CN104178057A - Composite organic matter/starch waterborne adhesive as well as preparation method and application thereof - Google Patents
Composite organic matter/starch waterborne adhesive as well as preparation method and application thereof Download PDFInfo
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- CN104178057A CN104178057A CN201410428613.5A CN201410428613A CN104178057A CN 104178057 A CN104178057 A CN 104178057A CN 201410428613 A CN201410428613 A CN 201410428613A CN 104178057 A CN104178057 A CN 104178057A
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Abstract
The invention relates to the field of adhesives for corrugated paperboards and particularly relates to a composite organic matter/starch waterborne adhesive as well as a preparation method and an application thereof. The adhesive is obtained by adding an oxidant, a gelatinizing agent and composite filler into cross-linked starch serving as a main ingredient and reacting, wherein the starch main ingredient comprises amylose and amylopectin, the cross-linked starch is obtained by pretreating amylose by virtue of a first crosslinking agent and a hydrophilc agent and then mixing with a second crosslinking agent and amylopectin and reacting, the first crosslinking agent is isophorone diisocyanate, the second crosslinking agent is trimethylolpropane, and the hydrophilc agent is selected from dimethylolpropionic acid or dimethylolbutanoic acid, wherein relative to 180-220 parts by weight of starch ingredient, the addition of the oxidant is 7-10 parts by weight. Due to adoption of the composite organic/starch waterborne adhesive disclosed by the invention, the problem of poor adhesion in the production process of the corrugated paper cases, the moisture resistance and the constructability of the adhesive for the corrugated paper cases are improved and the requirements of safety and environmental friendliness are met.
Description
Technical field
The present invention relates to corrugated cardboard sizing agent field, be specifically related to organism/starch composite water soluble sizing agent of a kind of environment-friendly type and its preparation method and application.
Background technology
China is packing big country in the world, Corrugated Box occupies critical role in China's packaging industry, especially after entering 21 century, the corrugation package paper industry of China has been accelerated development step especially, has formed the production base of North China, Yangtze River Delta, the Delta of the Pearl River three large fluting boards and products thereof at present.Why corrugation package paper and derived product thereof obtain high speed development, that the features such as the lightweight that it possesses, eleganceization, repeatability, designability can meet the packing demand of all trades and professions product greatly because the development of fluting board industry meets the demand of Environmental Protection in China, Sustainable development and conservation-minded society.
Because These characteristics, fluting board is more suitable for the developing direction as following package packing supplies, but in its production process, one of problem of most critical is a difficult problem for the Poor cohesion of fluting board.Corrugated Box is the plate object being bonded by Case Board and corrugating medium.Between them, by specific sizing agent, bond, so sizing agent is the main subsidiary material in corrugated board production process.Its quality diameter has affected the performance of Corrugated Box.In Corrugated Box production process, the sizing agent kind of use is a lot, mainly contains starch series, polyvinyl alcohol, acetate emulsion, water glass etc.At present, the most widely used is the sizing agent of starch series.This is mainly due to when preparing Sumstar 190, and the methylol in ative starch on glucose unit is oxidized to carboxyl, and the stability of sizing agent is improved significantly; Meanwhile, oxidizing reaction has reduced the quantity of hydroxyl in starch molecule, and molecular association is obstructed, and has weakened the binding ability of intermolecular hydrogen bonding.In addition, in reaction process, glucosides chain break makes macromolecules degradation, thereby has reduced the viscosity of starch adhesive, and improves the performances such as its mobility, rate of drying, makes it practicality and strengthens.
Summary of the invention
The technical problem that the present invention solves is: the inventor studies rear discovery with keen determination, there are some shortcomings in traditional starch series sizing agent, as prepared in starch adhesive process, need to use borax as linking agent, and borax is poisonous, be in contact with it for a long time acute poisoning phenomenons such as there will be neurasthenia, arthrodynia chronic poisoning or vomiting, diarrhoea, erythema, cycle system disorders, shock, stupor; The viscosity of the starch adhesive of preparation is not easy to control, and as hyperoxidation in preparation process, the agglutinating value(of coal) of sizing agent declines; When degree of oxidation is inadequate, the poor stability of sizing agent, mobility is little, and viscosity causes being difficult to greatly applying glue; The problems such as wet fastness is not good, when having a humid climate, exists corrugated cardboard partially soft, and the rate of drying of sizing agent is slow, Poor cohesion phenomenon increases.
