength adhesive for corrugated board and preparation method thereof |
| CN111040666A (en) * | 2019-12-31 | 2020-04-21 | 贵州佳德赛新材料有限公司 | Preparation method of plasticized gelatinized starch-based adhesive |
| CN111205794A (en) * | 2020-02-26 | 2020-05-29 | 江南大学 | Starch adhesive for thermosetting artificial board and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031078A (en) * | 2010-12-01 | 2011-04-27 | 江南大学 | Starch-based wood adhesive and preparation method and application thereof |
| CN102086360A (en) * | 2010-12-07 | 2011-06-08 | 江南大学 | Modified starch-based wood adhesive as well as preparation method and application thereof |
| CN102585741A (en) * | 2012-02-16 | 2012-07-18 | 江南大学 | Method for preparing starch adhesive for timber through emulsion polymerization |
| CN103627352A (en) * | 2013-12-16 | 2014-03-12 | 江南大学 | Emulsion type wood starch adhesive 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 |
-
2017
- 2017-07-04 CN CN201710539295.3A patent/CN107142053A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031078A (en) * | 2010-12-01 | 2011-04-27 | 江南大学 | Starch-based wood adhesive and preparation method and application thereof |
| CN102086360A (en) * | 2010-12-07 | 2011-06-08 | 江南大学 | Modified starch-based wood adhesive as well as preparation method and application thereof |
| CN102585741A (en) * | 2012-02-16 | 2012-07-18 | 江南大学 | Method for preparing starch adhesive for timber through emulsion polymerization |
| CN103627352A (en) * | 2013-12-16 | 2014-03-12 | 江南大学 | Emulsion type wood starch adhesive 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 |
Non-Patent Citations (1)
| Title |
|---|
| 刘程等: "《表面活性剂应用手册》", 30 September 2004, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110583299A (en) * | 2019-09-24 | 2019-12-20 | 吉林大学 | Acidic degradable biomass seedling raising tray with controllable water resistance and preparation method thereof |
| CN110964467A (en) * | 2019-12-24 | 2020-04-07 | 彭敏 | High-strength adhesive for corrugated board and preparation method thereof |
| CN111040666A (en) * | 2019-12-31 | 2020-04-21 | 贵州佳德赛新材料有限公司 | Preparation method of plasticized gelatinized starch-based adhesive |
| CN111205794A (en) * | 2020-02-26 | 2020-05-29 | 江南大学 | Starch adhesive for thermosetting artificial board and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107142053A (en) | A kind of environmentally friendly starch-based glue stick and preparation method thereof | |
| CN104250334B (en) | Preparation method for vinyl chloride-acrylic ester copolymer | |
| CN101418199B (en) | Method for preparing starch adhesive for monomer complex formulation wood | |
| US4044197A (en) | Thermally self-cross-linkable ethylene/vinyl acetate copolymers | |
| CN101367898B (en) | PVDC copolymerization emulsion, preparation and uses thereof | |
| CN111454402B (en) | Acrylate emulsion leather finishing agent and preparation method thereof | |
| CN102676091A (en) | Adhesive composition and application of adhesive composition | |
| CN105820780B (en) | A kind of starch adhesive for timber based on pre-emulsification technology and preparation method thereof | |
| RU2011101772A (en) | HEAT-RESISTANT POLYMERIC DISPERSION OBTAINED BY EMULSION POLYMERIZATION | |
| CN104293245A (en) | Vinyl acetate wood adhesive and preparation method thereof | |
| CN108251047B (en) | Preparation method of composite starch adhesive | |
| EP0066174B1 (en) | Vinyl acetate-ethylene emulsions for nonwoven goods | |
| CN104109220A (en) | Composite modified starch emulsion for coating and preparation method of emulsion | |
| CN107523244A (en) | A kind of acrylic ester adhesive with network blackboard and preparation method thereof | |
| CN103045136B (en) | Environment-friendly high-speed cigarette holder glue for cigarettes and preparation method thereof | |
| CN113072663A (en) | Heat-sealing acrylic emulsion for paper and preparation method thereof | |
| CN106749936A (en) | Vinyl acetate binder and preparation method thereof | |
| CN108822766B (en) | Low-solid high-viscosity polyvinyl acetate emulsion and preparation method thereof | |
| CN104194695A (en) | Grafted nano ambary fiber crystal whisker modified urea formaldehyde resin adhesive and preparation method thereof | |
| CN104893629B (en) | A kind of timber normal temperature cure bio oil starch adhesive and preparation method thereof | |
| CN105885743A (en) | Modified polyvinyl-alcohol binding agent | |
| CN108864628A (en) | A kind of preparation method of high temperature resistant biological plastics | |
| CN107383119A (en) | A kind of method using alkyl-glucoside Lipase absobed modified acrylate emulsion | |
| CN107459609A (en) | A kind of self-cross linking type epoxy/compound soap-free emulsion of polyacrylate and its preparation technology | |
| CN106634738A (en) | Starch-based wood adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170908 |