CN104178057B - A kind of Organic substance/starch composite water soluble adhesive and preparation method thereof and application - Google Patents
A kind of Organic substance/starch composite water soluble adhesive and preparation method thereof and application Download PDFInfo
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- CN104178057B CN104178057B CN201410428613.5A CN201410428613A CN104178057B CN 104178057 B CN104178057 B CN 104178057B CN 201410428613 A CN201410428613 A CN 201410428613A CN 104178057 B CN104178057 B CN 104178057B
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Abstract
The present invention relates to corrugated board adhesive field, be specifically related to a kind of Organic substance/starch composite water soluble adhesive and its preparation method and application.This adhesive is to add oxidant, paste agent and compounded mix reaction in starch major ingredient after cross-linking to obtain；Wherein, described starch major ingredient include amylose and amylopectin, the described starch after crosslinking be by first with the first cross-linking agent and hydrophilizing agent to amylose pretreatment after, then react after mixing with the second cross-linking agent and amylopectin and obtain；And described first cross-linking agent is isophorone diisocyanate, described second cross-linking agent is trimethylolpropane, and described hydrophilizing agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid；Wherein relative to starch major ingredient raw material 180 220 weight portion, oxidant addition is 7 10 weight portions.The present invention can solve the problem of Poor cohesion in corrugated case production process, improves moisture-proof and the application property of corrugated case gluing agent so that it is reach the requirement of safety and environmental protection.
Description
Technical field
The present invention relates to corrugated board adhesive field, the Organic substance/starch being specifically related to a kind of environment-friendly type is multiple
Close Aqueous Adhesives and its preparation method and application.
Background technology
China is packaging big country in the world, and corrugated case occupies critical role, especially in China's packaging industry
It is that the Concha Arcae package paper industry of China accelerates development step, at present especially after entering 21 century
Define the production base of North China, Yangtze River Delta, the big corrugated paper of the Delta of the Pearl River three and products thereof
Ground.Why Concha Arcae package paper and derived product thereof obtain high speed development, are because sending out of corrugated paper industry
Exhibition meets the demand of Environmental Protection in China, sustainable development and conservation-minded society, lightweight that it possesses, eleganceization,
The features such as repeatability, designability can meet the packaging demand of all trades and professions product significantly.
Because These characteristics, corrugated paper is more suitable for the developing direction of following package packing supplies, but raw at it
During product, one of problem of most critical is a difficult problem for the Poor cohesion of corrugated paper.Corrugated case is by case paper
The plate object that plate and corrugating medium are bonded.Bondd by specific adhesive between them, so,
Adhesive is the main auxiliary material during corrugated board production.Its quality diameter have impact on corrugated paper
The performance of case.In corrugated case production process, the adhesive kind of use is a lot, mainly have starch series,
Polyvinyl alcohol, acetate emulsion, sodium silicate etc..At present, the most widely used be starch series glue
Glutinous agent.This is mainly due to when preparing Oxytarch, and in ative starch, the methylol on glucose unit is by oxygen
Chemical conversion carboxyl so that the stability of adhesive is improved significantly；Meanwhile, oxidation reaction decreases starch and divides
The quantity of hydroxyl in son so that molecular association is obstructed, reduces the binding ability of intermolecular hydrogen bonding.It addition,
In course of reaction, glucosides chain break makes macromolecules degradation, thus reduces the viscosity of starch adhesive, and
Improve its performance such as mobility, rate of drying, be allowed to practicality and strengthen.
Summary of the invention
Present invention solves the technical problem that and be: the present inventor finds after studying with keen determination, traditional starch series glue
Glutinous agent there are disadvantages that, as need during preparing starch adhesive to use Borax as cross-linking agent, and boron
Sand is poisonous, be in contact with it for a long time there will be neurasthenia, arthralgia chronic poisoning or vomiting, diarrhoea, erythema,
Cycle system disorders, suffer a shock, the acute poisoning phenomenon such as stupor；The viscosity of the starch adhesive of preparation is not easy
Controlling, such as hyperoxidation in preparation process, then the cohesiveness of adhesive declines；When degree of oxidation is inadequate, glue
The poor stability of glutinous agent, mobility is little, and viscosity is big and causes being difficult to applying glue；Moisture-proof is the best, when weather tide
Wet, then there is corrugated board the softest, the problems such as the rate of drying of adhesive is slow, Poor cohesion phenomenon increases.