So, in order to overcome the deficiencies in the prior art, the invention provides a kind of technology of preparing the adjustable compound high viscosity Aqueous Adhesives of organism/starch of environmental protection, moisture-proof, viscosity without boron compound.A kind of safety and environmental protection, moisture resistance properties, adhesive property is good, viscosity is adjustable organism/starch combined corrugated board sizing agent are provided, and the preparation method of this environment-friendly type composite adhesive is provided.
Specifically, for the deficiencies in the prior art, the invention provides following technical scheme:
Organism/starch composite water soluble sizing agent, is characterized in that, it obtains by adding oxygenant, paste agent and compounded mix reaction in the starch major ingredient after crosslinked;
Wherein, described starch major ingredient comprises amylose starch and amylopectin, and described starch after crosslinked is by first with the first linking agent and hydrophilizing agent, amylose starch being carried out after pre-treatment, then mixes with the second linking agent and amylopectin afterwards and react and obtain;
Wherein, described the first linking agent is isophorone diisocyanate, and described the second linking agent is TriMethylolPropane(TMP), and described hydrophilizing agent is selected from dimethylol propionic acid or dimethylolpropionic acid; Wherein, with respect to starch major ingredient raw material 180-220 weight part, oxygenant addition is 7-10 weight part.
Preferably, in above-mentioned Aqueous Adhesives, with respect to starch major ingredient raw material 180-220 weight part, linking agent total amount is 60-80 weight part, is preferably 65-75 weight part, and hydrophilizing agent is 4.8-5.6 weight part, be preferably 5.0-5.4 weight part, oxygenant is 7-10 weight part, is preferably 8-9.5 weight part; Wherein, the mass ratio of the first linking agent and the second 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 part, is preferably 28-33 weight part, and compounded mix 10-20 weight part, is preferably 12-18 weight part.
Preferably, in above-mentioned Aqueous Adhesives, described oxygenant comprise hydrogen persulfate salt and or hydrogen peroxide; Described paste agent is selected from sodium hydroxide or potassium hydroxide; Described compounded mix is polynite.
Preferably, in above-mentioned Aqueous Adhesives, described in described starch major ingredient, the weight part of amylose starch is 40-50, and the weight part of described amylopectin is 140-170.
Preferably, in above-mentioned Aqueous Adhesives, when oxygenant is the mixture of persulfuric acid hydrogen salt and hydrogen peroxide, persulfuric acid hydrogen salt is 5-7.2 weight part, is preferably 5.5-6.8 weight part, and hydrogen peroxide is 2-2.8 weight part, is preferably 2.5-2.7 weight part.
Preferably, in above-mentioned Aqueous Adhesives, also need to add solubility promoter, be preferably acetone.
Preferably, in above-mentioned Aqueous Adhesives, the viscosity of described sizing agent is 25070-26800mPaS.
The present invention also provides the preparation method of above-mentioned organism/starch composite water soluble sizing agent, comprises the steps:
(1) with the first linking agent and hydrophilizing agent, the amylose starch in starch major ingredient is carried out to pre-treatment;
(2) in pretreated amylose starch, add the second linking agent and amylopectin to react;
(3) add paste agent, oxygenant, compounded mix to react and obtain organism/starch composite water soluble sizing agent;
Wherein, described the first linking agent is isophorone diisocyanate, and described the second linking agent is TriMethylolPropane(TMP), and hydrophilizing agent is selected from dimethylol propionic acid or dimethylolpropionic acid.
Preferably, in the preparation method of above-mentioned organism/starch composite water soluble sizing agent, comprise the steps:
(1) the pretreatment reaction stage of amylose starch comprises the steps:
(i) there is crosslinking reaction in 80-100 ℃ after mixing with the first linking agent in amylose starch;
(ii) add hydrophilizing agent to react in 40-60 ℃ with the reaction product that step (i) obtains;
(2) the normal reaction stage comprises the steps:
(i) add the second linking agent after 80-100 ℃ of reaction, to add again amylopectin to react in 30-50 ℃;
(ii) add after oxygenant, in 50-70 ℃, oxidizing reaction occurs;
(iii) add paste agent to react; And
Before or after arbitrary step after (i) in amylose starch pretreatment reaction stage step, add polynite generation complex reaction to obtain organism/starch composite water soluble sizing agent.