So, in order to overcome the deficiencies in the prior art, the present invention provides a kind of and prepares the ring without boron compound
Guarantor, moisture-proof, the adjustable Organic substance/starch of viscosity are combined the technology of high viscosity Aqueous Adhesives.I.e. provide one
Kind safety and environmental protection, moisture resistance properties, adhesive property are good, the adjustable Organic substance of viscosity/starch combined corrugated board
Adhesive, and the preparation method of this environment-friendly type composite adhesive is provided.
Specifically, for the deficiencies in the prior art, the technical scheme is that
A kind of Organic substance/starch composite water soluble adhesive, it is characterised in that it is by starch master after cross-linking
Material adds oxidant, paste agent and compounded mix reaction obtain；
Wherein, described starch major ingredient includes amylose and amylopectin, and the described starch after crosslinking is logical
After first amylose being carried out pretreatment with the first cross-linking agent and hydrophilizing agent, then with the second cross-linking agent and side chain
React after starch mixing and obtain；
Wherein, described first cross-linking agent is isophorone diisocyanate, and described second cross-linking agent is three hydroxyl first
Base propane, described hydrophilizing agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid；Wherein relative to starch major ingredient
Raw material 180-220 weight portion, oxidant addition is 7-10 weight portion.
Preferably, in above-mentioned Aqueous Adhesives, relative to starch major ingredient raw material 180-220 weight portion, crosslinking
Agent total amount is 60-80 weight portion, preferably 65-75 weight portion, and hydrophilizing agent is 4.8-5.6 weight portion, preferably
For 5.0-5.4 weight portion, oxidant is 7-10 weight portion, preferably 8-9.5 weight portion；Wherein, first
The mass ratio of cross-linking agent and the second cross-linking agent is 8-15: 1, and preferably the two mass ratio is 11-12: 1.
Preferably, in above-mentioned Aqueous Adhesives, paste agent is 25-35 weight portion, preferably 28-33 weight
Part, compounded mix 10-20 weight portion, preferably 12-18 weight portion.
Preferably, in above-mentioned Aqueous Adhesives, described oxidant includes persulfuric acid hydrogen salt and or hydrogen peroxide；
Described paste agent is selected from sodium hydroxide or potassium hydroxide；Described compounded mix is montmorillonite.
Preferably, in above-mentioned Aqueous Adhesives, described in described starch major ingredient, the weight portion of amylose is
40-50, the weight portion of described amylopectin is 140-170.
Preferably, in above-mentioned Aqueous Adhesives, when the mixture that oxidant is persulfuric acid hydrogen salt and hydrogen peroxide,
Persulfuric acid hydrogen salt is 5-7.2 weight portion, preferably 5.5-6.8 weight portion, and hydrogen peroxide is 2-2.8 weight portion,
It is preferably 2.5-2.7 weight portion.
Preferably, in above-mentioned Aqueous Adhesives, also need to add cosolvent, preferably acetone.
Preferably, in above-mentioned Aqueous Adhesives, the viscosity of described adhesive is 25070-26800mPa S.
The present invention also provides for the preparation method of above-mentioned Organic substance/starch composite water soluble adhesive, including following step
Rapid:
(1) with the first cross-linking agent and hydrophilizing agent, the amylose in starch major ingredient is carried out pretreatment；
(2) amylose after the pre-treatment adds the second cross-linking agent and amylopectin reacts；
(3) addition paste agent, oxidant, compounded mix carry out reaction and obtain Organic substance/starch composite water soluble
Adhesive；
Wherein, described first cross-linking agent is isophorone diisocyanate, and described second cross-linking agent is three hydroxyl first
Base propane, hydrophilizing agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid.
Preferably, in the preparation method of above-mentioned Organic substance/starch composite water soluble adhesive, comprise the steps:
(1) the pretreatment reaction stage of amylose comprises the steps:
Reaction is crosslinked in 80-100 DEG C after (i) amylose and the mixing of the first cross-linking agent；
(ii) product that addition hydrophilizing agent and step (i) obtain is in 40-60 DEG C of reaction；
(2) the normal reaction stage comprises the steps:
I () adds the second cross-linking agent and adds amylopectin after 80-100 DEG C of reaction and carry out in 30-50 DEG C anti-
Should；
(ii) there is oxidation reaction in 50-70 DEG C after adding oxidant；
(iii) add paste agent to react；And
Add before or after either step after (i) step in amylose pretreatment reaction stage
Montmorillonite generation compound reaction obtains Organic substance/starch composite water soluble adhesive.