That is, polynite can add before or after (ii) in amylose starch pretreatment reaction stage, also can in step (2), before or after arbitrary step, add and participate in reaction.
Preferably, in above-mentioned preparation method, after (i) step in pretreatment reaction stage of amylose starch, before (ii) step, add polynite and react with (i) products therefrom.
The present invention also provides a kind of organism/starch composite water soluble sizing agent, by above-mentioned preparation method, is made.
The present invention also provides the application of above-mentioned organism/starch composite water soluble sizing agent in corrugated cardboard sizing agent field.
The present invention can simplify the preparation technology of high-performance starch adhesive, solves the problem of Poor cohesion in Corrugated Box production process, improves wet fastness and the application property of Corrugated Box gluing agent, makes it reach the requirement of safety and environmental protection.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric analysis curve of the embodiment of the present invention one gained organism/starch composite water soluble sizing agent.
Embodiment
The present invention adopts two step method to prepare organism/starch composite water soluble sizing agent, adopt vulcabond and TriMethylolPropane(TMP) to replace poisonous borax as linking agent, change traditional method that oxidation pasted starch is prepared starch series sizing agent of passing through, by the part of hydroxyl on vulcabond and water soluble starch molecular chain, react, generate the carbamate groups of strong polarity, increase stability, lower temperature resistance and the adhesive property of starch adhesive.And use TriMethylolPropane(TMP) and isocyanate groups to react, increase the crosslinking degree of sizing agent, then add the raw materials such as oxygenant, paste agent, compounded mix, water and prepare high-performance environmentally-friendly type organism/starch composite adhesive.And to adopt the mixture of amylose starch and two kinds of starch of amylopectin be starch major ingredient, amylopectin, because wherein contain phosphoric acid ester, becomes a kind of good sizing agent so can there is gelatinization; In addition, amylose starch can promote starch generation gelation, thereby increases the viscosity of starch adhesive.In this patent, adopt the mixture of above-mentioned two kinds of starch to carry out the preparation of starch base-material, thus the starch of processability excellence series sizing agent.
Of the present invention a kind of preferred embodiment in, the invention provides a kind of organism/starch composite water soluble sizing agent, the component of this sizing agent and parts by weight are:
Amylose starch (yam starch): 40-50 weight part, amylopectin (W-Gum): 140-170 weight part, sodium hydroxide: 25-35 weight part, potassium hydrogen persulfate: 5-7.2 weight part, hydrogen peroxide: 2-2.86 weight part, isophorone diisocyanate: 53-75 weight part, TriMethylolPropane(TMP): 5-6.6 weight part, organo montmorillonite: 10-20 weight part, dimethylol propionic acid (DMPA) or dimethylolpropionic acid: 4.8-5.6 weight part, deionized water: 650-750 weight part, acetone: 10-30 weight part.
Of the present invention a kind of preferred embodiment in, the preparation method of organism/starch composite water soluble sizing agent of the present invention, comprises the steps:
A, amylose starch is put into 50 ℃, in the thermostatic drying chamber that vacuum tightness is 0.05MPa dry 4 hours standby.Amylopectin is dissolved in deionized water and uses glass stick rapid stirring to become uniform starch fluid standby;
B, isophorone diisocyanate is added to the clean four-hole boiling flask that has reflux exchanger, thermometer and whipping appts, flask is put into water bath with thermostatic control.In flask, add acetone as solubility promoter, dried amylose starch is slowly added in flask, in adding procedure, remain that whipping appts is mechanical stirring state, isophorone diisocyanate is mixed with dry starch Quick uniform under the effect of solubility promoter, then water bath with thermostatic control temperature is risen to 80-100 ℃, stirring reaction 2 hours;
C, water bath with thermostatic control is cooled to 40-60 ℃, dimethylol propionic acid and organo montmorillonite are mixed, add to fast in four-hole boiling flask, at 40-60 ℃, stirring reaction is 15 minutes, then water bath with thermostatic control temperature is risen to 80-100 ℃ of reaction 1 hour;
D, TriMethylolPropane(TMP) is evenly mixed with acetone, add in four-hole boiling flask stirring reaction to after 1 hour.Reduce bath temperature to 35-45 ℃, the amylopectin liquid modulating in a is slowly poured in four-hole boiling flask, tune up stirring velocity reaction 30 minutes;
E, the potassium hydrogen persulfate weighing up and hydrogen peroxide is soluble in water respectively, and successively slowly add in reaction system, in adding procedure, be slowly warming up to 50-70 ℃, rapid stirring reaction 20 minutes;
F, reduction bath temperature are to room temperature, and sodium hydroxide is soluble in water, are slowly added in four-hole boiling flask rapid stirring hybrid reaction 30 minutes.Obtain white organism/starch composite adhesive.
In the present invention, the polysaccharide chain that described amylose starch D-Glucose base connects with α-(Isosorbide-5-Nitrae) glycosidic link, and outside being connected divided by α-Isosorbide-5-Nitrae-glycosidic link between glucose molecule in amylopectin, also have with α-1,6-glycosidic link is connected, in the present invention, the first linking agent is selected isophorone diisocyanate, it is characterized in that, the activity of two isocyanatos (N=C=O) is different, the isocyanato being directly connected with carbocyclic ring is comparatively active, activity is lower due to sterically hindered effect for the isocyanato being connected with methylene radical, after the first linking agent is mixed with amylose starch, the part of hydroxyl of amylose starch is reacted with active stronger isocyanato on the first linking agent, form carbamate groups, the hydroxyl of follow-up hydrophilizing agent and the second linking agent reacts with active weak isocyanato on the first linking agent, form carbamate groups and complete crosslinked, in the present invention, hydrophilizing agent used is characterised in that, it comprises two kinds of groups: hydroxyl and hydrophilic radical (carboxyl).Wherein, hydroxyl reacts with the isocyanato of the first linking agent, generate carbamate groups, hydrophilic radical on hydrophilizing agent by hydrogen bond action and with the second linking agent keyed jointing, its hydrophilic radical is given organism/starch composite water soluble sizing agent wetting ability of the present invention, make its adjustability that realizes product viscosity in application process, can regulate by changing solvent quality the viscosity of product.
For technical characterictic of the present invention, object and effect being had more clearly, understand, now with embodiment, describe the specific embodiment of the 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 starch (yam starch), industrial goods, Aladdin reagent;
Amylopectin (W-Gum), industrial goods, Aladdin reagent;
Dimethylol 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, Shanghai Qing Xi Chemical Industry Science Co., Ltd;
Hydrogen peroxide, analytical pure, Tianjin Fu Yu Fine Chemical Co., Ltd;
TriMethylolPropane(TMP), analytical pure, Chengdu Ke Long chemical reagent factory;
Acetone, analytical pure, Yantai City is Chemical Co., Ltd. in pairs;
Organo montmorillonite, industrial goods, Zhengzhou great waves Chemical Co., Ltd..
Wherein, organo montmorillonite of the present invention can be by buying or to the inorganic imvite modified organo montmorillonite that obtains hydroxyl and carboxyl, (hydroxy radical content accounts for the more than 60% of functional group content with the conventional method of modifying in this area, carboxyl-content accounts for below 40% of functional group content), in following embodiment, organo montmorillonite used is the industrial goods of buying from Zhengzhou great waves Chemical Co., Ltd..
Embodiment mono-
Organism/starch composite water soluble sizing agent, proportioning raw materials is as shown in table 1.