That is, montmorillonite can add before or after (ii) in amylose pretreatment reaction stage, it is possible to
Reaction is participated in add before or after either step in step (2).
Preferably, in above-mentioned preparation method, amylose the pretreatment reaction stage (i) step it
Add montmorillonite afterwards before (ii) step to react with (i) products therefrom.
The present invention also provides for a kind of Organic substance/starch composite water soluble adhesive, above-mentioned preparation method prepare.
The present invention also provides for above-mentioned Organic substance/starch composite water soluble adhesive in corrugated board adhesive field
Application.
The present invention can simplify the preparation technology of high-performance starch adhesive, solves in corrugated case production process viscous
Close bad problem, improve moisture-proof and the application property of corrugated case gluing agent so that it is reach safety and environmental protection
Requirement.
Accompanying drawing explanation
Fig. 1 is the thermal gravimetric analysis curve of the embodiment of the present invention one gained Organic substance/starch composite water soluble adhesive.
Detailed description of the invention
The present invention uses two step method to prepare Organic substance/starch composite water soluble adhesive, use diisocyanate with
Trimethylolpropane replaces poisonous Borax as cross-linking agent, changes traditional being prepared by oxidation gelatinized starch
The method of starch series adhesive, is sent out with the part of hydroxyl on water soluble starch strand by diisocyanate
Raw reaction, generates highly polar carbamate groups, increase the stability of starch adhesive, lower temperature resistance and
Adhesive property.And use trimethylolpropane to react with isocyanate groups, increase the friendship of adhesive
Connection degree, then add the raw materials such as oxidant, paste agent, compounded mix, water and prepare high-performance environmentally-friendly type and have
Machine thing/Starch composite adhesive sticks agent.And use the mixture of amylose and two kinds of starch of amylopectin for forming sediment
Powder major ingredient, amylopectin is because wherein contain phosphate ester, it is possible to there is gelatinizing and become a kind of well
Adhesive；It addition, amylose can promote starch generation gelatification, thus increase the viscous of starch adhesive
Property.This patent use the mixture of above two starch carry out the preparation of starch base, thus processability
Excellent starch series adhesive.
The present invention one preferred embodiment in, the present invention provides a kind of Organic substance/starch Compound Water
Property adhesive, the component of this adhesive and parts by weight are:
Amylose (potato starch): 40-50 weight portion, amylopectin (corn starch): 140-170
Weight portion, sodium hydroxide: 25-35 weight portion, potassium hydrogen persulfate: 5-7.2 weight portion, hydrogen peroxide: 2-2.86
Weight portion, isophorone diisocyanate: 53-75 weight portion, trimethylolpropane: 5-6.6 weight portion,
Organo montmorillonite: 10-20 weight portion, dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid: 4.8-5.6
Weight portion, deionized water: 650-750 weight portion, acetone: 10-30 weight portion.
The present invention one preferred embodiment in, Organic substance of the present invention/starch composite water soluble glue
The preparation method of glutinous agent, comprises the steps:
A, amylose is put into 50 DEG C, vacuum be 0.05MPa thermostatic drying chamber in be dried 4 hours
Standby.Amylopectin is dissolved in and deionized water uses Glass rod quickly to stir into uniform starch fluid standby；
B, isophorone diisocyanate is added clean there are reflux condenser, thermometer and agitating device
Four-hole boiling flask, flask is put in water bath with thermostatic control.In flask, addition acetone is as cosolvent, will be dried
Good amylose is added slowly in flask, in adding procedure, remains that agitating device is that machinery stirs
Mix state, make isophorone diisocyanate and the starch being dried Quick uniform under the effect of cosolvent mix
Close, then water bath with thermostatic control temperature is risen to 80-100 DEG C, stirring reaction 2 hours；
C, water bath with thermostatic control is cooled to 40-60 DEG C, dihydromethyl propionic acid and organo montmorillonite are mixed, quickly
Adding in four-hole boiling flask, stirring reaction 15 minutes at 40-60 DEG C, then by water bath with thermostatic control temperature liter
React 1 hour to 80-100 DEG C；
D, trimethylolpropane is uniformly mixed with acetone, add stirring reaction 1 hour in four-hole boiling flask to
After.The amylopectin liquid modulated in a, to 35-45 DEG C, is poured slowly into four-hole boiling flask by reduction bath temperature
In, tune up mixing speed and react 30 minutes；
E, by the most soluble in water to the potassium hydrogen persulfate weighed up and hydrogen peroxide, and be successively added slowly to reaction
In system, in adding procedure, it is to slowly warm up to 50-70 DEG C, quickly stirring reaction 20 minutes；
F, reduction bath temperature are to room temperature, and sodium hydroxide is soluble in water, are added slowly in four-hole boiling flask,
Quickly stirring hybrid reaction 30 minutes.Organic substance/the Starch composite adhesive obtaining white sticks agent.