Table 1 organism/starch composite water soluble sizing agent proportioning raw materials table (quality, unit: g)
Preparation method:
A, the amylose starch of 45 weight parts is put into 50 ℃, in the thermostatic drying chamber that vacuum tightness is 0.05MPa dry 4 hours standby.The amylopectin of 155 weight parts being dissolved in the deionized water of 550 weight parts uses glass stick rapid stirring to become uniform starch fluid standby;
B, the isophorone diisocyanate of 65 weight parts is added to the clean four-hole boiling flask that has reflux exchanger, thermometer and whipping appts, flask is put into water bath with thermostatic control.In flask, add the acetone of 15 weight parts as solubility promoter, the amylose starch of 45 dried weight parts is slowly added in flask, in adding procedure, remain that whipping appts is mechanical stirring state, isophorone diisocyanate is mixed with dry starch Quick uniform under the effect of solubility promoter, then water bath with thermostatic control temperature is risen to 90 ℃, stirring reaction 2 hours;
C, water bath with thermostatic control is cooled to 50 ℃, the organo montmorillonite of the DMPA of 5.2 weight parts and 15.7 weight parts is mixed, add to fast in four-hole boiling flask, at 50 ℃, stirring reaction is 15 minutes, then water bath with thermostatic control temperature is risen to 90 ℃ of reactions 1 hour;
D, the TriMethylolPropane(TMP) of 5.5 weight parts is evenly mixed with the acetone of 5 weight parts, add in four-hole boiling flask stirring reaction to after 1 hour.Reduce bath temperature to 40 ℃, the amylopectin liquid modulating in a is slowly poured in four-hole boiling flask, tune up stirring velocity reaction 30 minutes;
E, the hydrogen peroxide of the potassium hydrogen persulfate of 6.3 weight parts and 2.5 weight parts is dissolved in respectively in the deionized water of 40 weight parts and 10 weight parts, and successively slowly adds in reaction system, in adding procedure, be slowly warming up to 60 ℃, rapid stirring reaction 20 minutes;
F, reduction bath temperature, to room temperature, are dissolved in the sodium hydroxide of 31 weight parts in the deionized water of 100 weight parts, are slowly added in four-hole boiling flask rapid stirring hybrid reaction 30 minutes.Obtain white organism/starch composite water soluble sizing agent.
The viscosity of using the HADV-II+PRO type rotational viscosimeter detection composite adhesive of U.S. Brookfield, the mean values of detection is 25070mPaS, meets the viscosity demand with sizing agent as corrugated cardboard; According to the solid content of the standard test sizing agent of ISO 124:1997, the solid content that obtains sizing agent is 32.5%, possesses non-volatile part of content of good sizing agent, and drying property is better; Use plum Teller-Tuo benefit thermogravimetric analyzer (model: METTLER TOLEDO TGA/DSC 1analyzer) sizing agent of preparation is carried out to thermal stability analysis, analytical results as shown in Figure 1, from figure, decomposition curve can be found out, the initial decomposition temperature of the sizing agent of preparation is about 272.1 ℃, final decomposition temperature is about 445 ℃, illustrates and uses the sizing agent that in this patent prepared by method to possess good thermotolerance.Use Hunan instrument H1850 type whizzer to carry out centrifugal Detection of Stability test to the sizing agent of preparation, sample is divided in two centrifuge tubes, centrifugal rotational speed is 3000 revs/min, have altogether centrifugal 3 times, each 5 minutes, find that the sample of one of them centrifuge tube is in centrifugal a little precipitation that occurs afterwards for the second time, centrifuged deposit increases for the third time; The sample of another one centrifuge tube is in centrifugal a little precipitation that occurs for the third time.Illustrate that shelf lives of sample of preparation greatly between 4 months to 6 months, illustrates that the composite adhesive that in this patent prepared by method possesses good stability in storage.
Embodiment bis-
Organism/starch composite water soluble sizing agent, preparation method is as follows:
A, the amylose starch of 40 weight parts is put into 50 ℃, in the thermostatic drying chamber that vacuum tightness is 0.05MPa dry 4 hours standby.The amylopectin of 140 weight parts being dissolved in the deionized water of 550 weight parts uses glass stick rapid stirring to become uniform starch fluid standby;
B, the isophorone diisocyanate of 53 weight parts is added to the clean four-hole boiling flask that has reflux exchanger, thermometer and whipping appts, flask is put into water bath with thermostatic control.In flask, add the acetone of 15 weight parts as solubility promoter, the amylose starch of 40 dried weight parts is slowly added in flask, in adding procedure, remain that whipping appts is mechanical stirring state, isophorone diisocyanate is mixed with dry starch Quick uniform under the effect of solubility promoter, then water bath with thermostatic control temperature is risen to 80 ℃, stirring reaction 2 hours;
C, water bath with thermostatic control is cooled to 40 ℃, the organo montmorillonite of the trishydroxymethyl butyric acid of 4.8 weight parts and 10 weight parts is mixed, add to fast in four-hole boiling flask, at 40 ℃, stirring reaction is 15 minutes, then water bath with thermostatic control temperature is risen to 80 ℃ of reactions 1 hour;
D, the TriMethylolPropane(TMP) of 5 weight parts is evenly mixed with the acetone of 5 weight parts, add in four-hole boiling flask stirring reaction to after 1 hour.Reduce bath temperature to 35 ℃, the amylopectin liquid modulating in a is slowly poured in four-hole boiling flask, tune up stirring velocity reaction 30 minutes;
E, the hydrogen peroxide of the hydrogen persulfate sodium of 5 weight parts and 2 weight parts is dissolved in respectively in the deionized water of 35 weight parts and 10 weight parts, and successively slowly adds in reaction system, in adding procedure, be slowly warming up to 50 ℃, rapid stirring reaction 20 minutes;
F, reduction bath temperature, to room temperature, are dissolved in the sodium hydroxide of 25 weight parts in the deionized water of 90 weight parts, are slowly added in four-hole boiling flask rapid stirring hybrid reaction 30 minutes.Obtain white organism/starch composite adhesive.