In the present invention, the polysaccharide chain that described amylose D-Glucose base connects with α-(Isosorbide-5-Nitrae) glycosidic bond,
And outside amylopectin is connected divided by α-Isosorbide-5-Nitrae-glycosidic bond between glucose molecule, also have with α-1,6-glycosidic bond
It is connected；In the present invention, isophorone diisocyanate selected by the first cross-linking agent, it is characterised in that two different
The activity of cyanic acid base (-N=C=O) is different, more active with the isocyanate group that carbocyclic ring is joined directly together, with
The isocyanate group that methylene is connected is active relatively low due to sterically hindered effect, is formed sediment with straight chain by the first cross-linking agent
After powder mixing, the isocyanate group that the part of hydroxyl of amylose is stronger with activity on the first cross-linking agent reacts, shape
Become activity on carbamate groups, follow-up hydrophilizing agent and the hydroxyl of the second cross-linking agent and the first cross-linking agent more weak
Isocyanate group reaction, formed carbamate groups and complete crosslinking；The feature of hydrophilizing agent used in the present invention
Being, it comprises two kinds of groups: hydroxyl and hydrophilic group (carboxyl).Wherein, hydroxyl and the first cross-linking agent
Isocyanate group reaction, generate carbamate groups, the hydrophilic group on hydrophilizing agent by hydrogen bond action with
Second cross-linking agent keyed jointing, its hydrophilic group gives Organic substance of the present invention/starch composite water soluble adhesive parent
Aqueous so that it is realize the adjustability of product viscosity in application process, can adjust by changing solvent quality
The viscosity of joint product.
In order to the technical characteristic of the present invention, purpose and effect are more clearly understood from, existing detailed with embodiment
Describe the detailed description of the invention of the bright present invention in detail.
In the following embodiments, the information of each reagent used is as follows:
Isophorone diisocyanate (IPDI), industrial goods, Aladdin reagent；
Amylose (potato starch), industrial goods, Aladdin reagent；
Amylopectin (corn starch), industrial goods, Aladdin reagent；
Dihydromethyl propionic acid (DMPA), industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product；
Dimethylolpropionic acid, industrial goods, Shanghai Peng Teng Fine Chemical Co., Ltd product；
Sodium hydroxide (NaOH), analytical pure, Tianjin good fortune chemical reagent factory in morning；
Potassium hydrogen persulfate, analytical pure, Brassica rapa L analyses Chemical Industry Science Co., Ltd；
Hydrogen peroxide, analytical pure, Tianjin Fu Yu Fine Chemical Co., Ltd；
Trimethylolpropane, analytical pure, Chengdu Ke Long chemical reagent factory；
Acetone, analytical pure, Chemical Co., Ltd. in pairs of Yantai City；
Organo montmorillonite, industrial goods, Zhengzhou great waves Chemical Co., Ltd..
Wherein, organo montmorillonite of the present invention can be by buying or with this area routine method of modifying to inorganic
(hydroxy radical content accounts for the 60% of functional group content to the imvite modified organo montmorillonite obtaining hydroxyl and carboxyl
Above, carboxyl-content accounts for less than the 40% of functional group content), in following embodiment, organo montmorillonite used is
The industrial goods bought from Zhengzhou great waves Chemical Co., Ltd..
Embodiment one
A kind of Organic substance/starch composite water soluble adhesive, proportioning raw materials is as shown in table 1.