Use method and the instrument identical with embodiment mono-, organism/starch composite water soluble the sizing agent prepared to embodiment bis-detects, known according to detected result, the mean values of described product viscosity value is 24800mPaS, meets the viscosity demand with sizing agent as corrugated cardboard; The solid content that records sizing agent is 31%, possesses non-volatile part of content of good sizing agent, and drying property is better; Use plum Teller-Tuo benefit thermogravimetric analyzer (TG) to carry out thermal stability analysis (not shown) to the sizing agent of preparation, the initial decomposition temperature that can obtain sizing agent is about 265.7 ℃, final decomposition temperature is about 440 ℃, illustrates and uses the sizing agent that in this patent prepared by method to possess good thermotolerance; By centrifugal test, the phase of depositing that can obtain sizing agent between 3 months to 5 months, illustrates that the composite water soluble sizing agent of preparing with method in this patent possesses good stability in storage greatly.
Embodiment tri-
Organism/starch composite water soluble sizing agent, preparation method is as follows:
A, the amylose starch of 50 weight parts is put into 50 ℃, in the thermostatic drying chamber that vacuum tightness is 0.05MPa dry 4 hours standby.The amylopectin of 170 weight parts being dissolved in the deionized water of 590 weight parts uses glass stick rapid stirring to become uniform starch fluid standby;
B, the isophorone diisocyanate of 75 weight parts is added to the clean four-hole boiling flask that has reflux exchanger, thermometer and whipping appts, flask is put into water bath with thermostatic control.In flask, add the acetone of 20 weight parts as solubility promoter, the amylose starch of 50 dried weight parts is slowly added in flask, in adding procedure, remain that whipping appts is mechanical stirring state, isophorone diisocyanate is mixed with dry starch Quick uniform under the effect of solubility promoter, then water bath with thermostatic control temperature is risen to 100 ℃, stirring reaction 2 hours;
C, water bath with thermostatic control is cooled to 60 ℃, the organo montmorillonite of the trihydroxy methyl propionic acid of 5.6 weight parts and 20 weight parts is mixed, add to fast in four-hole boiling flask, at 60 ℃, stirring reaction is 15 minutes, then water bath with thermostatic control temperature is risen to 100 ℃ of reactions 1 hour;
D, the TriMethylolPropane(TMP) of 6.6 weight parts is evenly mixed with the acetone of 5 weight parts, add in four-hole boiling flask stirring reaction to after 1 hour.Reduce bath temperature to 45 ℃, the amylopectin liquid modulating in a is slowly poured in four-hole boiling flask, tune up stirring velocity reaction 30 minutes;
E, the hydrogen peroxide of the hydrogen persulfate ammonium of 7.2 weight parts and 2.86 weight parts is dissolved in respectively in the deionized water of 45 weight parts and 15 weight parts, and successively slowly add in reaction system, in adding procedure, be slowly warming up to 70 ℃, rapid stirring reaction 20 minutes;
F, reduction bath temperature, to room temperature, are dissolved in the sodium hydroxide of 35 weight parts in the deionized water of 110 weight parts, are slowly added in four-hole boiling flask rapid stirring hybrid reaction 30 minutes.Obtain white organism/starch composite adhesive.