Table 1 Organic substance/starch composite water soluble adhesive proportioning raw materials table (quality, unit: g)
Preparation method:
A, the amylose of 45 weight portions being put into 50 DEG C, vacuum is the thermostatic drying chamber of 0.05MPa
In be dried 4 hours standby.The amylopectin of 155 weight portions is dissolved in the deionized water of 550 weight portions and make
Uniform starch fluid is quickly stirred into standby with Glass rod；
B, the isophorone diisocyanate of 65 weight portions is added clean there are reflux condenser, thermometer
With the four-hole boiling flask of agitating device, flask is put in water bath with thermostatic control.15 weight portions are added in flask
The amylose of 45 dried weight portions, as cosolvent, is added slowly in flask, is adding by acetone
During adding, remain that agitating device is mechanical agitation state, make isophorone diisocyanate and be dried
Starch under the effect of cosolvent Quick uniform mixing, then water bath with thermostatic control temperature is risen to 90 DEG C,
Stirring reaction 2 hours；
C, water bath with thermostatic control is cooled to 50 DEG C, by the DMPA of 5.2 weight portions and having of 15.7 weight portions
Machine montmorillonite mixes, and is rapidly added in four-hole boiling flask, stirring reaction 15 minutes at 50 DEG C, then will
Water bath with thermostatic control temperature rises to 90 DEG C and reacts 1 hour；
D, the trimethylolpropane of 5.5 weight portions and the acetone of 5 weight portions are uniformly mixed, add four to
After in mouth flask, stirring is reacted 1 hour.Reduction bath temperature is to 40 DEG C, and the side chain that will modulate in a forms sediment
Powder liquid is poured slowly in four-hole boiling flask, tunes up mixing speed and reacts 30 minutes；
E, the potassium hydrogen persulfate of 6.3 weight portions and the hydrogen peroxide of 2.5 weight portions are dissolved in 40 weight portions respectively
With in the deionized water of 10 weight portions, and successively it is added slowly in reaction system, in adding procedure,
It is to slowly warm up to 60 DEG C, quickly stirring reaction 20 minutes；
F, reduce bath temperature to room temperature, the sodium hydroxide of 31 weight portions is dissolved in 100 weight portions go from
In sub-water, it is added slowly in four-hole boiling flask, quickly stirring hybrid reaction 30 minutes.Obtain having of white
Machine thing/starch composite water soluble adhesive.
The HADV-II+PRO type rotating cylinder viscometer using U.S. Brookfield detects the viscous of composite adhesive
Degree, the mean values of detection is 25070mPa S, meets the viscosity requirement as corrugated board adhesive；
According to the solid content of the standard test adhesive of ISO 124:1997, the solid content obtaining adhesive is 32.5%,
Possessing preferable adhesive non-volatile part content, drying property is preferable；Prunus mume (sieb.) sieb.et zucc. Teller-torr benefit thermogravimetric is used to divide
The adhesive of preparation is carried out by analyzer (model: METTLER TOLEDO TGA/DSC 1analyzer)
Thermal stability analysis, analysis result as it is shown in figure 1, from figure decomposition curve it can be seen that preparation gluing
The initial decomposition temperature of agent is about 272.1 DEG C, and final decomposition temperature is about 445 DEG C, illustrates to use this patent
Adhesive prepared by middle method possesses preferable thermostability.Use Hunan instrument H1850 type centrifuge to preparation
Adhesive is centrifuged Detection of Stability test, is divided in by sample in two centrifuge tubes, and centrifugal rotational speed is
3000 revs/min, centrifugal 3 times altogether, each 5 minutes, find the sample of one of them centrifuge tube from
Occurring a little precipitation after heart second time, centrifuged deposit increases for the third time；The sample of another one centrifuge tube exists
Third time is centrifugal there is a little precipitation.Illustrate preparation sample the storage phase about 4 months to 6 months it
Between, illustrate that the composite adhesive that in this patent prepared by method possesses preferable storage stability.