Use method and the instrument identical with embodiment mono-, organism/starch the composite adhesive prepared to embodiment tri-detects, known according to detected result, the mean values of described product viscosity value is 26800mPaS, meets the viscosity demand with sizing agent as corrugated cardboard; The solid content that records sizing agent is 35.5%, possesses non-volatile part of content of good sizing agent, and drying property is better; Use plum Teller-Tuo benefit thermogravimetric analyzer (TG) to carry out thermal stability analysis (not shown) to the sizing agent of preparation, the initial decomposition temperature that can obtain sizing agent is about 284.3 ℃, final decomposition temperature is about 442 ℃, illustrates and uses the sizing agent that in this patent prepared by method to possess good thermotolerance; By centrifugal test, the phase of depositing that can obtain sizing agent between 3 months to 6 months, illustrates that the composite water soluble sizing agent of preparing with method in this patent possesses good stability in storage greatly.
Comparative example one
The raw material of the starch adhesive that comparative example one is prepared is:
W-Gum: technical grade, peak, Suzhou Fine Chemical Co., Ltd, described W-Gum is the mixture of amylose starch and amylopectin, the shared proportion of amylose starch and amylopectin is approximately respectively 28% and 72%;
Ferrous sulfate: technical grade, Changsha Yi Feng chemical industry Trade Co., Ltd.;
Montmorillonite: the inorganic polynite of sodium base, 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 tap water.
Described in comparative example one, the preparation process of starch adhesive is as follows:
(1) in 500mL beaker, add 230mL water and 0.5g FeSO
4, treat FeSO
4after dissolving, add 50.0g starch, stir 10min;
(2) by 1.8mL H
2o
2add in (1), continue to stir;
(3) in 100mL beaker, add 30mL water, put into 5.0g NaOH, after it dissolves, slowly add in the beaker of (1), continue to stir;
(4) in 100mL beaker, add 20mL water, add 1.0g borax, after it dissolves, slowly add in the beaker of (1), with 20mL water difference soda liquid beaker and borax beaker, and all pour in the beaker of (1), continue to be stirred to retrogradation, standing thinning, obtain hydrogen peroxide oxidation starch adhesive.
The viscosity that obtains afterwards after testing sizing agent described in comparative example one is 8520mPaS, solid content is 21%, compare with comparative example one, the viscosity 25070-26800mPaS of organism/starch composite water soluble sizing agent of the present invention, solid content is 31%-35.5%, this kind of viscosity is more suitable for the construction coating in starch adhesive, and higher solid content can be dried sooner sizing agent after coating, the performance that organism/starch composite water soluble sizing agent that the present invention is prepared can be described is better than prior art, has broad application prospects.
Claims (13)
1. organism/starch composite water soluble sizing agent, is characterized in that, it obtains by adding oxygenant, paste agent and compounded mix reaction in the starch major ingredient after crosslinked;
Wherein, described starch major ingredient comprises amylose starch and amylopectin, and described starch after crosslinked is by first with the first linking agent and hydrophilizing agent, amylose starch being carried out after pre-treatment, then mixes with the second linking agent and amylopectin afterwards and react and obtain;
Wherein, described the first linking agent is isophorone diisocyanate, and described the second linking agent is TriMethylolPropane(TMP), and described hydrophilizing agent is selected from dimethylol propionic acid or dimethylolpropionic acid; Wherein, with respect to starch major ingredient raw material 180-220 weight part, oxygenant addition is 7-10 weight part.
2. Aqueous Adhesives according to claim 1, wherein, with respect to starch major ingredient raw material 180-220 weight part, linking agent total amount is 60-80 weight part, be preferably 65-75 weight part, hydrophilizing agent is 4.8-5.6 weight part, is preferably 5.0-5.4 weight part, oxygenant is 7-10 weight part, is preferably 8-9.5 weight part; Wherein, the mass ratio of the first linking agent and the second linking agent is 8-15: 1, and preferably the two mass ratio is 11-12: 1.
3. Aqueous Adhesives according to claim 2, wherein, paste agent is 25-35 weight part, is preferably 28-33 weight part; Compounded mix is 10-20 weight part, is preferably 12-18 weight part.