Embodiment two
A kind of Organic substance/starch composite water soluble adhesive, preparation method is as follows:
A, the amylose of 40 weight portions being put into 50 DEG C, vacuum is the thermostatic drying chamber of 0.05MPa
In be dried 4 hours standby.The amylopectin of 140 weight portions is dissolved in the deionized water of 550 weight portions and make
Uniform starch fluid is quickly stirred into standby with Glass rod；
B, the isophorone diisocyanate of 53 weight portions is added clean there are reflux condenser, thermometer
With the four-hole boiling flask of agitating device, flask is put in water bath with thermostatic control.15 weight portions are added in flask
The amylose of 40 dried weight portions, as cosolvent, is added slowly in flask, is adding by acetone
During adding, remain that agitating device is mechanical agitation state, make isophorone diisocyanate and be dried
Starch under the effect of cosolvent Quick uniform mixing, then water bath with thermostatic control temperature is risen to 80 DEG C,
Stirring reaction 2 hours；
C, water bath with thermostatic control is cooled to 40 DEG C, by the trihydroxy methyl butanoic acid of 4.8 weight portions and 10 weight portions
Organo montmorillonite mixes, and is rapidly added in four-hole boiling flask, stirring reaction 15 minutes at 40 DEG C, then
Water bath with thermostatic control temperature rises to 80 DEG C react 1 hour；
D, the trimethylolpropane of 5 weight portions and the acetone of 5 weight portions are uniformly mixed, add four mouthfuls to
After in flask, stirring is reacted 1 hour.Reduce bath temperature to 35 DEG C, the amylopectin that will modulate in a
Liquid is poured slowly in four-hole boiling flask, tunes up mixing speed and reacts 30 minutes；
E, the hydrogen persulfate sodium of 5 weight portions and the hydrogen peroxide of 2 weight portions are dissolved in respectively 35 weight portions and
In the deionized water of 10 weight portions, and successively it is added slowly in reaction system, in adding procedure, slow
Slowly 50 DEG C it are warming up to, quickly stirring reaction 20 minutes；
F, reduce bath temperature to room temperature, the sodium hydroxide of 25 weight portions is dissolved in 90 weight portions go from
In sub-water, it is added slowly in four-hole boiling flask, quickly stirring hybrid reaction 30 minutes.Obtain having of white
Machine thing/Starch composite adhesive sticks agent.
Use the method identical with embodiment one and instrument, multiple to the Organic substance/starch prepared by embodiment two
Closing Aqueous Adhesives to detect, according to testing result, the mean values of described product viscosity value is
24800mPa S, meets the viscosity requirement as corrugated board adhesive；Record the solid content of adhesive
Being 31%, possess preferable adhesive non-volatile part content, drying property is preferable；Use prunus mume (sieb.) sieb.et zucc. Teller-Tuo Li
Many thermogravimetric analyzers (TG) carry out thermal stability analysis (not shown) to the adhesive of preparation, can obtain glue
The initial decomposition temperature of glutinous agent is about 265.7 DEG C, and final decomposition temperature is about 440 DEG C, illustrates to use this specially
The adhesive that in profit prepared by method possesses preferable thermostability；By centrifugal test, can obtain adhesive deposits the phase
About between 3 months to 5 months, illustrate that the composite water soluble adhesive prepared with method in this patent possesses
Preferably storage stability.
Embodiment three
A kind of Organic substance/starch composite water soluble adhesive, preparation method is as follows:
A, the amylose of 50 weight portions being put into 50 DEG C, vacuum is the thermostatic drying chamber of 0.05MPa
In be dried 4 hours standby.The amylopectin of 170 weight portions is dissolved in the deionized water of 590 weight portions and make
Uniform starch fluid is quickly stirred into standby with Glass rod；
B, the isophorone diisocyanate of 75 weight portions is added clean there are reflux condenser, thermometer
With the four-hole boiling flask of agitating device, flask is put in water bath with thermostatic control.20 weight portions are added in flask
The amylose of 50 dried weight portions, as cosolvent, is added slowly in flask, is adding by acetone
During adding, remain that agitating device is mechanical agitation state, make isophorone diisocyanate and be dried
Starch under the effect of cosolvent Quick uniform mixing, then water bath with thermostatic control temperature is risen to 100 DEG C,
Stirring reaction 2 hours；
C, water bath with thermostatic control is cooled to 60 DEG C, by trihydroxy methyl propanoic acid and 20 weight portions of 5.6 weight portions
Organo montmorillonite mixing, be rapidly added in four-hole boiling flask, at 60 DEG C stirring reaction 15 minutes, so
After water bath with thermostatic control temperature risen to 100 DEG C react 1 hour；
D, the trimethylolpropane of 6.6 weight portions and the acetone of 5 weight portions are uniformly mixed, add four to
After in mouth flask, stirring is reacted 1 hour.Reduction bath temperature is to 45 DEG C, and the side chain that will modulate in a forms sediment
Powder liquid is poured slowly in four-hole boiling flask, tunes up mixing speed and reacts 30 minutes；
E, the hydrogen persulfate ammonium of 7.2 weight portions and the hydrogen peroxide of 2.86 weight portions are dissolved in 45 weight portions respectively
With in the deionized water of 15 weight portions, and successively it is added slowly in reaction system, in adding procedure,
It is to slowly warm up to 70 DEG C, quickly stirring reaction 20 minutes；
F, reduce bath temperature to room temperature, the sodium hydroxide of 35 weight portions is dissolved in 110 weight portions go from
In sub-water, it is added slowly in four-hole boiling flask, quickly stirring hybrid reaction 30 minutes.Obtain having of white
Machine thing/Starch composite adhesive sticks agent.