4. according to the Aqueous Adhesives described in claim 1-3 any one, wherein, described oxygenant comprise hydrogen persulfate salt and or hydrogen peroxide; Described paste agent is selected from sodium hydroxide or potassium hydroxide; Described compounded mix is polynite.
5. Aqueous Adhesives according to claim 1 and 2, wherein, described in described starch major ingredient, the weight part of amylose starch is 40-50, the weight part of described amylopectin is 140-170.
6. Aqueous Adhesives according to claim 4, wherein, oxygenant is the mixture of persulfuric acid hydrogen salt and hydrogen peroxide, described persulfuric acid hydrogen salt is 5-7.2 weight part, be preferably 5.5-6.8 weight part, described hydrogen peroxide is 2-2.8 weight part, is preferably 2.5-2.7 weight part.
7. according to the Aqueous Adhesives described in claim 1～6 any one, raw material also comprises solubility promoter, is preferably acetone.
8. according to the Aqueous Adhesives described in claim 1～7 any one, the viscosity of described sizing agent is 25070-26800mPaS.
9. according to the preparation method of the Aqueous Adhesives described in claim 1～8 any one, comprise the steps:
(1) with the first linking agent and hydrophilizing agent, the amylose starch in starch major ingredient is carried out to pre-treatment;
(2) in pretreated amylose starch, add the second linking agent and amylopectin to react;
(3) add paste agent, oxygenant, compounded mix to react and obtain organism/starch composite water soluble sizing agent;
Wherein, described the first linking agent is isophorone diisocyanate, and described the second linking agent is TriMethylolPropane(TMP), and hydrophilizing agent is selected from dimethylol propionic acid or dimethylolpropionic acid.
10. preparation method according to claim 9, comprises the steps:
(1) the pretreatment reaction stage of amylose starch comprises the steps:
(i) there is crosslinking reaction in 80-100 ℃ after mixing with the first linking agent in amylose starch;
(ii) add hydrophilizing agent to react in 40-60 ℃ with the reaction product that step (i) obtains;
(2) the normal reaction stage comprises the steps:
(i) add the second linking agent after 80-100 ℃ of reaction, to add again amylopectin to react in 30-50 ℃;
(ii) add after oxygenant, in 50-70 ℃, oxidizing reaction occurs;
(iii) add paste agent to react; And
Before or after arbitrary step after (i) in amylose starch pretreatment reaction stage step, add polynite generation complex reaction to obtain organism/starch composite water soluble sizing agent.
11. preparation methods according to claim 10 wherein, add polynite and react with (i) products therefrom after (i) step in pretreatment reaction stage of amylose starch before (ii) step.
12. 1 kinds of organism/starch composite water soluble sizing agents, are made by the preparation method described in claim 9-11 any one.
Described in 13. claims 1～8 or claim 12 any one, organism/starch composite water soluble sizing agent is in the application in corrugated cardboard sizing agent field.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108084283A (en) * | 2017-12-19 | 2018-05-29 | 东莞东美食品有限公司 | A kind of crosslinked starch and preparation method thereof |
| CN112707973A (en) * | 2020-12-24 | 2021-04-27 | 中化石化销售有限公司 | Method for preparing starch ionomer and modified fully-degradable plastic thereof |
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|---|---|---|---|---|
| CN101134881A (en) * | 2007-10-22 | 2008-03-05 | 大庆石油管理局 | Starch adhesive for producing highly intensified waterproof corrugated paper |
| CN101676308A (en) * | 2008-09-18 | 2010-03-24 | 长春大成特用玉米变性淀粉开发有限公司 | Waxy modified starch, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134881A (en) * | 2007-10-22 | 2008-03-05 | 大庆石油管理局 | Starch adhesive for producing highly intensified waterproof corrugated paper |
| CN101676308A (en) * | 2008-09-18 | 2010-03-24 | 长春大成特用玉米变性淀粉开发有限公司 | Waxy modified starch, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084283A (en) * | 2017-12-19 | 2018-05-29 | 东莞东美食品有限公司 | A kind of crosslinked starch and preparation method thereof |
| CN112707973A (en) * | 2020-12-24 | 2021-04-27 | 中化石化销售有限公司 | Method for preparing starch ionomer and modified fully-degradable plastic thereof |
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