Use the method identical with embodiment one and instrument, multiple to the Organic substance/starch prepared by embodiment three
Closing adhesive to detect, according to testing result, the mean values of described product viscosity value is
26800mPa S, meets the viscosity requirement as corrugated board adhesive；Record the solid content of adhesive
Being 35.5%, possess preferable adhesive non-volatile part content, drying property is preferable；Use prunus mume (sieb.) sieb.et zucc. Teller-torr
Benefit thermogravimetric analyzer (TG) carries out thermal stability analysis (not shown) to the adhesive of preparation, can obtain
The initial decomposition temperature of adhesive is about 284.3 DEG C, and final decomposition temperature is about 442 DEG C, illustrates to use this
The adhesive that in patent prepared by method possesses preferable thermostability；By centrifugal test, depositing of adhesive can be obtained
Phase, about between 3 months to 6 months, illustrates the composite water soluble adhesive tool prepared with method in this patent
Standby preferable storage stability.
Comparative example one
The raw material of the starch adhesive prepared by comparative example one is:
Corn starch: technical grade, peak, Suzhou Fine Chemical Co., Ltd, described corn starch is that straight chain forms sediment
Powder and the mixture of amylopectin, amylose with shared by amylopectin proportion respectively be about 28% and
72%；
Ferrous sulfate: technical grade, Changsha Yi Feng chemical industry Trade Co., Ltd.；
Montmorillonite: the inorganic montmorillonite of sodio, technical grade, Sanding Sci. & Tech. Co., Ltd., Zhejiang；
Sodium hydroxide: technical grade, Hangzhou industrial chemicals company limited；
Borax: technical grade, Lianyungang Hong Fangpeng Products Co., Ltd；
Hydrogen peroxide: technical grade, Shijiazhuang chemical reagent work；Water is drinking water.
Described in comparative example one, the preparation process of starch adhesive is as follows:
(1) in 500mL beaker, 230mL water and 0.5g FeSO are added4, treat FeSO4After dissolving,
Add 50.0g starch, stir 10min；
(2) by 1.8mL H2O2Add in (1), continue stirring；
(3) in 100mL beaker, add 30mL water, put into 5.0g NaOH, after it dissolves,
It is slowly added in the beaker of (1), continues stirring；
(4) in 100mL beaker, add 20mL water, add 1.0g Borax, after it dissolves, slow
In the slow beaker adding (1), distinguish soda liquid beaker and Borax beaker with 20mL water, and all pour into
(1), in beaker, continue to stir to retrogradation, stand thinning, obtain hydrogen peroxide oxidation starch adhesive.
Obtaining the viscosity of adhesive described in comparative example one the most afterwards is 8520mPa S, and solid content is
21%, compared with comparative example one, the viscosity of Organic substance of the present invention/starch composite water soluble adhesive
25070-26800mPa S, solid content is 31%-35.5%, and this kind of viscosity is more suitable for executing of starch adhesive
Work is coated with, and higher solid content makes adhesive can faster be dried after coating, can illustrate that the present invention is made
The performance of standby Organic substance/starch composite water soluble adhesive is better than prior art, has broad application prospects.
Claims (17)
1. Organic substance/starch composite water soluble adhesive, it is characterised in that it is by starch after cross-linking
Major ingredient adds oxidant, paste agent and compounded mix reaction obtain；
Wherein, described starch major ingredient includes amylose and amylopectin, and the described starch after crosslinking is logical
After first amylose being carried out pretreatment with the first cross-linking agent and hydrophilizing agent, then with the second cross-linking agent and side chain
React after starch mixing and obtain；
Wherein, described first cross-linking agent is isophorone diisocyanate, and described second cross-linking agent is three hydroxyl first
Base propane, described hydrophilizing agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid；Wherein relative to starch major ingredient
Raw material 180-220 weight portion, oxidant addition is 7-10 weight portion.
Aqueous Adhesives the most according to claim 1, wherein, relative to starch major ingredient raw material 180-220
Weight portion, cross-linking agent total amount is 60-80 weight portion, and hydrophilizing agent is 4.8-5.6 weight portion, and oxidant is 7-10
Weight portion；Wherein, the mass ratio of the first cross-linking agent and the second cross-linking agent is 8-15:1.
Aqueous Adhesives the most according to claim 2, wherein, cross-linking agent total amount is 65-75 weight portion,
Hydrophilizing agent is 5.0-5.4 weight portion, and oxidant is 8-9.5 weight portion；Wherein, the first cross-linking agent and second is handed over
The mass ratio of connection agent is 11-12:1.
4. according to the Aqueous Adhesives described in Claims 2 or 3, wherein, paste agent is 25-35 weight portion；
Compounded mix is 10-20 weight portion.
Aqueous Adhesives the most according to claim 4, wherein, paste agent is 28-33 weight portion；Multiple
Closing filler is 12-18 weight portion.
Aqueous Adhesives the most according to claim 1, wherein, described oxidant includes hydrogen persulfate
Salt and/or hydrogen peroxide；Described paste agent is selected from sodium hydroxide or potassium hydroxide；Described compounded mix is de-for covering
Soil.
Aqueous Adhesives the most according to claim 1 and 2, wherein, described in described starch major ingredient
The weight portion of amylose is 40-50, and the weight portion of described amylopectin is 140-170.
Aqueous Adhesives the most according to claim 6, wherein, oxidant is that persulfuric acid hydrogen salt is with double
The mixture of oxygen water, described persulfuric acid hydrogen salt is 5-7.2 weight portion, and described hydrogen peroxide is 2-2.8 weight portion.
Aqueous Adhesives the most according to claim 8, wherein, described persulfuric acid hydrogen salt is 5.5-6.8
Weight portion, described hydrogen peroxide is 2.5-2.7 weight portion.
Aqueous Adhesives the most according to claim 1, raw material also includes cosolvent.
11. Aqueous Adhesives according to claim 10, described cosolvent is acetone.
12. according to claims 1 to 3, the Aqueous Adhesives described in 6,8-11 any one, described adhesive
Viscosity be 25070-26800mPa S.
The preparation method of the Aqueous Adhesives described in 13. any one of claim 1～12, comprises the steps:
(1) with the first cross-linking agent and hydrophilizing agent, the amylose in starch major ingredient is carried out pretreatment；
(2) amylose after the pre-treatment adds the second cross-linking agent and amylopectin reacts；
(3) addition paste agent, oxidant, compounded mix carry out reaction and obtain Organic substance/starch composite water soluble
Adhesive；
Wherein, described first cross-linking agent is isophorone diisocyanate, and described second cross-linking agent is three hydroxyl first
Base propane, hydrophilizing agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid.
14. preparation methoies according to claim 13, comprise the steps:
(1) the pretreatment reaction stage of amylose comprises the steps:
Reaction is crosslinked in 80-100 DEG C after (i) amylose and the mixing of the first cross-linking agent；
(ii) product that addition hydrophilizing agent and step (i) obtain is in 40-60 DEG C of reaction；
(2) the normal reaction stage comprises the steps:
I () adds the second cross-linking agent and adds amylopectin after 80-100 DEG C of reaction and carry out in 30-50 DEG C anti-
Should；
(ii) there is oxidation reaction in 50-70 DEG C after adding oxidant；
(iii) add paste agent to react；And
Add before or after either step after (i) step in amylose pretreatment reaction stage
Montmorillonite generation compound reaction obtains Organic substance/starch composite water soluble adhesive.
15. preparation methoies according to claim 14, wherein, at the pretreatment reaction of amylose
Add montmorillonite after (i) step in stage before (ii) step to react with (i) products therefrom.
16. 1 kinds of Organic substance/starch composite water soluble adhesives, by the system described in any one of claim 13-15
Preparation Method prepares.
17. claim 1～12 or any one of claim 16 described in Organic substance/starch composite water soluble adhesive
Application in corrugated board adhesive field.
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